EUROPEAN

C OATINGS
www.european-coatings.com dossier 2018

PIGMENTS
The best technical papers on pigments for
high-performance coatings published in the
European Coatings Journal within the past
three years.

PRESENTED BY

22 EFFECT PIGMENTS 94 FORMULATION TRAINING

Shining under the spotlight. How to formulate a metallic basecoat.
2 E D I T OR IA L

Join our Group

“European Coatings Industry”

FUNCTION AND
APPEARANCE
Today´s high-performance coatings require high-end raw materials. This in-
Dr. Sonja Schulte
Editor-in-Chief
cludes pigments, of course. No matter if you require brilliant effects, weather
T +49 511 9910-216 and chemical resistance, corrosion protection or specific colour tones -
sonja.schulte@vincentz.net pigments can do the job!

As a formulator, you are continually called on to be au fait with the latest ad-
vances in research and development. Such knowledge is rarely to be found in
a single package. European Coatings Journal is about to change that. This the-
matic dossier is bursting with information on pigments that we have compiled
for you. In it you will find all the relevant technical papers on pigments that
have been published in European Coatings Journal over the last three years.
Now there’s a welcome development! 

E U R O P E AN CO AT I NGS J O UR N AL 2018
 ECKART EFFECT PIGMENTS

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 4 C ON T E N T S

Source: BASF SE
MARKET REPORT
Global market forcast
for pigments from
2014

08
Source: Werner Rudolf Cramer

PRODUCT
OVERVIEW
Interference
pigments

16 22
EFFECT PIGMENTS
How metallic effects can be best
achieved in UV curing finishes

EUROPEAN COATINGS JOURNAL 2018

6 MARKET REPORT I 22 SHINING UNDER THE SPOTLIGHT

Global market forcast for high performance How metallic effects can best be
pigments in 2013 achieved in UV curing finishes
Oliver Kipfmüller, Eckart
8 MARKET REPORT II
Global pigment market in 2014 26 NEW SHADES GROWN FROM SILVER
Surface modification of aluminium gibes strong
colour travel properties
12 TOP INDUSTRY MOVE I
Jonathan D. Doll and Jennifer Louis, Sunchemical
Lanxess: New reds from China

32 FORMULATING EXCELLENT
14 TOP INDUSTRY MOVE II AUTOMOTIVE EFFECTS
Ferro Corporation acquired Capelle Pigments NV Eight golgen rules
and certain assests of Delta Performance Products Werner Rudolf Cramer, Cramer

38 RAINBOWS MADE TO ORDER

16 PRODUCT OVERVIEW
The effective use of interference and
Interference pigments
polychromatic colorants
Werner Rudolf Cramer,
18 MIX AND MATCH Cramer and Frank J. Maile, Calr Schlenk
The interplay of various pigment types in strategic
colour design
44 A SPARKLING FUTURE FOR EFFECT PIGMENTS
Werner Rudolf Cramer, Cramer
Advances in technology will open up a wealth of
opportunities
Carsten Handrosch and Carsten Plüg, Merck KGaA

E U R O P E AN CO AT I NGS J O UR N AL 2018
 C O NT E N T S 5

Source: Heraeus

Source: Andrea Lehmkuhl - Fotolia.com

Source: bizoo_n - Fotolia.com

INTERFERENCE
PIGMENTS
A more intense
colour for all
systems

60
Source: Matthias Haas - Fotolia.com

IRON OXIDES
Establishing FORMULATION TRAINING
the causes of How to formulate a
colouring conventional metallic basecoat

74 94

50 SPECIAL EFFECTS 74 COLOUR CHART

Development of new effect pigments that add more Establishing the causes of colouring in iron oxide
than just colour to paint pigments
Raimund Schmid, BASF SE Peter Köhler and Jürgen Kischkewitz, Lanxess

56 SPECIAL EFFECTS - PART 2 80 STRUCTURE DETERMINES SHADE

New effect pigments achieve aged How the crystal lattice of iron spinells affects their
and weathered appearances for coatings appearance
Raimund Schmid, BASF SE Peter Köhler and Jürgen Kischkewitz, Lanxess

60 A MORE INTENSE COLOUR FOR ALL SYSTEMS
Coated aluminium flake interference pigments are
highly stable
Gehard Pfaff and Kirsten Fritsche, Merck KGaA
66 IN SEARCH OF THE PERFECT BLACK PEARL
Darker colour enhances tining options in powder
and liquid coatings
Jonathan D. Doll, Aaron Hollman and
Adam Andreas, Sunchemical
86 FAST FADING BLUES: THE INSIDE STORY
Indoor durability of phytaloyanines can be worse
than expected
Roberto Mazzari, Umberto Dainese and Giovanni
Marsili, Colorificio San Marco S.p.a.
90 GLOWING WITH PROMISE
Daylight fluorescenzt pigments for paints, PVC and
PU open up new applications in packaging
Rami Ismael, Aralon

70 LEAD IS DEAD 94 FORMULATION TRAINING

Maintain opacity and durability and expand the How to formulate a metallic basecoat
colour range with new pigment chemistries Roland Somborn, Axalta
Mark Ryan, The Shephered Color Company
Source cover: Eckart

E U R OP E AN COAT I NGS JO UR N A L 2018

 6 M A R K E T R E P OR T
Source: Adam Radosavljevic - Fotolia.com
HIGH PERFORMANCE PIGMENTS:
A GLOBAL MARKET FORECAST
Despite uncertain economic conditions, the market continues growing. By Roger Rothom (published in ECJ 01/2013).
The global market for high-performance pigments (HPPs) is es-
timated at 144,098 tonnes for 2011, a figure expected to climb
to 168,289 tonnes by 2017. The value of the market is estimat-
ed as $3,603 million in 2011; rising to $4,208 million by 2017 - in
constant money terms. This represents a fairly conservative
CAGR of 2.6% per annum, reflecting the high level of uncer-
tainty over the world economic prospects.
O ur estimate for the HPP markets in 2011 and forecasts for 2017 are
presented in Figure 1, given in thousand tonnes and broken down
by application area.
The largest end-use sector, by some margin, is coatings, forecast to
consume just over 90,000 tonnes by 2017, slightly over half the total
at 56%. This sector is forecast to reach $2,434 million in value by 2017.
This is followed by the plastics segment, which is forecast to account
for almost 38,000 tonnes of HPP sales in 2017, or 22% of the total,
valued at $915 million.
E U R O P E AN CO AT I NGS J O UR N AL 2018
At the other end of the scale, the two smallest end-use markets, non-
impact printing (NIP) and electronics, are each forecast to show pig-
ment sales levels of less than 2,000 tonnes. We expect sales into the
NIP segment to stand at just under 1,000 tonnes and those into the
electronics industry at about 1,400 tonnes in 2017. While these num-
bers are small, these are expected to be the fastest growing areas.
ORGANIC PIGMENTS: LOWER VOLUMES, HIGHER VALUE
Among the different classes of HPP, the market in 2011 was split as
follows.
ąą Inorganic effect pigments: 79% by tonnage and 57% by value (of
which aluminium and bronze contributed 45% by volume and 38%
by value; pearlescent 34% by volume and 18% by value).
ąą Organic HPP: 20% by volume, 42% by value. This shows how much
higher prices are for this class of pigment compared to the effect ones.
We expect this split to remain the same in 2017.
Source: Smithers Rapra
Figure 1: Global forecast for HPP by region, 2011 and 2017 (tonnes)
Source: Smithers Rapra
Figure 3: Global forecast for HPP by end-use market, 2011 and
2017 (thousand tonnes)
USA REMAINS LARGEST SINGLE MARKET
In 2011 the European and Asian markets are estimated to have been
similar in size and value at 54-56 thousand tonnes and $1.3 -1.4 bil-
lion. The faster growth of most Asian markets leads to our forecasting
that Asia will move slightly ahead of Europe by 2017 at 66 thousand
tonnes and $1.56 billion compared with 63 thousand tonnes and
$1.55 billion.
We estimate that the United States was the largest single country
market in 2011 at 26-27 thousand tonnes, followed by Japan at just
under 22 thousand tonnes and China at close to 20 thousand tonnes.
We forecast that the US will grow to 30 thousand tonnes by 2017
and remain the leading market, but that China will have moved into
second place at 25-26 thousand tonnes overtaking Japan at around
24 thousand tonnes.
Due to the economic problems in Europe, we are expecting weak
growth in this region of only about 2% per annum over the next five
MA R KE T R EP O R T 7
Source: Smithers Rapra
Figure 2: Global forecast for HPP by pigment class, 2011 and
2017 (million USD)
years. We expect North America to fare slightly better at 2.1% and
Asia as a whole to be at 3.3%. The Asian growth forecast is affected
by a low value of 1.9% for Japan. We see China (4.7%) and India (5.7%)
doing significantly better.
CHINA REMAINS LARGEST PRODUCER AND EXPORTER OF HPP
The almost unprecedented economic issues prevailing at the time of
writing mean that these figures have a higher degree of uncertainty
than would normally be the case. In particular, the Asian growth rates
could be higher if they can substantially isolate themselves from the
problems of the Western economies, especially Europe.
China is now the biggest pigment producer in the world with rapidly in-
creasing output in recent years. It is estimated that total pigment out-
put (including titanium dioxide, carbon black and iron oxide) in China
reached 2.4 million tonnes in 2010. Organic pigment production was
estimated as 200,000 tonnes in 2010; 40% of the world total. HPP pro-
duction, on the other hand was quite modest.
China is also the world’s biggest pigment exporter. Exports of all pig-
ment types reached 900,000 tonnes in 2007, and increased to 1.1 mil-
lion tonnes in 2009, a year-on-year rise of 11%. Organic pigment exports
reached 140,000 tonnes in 2010, up a staggering 30% on the previous
year, with foreign exchange earnings of just over $1 billion. Pigments
produced in China are exported mainly to the US, Germany, Belgium,
Japan, the Netherlands, South Korea, Italy, the UK and some south-east
Asian countries.
Other countries worth mentioning are Russia and Turkey. Both of these
are relatively small markets, but have grown significantly recently. In nor-
mal circumstances they would be expected to continue their progress,
but they are strongly influenced by the developed European markets
and so we have scaled back expectations of annual volume growth to
2.9% for Russia and 4.4% for Turkey. 
E U R OP E AN COAT I NGS JO UR N A L 2018
 8 M A R K E T R E P OR T
Source: BASF SE
A COLOURFUL PICTURE
An over view of the pigment market. By Damir Gagro (published in ECJ 01/2015).
The developments in the pigment market were pleasant in
2014. At least, this is the pigment producers’ perception who
talked to the editorial staff of European Coatings Journal. For
the coming years they are expecting further growth in the
pigment market. Read their views on further market develop-
ments, challenges through regulations and possible over ca-
pacities in the pigment business.
S urging demand for pigments in key end-use markets such as
paints and coatings, plastics, paper, and printing inks, among oth-
ers, represent the primary driver for the strong evolution of the mar-
ket over the past few years.
According to the market research companies Global Industry Analysts
(GIA) and Markets and Markets, the paint and coatings industry glob-
ally consumed 7.5 million metric tonnes of pigments in 2013. Inor-
ganic pigments account for the lion’s share of 93 %. The consumption
of organic pigments was at 0.5 million metric tonnes, state the two
market research companies.
According to Markets and Markets, the pigment market will grow at a
CAGR of 3.6 % and reach 11 million metric tonnes by 2018. The con-
struction industry, which uses pigments in paints and varnishes and
in construction materials in the form of roof tiles, paving stones, etc.,
also represents an important growth indicator for the pigments mar-
ket. Demand for pigments in the printing ink segment is expected to
E U R O P E AN CO AT I NGS J O UR N AL 2018
grow significantly supported by increased printed packaging across
F&B, pharmaceutical, and consumer health industries as well as the in-
creased use of colour printers. GIA, too, expects the market to reach a
volume of 11 million tonnes, but not before 2020 (Table 1 and Table 2).
2014: POSITIVE DEVELOPMENT
As usual, Asia-Pacific holds the leading position in the pigment con-
sumption with a share of roughly 41 % of the total volume. The players
active in the market predict a higher growth rate in this region, too. “
We expect an above-average pigments volume growth in regions with
currently low consumption of paints in relation to the number of oc-
cupants, and respectively in comparison to traditional markets in Eu-
rope and North America. Above all, this applies mainly to architectural
paints in regions like Asia and Latin America. In Europe we expect a low
volume growth of pigment consumption. A more or less constant value
of the pigment market is the result of decreasing price developments
besides overall volume increase”, says Dr Thomas Metz, Clariant.
Referring to the market developments in the last year, Stefan Süt-
terlin, BASF, states: “The 2014 pigment market presents an uneven
picture. Some industries such as, for example, automotive coatings
have shown a positive global development whereas other segments
– and the paint market is one of them – are flagging in many regions.
Regionally, the first six months were promising in Europe but since
the summer, the economy appears to be weakening. The situation in

Region/Country 2013 2020
Source: GIA
US 88,901.5 131,087.5
Europe 100,629.7 138,858.9
Asia-Pacific 290,149.2 475,128.7

Rest of World 36,723.2 54,439.8
Total 516,403.6 799514.9
Tab.1: Organic Pigment consumption in tonnes by country/region
South America was difficult in 2014 and even China did not generate
the usual growth rates, in particular at the beginning of the year”.
The uneven picture is confirmed by Axel Schneider,
Cathay, Industries: “The market situation is certainly different with
regards to the various pigment types. Looking at our own core busi-
ness, synthetic iron oxides, the market is in significant movement. Old
production plants are closing, new ones are being built. The currency
developments hit producers in the regions in different ways. On the
consumption side we have experienced the year 2014 pleasantly viv-
id, which has shown this market deviating from the overall economy”.
MODERATE GROWTH EXPECTED
The suppliers are looking into the future with confidence. “Without
a doubt the demand will grow in North America and in the currently
very dynamic African region. Governmental investment programs will
determine for iron oxides if there will be reductions on a regional ba-
sis. If savings receive priority to investments, there could be decreases
in consumption on a country to country level. In total we expect a
continuous moderate growth”, predicts Schneider.
The unstable situation in Ukraine as well as in the Near East is another
factor that is going to hamper growth in Europe, however Sütterlin an-
ticipates little tailwind from the economic situation: “In Asia, the growth
engine China is bound to kick back albeit on a slightly lower level. We
believe that the demand for coatings in North America is going to con-
tinue. Concerning the automotive industry, we anticipate overall growth
in 2015 to be slightly stronger than in 2014, above all driven by the eco-
nomic recovery in South America and China. We expect stable growth
in the construction sector, which is bound to be a bit more pronounced
in the US and slightly weaker in Asia”.
The segments automotive and industrial coatings are very promising
for high performance pigments, according to Michael T. Venturini, Sun
Chemical. “ Automotive and industrial coatings will remain the founda-
tion for growth of high performance pigments markets, however, grow-
ing requirements for improved stability and functionality will position
architectural and building materials for tremendous potential growth.
Globally, we expect to see further growth in high performance pigments
as the replacement of heavy metal pigments continues. Legislative re-
quirements will play an increasing role in the reformulation.
The underlying long-term trend is for continued global growth in the
MA R KE T R EP O R T 9
Region/Country 2013 2020
US 1,280,875.6 1,747,369.7
Europe 1,502,573.5 1,860,069.4
Asia-Pacific 3,430,464.9 5,207,168.5
Rest of World 834,173.0 1,191,300.3
Total 7,048,087.0 10005907.9
Tab 2. Inorganic pigment consumption in tonnes by country/region
coatings sector and, combined with continued underlying growth in
the construction sector globally. “We expect a constant rise in de-
mand for synthetic iron oxides. The global economic crisis of 2009
had a significant impact and since then we have experienced greater
volatility and regional variation due to macro-economic factors. This
development is mainly driven by the urbanization megatrend and
thus increasing demand for pigments in emerging markets and a re-
bound of construction activities in North America and Europe”, says
Thomas Pfeiffer, Lanxess.
CONSOLIDATION INCREASES
The pigment producers expect an increasing competitive environment
in the market. “A further market consolidation in favour of large paint
and coatings manufacturers is expected, whereby global competition
puts pressure on pigments”, says Metz. The consolidation is noticeable
in the market for iron oxides, agrees Pfeiffer: “The global manufacturing
industry for synthetic iron oxide is undergoing a period of consolida-
tion. This effect is most noticeable in China where a significant number
of small and medium-sized producers have exited the market in the
last 18 months. Enforcement of environmental regulations by the Chi-
nese authorities is having a significant impact and will continue to do so
in the coming years, something that is confirmed also in the five-year
plans of the People’s Republic of China. The country remains the larg-
est source of synthetic iron oxide but total manufacturing capacities in
China have fallen significantly in recent years”.
EXPANSIONS DO NOT LEAD TO OVER-CAPACITIES
Recent announcements regarding increasing production volumes
and investments in expansions may lead to the thought that capaci-
ties are rapidly growing around the globe. The producers are not con-
cerned about over-capacities. “This is particularly the case in the iron
oxide market. Different manufacturers are erecting new capacities for
different reasons, Cathay Industries included. On the other side there
are also some capacities that have been closed down and further
closures will follow, so that in total we do not expect over-capacities.
Hopefully we will see some excess capacity after all these changes
that can then cover the future growth in demand”, says Schneider.
A similar view on the situation is shared by Pfeiffer: “In reality, global 
E U R OP E AN COAT I NGS JO UR N A L 2018
 10 M A R K E T R E P OR T
 synthetic iron oxide manufacturing capacities have significantly fallen
in recent years due to the many plant closures in China. This trend is
likely to continue as the capacities being closed down are larger than
the new additional capacities which are becoming available and we
do not anticipate any risk of over-capacity”. He adds: “A lack of clarity
about the development of manufacturing capacities can also arise as
a result of joint ownership of manufacturing facilities. The iron oxide
industry in China has a strong network of intercompany trading and a
history of joint venture ownership. In many cases, joint venture part-
ners – often relatively junior ones – each claim to own the total manu-
facturing capacity of the joint enterprise and this results in misleading
cumulative capacity figures”.
DIFFERENT PICTURE FOR STANDARD PIGMENTS
Regarding standard pigments, there is a little different picture, according
to Sütterlin. “Most of the announced capacity increases concern the clas-
sical standard pigments such as Azo pigments and they are mainly taking
place in China and India. Even in today’s market there are overcapacities
for these pigments, which has resulted in intense price pressure and has
ultimately led to a consolidation among the manufacturers. We expect this
trend to continue. Further capacity increases have been announced for
some high-performance pigments such as PV 23 or PR122, of which some
have already been completed. Similar to standard pigments, we are aware
of greater competitive pressure in this field”, he explains. Metz explains: “An
over-capacity for certain pigments in the market already exists for years. In
the medium and long term, we expect a reduction of capacities, because
an economical production will become more and more difficult. Neverthe-
less, there will also be a selective expansion of capacities of traditional pig-
ment manufacturers in emerging markets, e.g. BRIC, in the future to quickly
serve markets with economic and local production”.
SEEING CHALLENGES THROUGH REGULATIONS AS CHANCES
An increased focus on technical service, quality, performance and
environmental considerations is expected by Venturini. “Consumers
today have access to more information than ever before and in-
creasingly educate themselves prior to making purchases to be sure
the product meets their socio-environmental requirements. Paint
producers are responding and this in turn drives upstream sup-
pliers, including pigment suppliers”, he explains. However, even if
the regulations are increasing regarding the topic environment, the
E U R O P E AN CO AT I NGS J O UR N AL 2018
pigment producers do not see this as a burden. “For many years the
regulatory side has increasingly been impacting the market players,
who have become familiar with such movements. Who considers
this exclusively a thread, uses his resources for developments that
are hard to hold up. But who takes on the challenges pro-actively,
will have best chances to shape his future business successfully,
avoiding a too fast commoditization of his products”, says Schnei-
der. A similar attitude shares Metz, who points at the chances for
the pigment suppliers. “Short-termed new and more stringent regu-
lations often give the impression of an increase in pressure on the
coatings manufacturers as well as pigments manufacturers and raw
material suppliers. In reality, these changes almost always are an
advantage for companies along the supply chain, which foster inno-
vation and use forward-looking existing and future possibilities for a
sustainable pigment and paint and coating manufacturing. Thereby,
companies are able to differentiate and develop their market po-
sition”. However, it must be remembered that in regulations new
limits and transitional periods for the realization should be chosen
in a way that a realistic change to more sustainability in the supply
chain is possible, adds Metz.
“Environmental regulations and social change for sustainable raw
materials are driving rapid change and innovation in all segments of
the paints and coatings market. The trend is well established in Eu-
rope and the United States, but is quickly growing in other regions.
We see self-regulation by paint producers and trade organizations
playing a larger role affecting everything from end-of-life directives
to VOCs to environmental footprints. This drives change and cre-
ates opportunities that will favour those that manufacture to the
highest global standards. We see these challenges as great oppor-
tunities for growth”, says Venturini.  
THIS ARTICLE CONTAINS INFORMATION AND DATA FROM THE
FOLLOWING MARKET STUDIES:
„Pigments and Dyes - a Global Strategic Business Report” by Global
Industry Analysts (GIA)
E-Mail: info411@strategyr.com
„Dyes and Pigments Market - Global Trends & Forecast to 2018“ by
Markets and Markets
E-Mail: ishita.sarkar@marketsandmarkets.com
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12 T O P I N D U S T RY MO VE

Source: Freepik - www.flaticon.com

PIGMENTS: NEW REDS FROM CHINA
In November specialty chemicals company Lanxess has celebrated the completion of construction works at its new plant for
inorganic pigments in Ningbo, China. In the first quarter of 2016, highly saturated red iron oxide pigments will be produced
for the global market using an innovative and highly sustainable new process. By Damir Gagro (published in ECJ 01/2016).

The total investment at the Ningbo site is around EUR 60 mil-
lion for an initial annual synthesis capacity of 25,000 metric
tons. On the same site, Lanxess is building a mixing and milling
plant for inorganic pigments with an annual capacity of 70,000
metric tons. The company has created a total of around 200
new jobs with these two plants which are scheduled to start
production in the first quarter of 2016.
In the future, the company will market their new red iron oxide pig-
ments globally under the well-known “Bayferrox” brand. The main
customers for these pigments are manufacturers of paints and
coatings, as well as the plastics industries. „The mechanical com-
pletion of our plant was in September. Currently we are in the start-
up phase and conducting further tests. It is important to bring the
new pigments into the market with a reproducible quality“, said
Hellwig. As this is the case now, the production is scheduled to start

C hina is the world’s major iron oxide pigments consumer. The

country’s closer focus on sustainable development is leading
to rising demands for environment-friendly premium iron oxide pig-
during the first quarter 2016.

NEW PRODUCTION PROCESS

ments - particularly for red pigment production. “The new plant mani-
fests our continuous investments into new technologies and capacity
expansions. It not only expands our global production capacity but
furthermore strengthens our position as a reliable partner to the cus-
tomers industries with a broader product portfolio, especially with our
new red pigments range”, said Jörg Hellwig, Head of Lanxess Inorganic
Pigments business unit.
The new red iron oxide pigments with an unmatched color hue are pro-
duced by using the innovative Ningbo production process – for which
Lanxess has seeked broadly for patent protection. It will be the first sus-
tainable iron oxide production process in China with a consequent re-
cycling and treatment of all by-products. For example, process optimi-
zation will lead to a significant reduction of carbon dioxide equivalents.

E U R O P E AN CO AT I NGS J O UR N AL 2018

FACTS ABOUT LANXESS‘ NEW NINGBO SITE
Investment: EUR 60 million
Employees: 200
Production capacity: 25,000 tonnes per annum
Another example is that a recycling process of off-gases will lead to
fresh raw materials for production. Compared with the traditional
Penniman Red process, the „Ningbo Process“ uses a special catalyst
to convert laughing gas to air and water. Thanks to the particularly
energy-efficient process, the plant will meet the highest international
environmental standards.
EXPANDING FOOTPRINT IN CHINA
“The new pigment plant in Ningbo will further expand our footprint in
the China market which is of strategic importance to Lanxess. It will
also enable us to meet local customers’ needs for customized and
innovative products in a more efficient manner,” said Rafael Suchan,
Vice President - Asia-Pacific for Lanxess Inorganic Pigments.
Lanxess already operates one of China’s largest plants for iron oxide
pigments in Jinshan, Shanghai. This plant has an annual capacity of
38,000 metric tons of iron oxide yellow and black pigments each year.
The company has an annual production capacity of roughly 375,000
tonnes of iron oxide pigments around the globe – once the Ningbo
site goes on-stream. Apart from China, the pigment producer opera-
tes manufacturing facilities in Germany and Brazil as well as running
additional mixing and milling facilities in Australia, the UK, Spain and
the United States.
T O P I N DU S T R Y M O VE 13
Source: Freepik - www.flaticon.com
“No danger of
overcapacities“
Jörg Hellwig, Head of Lanxess Inorganic Pigments business unit
Five questions to Jörg Hellwig
Why did you choose China for your new plant? The entire Asia-
Pacific region, and in particular China, remains the largest market for
pigments. Apart from the high demand, China offers an excellent raw
materials supply situation.
How do you rate the demand for your new reds? We can offer
more yellowish reds. Especially the paints industry likes mixing colours.
Now they can start mixing with a brighter colour tone. Our customers
have shown that there is a great demand for our new pigments. This
puts up the pressure to start production as early as possible. But it is
important to make sure that we can supply reproducible quality once
we go on-stream. This is now the case. We have scheduled to start with
production in the first quarter in 2016.
What is so special about the new plant and process? It will be the
first sustainable iron oxide production process in China with a conse-
quent recycling and treatment of all by-products. Compared with the
traditional Penniman Red process, the Ningbo Process uses a special
catalyst to convert laughing gas to air and water. We have named it
Ningbo Process to show our appreciation to the city.
To what extent do you see the danger of overcapacities in the
market? Not all announcemnets are actually realised. In many cases
these projects are replacement investments. Environmental restric-
tions are becoming more similar worldwide, one could even say they
are becoming almost standardized. If this is advancing further, older
sites in China will not be expanded or will be completely closed. An
new-built is most likely linked to a previous reduction in capacities. The
demand for pigments is increasing, therefore I do not see the danger
of having an overcapacity now or in the future.
How do you rate the competition in the market for iron oxide
pigments? In the past we had some 70 players in the market, now
the number has declined to roughly 30. The competition stirs the en-
vironmental restrictions and this will lead to a further consolidation.
in the market. This may bring advantages for producers from mature
regions. It is not possible to produce cheaply if you have a certain
demand of quality for products.

E U R OP E AN COAT I NGS JO UR N A L 2018
14 T O P I N D U S T RY MO VE

Source: Freepik - www.flaticon.com (Icons) , Nathalie Nuhn (composing)

GROWING THE
PIGMENT BUSINESS
Ferro Corporation has announced entering into an agreement to acquire Cappelle Pigments NV (“Cappelle”) and the
acquisition of certain assets of Delta Performance Products (“Delta”), for aggregate consideration of approximately
EUR 55.2 million. By Damir Gagro (publishec in ECJ 11/2016(.

Sales for the two businesses in 2016 are estimated to be
approximately EUR 69.9 million in the aggregate and ad-
justed EBITDA in 2016 is expected to be approximately
EUR 10.1 million. Based on estimated 2016 adjusted EBITDA,
excluding expected synergies, the purchase price of the two
businesses represents a combined transaction multiple of ap-
proximately 5.6.
coatings, inks and plastics and sells its products in more than 75 coun-
tries. The company specializes in weather-, heat-, and light-resistant
organic pigments. The pigment producer is also a market leader in
certain inorganic pigments that complement Ferro’s market positions
in complex inorganic coloured pigments (CICP) and ultramarine blue
pigments.
Cappelle is headquartered in Belgium with an additional production
site in France and has a worldwide representation and sales in more

O n October 14 2016, Ferro signed a definitive agreement to ac-

quire 100% of the stock of Belgium-based Cappelle Pigments for
EUR 50.5 million on a cash-free and debt-free basis. The transaction
than 75 countries. Main products are Bismuth Vanadates, transparent
iron oxides and organic high-performance pigments.

is expected to close by year end, subject to customary closing condi- ADDITIONS TO FERRO‘S GROWING PIGMENTS BUSINESS
tions, including regulatory review.
Cappelle is a 125-year-old, privately held company that produces On August 1, 2016, Ferro purchased certain assets of Delta Perfor-
specialty, high-performance inorganic and organic pigments used in mance Products. This business produces customised colourant

E U R O P E AN CO AT I NGS J O UR N AL 2018
 T OP I NDU S TRY MO VE 15
ADD SOME
SHINE TO YOUR

Source: Freepik - www.flaticon.com

FACTS ABOUT FERRO CORPORATION COATINGS!
www.european-coatings.com/shop

Production sites: more than 30 in 26 countries

Sales in 2015: EUR 1 billion

Number of employees: 4,846

Ulrich Poth
METALLIC EFFECT PIGMENTS
blends that utilise Ferro’s CICPs for the concrete and outdoor
hardscape markets. Silver cars, gold labels on beer bottles, glittering
Peter Thomas, Chairman, President and CEO of Ferro Corpora- lipsticks, and sparkling fireworks: metallic effect
tion, said: “These acquisitions are great additions to our growing pigments and their applications are becoming
pigments business. Both fit extremely well into the strategy for
more widespread and more diverse every day.
our colour solutions businesses, and we are excited about the op-
portunities these assets present to enhance shareholder value. Get a concentrated overview of these pigments
Over the next 12 to 24 months, between the two businesses, we and learn more about their chemical, physical,
expect to realize commercial and operating synergies of EUR 2.7 and optical properties, and their wide range of
million to EUR 3.7 million.
applications – including related specifications
He further compared these acquisitions to the Nubiola acquisition
Ferro made last year for EUR 149 million. The new additions both and future potential for development.
increase the breadth of options Ferro can offer, they increase tech-
nical capabilities and enhance the company‘s market position. The
2006, 234 pages, hardcover,
transactions will increase Ferro’s PPO business by approximately 30%
155 x 225 mm, 149 €,
and expand its addressable market for pigments by a factor of four,
order no. 310
to approximately EUR 3.7 billion, Thomas elaborated. The addition of
Look inside
Cappelle’s proprietary pigments and capabilities is expected to advan- the book!
ce expansion into the specialty organic pigment market and round
out Ferro‘s product portfolio. The Delta transaction enhances posi-
tion as a manufacturer of engineered colorants and custom blends.”
Thomas concluded: “These businesses demonstrate the value pro- EUROPEAN
position of our Pigments business. We create value for our custo-
mers by combining and manipulating pigments to produce spe- C OATINGS library
cialised color solutions that provide functional attributes for our
customers’ end products, or improve the effectiveness and efficien-
cy of their supply chain and manufacturing processes.” 
Vincentz Network · P.O. Box 6247
30062 Hannover · Germany
E UR OP E AN COAT I N GS JOUR N AL 2018 info@european-coatings.com
16 P R O D U C T O VE R VIE W

GREAT-LOOKING THANKS TO
INTERFERENCE PIGMENTS
The first interference pigments were only used for automotive styling. Today, they are an indispensable part of the automo-
tive industry and OEM finishes containing them come in all colours. By Werner Rudolf Cramer (publishes in ECJ 06/2016).

I nterference pigments were initially offered by automotive paint

makers for styling vehicles. They made the breakthrough into OEM
finishes in 1985 when Renault and Volvo each pioneered models in
Pearl White. Originally applied in a 3-layer system comprising white
basecoat, pearl white interference coat, and clear coat, it was not long
before they were combined with coloured pigments that quickly con-
quered the market. In the mid-1990s, blues and greens were especially
popular. Since then, blends with coloured, aluminium and interference
pigments have come to dominate. These are usually 2-coat systems; a
tendency towards coloured clearcoats is emerging, however.
Looking back, 1969 can be regarded as the dawning of a new pigment
era. This was when DuPont entered into a cross-licensing agreement
with both Mearl and Merck, both of which adopted DuPont’s produc-
tion process and some of the designations and names that it had
been using for its interference pigments. These pigments are derived
from natural mica flakes, which are coated with highly refractive metal
oxides, such as those of titanium and iron. When light strikes the sur-
face, a portion of it is reflected and a portion is refracted through the
metal oxide layer. At the next boundary layer, some more light is re-
flected and it exits the pigment surface parallel with the first reflected
portion. As the path lengths of these two light portions differ, the light
waves are displaced relative to each other. These interfere, producing
a mixture of strong and weak waves.
Interference pigments have two particular characteristics. First, the
perceived colour varies with the angle of the incident light. Second,
they work on the principle of additive mixing. Thus, a mixture of pearl
yellow and pearl blue does not appear green, but instead is white.
Details of how to measure the colours and the effects are contained in
the “Standard Test Method for Multiangle Colour Measurement of In-
terference Pigments” (ASTM E2539), issued in 2008. This recommends
the use of two different angles of illumination, and taking readings on
either side of the specular angle. For physically plausible measure-
ment and representation of the interference pigments, an arrange-
ment of three illumination angles and the same aspecular angle from
the respective specular is advisable. The aspecular angle in this case
should be smaller than 20°.
The colours of the interference pigments based on natural or syn-
thetic mica range from silvery-white to yellow, red, green and finally
to blue. The resulting primary colour depends on the thickness of the
layer of titanium dioxide. Pigments coated with iron oxide pigments
are red to reddish-violet while combinations of titanium dioxide and
iron oxide are golden. Other carrier materials – as described below –
produce similar colour reactions, but yield different effects.
Ongoing development work on interference pigments has spawned
fascinating, new types. Aside from the original pigments based on
natural and synthetic mica, several manufacturers offer pigments
supported by other carrier materials, such as silica and alumina. Both
of these materials are transparent and are also coated with titanium
dioxide or iron oxide. Silica as carrier material yields pigments which
have large colour travel, which means they undergo a marked col-

The specified names are registered trademarks of the respective manufacturers.

Kuncai CQV BASF Merck Eckart

Pigment Name Pigment Name Pigment Name Pigment Name Pigment Name
group group group group group

XillaMaya Crystal Silver Adamas Splendor Paliocrom® Bright Orange Iriodin Pearl Gold Symic OEM Medium
White Silver

XillaMaya Galaxy Blue Adamas Splendor Paliocrom® Bright Gold Xirallic Crystal Silver Symic OEM Medium
Blue Copper

XillaMaya Electric Blue Adamas Dazzling Mearlin Fine Red Colorstream Viola Fantasy Luxan CFX Red
Red Exterior

Setallic Desert Orange Kromax Corona Mearlin Aztec Gold Pyrisma Liquid Blue
Violet Exterior

Automotive Rutile Green Automotive Splendor Glacier Ext. Frost White Meoxal Wahiba
Pearl Red Orange

E U R O P E AN CO AT I NGS J O UR N AL 2018
 P R O DU C T O V ER VIE W 17

10 million tonnes of in-

Source: Werner Rudolf Cramer

organic pigments are
expected to be sold
annually by 2020.


HOW TO EFFICIENTLY CHARACTERIZE
SPECIAL EFFECT COATINGS
In this paper, a simple and efficient approach is present-
ed on how to characterize the appearance of surfaces
composed of metallic and interference pigments.

Journal of the Optical Society of America A Vol. 33, 2016,

Issue 1, pp. 1-8

our change, for example, from green to yellow to violet. Alumina as

carrier material produces a phenomenon known as sparkle in addi-
tion to the colour effect.
Coated aluminium flakes also count as interference pigments. Cur-
rently, several are offered in colours ranging from gold to red, with a
slight colour change. Interference pigments produced in high vacuum
also exhibit extensive colour travel across several colour quadrants.
As they are very expensive, they are little used in OEM finishing. Paint
makers tend to offer them as specialist and styling refinishes.  (65°). The aspecular angle in each case is a constant 15°.
COLOUR MEASUREMENT OF
INTERFERENCE PIGMENTS
The colour travel produced by interference becomes evident
when the angle of incidence is changed. In this example, the
angle of incidence varies from steep (20°) to classic (45°) to flat
The aspecular curve shows the readings obtained under constant
illumination at an angle of less than 45° and a modified aspecular
angle. The latest portable instruments also offer this capability.

100
Schlenk Viavi Solutions (Flex Products)
ChromaFlair 190
80
Pigment Name Pigment Name
group group
60
Multiflect Polychromatic ChromaFlair Green/Purple 190 65°/15°
40

20°/15° 20
SpectraFlair Silver 1500
0
-100 -80 -60 -40 -20 20 40 60 80 100
-20
45°/25°
-40

-60
45°/15°
interference -80
aspecular
-100

E U R OP E AN COAT I NGS JO UR N A L 2018

 18 C OL OU R D E S IGN
Cornelia Hoffmann - Fotolia.com
MIX AND MATCH
The interplay of various pigment types in strategic colour design. By Werner Rudolf Cramer (published in ECJ 01/2013).
In paint formulation, achieving the right colour depends on
the pigments used. When conventional pigments and modern
effect pigments are mixed, many things have to be considered
to obtain the desired result.
J ust as in other fields of application, the creation of colours for motor
cars depends on the choice of pigments. They dictate what colour
ranges and effects can be achieved. Availability can, however be an is-
sue. For example, health and safety and environmental protection is-
sues forbid the production of pigments with certain blue effects, thus
curtailing their use in designing new colours.
To ensure the optimal and cost-effective use of pigments, it is im-
portant to consider their optical characteristics. Conventional colour
pigments (sometimes referred to as solid-colour pigments) usually
display the same colour at all angles of illumination and observation
and are therefore easy to understand. However, aluminium and in-
terference pigments differ in appearance depending on the angles of
the incidence of light and observation. I.e. the perceived colour and/
or brightness of these materials vary. Conventional colours have an
almost even distribution, while effect colours are more effective close
to the gloss angle than far away from it. The following are the materi-
als illustrated:
ąą 91002 solid_2 + White
ąą 91014 Aluminium Silver Dollar pure
ąą 91265 Aluminium Cornflake pure
E U R O P E AN CO AT I NGS J O UR N AL 2018
ąą 91015 Pearl Blue pure
ąą 91237 pure Xirallic Galaxy Blue
ąą 91006 Aluminium Silver Dollar + solid_2
ąą 91019 Pearl Blue + solid_2
ąą 91229 Xirallic Galaxy Blue + solid_2
(solid 2 = mixture of blue, green and black solids)
Aluminium pigments appear to shine, because they reflect incident
light directly, rather like a mirror. The closer the observation angle
is to the gloss angle, the stronger the reflection. In some cases, the
reflection parameters vary considerably, depending on the pigment
type (e.g silverdollar or cornflake) and size. In contrast to conventional
pigments, these angle-dependent characteristics must be taken into
consideration when creating a new colour. A shift in the height of the
reflection curves demonstrates these optical characteristics.
As their name suggests, interference pigments are distinguished by
the optical-physical phenomenon of interference. The wave-length of
their reflection colours shortens as the angle of illumination becomes
flatter. For example, red moves towards yellow or yellow towards
green when the angle of the light falling on it increases. Maximum
reflection in the blue range can also move into the invisible UV range,
while invisible IR can appear in the maximum visible red range.
The reflection colour of an interference pigment is always visible close
to the gloss angle. However, if it is hidden due to the presence of a
high level of colour or aluminium pigment, it makes no sense to use
it. A transparent, blue interference pigment is also always visible close

RESULTS AT A GLANCE
 The creation of new car-paint colours is dictated by the pig-
ments available. Their optical characteristics are a key factor.
 Interference pigments produce interesting effects, be-
cause the perceived colour changes with the angle of observa-
tion.
 Mixing interference and solid-colour pigments enlivens
the colour palette.
 The choice of pigments is crucial as mixtures can either
increase or reduce a colour effect.
 Transparent coloured or interference pigments have the
biggest influence over the colour impression at a wide angle of
observation.
to the gloss angle when mixed with absorbing blue pigments. Figure
1 shows an example of this. Here, a pearl blue interference pigment
is mixed with solid-colour pigments. As the concentration increases,
the interference line shifts almost in parallel with the colour pigment.
The interference line results from the colour travel when the geom-
etry changes. As modern portable devices do not measure interfer-
ence lines, a interim solution has been selected from the geometries
Figure 1: The shift of the interference line in mixtures of a pearl blue interfer-
ence pigment with colour pigments at different concentrations
C O L O U R DE S IG N 19
45°/-15°, 45°/15° and 15°/15° (illumination/aspecular in each case).
The aspecular lines (grey, respectively 45°/15° - 45°/110°) all point in
the same direction (the exception is the transparent pearl blue with-
out admixture).
Interference pigments with strong colour travel are always identifiable
in all possible colour combinations by their unique interference line
as in Figure 2, where, in mixtures of such interference pigments with
various solid-colour pigments or mixtures, the typical interference line
for the interference pigment remains unchanged.
This is clear from observations or measurements at various illumina-
tion angles and the aspecular angle relative to the respective gloss
angle.
The reflection colour is always visible close to the gloss angle, a fact to be
kept in mind when creating new paints.
Transparent interference pigments with specially coated platets have
a transitional area between 20° and 30° from the gloss angle. At as-
pecular angles far from the gloss angle, absorption characteristics
have the greatest influence on the overall colour impression. The
transmission colour of these pigments, which is complementary to
the reflection colour, also influences the overall colour impression at
these difference angles.
Interference pigments are unique in two ways: They cannot be pro-
duced by mixing and, unlike colour pigments, their colour travel de-
pends on angle.
VISUAL OBSERVATION
The most important aspect in evaluating effect colours is the geom-
etry of illumination and observation. In the case of car paints, they
are so-called off-plane geometries, i.e. observation is not on the same
plane as that formed by the illumination and the perpendicular.
In-plane geometries are used in standard visual and instrumental
observation and measurement methods. The geometries of portable
measuring instruments do not match with those measured either at
the testing-room window or in standard light booths. This is less obvi-
ous in colour formulations with aluminium or classical interference
pigments than with modern interference pigments with a greater
travel of colour.
Figure 2: The unchanging, typical interference line of Color-
E U R OP E AN COAT I NGS JO UR N A L 2018
 20 C OL OU R D E S IGN
 In visual observation and assessment of sample panels at the window
and in most light booths, the offset angle between illumination and
observation is always the same. If the panel is held at the window such
that you are looking at it at the gloss angle, the illumination angle is
15° from the perpendicular, for example. The gloss angle – and in this
position also the angle of observation – is therefore -15°. The result
is an offset angle of 30° between illumination and observation. This
remains the same when the panel is tilted backwards and forwards.
The panel always remains in the cis-position when it is tilted towards
the observer, it, i.e. the sample is always seen on the illumination side.
If it is tipped it away from him, it is initially seen in the trans-position,
i.e. on the opposite side of the gloss angle to the illumination. Tipping
it further away, moves it into the cis-position.
OPTICAL BEHAVIOUR IMPORTANT
Unfortunately, current portable devices offer hardly any method of
measuring interference. The -15° aspecular geometry established in
the “ASTM E2539-12 Standard Practice for Multiangle Color Measure-
ment of Interference Pigments” provides an interim solution. Compar-
ing reflection curves at +15° and -15° enables coloured interference
pigments to be distinguished from aluminium and white interference
ones (see Figure 3). A significant difference regarding optical behav-
iour should be considered when creating new effect paint. Aluminium
pigments and white interference pigments show an increase in their
reflection when the observation point changes from the cis-position
(+15° aspecular) to the trans-position (-15° aspecular).
Coloured interference pigments also demonstrate colour travel to-
wards the shorter wavelengths.
The second illumination at 15° formulated in the ASTM standard prac-
tice is also helpful. With these measurement values and those at 45°
illumination, an interference line can be created, although it is only a
stopgap. However, it can be used to describe optical properties.
During visual assessment of effect paints at the window or in the light
booth, the sample panel should not be tilted backwards and forwards.
Rather, it should be viewed with arms outstretched against the light
source. The arm is then moved downwards with the panel held parallel.
Thus, the distance to the light source is simultaneously reduced, so that
the sample is always viewed close to the gloss angle. In this way, the
colour travel of the interference can be identified. This can be seen very
clearly with the modern developments in interference pigments.
Figure 3: A comparison of geometries of 45°/-15° and
45°/+15°
250
200
150
R [%]
100
50
0 0
400 500 600
Wavelength λ [nm]
Alu + blue 45°/15° Viola Fantasy + blue 45°/15°
Alu + blue 45°/–
45°/–15° Viola Fantasy + blue 45°/–
45°/–15°
E U R O P E AN CO AT I NGS J O UR N AL 2018
BRINGING COLOUR TO LIFE
The yellow, orange and red colour families are strong pigments that have
high chroma and high lightness. Both characteristics have a disruptive
effect when mixed with interference pigments, particularly transparent
interference pigments which are less prominent when they are close to
the gloss angle, because of the colour reflection. For the above colour
groups, interference pigments whose platelets are coated with iron ox-
ide or a combination of titanium dioxide and iron oxide are more suit-
able. This particularly applies to reds, which are very much in demand at
present, intersesting colour reactions can be created with interference
pigments coated with iron oxide.
Green, blue and violet are the most interesting colour groups for use
with transparent interference pigments.
When aluminium and interference effect pigments are mixed with sol-
id-colour pigments, similar behaviour is seen to that achieved by mix-
ing solid-colour pigments with white (titanium dioxide). For example,
if a yellow or red solid-colour pigment is mixed with white, the colour
line travels from yellow or red towards white. Green or blue solid-col-
our pigments look black and become coloured only when diluted, i.e.
by mixing them with white, the chroma and lightness increase initially,
until the chroma peaks and then falls away again. Further addition of
white makes the colour paler and lighter.
Similar behaviour is seen in interference pigments. A white interfer-
ence or an aluminium pigment is brought to life by using them in
mixtures. The overall colour impression initially increases in chroma
and brightness. Once the peak, has been reached, only the lightness
increases and the chroma falls away to create an achromatic effect
mixture. This is illustrated in Figure 4. Mixtures of coloured interfer-
ence pigments with solid-colour pigments show direct colour gradi-
ents between the pigments.
Interference and aluminium pigments can also be mixed with white
pigment(titanium dioxide). However, the effects achieved are quite
weak. Titanium dioxide pigment particles are comparatively large,
which means that the effects may turn out to be inadequate.
Some specific features need to be taken into consideration when
interference and aluminium pigments are mixed. Fundamentally,
coloured interference pigments move towards shorter wavelengths
when the angle of illumination becomes flatter. However, this travel
is reduced and restricted by the presence of aluminium pigments. As
from a certain mixture ratio, it is worth replacing a coloured interfer-
Figure 4: Mixtures of aluminium and pearl blue effect pigments
with blue at 45°/15°
50
40
30
R [%]
20
10
700

ence pigment with a white version.
Samples painted with an aluminium pigment appear grey. Corre-
spondingly, those painted in white interference pigments are per-
ceived to be white. The panels, which are of a normal size, are studied
vertically across their whole surface at an angle of about 20°. When
observed close to the gloss angle, the reflection of the aluminium pan-
el is stronger than the interference panel. The addition of white inter-
ference pigments would reduce its lightness close to the gloss angle.
Close to the gloss angle (illumination 45°/observation 60° = -15° as-
pecular), different pigments reflect differently: Silverdollar aluminiums
(91014) reflect more strongly than cornflake aluminiums (91265), Xiral-
lic Galaxy Blue (91237) more strongly than Iriodin Pearl Blue (91015).
The effect can also be changed with the addition of a flop controller or
micronised titanium dioxide. This applies in particular to formulations
containing aluminium.
STRATEGIC APPROACH
In most cases, a new paint is created by replacing the effect pigments
in an existing formulation. The advantage of this method is that the
formulation has been already used and tested. The disadvantage,
however, is that it is impossible to predict how prominent the effect
pigment will be in the formulation and how strong it may become. It
is rather like putting a new F1 racing car engine in a small used car. It
can give surprising results!
A strategic approach is always better. It is certainly possible to use
existing formulations as a guide, but effect pigments are unique, in-
terference pigments in particular. The choice of effect pigment should
therefore be considered at the outset.
The intensity of an effect can be shown in a comparison between ge-
ometry close to and far away from the gloss angle. For example, alu-
minium pigments of the cornflake and silverdollar type and various
types of interference pigments show comparatively strong differences
in reflection between these geometries. Figure 5 demonstrates that,
away from the gloss angle (illumination 45°/observation -20° = 25°
aspecular), the reflection of pigments such as aluminium Silverdollar
and interference pigments reduces significantly, which illustrates the
intensity of the effect.
Having chosen the colour range of a new paint and what effects are to
be achieved, if it is decided to use one or more interference pigments,
one begins with that which is intended to have the greatest influence
Figure 5: A comparison of the reflection of Silverdollar and inter-
ference pigments with other effect pigments
150
100
R [%]
50
0
400 500 600 700
Wavelength λ [nm]
91014 91015 91006 91229
91265 91237 91019 91002
C O L O U R DE S IG N 21
on the overall colour impression. The work does not necessarily have
to start off in the colour range required. The colour can be shifted
with other interference pigments of the same type or of a different
one. For example, a green interference pigment can be moved in two
directions by adding a yellow or blue pigment. With a white or a red in-
terference pigment, the interference becomes smaller and therefore
the interference line as well. And with a white interference pigment,
the mixture becomes paler.
Interestingly, transparent and other interference pigments can be
mixed in almost any combination. As they obey additive mixing rules,
a pearl green and a pearl red result in a whitish yellow. Adding a pearl
blue to the yellow can make it travel in the direction of the colour
position of the starting pigments. If, for example, a mix of Xirallic Stel-
lar Green and Solaris Red together with a “dash” of Galaxy Blue gives
an interesting white with a different sparkle effect to that of Xirallic
Crystal Silver. As shown in Figure 6, the interference line can be shift-
ed completely by mixing with other interference pigments. Here the
black mixture of Viola Fantasy has been mixed respectively with Pearl
Lilac, Pearl Green and Pearl Blue. The aspecular lines (grey) all run in
the same direction.
At the next stage, absorbent, perhaps even transparent, colour pig-
ments are added. Here it should be noted that these have the biggest
influence on the overall colour impression at angles a long way from
the gloss angle.
If interference and aluminium pigments are to be mixed, it is best
to begin with the stronger partner in the mixture. In the case of an
aluminium pigment, this is then added to the interference pigment
required in order to create colour in the interference geometries (dif-
ferent illumination angles with the same aspecular angle). Although
the aluminium pigment flop effect is substantial in terms of lightness,
it can be altered by using an appropriate flop controller – if the inter-
ference pigment added has a crucial effect on the colour close to the
gloss angle. The addition of solid-colour pigments and appropriate
white pigments serves to steer the character of the aluminium and
interference effects in a coloured or achromatic direction.  
Figure 6: How the interference line shifts when differing interfer-
ence pigments are mixed
E U R OP E AN COAT I NGS JO UR N A L 2018
22 R A D IAT IO N C UR I NG
SHINING UNDER THE SPOTLIGHT
How metallic effects can best be achieved in UV curing finishes. By Oliver Kipfmüller (published in ECJ 03/2013).
The challenges of achieving a good metallic finish in UV-cura-
ble coatings are assessed. Aqueous systems provide the best
compromise between visual and performance properties. To
achieve effective cure despite the UV-reflection of the pig-
ment, the pigmentation level must be optimised for the ap-
plication and pigment grade.
T he attainment of highly brilliant metallic effects in UV-curable
coating systems is a task with many aspects. Current investiga-
tions reveal how formulations can be optimised for this purpose.
Solvent-free, conventional or aqueous: in what system can the ad-
vantages of UV technology be combined with attaining highly brilliant
effects? As a rule, the following factors must be considered to attain
metallic effects with ideal flop characteristics in coatings:
ąą Correct pigment selection and formulation;
ąą Coating production;
ąą Application as well as drying and curing.
Visual criteria as well as the particle size distribution or particle struc-
ture and the stability of the aluminium pigments are crucial for pig-
ment selection. For UV coatings in particular, it must be noted that
aluminium has a catalytic effect on the radical curing reaction. This
catalysis leads to a gelling of the coating after only a short storage
period [1].
In aqueous UV formulations, the pigment must also be protected
against water. The use of encapsulated aluminium pigments is there-
fore recommended, as these provide maximum resistance to gassing
E U R O P E AN CO AT I NGS J O UR N AL 2018
and gelling in comparison to additive-stabilised types.
In addition to the dispersion, drying is especially important for the
orientation of aluminium pigments. High film shrinkage and rapid
physical drying favour parallel alignment of the pigments. This is not
available in the case of high solids and 100 % solids systems, which
thus leads to less effective flop characteristics.
In UV systems, the effect attainable therefore essentially depends on
the type of formulation. Aqueous, conventional or solvent-free sys-
tems consequently pose differing requirements for aluminium pig-
ments and their processing.
ADVANTAGES AND DISADVANTAGES OF VARIOUS APPROACHES
What UV coating system represents the ideal solution for combining
the desired brilliance with a high resistance? This question can only
be answered definitively if the objective is clearly defined. The relevant
requirements can range from purely visual applications through to
functional purposes, including all conceivable combinations. The first
step involves illustrating the fundamental advantages and disadvan-
tages of the various approaches.
SOLVENT-FREE: MODERATE EFFECTS BUT BEST ECONOMICS
Solvent-free systems represent the ideal case for the development of
UV-curable metallic coatings. Only in the case of 100 % systems can the
advantages of UV technology be utilised to the full. They allow curing
immediately after application, leading to considerable savings – both in

RESULTS AT A GLANCE
 When comparing various approaches, aqueous UV metal-
lic coatings provide the best compromise between visual and
technical coatings properties.
 The curing of aluminium-pigmented UV coatings is possi-
ble despite reflection. The coating formulation must be coordi-
nated to the pigment used here.
 The pigmentation level has a massive effect on the full
hardening and the coating properties. Excess pigmentation is
to be avoided.
respect of space for paint spray lines as well as in respect of time and
energy for drying and curing.
However, the coating formulation specialist soon encounters limits if
brilliant metallic effects are required. 100 % UV systems dispense with
the physical drying stage mentioned above. Curing within seconds
means that pigments are frozen into their position and do not have
much scope to achieve an ideal alignment. This leads to reduced flop
characteristics.
Coarser pigments usually have a more distinct bright-dark flop and
therefore also still have a metallic effect, even with somewhat poor-
er alignment, while very fine pigments almost entirely lose their flop
characteristics. Figure 1 outlines the pigment orientation in diagram-
matic form. In the optimum case of parallel alignment (left), the light
reflection is directional – a highly metallic effect is attained. In the
Figure 1: Schematic representation of the effects of metallic pigment orientation: optimal (left) and unfavourable (right)
R ADI AT I O N CU R I N G 23
right-hand picture, on the other hand, the reflection is diffuse, which
means that a metallic brilliance is not really obtainable.
In conventional and aqueous coating systems, the aluminium pig-
ments are primarily oriented through the evaporation of the relevant
solvents and the associated film shrinkage parallel to the substrate.
This process is completely lost in a solvent-free system. The use of
essential rheological additives means the viscosity increase resulting
from the evaporation can be partially compensated for. The aim is as
rapid a viscosity increase as possible after the application.
When selecting the pigments, the use of coated aluminium powder
is recommended, so as not to introduce any solvents via a paste. The
binding agents for these types of systems are distinguished by low
viscosity. Nevertheless, reactive thinner contents of up to 50 % are
sometimes necessary to allow processing [2].
The use of 100 % solids metallics is not recommended at present for
applications in which the highest visual properties are required. These
systems are an economical solution if moderate metallic effects are
adequate, or specific mechanical and chemical resistance properties
are paramount.
CONVENTIONAL: VOC CONTENT DETERMINES BRILLIANCE
‘Conventional’ UV systems with solvents have the advantage that it is
not the viscosity of the oligomers that plays a critical role in selection
of the binding agent, but rather the property profile. The processing
viscosity can be better controlled by using organic solvents. As the sol-
vents are not incorporated in the film, they do not affect its properties,
in contrast to reactive thinners.
Atomisation and final appearance improve, while solvent evaporation
and film shrinkage favour parallel alignment of the pigments. During
application and drying, this leads to an optimised viscosity profile,
physical drying and ultimately more brilliant properties in the cured
coating film.
The metallic brilliance is proportional to the amount of organic sol-
vents used. From high solids via medium solids through to low solids,
the VOC content increases in parallel to the improvement of the me-
tallic effect.
In terms of coating technology, the ‘solvent and UV’ approach offers
an interesting option for producing brilliant and resistant paints with
high performance. However, the economic and ecological benefits of
UV coating are mostly lost, as the solvent has to be removed by drying
in the oven before curing and the resultant VOC emissions are very
high in this respect. In Europe at least, conventional UV coatings are to
be regarded as an interim solution and not as future-oriented alterna-
tives, especially when it comes to new developments. 
E U R OP E AN COAT I NGS JO UR N A L 2018
 24 R A D IAT IO N C UR I NG

 Figure 2: Comparison bet ween application of an aqueous UV Figure 3: Development of covering power as pigmentation level
coating and a conventional chemically cured coating increases, for three different sizes of aluminium pigment

Figure 4: Double bond conversion at the underside of coatings, Figure 5: Results of the König pendulum hardness test
in per cent

Figure 6: Results of the cross-cut tests Pigments used, wiht average particle size

Pigment D10 D50 D90

Silver dollar 10 µm 5 10 10

Silver dollar 15 µm 7 15 26

Silver dollar 20 µm 10 20 32

E U R O P E AN CO AT I NGS J O UR N AL 2018

AQUEOUS: GOOD RESULTS WITH AN INTERMEDIATE STEP
Aqueous UV technology represents a promising way to exploit the ad-
vantages of UV technology in the best possible manner while attaining
brilliant effects at the same time. The only drawback is that a drying
step has to be implemented upstream of the actual curing process.
It is necessary to remove water and cosolvents from the coating,
which has a significant effect on the finished coating. A time saving
nevertheless results as, in comparison to other chemically curing
coatings, this preliminary drying only takes a fraction of the process
time (see Figure 2).
Aqueous UV systems are free of monomers and can guarantee high
resistance properties through the use of high molecular weight dis-
persions in combination with radical crosslinking [3]. The formulation
is in principle similar to known aqueous metallic formulations.
Essentially, the same adjustment techniques can be used to optimise
the effect as for other aqueous metallic coatings, thus for example
dispersing additives, thickeners or wax dispersions may be used. Ow-
ing to the high resistance properties that result from the crosslinking,
an additional clear coating can even be omitted in some cases.
WATER AND UV CURING: REFINING THE BEST APPROACH
This combination of waterborne systems and UV curing represents
the best solution at present, in order to attain both metallic brilliance
as well as high chemical resistance properties, especially in the area
of single-layer coatings.
This insight led to extensive test series being conducted in an aque-
ous formulation based on a polyurethane dispersion suitable for UV
cross-linking. These tests were to demonstrate what effect various
types of effect pigments have on the properties of the coating.
Coated silver dollar pigments with an average particle diameter of 10,
15 and 20 µm were used for the tests (Table 1). The particle size dis-
tribution is approximately the same here. The pigmentation level was
increased incrementally from one per cent (pigment solids) to five per
cent.
Of all the finished coatings, the conversion of double bonds was de-
termined using FTIR spectroscopy and the degree of coverage was
measured. Further tests evaluated the hardness and adhesion.
EXPLORING THE CONFLICT BETWEEN COVERAGE AND CURING
The visual impression of a metallic coating results from light reflection
and scattering by the aluminium pigments. The higher the compo-
nent of reflected light, the more brilliant and appealing the coating
appears.
In the case of a ‘covering’ coating, no light from the substrate reaches
the viewer’s eye, but instead it is reflected or scattered from the pig-
ments beforehand. This can be measured by determining the colour
values on a black and white substrate. If a colour difference of less
than one unit occurs, this denotes a covering coating [4]. The finer
the pigment, the lower the pigment level required to attain this value
(see Figure 3).
For the production of UV metallic coatings, it is necessary for the high-
ly energetic UV radiation to penetrate as deeply as possible into the
coating layer so as to start the polymerisation reaction. This is in con-
trast to the desired light reflection of the pigments. In order to evalu-
ate whether the complete conversion of the reactive double bonds is
still ensured in the case of covering coating layers, their content was
determined by FTIR spectroscopy.
The percentage conversion can be determined based on measure-
ments on both the top and underside of the coating. No effect can be
discerned at the coating surface –either in relation to the particle size
or the pigmentation level. On the underside of the coating, however,
R A DI AT I O N CU R I N G 25
it is clear that the conversion decreases as the pigmentation level in-
creases (Figure 4). This is a logical consequence of the increasing re-
flection or scattering of the incident radiation.
This increasingly poor curing leads to a gradient in respect of cross-
linking and hence also of hardness within the coating layer. This dif-
ference has an adverse effect on the properties of the coating. König
pendulum hardness tests and cross-cut tests among others were car-
ried out for the evaluation. These are standard tests for curing in the
coatings industry.
PENDULUM HARDNESS TEST FAILS TO CORRELATE WITH CURING
A decrease in hardness as the pigmentation increases can be observed
in the pendulum hardness test. It is notable that the varying degrees of
decrease in the cross-linking between the test series that can be seen in
Figure 5 cannot be found here. Rather, the aluminium pigments have
a negative effect on the hardness of the coating film as the pigmenta-
tion level increases, irrespective of the particle size.
The pendulum hardness obviously depends more strongly on the
aluminium content than on the degree of cross-linking and is there-
fore not a suitable test for evaluating the chemical cross-linking in this
case.
The adhesion testing values reveal a similar picture. Here too, the
compositions are significantly more complex and do not permit any
clear conclusion in respect to the degree of curing determined by
FTIR spectroscopy (see Figure 6). In the case of low pigmentation, the
coating tends towards embrittlement and reduced adhesion, as a very
close-meshed network can form.
The cross-linking density decreases as the pigment content increases.
Nevertheless, this decrease cannot be observed in the conversion of
the double bonds. At first, this leads to an improvement in the adhe-
sion test (see Figure 6), but the values deteriorate further upon reach-
ing the coverage limit. This return to a negative development can also
be observed from the double bond density (Figure 4).
FORMULATION RECOMMENDATIONS
The formulation must be precisely coordinated to the aluminium pig-
ment for covering UV metallic coatings. Excess pigmentation results
in less favourable coating properties. The ideal coating properties in-
volve working precisely at the limit of coverage during the pigmenta-
tion. This limit should be determined via a test series for every type of
coating or pigment.
These tests consider pigments with similar particle size distribution,
which means the D50 value can be compared here. In general, the
particle size distribution should be used for the evaluation of the pig-
ment.
When selecting the binding agent, aqueous systems are recommend-
ed to satisfy high visual requirements. These can be formulated with
relatively low solids, thereby ensuring a better orientation.
Solvent-free UV metallic finishes are achievable, but contain a signifi-
cant content of monomers in the case of spray application and only
achieve moderate effects owing to the lack of film shrinkage.  
REFERENCES
[1] Wissling P., Metalleffekt-Pigmente, Vincentz Net work, 2005.
[2] Garret P. G., Strahlenhärtung, Vincentz-Verlag, 1996.
[3] L ippenmeier J., Weikard J., Wässrige UV-Technologie: effizient,
vielseitig,umweltfreundlich und zukunftsweisend, VILF Conference
2007.
[4] M eichsner, Metzger, Schröder, Lackeigenschaften messen und
steuern, Vincentz Net work, 2003.
E U R OP E AN COAT I NGS JO UR N A L 2018
 26 E F F E C T P IG MENT S
Source: Luftbildfotograf - Fotolia.com
NEW SHADES GROWN FROM SILVER
Surface modification of aluminium gives strong colour travel properties. By Jonathan D. Doll & Jennifer Louis (published
in ECJ 09/2013).
A new type of aluminium pigment is de-
scribed which shows gold to blue colour
travel as a result of controlled oxidation
of the flakes. This creates a uniform na-
nostructured surface on the pigments,
promoting scattering of blue light and re-
flection of red and green light. These prop-
erties lead to further interesting effects
when blended with other colour pigments.
I n recent years there has been an interest
in designing metallic pigments with colours
other than silver. One way to make coloured
aluminium pigments is to coat them with a
layer of iron oxide to produce pigments with
shades in the red to yellow region of colour
space [1]. However, this deposition of iron
oxide onto finely divided aluminium flakes is
usually via chemical vapour deposition, re-
quiring high temperatures and specialised
equipment. Further, preparation of these
pigments may lead to a highly exothermic
and dangerous thermite reaction.
Another way to obtain coloured aluminium
E U R O P E AN CO AT I NGS J O UR N AL 2018
is through a controlled oxidation process in
which water and a basic catalyst are added
to a suspension of aluminium in a water-mis-
cible solvent [1, 2]. This strategy produces
champagne-coloured metallic pigments. In
both cases, colour travel is limited mainly to
the first quadrant of CIELab colour space. To
extend the colour space of metallic pigments
to other quadrants, other fabrication strate-
gies are needed.
THREE WAYS TO EXTEND THE RANGE OF
COLOUR TRAVEL
Diffraction pigments provide a route to ex-
treme colour travel. They are made by first
vapour-depositing aluminium onto an em-
bossed release film. The aluminium is then
removed from the release film to produce
flakes that have the embossed pattern
built into their structure. The pattern on
the flakes acts as a diffraction grating and
results i n multi-quadrant colour travel in
CIELab colour space [3].
Colour travel in aluminium pigments is also
achieved by blending them with nano-sized,
transparent titanium dioxide (TiO2) particles
[1,4]. In this case, the colour travel extends
subtly from the first to the fourth quadrant
of CIELab colour space, giving a ‘frosted’ ef-
fect. However, it is difficult to obtain highly
chromatic colours by this method. Addition-
ally, nano-TiO2 must be dispersed in a liquid
system prior to blending, restricting its use
to liquid coating formulations and not, for
example, to powder coatings, which require
a solvent-free system.
An aluminium pigment has now been devel-
oped that shows angle-dependent colour
travel from gold to blue. Unlike other alu-
minium pigments, there is a nanostructured
oxide layer on the flake surface that leads
to an attractive flip-flop effect in a number
of different media. Although the discussion
in this paper will be limited to liquid and
powder coatings, the effects in colour travel
aluminium are observed in a number of dif-
ferent applications including inks, cosmet-
 EFFE C T P I G MEN T S 27

Figure 2: Display of colour travel aluminium (centre) compared to unoxidised aluminium

(left) and oxidised aluminium (right)

RESULTS AT A GLANCE
űű A new type of aluminium pigment
is described showing gold to blue col-
our travel. Colour generation is due
to the nanostructured surface of the
pigments, which promotes scattering
of blue light and reflection of red and
green light.

űű This pigment is produced by a novel

controlled oxidation process that gen-
erates uniform nanostructures on the
surface of the individual metal flakes.
By tuning the processing conditions for
the pigments, the chroma and degree
of colour travel can be tuned.

űű Colour travel aluminium pigments

can be used in a number of different
application media including solvent and
powder coatings and lead to interest-
ing colour properties such as a dark to
light flop when blending with other pig-
ments.

Figure 1: SEM micrographs of (a) oxidised aluminium and (b) colour travel aluminium; the scale bar in each picture is 2.5 µm

E U R OP E AN COAT I NGS JO UR N A L 2018

 28 E F F E C T P IG MENT S
 ics, and plastics. The mechanism of colour
generation and the properties of the colour
travel aluminium pigments in both liquid
and powder coatings will be described.
HOW OXIDATION CHANGES THE COLOUR
OF ALUMINIUM FLAKES
Oxidised aluminium pigments are metallic
pigments in which the surface of the alumini-
um flake is modified by oxidation reaction (1):
2 Al + 6 H2O  2 Al(OH)3 + 3 H2 (1)
This class of pigments have a metallic alu-
minium core and a hydrated aluminium ox-
ide (Al(OH)3) shell. Traditionally, oxidised alu-
minium pigments have been made through
surface oxidation in a single-phase system
Figure 3: Brightness comparison at five different observation angles for unoxidised, colour
travel and oxidised aluminium pigments
Figure 4: Plot of the colour travel through five obser vation angles of unoxidised, colour
travel and oxidised aluminium pigments in CieLAB colour space
E U R O P E AN CO AT I NGS J O UR N AL 2018
of water in isopropanol and a basic catalyst
where the amount of each determines the
degree of oxidation and, the thickness of the
Al(OH)3 layer. uring oxidation and escapes
by tunnelling through the Al(OH)3 layer. From
a morphological standpoint, this makes the
layer uniform but porous as shown in the
SEM micrograph in Figure 1a. The colour of
these pigments ranges from champagne to
gold, depending on the purity of the starting
flake and the thickness of the Al(OH)3.
By using a two-phase oxidation system, a new
type of oxidised aluminium pigment, display-
ing colour travel from gold to blue, can be
produced. The two-phase system comprises
water, a water-immiscible solvent, a surfactant
and a base. Using a multiphase oxidation sys-
tem results in a non-uniform surface that is
composed of particulate Al(OH)3, as shown in
the SEM micrograph in Figure 1b.
Although not regularly arranged, the particu-
late moieties on the flake surface are relatively
monodisperse (about 250 nm in Figure 1b), and
can be described as a ‘pseudo diffraction grat-
ing’. The presence of these particles results in
a colour change from gold to blue as the ob-
servation angle is increased from 15 ° to 110 °.
COLOUR BEHAVIOUR OF DIFFERENT
ALUMINIUM PIGMENTS
Because it has a nanostructured surface,
colour travel aluminium has different colour
properties in comparison to unoxidised and
oxidised aluminium pigments. This is exem-
plified in Figure 2 which shows a display of
colour travel aluminium (centre) compared
to unoxidised (left) and oxidised (right) alu-
minium pigments of similar particle size and
distribution.
On the face, unoxidised aluminium appears
silver and is the brightest of the three pig-
ments. Meanwhile, oxidised and colour
travel aluminium pigments are champagne
and have a slightly decreased brightness. At
steeper angles, the silver and oxidised alu-
minium pigments behave predictably, show-
ing a dark flop and a relatively consistent hue.
In contrast, colour travel aluminium has a
light flop that is in a different region of col-
our space (i.e. blue) from the face. The effect
is pronounced, and the drawdown of colour
travel aluminium appears to ‘lighten up’ at
large angles, an effect not previously ob-
served in unblended metallic pigments.
COLOUR TRAVEL ALUMINIUM DETAILED
To understand the behaviour of colour travel
aluminium, the brightness (L*) and colour
travel (a* vs. b*) are plotted in Figures 3 and
4 respectively. These graphs were measured
on displays of the pigments in a solventborne
automotive refinish system using an X-Rite
multi-angle spectrometer. The incident beam
is d65 light at 45 ° with respect to a plane
normal to the display. The colour and reflec-
tance at five different aspecular angles (15 °,
25 °, 45 °, 75 ° and 110 °) are measured.
As expected, at 15 ° the brightness (Figure 3)
of unoxidised aluminium is the highest while
both colour travel and oxidised aluminium
are at the same level. However, as the meas-
urement angle is increased to 110 °, colour
travel aluminium provides an L* value that is
more than ten units higher than both the oxi-
dised and the unoxidised grades.
The effect of this can be seen in the flop in-
dex (FI) calculated from the data in Figure 3,
which is 20.25 and 21.69 for unoxidised alu-
minium and oxidised aluminium respectively.
 EFFE C T P I G ME N T S 29

In contrast, the FI for colour travel aluminium flection are suppressed for the 110 ° measur- ber of different applications. It has a light flop
is 14.96, indicating that the pigment scatters ing angle. while maintaining the sparkle and shine that
light to steep angles. In some respects, the physics of colour is characteristic of most effect pigments. Fab-
The colour of the pigments in CIELab colour generation are similar to that of blends of rication of these pigments is also simple and
space is shown in Figure 4 for all five angles. transparent nano-TiO2 dispersions with alu- can be tuned for a variety of aluminium flake
The colour of unoxidised aluminium is always minium flake pigments in liquid paint system types (i.e. cornflake, metallic, silver dollar)
located in the achromatic region of colour [5]. However, because the Al(OH)3 particles and sizes, making these pigments suitable for
space and is within ± 5 units from the origin are directly attached to the surface of the a number of different applications. The effect
at all angles. aluminium flake, the colours observed are of colour travel aluminium is readily appar-
For the oxidised aluminium pigment, the col- more coherent and the scattering patterns ent in a number of different media, including
our is initially chromatic (champagne) and are sharper. liquid coating, powder coatings, liquid inks,
travels to a location near the origin in the plastics and cosmetics, among others.
achromatic region, a characteristic that is PRACTICAL APPLICATIONS OF THE TECH- In liquid coatings, the behaviour of colour
typical of interference pigments. Finally, the NOLOGY travel aluminium with respect to stability and
hue of the colour travel aluminium pigment dispersability is similar to standard unpassi-
begins in the first quadrant, passes through Because of its unique behaviour, colour trav- vated aluminium pigments. Thus, these ma-
the achromatic region, and ends in the third el aluminium has a colour desirable in a num- terials can be readily incorporated into these 
quadrant, corresponding to a colour shift
from gold to blue.
It is also worth mentioning that the hue of col- Figure 5: Colour travel for a variety of colour travel aluminium pigments plotted in
our travel aluminium pigments can be tuned CieLAB colour space
by changing the reaction conditions. Figure
5 shows the colour graphs of a few different
colour travel aluminium pigments for all five
angles. Generally speaking, although it is not
always the case, a more oxidative environment
during fabrication leads to a more red-gold
pigment with higher chroma, more drastic
colour travel and a brighter flop, while a less
oxidative environment leads to a lighter, silver/
champagne-coloured pigment with less chro-
ma and colour travel and a darker flop.

PHYSICAL EXPLANATION OF THE COL-

OUR EFFECTS

Colour generation in colour travel aluminium

is entirely surface-based. Figure 6a shows a
schematic depiction of light interaction with
the oxidised aluminium flake. The case of
specular reflection is depicted on the left
hand side and aspecular reflection on the Figure 6: (a) Model of specular and aspecular light reflection of the colour travel alu-
right hand side of Figure 6a. minium flake; (b) Reflectance cur ve for specular reflection at 45as15; (c) Reflectance
As mentioned earlier, the average size of par- cur ve for aspecular reflection at 45as110
ticles on the flake surface is in the 200-250
nm range. Particles of this size will tend to
scatter blue light, while allowing green and
red light to pass through unscattered. For
colour travel aluminium, this leads to a situ-
ation where at specular or close to specular
observation angles, green and red light are
reflected from the surface of the colour travel
aluminium flake, while blue light is scattered,
as shown on the left side of Figure 6a.
The reflectance spectrum in Figure 6b for a 15
° observation angle exhibits a classic scatter-
ing pattern and shows a lower reflectance for
blue light. At aspecular angles, as seen on the
right side of Figure 6a, the scattered blue light is
observed while red and green light show typi-
cal aspecular reflection, causing the pigment
to appear pale blue. The reflectance spectrum
of Figure 6c shows the amplification of the re-
flected blue light while green and red light re-

E U R OP E AN COAT I NGS JO UR N A L 2018

30 E F F E C T P IG MENT S

systems with minimal modification to coating
formulation, although their higher surface
area may require tuning the pigment to bind-
er ratio to get an ideal formulation.
Colour travel aluminium has unique behav-
iour both as an unblended and as a blended
pigment. Figure 7 shows various colour blends
of colour travel aluminium with organic and
effect pigments. The champagne to gold face
colour is ideal for blending with red, orange,
or yellow pigments to give intense chromatic
reds (Figure 7 top), while blending with blue
or green pigments results in an attractive
patina (Figure 7 centre). Finally, tinting with
carbon black can amplify the gold face col-
our of these pigments while slightly toning
down the flop colour (Figure 7 bottom). It is im-
portant to note again here that colour travel
aluminium pigments flop light with respect to
other metallic pigments, creating an interest-
ing dark to light travel effect when blended.
Colour travel aluminium can also be incor-
porated into powder coatings, either by dry
blending or bonding, leading to a number of
interesting effects. Figure 8 shows three pow-
der coated speed shapes of colour travel alu-
minium at 5 % loading. The bases used in the
shapes in Figure 8 are black (left), clear (cen-
tre), and white (right).
When colour travel aluminium is blended
with a black base, interesting speckled an-
tique effects can be obtained, while blending
with a white base causes the flop colour to
become accented. Blending with coloured
bases results in colour properties similar to
the cases reported for liquid coatings, al-
though the effect in powder coatings is more
subtle due a lower alignment of the pigment
flakes in these applications.
PIGMENT PERFORMANCE IN SUMMARY
A new type of oxidised aluminium pigments
has been devised, characterised by having a
structured surface. Although other oxidised alu-
minium pigments exist, structured oxidised alu-
minium pigments have so far not been reported.
The structured surface behaves like a pseu-
do diffraction grating and leads to interest-
ing optical effects such as gold to blue colour
travel and a light flop as the aspecular obser-
vation angle is increased.
These pigments can be used in a number of
applications, such as liquid and powder coat-
ings, where their unique colouration prop-
erties can lead to interesting colour blends
and effects that have not been previously
achieved.  
REFERENCES
[1] Wißling P., Metallic Effect Pigments,
Vincentz Net work GmBH & Co., Hannover,
Germany, 2006.
[2] Reisser W., Oxidized colored aluminium
pigments, process for their production and
their use, US 5,964,936, Oct. 1999 (Eck-
art).
[3] Klein G. A., Industrial Colour Physics,
Springer Science + Business Media, Inc.,
New York, USA, 2010.
[4] Shimizu, h., Fujita N., Coating Composition
and Coating Film Form-
ing Method, US 2012/0295032, Nov.
2012
[5]  http://www.iskiweb.co.jp/eng/products/
functional02.html

Figure 7: Displays showing panels sprayed with various paint Figure 8: Powder coated speed shapes containing a colour
blends containing colour travel aluminium; the unblended pig- travel aluminium pigment; left to right, the pigment is sprayed in
ment used in each of the blends is sprayed on the panel to the black, clear and white bases
far bottom

E U R O P E AN CO AT I NGS J O UR N AL 2018
 W O R LD O F C O L O UR 31

Source: phanuwatnandee - Fotolia.com

LIKE CLOCKWORK
Big factories can coat up to
100,000 pencils a day. The
pencils are pushed in a pipe-
like case with paint. Surplus
coating is then wiped off
when they are extruded from
the container. The process is
repeated up to seven times.

LESS IS MORE
Only small amounts of coa-
ting are needed to coat a
pencil – less than one gram
is used apiece. The pencil
has a long history – its first
precusors were produced in
1565 in England.
Source: Deutsches Lackinstitut

E U R OP E AN COAT I NGS JO UR N A L 2018

 32 E F F E C T P IG MENT S
Source: karlandreasgross - Fotolia.com
FORMULATING EXCELLENT
AUTOMOTIVE EFFECTS
Eight golden rules for creating automotive coatings using effect pigments. By Werner Rudolf Cramer (published in
ECJ 01/2016).
Modern automotive surfaces shine through the use of inter-
ference and aluminium effect pigments. Effective use of these
pigments in formulating automotive coatings depends on deep
knowledge on their properties and features in application.
E xciting colours and effects make modern automotive finishes
shine. Interference pigments, introduced in the mid-80s for
automotive OEM coatings, are the stars in providing great visual
effects. The first series of automotive colours containing white in-
terference pigments were applied in a three-layer system, using a
white basecoat, a white interference coat and a clear coat. After
that, the trend turned to coloured coatings, using mixtures of colour
pigments, together with white and colour interference pigments.
At the end of the 90s, these coloured coating systems were again
enhanced by the introduction of aluminium pigments, which had
been used for some time for effect finishing. With the development
of new effect pigments also came the development of new meas-
urement methods. This included the multi-angle measurement of
aluminium and interference pigments and the use of these meas-
urements in characterising visual surface effects. The multitude of
innovations with regard to pigments – and also to coatings and ap-
plication technologies – has influenced how a new colour standard
is created and what aspects are to be considered in its creation.
Here are eight golden rules for the effective creation of automotive
E U R O P E AN CO AT I NGS J O UR N AL 2018
colours.
MINDING THE GEOMETRIES
In most cases, modern automotive coatings have visual effects that in-
volve differences – either in the lightness of the coating, or in both the
lightness and the colour of the coating – which depend on the location
of the illumination and the location of the observer with respect to the
coating surface, and the geometries that arise from the path of light
from one to the other.
The light source – let’s take the sun, as an example – illuminates each
point on the vehicle with a quantifiable angle of incidence from the
“normal” (which is the perpendicular to the car body surface at the
point of incidence) and is reflected from it at the same angle to the
normal. Together with the illumination, the normal and the “gloss” (or
reflected light) all lie in the same plane, as shown in Figure 1. Within
this plane, the positions of the illumination and the observer are de-
fined by their angles of difference from the normal: an illumination of
15° means that the light source (the sun) illuminates the surface (our
vehicle) at an angle of 15° from the normal.
The “specular angle” (the angle of reflected light, or gloss) corresponds
to the illumination angle (for practical reasons, the angle notation for
this is preceded by a minus sign, which is physically incorrect), while
the “aspecular angle” is the angle of difference between the reflected
light and the observer. If one would be observing the gloss of the ve-

RESULTS AT A GLANCE
űű Angle-dependent visual effects have arisen since the 80s
and can be characterised by multi-angle measurements.
űű Interference pigments create angle-dependent colour ef-
fects and can be used additively.
űű Aluminium pigments can be used to create metallic effects.
űű Mixing colour pigments with the effects of interference pig-
ments and aluminium pigments creates dazzling new coatings.
hicle (i.e. if the observer were to be at the same angle as the reflected
light, as in Figure 1), the aspecular angle between gloss and observer
would be 0°. However, if the observer’s eye moves away from the
gloss direction, the aspecular angle starts to grow. In the example in
Figure 2, the car body panel has been tilted and the illumination and
the gloss/specular angle are now both at 5° from the new normal, but,
as a result of the tilt, the gloss has moved 20° away from the observer.
The ASTM E2539 Standard Test Method for Multiangle Color Meas-
urement of Interference Pigments proposes characterising the colour
reflection effects of effect pigments in a coated surface by collecting
measurements at multiple angles in the plane formed by the illumina-
tion, the normal and the gloss, including on the “opposite” side of the
gloss.
For formal reasons, these aspecular angles are given a negative sign.
Thus, the aspecular angle of -15° corresponds to an observation angle
at -60° when illuminated at 45°. To distinguish between the positions,
the prefixes “cis” and “trans” may be cited. “Cis” angles are located on
Figure 1: The geometries of the illumination, the surface and its
normal, the obser ver and the gloss (= reflection). In this exam-
ple, the obser ver is obser ving from the same angle from the
normal as the gloss/reflection.
EFFE C T P I G MEN T S 33
the illuminated side, while “trans” angles are on the opposite side of
the gloss. Manufacturers of measurement instruments refer to these
standard aspecular angles, usually -15°, 15°, 25°, 45°, 75° and 110°,
which correspond to absolute observation angles of -50°, -30°, -20°,
0°, 30° and 65° (see Figure 3). The measurement results at 45°/as-
15° are similar to those at 65°/as15°: if the connecting line between
the two geometries 45°/as15° and 45°/as-15° in the extension of the
two geometries 45°/as25° und 45°/as15°, then the coating mix does
not contain a colour interference pigment. With a colour interference
pigment, the curve bends counterclockwise. Coatings with aluminium
pigments do not have this kink; the connecting line for these occurs
between the measured values at 45°/as25°, 45°/as15° and 45°/as-15°
and is nearly straight (see Figure 4).
GETTING TO KNOW EFFECT PIGMENTS
While colour pigments partially absorb incoming light and partially scat-
ter it undirected in all directions, interference pigments additionally
partially transmit the light. Particularly, in the case of transparent inter-
ference pigment types, one can recognise the intense reflection colour
and the transmission colour, which are complementary to each other.
Transparent interference pigments consist of a substrate particle
(of e.g. mica, aluminium oxide, or silicon oxide) covered with a highly-
refractive metal oxide layer. When light strikes the surface, a part of
this light is reflected, while the other part travels through the metal ox-
ide layer until it arrives at the boundary layer to the substrate, where it
is, again, partially reflected. This reflected portion of the light exits the
pigment particle parallel to the first reflection component, and both
component light waves then interfere with each other constructively
or destructively, depending on the path length difference (the “phase
shift”) taken by the passage through the metal oxide layer. The degree
of constructive or destructive interference differs by wavelength of
light, and the thickness of the metal oxide layer can be tailored to
interference of certain wavelengths. Light of certain wavelengths is
therefore seen to be selectively reflected, depending on the thickness
of the highly refractive layer (or layers), their refractive indexes and
the angle of the incoming light.
The rays of light that pass all the way through transparent interfer-
ence pigments experience something similar on the reverse side of
the pigment and also interfere. Since the rays of light are moving from
optically denser to optically thinner media, the phase shift is absent.
For this reason, the transmission colour complements the reflection
colour: if the interference pigment reflects blue, then its transmission 
Figure 2: If a test panel is tilted by the obser ver, the angle
bet ween the light source and the obser ver does not change: it
remains at 30°, but there is now an aspecular angle bet ween
the obser ver and the gloss/reflection.
E U R OP E AN COAT I NGS JO UR N A L 2018
 34 E F F E C T P IG MENT S
 colour is yellow. This can be observed when the pigment on a trans-
parent film or a white substrate is applied: the colour perceived on
the surface appears to be blue while the transmission colour is yellow.
Figure 5 shows how there can be a viewing angle transition from the
reflection colour to the transmission colour.
There are different types of interference pigments, which can roughly
be distinguished by how they were produced: transparent, or semi-
transparent ones are made in wet-chemical processes for which the
carrier materials consist of natural mica, aluminium oxide or silicon
oxide. These carrier particles can be coated with metal oxides such as
titanium dioxide, iron oxide or chromium oxide.
APPLYING SPECIFIC INTERFERENCE PIGMENTS
Since interference pigments are mostly transparent, appropriate pig-
ments need to be added to the coating formulation to increase hid-
ing power. By mixing transparent interference pigments with blue, or
green colour pigments, the transparency of the mixture decreases.
Simultaneously, the chroma (colour intensity) of the mixture initially
increases, only to decrease again after a certain point. This phenom-
enon is also common in white colour mixtures: a blue pigment or its
corresponding paste is usually bluish black. When more white is add-
ed, the mixture becomes more colourful and chromatic (bluer) – up
until a certain point. Beyond this point of the highest chroma, further
addition of white makes the mixture start to become paler and more
achromatic again.
These days, aluminium pigments are also added to finishing mixtures
to achieve an optimum colour mix with maximum chroma of the in-
terference pigment and also a high degree of hiding power. However,
it should be noted that both coloured and aluminium pigments can
strongly influence the interference effect, or even prevent it. When mix-
ing a new colour, it is crucial to make sure that using an interference
pigment only makes sense when it emphasises or enhances the colour.
USING ALUMINIUM PIGMENTS WISELY
Similarly to the interference pigments, this type of pigment comes in
different sizes: fine aluminium pigments have a lower gloss (a “satin”
gloss), whereas coarse pigments have a much stronger one. However,
increasing coarseness decreases the hiding power. Different pigment
sizes are offered by manufacturers. In addition to classifications by
size, aluminium pigments are also distinguished by how they were
produced – which results in different optical characteristics. Normal
Figure 3: Modern portable measurement instruments illumi-
nate at 45° and measure at -15°, 15°, 25°, 45°, 75° and 110°
aspecular.
E U R O P E AN CO AT I NGS J O UR N AL 2018
aluminium pigments are formed by pulverising aluminium into tiny
particles, after which small particles that resemble potato tubers are
formed. When these are flattened, they become aluminium pigment
“flakes” (so named because of their irregular appearance, similar to
“cornflakes”). When the pulverisation is carried out with an inert gas
process, then the result is small beads, that, when flattened, lead to
flat, round pigments called “silver dollars”. Aluminium pigments vary in
sizes ranging from 11 µm to 24 µm for the cornflakes and 14 µm to
34 µm for the silver dollars (the numbers quoted are median diam-
eter, or D50).
In a visual assessment, for example, when tilting the test panel at the
window, the illumination and observation angles change. However, as
can be seen in Figure 2, during this process, the positions of the illu-
mination (sun) and the observer – and thus the angle between them
– remain the same. The geometries for visual observation do not cor-
respond to those of measuring instruments. This would require that
the light source would always have to shine at the same angle.
Aluminium pigments and pastes react to colour pigments in the same
way that white or colour interference pigments do: the chroma in-
creases to a maximum, and then falls again, while the lightness in-
creases continues to increase.
SELECTING THE DESIRED COLOUR RANGE
To create a new colour with visual effects, start with a special effect
Figure 4: Coloured interference pigments show significant colour
changes depending on the illumination and aspecular angle.
Tilting a panel in the light booth or at the window, the geometries
are different to those of portable instruments.
45° illum.
15° asp.
15° illum.
65° illum. 15° asp.
15° asp. 45° illum.
25° asp.
45° illum.
45° asp.
45° illum.
75° asp.
Figure 5: Transparent interference pigments change their colour
due to the aspecular angle. Near gloss – bet ween 20° and 30°
from gloss – there is a transition area where the reflection colour
changes to the complementary transmission colour.
-15° 0 +15° +20° +30° +75°
Transition area

pigment and observe its behaviour. If, for example, one takes a col-
ourful interference pigment, then the first step is to mix it with black to
determine the effect. The next step is to repeat the experiment with a
blue or green colour pigment (or their corresponding pastes). The ac-
tual colour and effect possibilities of such interference pigments can
be very quickly recognised in experimenting with these combinations.
From these trials, a number of ideas will arise for new colours, which
can be prepared in OEM applications.
On the other hand, one can also control the desired colour range
in a targeted manner by adjusting the combination of different pig-
ment types: if the formulation is dominated by a colour pigment, then
this will determine the overall colour. The addition of an aluminium
pigment will determine the shine effect of the mixture; here one can
choose from a spectrum, between fine to coarse aluminium pigments,
as well as between “cornflakes” and “silver dollars”. Additional interfer-
ence pigments allow one to determine the visual effect behaviour of
the complete mixture. Here again, there is a large range of options
that opens the door to many possibilities.
If, for example, one starts with a blue pigment, then white and colour
interference pigments may be added. White interference pigments
give a silvery effect, while colour interference pigments create more
colour effect. Even gold or red copper interference pigments can be
added to the original blue pigment: since they have absorbent ele-
ments, subtractive mixing behaviour also occurs in such mixtures, and
therefore blue colour pigments combined with gold interference pig-
Figure 6: Metallic colours show a powerful change in intensity
depending on the obser vation angle.
Figure 8: Matte finishes are the latest trend, but are still not that
popular. They can pose difficulties in OEM coatings and refinish-
ing repair jobs.
EFFE C T P I G MEN T S 35
ments can also produce beautiful green hues. If one wanted to mix
bright metallics or silver, as in the coating seen in Figure 6, then one
could conveniently choose an aluminium pigment from the beginning.
Since different types and sizes are offered, the decision for the level
of shine and the coarseness of the complete mixture is made at this
point. Afterwards, colour pigments can be added to provide a gen-
eral, directional tint to the colour. Interference pigments can also be
added, depending on the type and proportions of the overall mixture,
to give a more, or less pronounced colour effect – as in the bright red
in Figure 7.
THINKING IN COLOUR SYSTEMS
The portfolio of colour and effect pigments offered is so expansive
that it is possible to create virtually any colour, nowadays. Neverthe-
less, it is always important to remember that these pigments are real
and not theoretical. It is not possible to produce an “ideal” (neutral)
yellow. Yellow colour pigments have either a red, or a green compo-
nent. Furthermore, a red colour pigment, can produce many red col-
our effects. The reason for this is, firstly, the same as for the yellow,
and, secondly, the reaction of red pigments with white or in mixtures
is not ideal, and instead can turn to, for example, violet, or more blu-
ish hues in mixtures with white. Adding a colour pigment to a mixture
leads to a movement of its location in all three dimensions of colour
space, changing chroma, colour and lightness. 
Figure 7: The effect of a metallic red (left) is very clear.
Figure 9: Black, white and silver are favourites around the
world. Very few bold colours become an OEM finish.
E U R OP E AN COAT I NGS JO UR N A L 2018
 36 E F F E C T P IG MENT S

“Currently, golden pigments

are in the focus.“
3 questions to Werner Rudolf Cramer

What difficulties pose matte clearcoats for OEM coatings and refinish jobs? The result of a
painting with matte clearcoat depends on components such as the hardener and thinner as well of
application conditions such as booth temperature and humidity. This applies to OEM coatings and
refinishes. In refinishes, there are different grades of matte clearcoats which are caused by different
car models and parts.

How do colour and aluminum pigments influence the interference effect? Colour pigments Werner Rudolf Cramer
affect the overall colour impression. The interference effect is usually reached. Aluminum pigments Freelance
have a direct influence on the interference effect because both have their strongest reflection near consultant and journalist
gloss. You obtain fairly “hard” colours with aluminum pigments and their blends with colour pig- wrcramer@muenster.de
ments, while interference pigments lead to more “soft” blends in ad-mixtures with colour pigments.

In addition to metallic paints, what are other popular effects coatings? Besides metallic col-
ours, interference pigments are often used in combination with colour and aluminum pigments. De-
pending on the area of application, various popularities of interference pigments can be determined.
Currently, golden pigments – aluminum as well as interference pigments – are in the focus. They are
not only useful to create gold-yellow colours, but also helpful to create different colour compositions

 Interference pigments with a strong colour effect are singular pig-
ments, meaning that they do not constitute a colour system of many
components. On the other hand, they can still also be mixed with
other coloured and interference pigments. The latter is, however, less
advisable since it is quite likely that the overall final effect is not pre-
dictable.
OBEYING THE MIXING LAWS
Automobile finishes and many industrial mixtures are typically blends
of various pigments or pastes. These not only have different colours
and effects, but also behave differently when mixed. When colour pig-
ments such as yellow and blue are combined to make green, this is
referred to as subtractive mixing. If, on the other hand, transparent
interference pigments such pearl yellow and pearl blue are blended
together, the result is not green, but a white. They mix additively.
It is possible to imagine the different mixing characteristics by using
two colour filters of yellow and blue as an example: in subtractive mix-
ing these two filters are in sequence, light passes through one, then
the other. The first filter – the yellow one, for example – first filters out
all wavelength ranges from the white light except for the yellow range.
After that, the blue filter filters out all rays of light except wavelengths
in the blue range. The transmission profile of both filters overlaps in
the green area of the spectrum so green remains as the resulting
colour of light allowed through both filters.
For additive mixing, imagine the filters in parallel, alongside one an-
other: in this case, again, the yellow filter allows all the light rays of the
yellow spectral range to pass through and the blue filter allows all the
light rays of the blue spectral range to pass through. Where the light
from both filters converge, they add up to white again.
To shift the colour of absorbing pigments in a certain direction, one
can conveniently use neighbouring pigments, or pigments with a simi-
E U R O P E AN CO AT I NGS J O UR N AL 2018
lar tint: a blue does not become more reddish with a red, but with a
violet. A yellow becomes more reddish when mixed with an orange. In
this case, a red would force the mixture too quickly into the red area;
and one would not begin with a greenish yellow, but with a reddish
yellow.
Transparent interference pigments blend more or less ideally to cre-
ate intermediate colours. Semi-transparent or hiding interference pig-
ments can also be mixed to achieve the desired effect. However, many
attempts and a lot of experience are necessary for successful results.
FINDING AN EXTRAORDINARY COLOUR CREATION
The variety of colours and effects is so expansive that selecting or
discovering a new colour is hard to do, at first glance. Here are three
suggestions for modern colours relevant to today’s taste:
ąą To create a radiant, plain white, avoid adding pigments in the
yellow-red-brown area. A little blue does wonders to make a white
turn into a bright white. To create a corresponding whiter-than-
white effect, use a pure white interference pigment instead of an
interference pigment based on natural mica. These do not appear
yellowish at higher aspecular angles.
ąą A metallic colour may have a slightly glossy effect if fine aluminium
pigments are used. By combining coarse “silver dollar” and fine
“cornflake” pigments, a metallic effect can be “taken to extremes,”
as one might say. Additional interference pigments can enhance
this effect because this type of pigment reflects extremely close to
the gloss.
ąą Colour effects that dazzle the onlooker can optimally be created
using colour interference pigments. These pigments can more or
less be mixed haphazardly together with colour pigments. Applying
such pigments allows one to control not only the colour effects, but
also their chroma. All in all, there are so many fascinating interfer-
ence and aluminium pigments available that their full potential is
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 38 E F F E C T P IG MENT S
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RAINBOWS MADE TO ORDER
The effective use of interference and polychromatic colorants. By Werner Rudolf Cramer, free consultant, and Frank J.
Maile, Carl Schlenk.
Interference pigments can deliver a wider range of optical ef-
fects than other pigment types, since their angle-dependent
behaviour involves superimposing light waves rather than
purely absorbing or reflecting them. Factors affecting the ap-
pearance of these pigments are discussed and the use of dif-
fraction pigments is considered.
I nterference pigments are among the most optically sophisticated
pigments. Unlike colour pigments that absorb some of the inci-
dent light and metallic pigments that reflect it, interference pigments
involve superimposed light waves that are shifted together due to
reflections and refractions. This causes strengthening or weakening
of the resulting light waves. Various factors, such as the structure
of the pigment, its application and the lighting, make for optimum
conditions.
Pigments manufactured with wet chemistry generally have a carrier
platelet of natural mica, silicon dioxide or aluminium oxide. High re-
fractive index metal oxides such as titanium dioxide or iron oxide are
applied to this carrier platelet. Depending on the layer thicknesses
of the oxide, these pigments change their colour from white, yel-
low, red or blue to green. This unusual colour shift results from the
fact that the maxima - and also the minima - move to longer wave-
lengths. For yellow, the minimum shifts from the UV range into the
E U R O P E AN CO AT I NGS J O UR N AL 2018
visible region, while white becomes a yellow. If the layer thickness
of titanium dioxide is further increased, this minimum shifts further
into the longer wavelengths, which results in a red. The maximum
following the minimum in the UV range migrates into the visible
range, while the maximum in the long wavelength range travels into
the invisible infrared range.
With higher layer thickness the blue maximum shifts into the green
range. Such pigment group colour sequences are thus chemically
identical, differing only in the layer thickness.
ORIENTATION, ANGULAR AND SUBSTRATE EFFECTS
Interference pigments have been used in automotive paints since the
mid-Eighties. Since that time, there has been increasing interest in
quantifying their colours and effects. They are applied as so-called
basecoats, which are then sealed with a clear coat. These basecoats
have a layer thickness of 10-15 µm; the interference pigments are in
the range of 5-100  µm long and about 0.05  µm thick. Due to their
size, the pigments can only be situated as platelets lying more or less
parallel to the coating layer in the paint. This orientation is enhanced
by additives during the drying process of the basecoat. The theoretical
calculation of the orientation of the pigments on the basis of measur-
ing angles must therefore be studied.

RESULTS AT A GLANCE
űű Interference pigments can deliver a wider range of optical
effects than other pigment types, since their angle-dependent
behaviour involves superimposing light waves rather than
purely absorbing or reflecting them. Their appearance depends
largely on the thickness of the high refractive index material ap-
plied to the carrier platelet.
űű Factors affecting the appearance of these pigments are dis-
cussed, as well as the differing effects that can be obtained by
mixing them with other types of pigment or changing the un-
derlying paint colour.
űű The use of diffraction (polychromatic or ‘rainbow effect’)
pigments is also discussed. These pigments used alone always
show a complete rainbow as the viewing angle is changed, but
adding colour pigments can suppress part of it.
űű The use of mixtures of different types of pigment and dif-
ferent background colours allows a vast range of effects to be
achieved.
Patterns in the electron microscope show a relatively flat orientation;
in the light microscope, the change in the illumination angle shows
that the colours observed almost always arise from the type of pig-
ment and not from differently oriented pigments. Most interference
pigments are transparent, which is why the colour of the background
or environment also plays a role. Since the incident light is divided
into the reflection colour and complementary transmission colour,
the change can be observed well on a white background.
With measurements close to the gloss angle, the reflection colour is
detected and the transmission colour is removed from the gloss. This
transmission colour is produced on the opposite side of the pigment,
reflected by the white background. If angular differences are meas-
ured aspecular with an illumination angle of 45°, the reflection colour
in the range can be detected up to about 20°. Between 20° and 30°
aspecular there is a so-called transition range.
With large aspecular angles, the complementary transmission colour
that is reflected from the white background is measured. A black back-
ground absorbs the transmission colour. Coloured substrates as well
as admixtures of colour pigments show similar patterns (see Figure 1).
MEASURING THE APPEARANCE OF INTERFERENCE PIGMENTS
The laws of optics describe three properties that can be applied to
EFFE C T P I G MEN T S 39
interference pigments. On the one hand, the reflection maximum
shifts to shorter wavelengths when the illumination is flatter. This is
a crucial property for the characterisation and identification of in-
terference pigments. This optical property can be technically meas-
ured in that the illumination angle is changed from a steep angle to a
flatter one or vice versa, while the aspecular angle remains constant
for each gloss angle. This results in a typical interference line for the
individual pigment. An aspecular angle of 15° has proved particularly
useful here. Measurements at aspecular angles closer to the gloss
often run the risk of giving implausible measurements, especially
when it comes to samples with a clear coat. The second property is
demonstrated in the changes of the reflection curves. They not only
shift to a shorter wavelength, but their maxima rise considerably with
flatter illumination. As a result of this property, the interference line
in the a*b* colour space diagram always runs in a counter-clockwise
direction with flatter illumination. Thus, the colour of a red interfer-
ence pigment shifts from bluish red to yellowish red, and a green
shifts from yellowish green to bluish green. The third characteristic
relates to measurements at constant illumination: commonly, a con-
stant illumination angle of 45° is recorded, but other angles such as
65° are possible. Since all interference pigments show their reflec-
tion colour – which can also be measured – close to the gloss angle
it can also be observed and measured even in unusual mixtures with
colour pigments.
Thus, the blue reflection colour is retained even if the corresponding
pigment is mixed with a green or red colour pigment. Basically, an
effect arises from the fact that the colour and/or brightness changes
depending on the geometry. And with interference pigments the re-
flection colour is always detected close to the gloss.
HOW ADDING OTHER PIGMENT TYPES AFFECTS APPEARANCE
The overall colour appearance of a pigment mixture is affected differ-
ently by the pigments it contains. This applies to the colour pigments,
aluminium pigments and interference pigments. Colour pigments af-
fect the overall colour impression across all geometries, aluminium
pigments close to the gloss and interference pigments mainly up to
about 25° aspecular. Thus, the colour of the interference pigment is 
Figure 1: Up to 25° aspecular, both the reflection and transmis-
sion colours are obser ved when the transparent pigment is
applied over a white background. The transmission colour is
absorbed over a black background.
E U R OP E AN COAT I NGS JO UR N A L 2018
 40 E F F E C T P IG MENT S
 affected by the colour pigments, as they also reflect close to the gloss.
But measurements at a constant illumination angle and varied angu-
lar differences to each gloss angle are not limited to an illumination
angle of 45°. In principle, 45° illumination has simply emerged as the
most suitable for characterisation.
The combination of these measurements results in the so-called ‘as-
pecular line’; the combination of the measured values at a constant
differential angle is referred to as the ‘interference line’. Again, the
indication of the aspecular angle is necessary because there may be
multiple connection lines. At an aspecular angle equal to or greater
than 30°, the transmission colours are measured with transparent in-
terference pigments on a white background.
Figure 2: At 25° aspecular, no maximum is detectable in the vis-
ible region. When the aspecular angle is increased, the maxi-
mum shifts into the visible region and moves away from it again
at or above 65° aspecular.
Figure 4: Different pigment concentrations reflect the rainbow in
various strengths.
E U R O P E AN CO AT I NGS J O UR N AL 2018
ALL THE COLOURS OF THE RAINBOW IN ONE PIGMENT
In addition to the known interference pigments, which are prepared
by wet chemistry or in a high vacuum, there are special types of inter-
ference pigments. Their optical response corresponds to reflections
on a diffraction grid. The incident light is spectrally fragmented, from
blue-violet over blue, green, yellow to red.
Unlike ‘normal’ interference pigments, which show a colour gradient
depending on the angle of illumination, a complete rainbow is always
evident in the polychromatic pigments. Their colours can be meas-
ured individually - the eye has a greater observation and detection
range than a measuring instrument and sees a complete rainbow.
Figure 3: The colours of the rainbow flow clockwise in the a*b*
diagram. Modern colour instruments detect the rainbow at 45°
and 75° from gloss.
Figure 5: The rainbow can be obser ved on both sides of the
gloss angle (top); an interference pigment that shows its reflec-
tion colour at up to 25° aspecular is placed in this ‘gap’ (bottom).

The range of the rainbow lies in an angular range of 20 to 30 degrees
depending on the angle of illumination. With flat 65° illumination the
rainbow starts at about 45° and extends to about 75° aspecular. With
steeper illumination at 45°, the range shifts from 35° to 65°. These are
the limits for the colours of the first order. The colours of the second
order follow in this range; they are measurable, but barely visible.
From the reflectance curves it is clear that the reflections and their
maxima shift from the UV range into the visible range as the aspecular
angle increases in relation to the gloss angle. With further increases in
the aspecular angle they leave the visible spectral range, moving into
the infrared region, while maxima of the 2nd order move from the UV
into the visible range (see Figures 2 and 3).
The interference laws - the shift of the reflections to shorter wave-
lengths with flatter illumination - also apply to these pigments. Presum-
ing aspecular geometry – for example, at 55° – and if the reflections of
different illumination angles have this constant differential angle, the
shift of the maxima to shorter wavelengths with flatter angles of illumi-
nation can be clearly seen. Thus, in these pigments, the optical reflec-
tion laws apply both on the diffraction grid and in terms of interference.
MODIFYING THE APPEARANCE OF EFFECT PIGMENTS
Interference pigments have typical reflection colours with a small or
large colour gradient. They are found in many car colours in combina-
tion with colour and aluminium pigments. In order to create a blue
colour effect, for example, a white interference pigment can be mixed
with a blue colour pigment. Instead of the white interference pigment
a blue or green may also be used. The possibilities for combinations
here are almost infinite.
In the case of polychromatic pigments, the combinations are made
rather differently: admixtures of colour and aluminium pigments in-
fluence the polychromatic rainbow effect. Polychromatic pigments
are inherently silver-white to silver-grey from their base colour. The
rainbow effect occurs most clearly with these neutral pigments. Ad-
mixtures of colour pigments suppress the rainbow partially or even
completely, so that in principle some preliminary considerations are
necessary.
ąą The complete rainbow exists only in polychromatic pigments alone or
with minimal admixtures. To retain the rainbow, the possibilities for
Figure 6: The initial values of the rainbow are shifted toward the
admixed interference pigment. As anticipated, the influence of the
polychromatic pigment predominates at or above 35° aspecular.
EFFE C T P I G MEN T S 41
combination are limited. Admixtures of black are ideal, because in this
case the rainbow colours are not affected. And because of the greater
contrast, the rainbow effect is more intense. When such pigments are
used, the full rainbow is always seen; there are no pigments which
show only a half or a quarter of the rainbow. In this case the effect
must be controlled with admixtures with other pigments (Figure 4).
ąą The rainbow starts at about 35°-45° aspecular; interfer-
ence pigments show – depending on the type – their reflec-
tion colour up to about 25° aspecular. In this respect, two
colour ranges can be used by mixing both types of pigment.
ąą Looking at a spray-out of a polychromatic pigment from above,
one can detect the ‘gap’ between the two rainbows on either side
of the angle of observation. An interference pigment can be in-
corporated that so to speak fills this ‘gap’. Such mixtures can be
created in various ways, where the selected colour of the interfer-
ence pigment may also affect the rainbow (see Figures 5, 6 and 7).
ąą Admixtures of colour pigments influence the colour impres-
sion over the entire illumination and observation range. De-
pending on the shade of the colour pigment, the rainbow is
affected and may no longer be recognisable in its entirety.
ąą Like the colours of the interference pigments, the rainbow ap-
pears intense only in a narrow angular range. Despite their rela-
tively lower intensity close to the gloss, colour pigments produce
a stronger overall colour impression. As such, they often have
a strong influence on the rainbow, which can only demonstrate
a strong presence in combination with dark colour pigments.
DETAILED EXAMPLE OF MIXING DIFFERENT PIGMENT TYPES
Examples of mixtures of a pigment of this rainbow type called “MultiFlect”
with blue colour pigment and blue interference pigment show the respec-
tive influences in the geometrics areas: near the gloss at 15° aspecular - in
this case with an illumination of 45° - the rainbow pigment reflects with
a slight valley in the green range; away from the gloss angle - in this case
at 50° aspecular - the green of the rainbow can be seen. By adding a
blue pigment, the 45° aspectral reflectance curve shifts to higher values,
above all in the blue spectral range; close to the gloss the 15° aspectral
reflectance curve is slightly increased in the blue and red range. The differ-
ences in mixtures with blue interference pigment are even more distinct. 
Figure 7: The reflectance cur ves also show the combination of
the optical properties of both pigments: the mixture shows colour
reflections both close to the gloss as well as away from it.
E U R OP E AN COAT I NGS JO UR N A L 2018
42 E F F E C T P IG MENT S

“Individuality is in the
foreground.“

3 questions to Werner Rudolf Cramer Werner Rudolf Cramer

Free consultant and journalist
For which applications are polychromatic pigments most suitable? With polychromatic pig- wrcramer@muenster.de
ments a variety of applications are possible – everywhere where special effects are desired. Auto-
motive coatings, industrial and powder coatings are only some examples in which effects are in
demand. With this kind of pigment – as with all effect pigments – individuality is in the foreground.

Does it make sense to only use polychromatic pigments – as opposed to a combination

with other types of pigments? Through combination with other pigments, the range of possible
applications is increased. In this respect, the decision will depend on the application: what should be
in the foreground, the individual effect or the total colour impression of the combination with other
pigments?

Can the optical properties of mixing diverse pigment types easily be obtained? There are
two main points that help facilitate the introduction into the mixing behaviour of different kinds of
pigments: firstly, it should be noted that two different mixing behaviours encounter each other, namely
the subtractive and additive mixing. Secondly, it is always worth looking at the reflectance curves, which
show the real optical behaviour of effect pigments.

Their reflections close to the gloss affect the resulting reflectance curve
with a strong maximum at 15° aspecular. The reflections of this pigment
shift, so to speak, between the rainbow reflections of the special effect pig-
ment. This optical behaviour can also be observed visually: left and right
of the gloss the rainbows can be seen as well as the blue interference
colour between them. Interference pigments in other colours provide the
same results, where their reflection colour provides a more or less strong
contrast to the rainbow. Plotting the a*b* values shows a shift of the
rainbow circle into the blue area with the addition of a blue colour pig-
ment. The addition of a blue interference pigment causes the unfold-
ing of this circle in the blue region. Experiments with different colour
Certainly the use of this type of pigment is particularly limited in the
automotive sector, but it can be used for attractive concepts in special
series. This requires detailed knowledge of the geometric constraints
of the colours. The difficulty in developing this knowledge stems from
the fact that the geometries of the rainbow are only partially recorded
by the measuring geometries of most spectrophotometers.  
LITERATURE
[1] Maile F.J., Martins A.C., A new Generation of Aluminum-based Pigments,

pigments and interference pigments show similar colour responses.
MAKING MOST EFFECTIVE USE OF POLYCHROMATIC PIGMENTS
As with all effect pigments, the use of polychromatic pigments re-
quires an intensive examination of illumination and observation
geometries, if useful and interesting colour creations are to be pro-
duced. Although these pigments ‘only’ show a rainbow, admixing in-
terference pigments in particular can create effects that exploit the
optical properties of both types of pigment.
In addition, colour pigments can be used, which can have a crucial
effect on the overall colour across all geometries. Starting from the
polychromatic pigment, different approaches for colour creations can
be implemented.

Paper 137, ABRAFATI Coatings Congress, São Paulo, Brazil, Oct. 2015.
[2] Maile F.J., Pfaff G., Reynders P., Prog. Org. Coat., 2005, Vol. 54 pp150–
163.
[3] Loewen E.G., Popov E., Diffraction Gratings and Applications, Marcel Dek-
ker, Inc. N.Y., Basel, 1997.
[4] Cramer W.R., Visual & instrumental geometries in colour matching, CCJ,
2012, No. 7.
[5] Cramer W.R., Reflections on the right angle, ECJ, 2012, No. 4.

E U R O P E AN CO AT I NGS J O UR N AL 2018
 W O R LD O F C O L O UR 43

Source: Leo Lintang - Fotolia.com

HEAVY WEIGHTER
Around 650 kilograms of
coating are used on an Air-
bus A380. The Airbus A320
family of planes with a single
aisle accounts with the com-
paratively small amount of
150 kg.

A LOOK BACK
Airbus, the largest European
plane manufacturer, was
founded in 1970 in Tou-
louse, France. Two years la-
ter, their first model called
Airbus A300 was released.
Planes of this family were
sold until 2007.

E U R OP E AN COAT I NGS JO UR N A L 2018

 44 E F F E C T P IG MENT S
Source: akf - Fotolia.com
A SPARKLING FUTURE
FOR EFFECT PIGMENTS
Advances in technology will open up a wealth of opportunities. By Carsten Handrosch, Carsten Plüg, Merck KGaA
There is great potential in the coatings industry for high-sparkle,
highly reflective and photonic pigments. While research has pro-
duced exciting results, challenges lie in their industrial applica-
tion before these types of pigments become commercially viable.
A ngle-dependent, iridescent and lustrous colour effects in nature
are limited to only a few animals, including mussels, butterflies
and beetles, and to a few gem stones, e.g. opals [1]. Artificial pigments
try to mimic these effects by using combinations of materials with dif-
ferent refractive indices.
In particular, effect pigments that create interference effects through
a layer structure of high and low refractive materials have gained
significant importance in applications such as automotive coatings.
These materials can create an illusion of depth due to their parallel
arrangement in the coating and semitransparent appearance. The op-
tics, physics and functional properties of these fascinating materials
have been reviewed in various papers [2].
Typical decorative applications of these effect pigments include coat-
ings, plastics, printings and ceramics, whereas functional applications
include security, heat management, laser marking, and thermal or
electrical conductivity applications. The application of these pigments
in coatings has been described in detail [3].
This paper therefore focuses on the impact of recent developments
in effect pigments on coatings in general, and automotive coatings
in particular. By discussing examples of three different technologies,
their potential for coating applications shall be demonstrated: high
E U R O P E AN CO AT I NGS J O UR N AL 2018
sparkling pigments based on alumina, highly chromatic, opaque pig-
ments based on aluminium, and photonic crystals. These three class-
es of pigments are current focus fields of research in both industry
and academia. They have good potential to create further unique and
new effects in coatings.
HIGH SPARKLING PIGMENTS BASED ON ALUMINA
Since the early 2000s, effect pigments based on alumina flakes have
enjoyed attention particularly in automotive coatings. The flat nature
of mono-crystalline alumina, particularly in the corundum crystal form,
allows the formation of well-defined effect pigments (Figure 1) when
coated with highly refractive oxides such as titania and iron oxide. The
resulting alumina-based pigments provide an extremely even and paral-
lel orientation in the coating process, e.g. by bell spraying. The resulting
coatings reveal an outstanding effect, referred to as living sparkle [4].
The impression of the depth of the coating is created through individual
sparkle points. This living sparkle is a complex phenomenon. There is
evidence that the flatness of the individual particle predominantly de-
fines the area of sparkle in the observer’s eyes [5]. Alumina as a single
crystalline substrate is almost perfectly flat. In contrast, glass as a sub-
strate has some tilt in the particles that cannot be avoided during the
manufacturing process of flakes made from glass melt [6].
Particles of alumina-based pigments range in thickness from 300-1200
nm, depending on the colour, and are often provided in a narrow particle
size distribution of 5-30 µm (this applies to 80% of particles). These di-

RESULTS AT A GLANCE
 Research is currently focused on high-sparkle pigments,
highly reflective gold-orange-red pigments and photonic pig-
ments.
 Decorative photonic systems are not yet industrially viable.
Application hurdles must be overcome before they can enter
the market.
 New technologies are being developed for sparkling pig-
ments. Alumina-based interference pigments currently offer
the best results.
 Highly reflective pigments produced using wet coating tech-
nology provide a good starting point for developing pigments
that combine high chroma with high reflectivity and opacity.
mensions, as well as the tailor-made surface treatment of the pigments,
allow easy handling of the pigments in all major paint systems. Glass
flake-based pigments only achieve similar sparkling effects at a much
higher particle thickness, usually greater than 1200 nm, and particle size
of 60-100 µm or larger. These products can be only used in coatings if
the substrate can be oriented so that it is perfectly parallel in the coating
layer, to avoid defects caused by particles jutting out of the coating layer.
Alumina-based pearlescent pigments have consequently become im-
portant in almost all shade areas. Particularly strong sparkle can be
achieved in three-layer coatings, in which the sparkling effect is not
quenched by opaque absorption pigments [7].
SPECTACULAR SPARKLE AND COLOR EFFECTS
In dark formulations, the best sparkle results with silver-white alumi-
na-based pigments are actually achieved with small amounts of effect
pigment alongside high loadings of carbon black. In contrast the new
Figure 1: Colour-forming principles of the three classes of pigments.
Special Effect Pigments
(Pearl Luster Pigments)
Coloured Metallic Pigments
Photonic Crystals
EFFE C T P I G ME N T S 45
dark-silver pigment, based on titania and iron oxide combinations,
provides extremely deep living-sparkle effects in the dark-silver shade
area and creates new styling opportunities (Figure 2).
It is worth mentioning that the elementary composition of this new pig-
ment consists only of the oxides aluminium, iron, titanium and, option-
ally, silicon and tin, and does not require hazardous heavy metals such
as copper, chromium or nickel as body colour donating components.
An alumina-based masstone pigment in the golden colour range,
with an unrivalled sparkling intensity, also expands styling options. A
special multilayer arrangement, again using only the classical metal
oxides, gives a unique appearance combining very high chroma with
the highest sparkle intensity of all alumina-based effect pigments. The
pigment can even provide sparkle with high loadings of titania white
or carbon black.
As illustrated in Figure 3, the particles of this pigment contain a very
smooth and homogeneously coated surface, providing high gloss.
The last example of a recent development of alumina pigment is a
highly chromatic blue interference pigment. Created using similar
technology as previous blue alumina-based pigments, this material
provided much higher chroma at an outstanding, blue sparkle inten-
sity. This attractive blue sparkle offers new styling options in dark-blue
and even black shades (Figure 4).
The three examples described above illustrate that alumina-based pig-
ments have more potential with respect to higher chroma, different spar-
kle appearance and higher sparkle intensity, even in opaque formulations.
Researchers are concentrating on providing pigments with high spar-
kle intensity and a high degree of reflectivity in dark-grey and black
formulations. New concepts and technologies need to be identified
to achieve the desired colour properties without neglecting the con-
straints of technically demanding coating applications.
NEW TECHNOLOGY ENABLES HIGHLY CHROMATIC PIGMENTS
IN THE YELLOW TO RED COLOR RANGE
Relatively few transparent organic pigments provide the weather fast-
ness that is required for automotive coatings in the shade areas gold,
orange and yellowish to neutral red [8]. Combining transparent or-
ganic pigments with aluminium pigments achieves a limited variety
of shades, and pearlescent effects cannot be easily attached to such
combinations due to the quenching of interference pigments in highly
loaded alumina formulations.
To close this gap for pearlescent reflective coatings, highly reflective
pigments were developed by coating aluminium platelets with iron- 
Specific colour, luster and colour flop due to interference
(reflection and refraction) of light
Metallic gloss by reflection combined with absorption
and interference
Specifc colour and colour flop due to multiple interferences
of light
E U R OP E AN COAT I NGS JO UR N A L 2018
 46 E F F E C T P IG MENT S
 oxide layers of varying thicknesses. The thickness of the layer defines
the resulting colour [9].
The resulting pigments provide attractive shades and can be easily
combined with transparent organic pigments to achieve reflective and
brilliant coatings.
Iron-oxide coated alumina pigments are offered as pastes, e.g. in
Naphta. Pigment pastes obtained by dry deposition of iron oxide have
a limited shelf life and when used in waterborne systems require fur-
ther stabilisation due to the undesired formation of hydrogen[10].
Recent developments of such pigments employ a wet-coating technol-
ogy, which is standard for depositing metal-oxide layers on platelet sub-
strates [2a]. This technology requires the use of entirely inert aluminium
flakes to prevent hydrogen forming in an aqueous environment. This
passivation is achieved using a new technology [11, 12] and uses phos-
phates as its key ingredients. The new passivation technology provides
robust protection and allows layers to be added with good bonding.
As metal oxide coating of alumina particles can be performed in an
Figure 2: Microscopic image of high sparkle dark-silver pigment.
Figure 4: Colour travel (in a*b* plain, aspecular line: 45°/-
30°/+15°, 45°/-20°/+25°, 45°/0°/+45°, 45°/30°/+75°,
45°/65°/+110°; PMC =18%, black background, angles marked
according to DIN 6175-2) of new alumina blue pigment in
comparison to mica and existing alumina-based blue pigments
indicates high chroma at neutral blue shade.
10
5
Full shade over black
0
0 -50
-5
-10
-15
b*
 High performance Mica Blue 
 Existing Alumina Blue 
E U R O P E AN CO AT I NGS J O UR N AL 2018
aqueous environment, very dense and homogeneous layers of iron
oxide can form (Figure 5, Figure 6). This new technology leads to even
more chromatic pigments compared with those obtained by the dry
coating process. The very high chroma of the aqueous-coated pig-
ments allow new styling options (Figure 7). The potential of this pro-
cess has still not been fully explored. Research is currently focused on
providing new highly chromatic pigments with outstanding reflectivity
and a high level of opacity.
Recently, the use of ultra-thin aluminium platelets as obtained by
physical vapour deposition was suggested for iron oxide-coated pig-
ments [13]. It remains to be seen if these materials can outperform
existing pigments. Until now, there has been little interest in titania-
coated aluminium pigments due to their weak interference colour.
In summary, iron oxide-coated aluminium pigments continue to enjoy
a high level of research. It is highly possible that new pigments com-
bining high chroma, reflectivity and opacity will be commercialised in
the near future.
Figure 3: Electron micrograph image of alumina flakes coated
with multiple layers of TiO 2 (rutile), SnO 2 and SiO 2.
Figure 5: Electron micrograph image of homogeneous iron-oxide
coated aluminium platelets.
Face
-100
New alumina blue
Mica Rutile Blue Pearl

STRUCTURAL COLORS - ARTIFICIAL OPAL EFFECTS
Effect pigments with a photonic effect (“photonic effect pigments”) are
a class of their own and not related to the pigment types discussed
earlier. Colour is obtained through microscopically structured surfac-
es that exhibit periodic variations in dielectric constant in up to three
dimensions. The period of the differences has to follow the order of
the wavelength of visible light to allow colour-creation through inter-
ference effects. We observe this interference effect as vivid iridescent
colours. As these structures resemble macroscopic crystals, the terms
“photonic crystals” and “structural colours” are used [14].
The interference colours in birds feathers and the wings of butterflies
and beetles are created by periodical structures of channels, gratings,
holes or fibres consisting mostly of chitin or proteins. It was found
recently that the colour change of chameleons is based on photonic
structures too. The ability of specialised skin cells to change the form
and dimension of their photonic structure enables the body to mimic
its background [15].
Researchers have been particularly interested in trying to copy the
“fire” of opal, which is based on very regular-sized silica beads with a
diameter of 150–300 nm +/- 5% [16]. Attempts to mimic the photonic
effect of opal started with synthesising monodisperse silica particles
of 150-300 nm that arranged themselves into photonic crystals from
alcoholic suspension [17]. This principle has been extended to poly-
mer-bound matrices in order to freeze the high orientation [18].
Figure 6: Electron micrograph image of a single damaged particle
illustrating the homogeneous iron-oxide layer (white micro-struc-
tured area) and the dense passivation layer (dark grey area).
Figure 8: Angle dependent colour of t wo polymer-opals according to ref. [19a]: top left image - obser vation at flat angle of view; top
right image - obser vation at medium angle of view; bottom image - obser vation at steep angle of view.
EFFE C T P I G MEN T S 47
A similar approach uses organic beads with very narrow particle size
distribution, typically composed of a hard, rigid polystyrene (PS) core
and a soft, curable polyacrylate (PA) shell. The arranged photonic crys-
tal can be cured radically to obtain a polymeric material that can be
cut into particles. Curing conditions and particle size determine the
resulting colour (Figure 8) [19]. This technology enables brilliant colour
travel effects.
The distance between the PS particles determines the resulting col-
our, which means these pigments are very sensitive to process condi-
tions, preventing commercialisation for now.
Although the concept of photonic pigments offers attractive options
for new colour effects and has been studied for more than 15 years,
obstacles such as colour reproducibility are still a challenge. However,
new methodologies being explored might offer a solution soon [20].
EXCITING OPORTUNITIES - SOME DEPEND ON ADVANCES IN
TECHNOLOGY
Focus areas for research for new effect pigments are high-sparkle pig-
ments, highly reflective gold-orange-red pigments and photonic pig-
ments.
The area of decorative photonic systems is still in the early stages of
becoming an industrially viable technology. The specified application
hurdles will have to be overcome first, before these attractive prod-
ucts are ready to enter the market. 
Figure 7: Examples of lacquer panels with a golden, orange and
red aluminium-based pigment obtained by aqueous metal-oxide
coating.
E U R OP E AN COAT I NGS JO UR N A L 2018
 48 E F F E C T P IG MENT S
 For sparkling pigments, alumina-based interference pigments offer
the best technology, having recently led to new products in the blue,
gold and dark-silver shade areas. In order to achieve exciting new
sparkle effects new technologies are under development.
For highly reflective pigments, the wet coating technology offers po-
tential for further steps towards pigments combining high chroma
with high reflectivity and opacity. Recent examples indicate the poten-
tial of this technology.   Dr. Carsten Plüg
 
REFERENCES
[1] G reanye V., Bioinspired Photonics: optical structures and systems
inspired by nature, CRC Press, Boca Raton, 2015
[2] a ) Maile F. J., Pfaff G., Reynders P., Progress in Organic coatings
2005, 54, 150.
b) Greenstein L. M., in P.R. Lewis (Ed.), Pigments Handbook, vol. I, 2nd
ed., John Wiley & Sons, New York, 1998, 829. c) Maisch R., Weigand
M., Pearl Luster Pigments, Verlag Moderne Industrie, Landsberg/
Lech, 1991. Glausch R., Kieser M., Maisch R., Pfaff G., Weitzel J., in
Zorll U. (Ed.), Special Effect Pigments, Vincentz Verlag, Hannover,
1998.
d) Pfaff G., Reynders P., Chem.Rev. 1999, 99, 1963.
e) Pfaff G., Chemie in unserer Zeit 1997, 31, 6.
[3] P faff G., Gabel P., Kieser M., Maile F.J., Weitzel J., Spezielle Effektpig-
mente, 2nd Ed, Vincentz Net work, Hannover, 2007.
[4] Cramer W.R., Fahr zeug + Karosserie 2012 (12/04), 20.
[5] S chier D., Fritsche K., “Appearance von Automobilbeschichtungen –
Orientierung von Effektpigmenten”, Presentation at 79. Lacktagung,
GDCh, Schwerin, 16.-18.09.2015.
[6] Int. Patent Application WO2004056716.
[7] Patzlaff J., Rösler M., Eur.CoatingsJ 2006, 56.
[8] H erbst W., Hunger K., Industrial Organic Pigments, 3rd ed., Wiley,
Weinheim 2006.
[9] European Patent Application EP0033457.
[10] Ostertag W., Mronga M., Hauser P., Farbe + Lack 1987, 93, 973.
[11] Int. Patent Application WO03/014228 A1.
[12] Int. Patent Application WO2006/066825 A2.
[13] Int. Patent Application WO2015/014484 A1.
[14] a ) Srinivasarao M., Chem. Rev. 1999, 99, 1935-1961.
b) Tayeb G., Gralak B., Enoch S., Optics & Photonics News; February
2003, 38-49.
c) Welch V. L., Vigneron J.-P., Opt Quant Electron 2007, 39,
295–303. v) Xia F., Jiang L., Adv. Mater. 2008, 20, 2842–2858; e)
Kinoshita S., Yoshioka S., Miyazaki J., Rep. Prog. Phys. 2008, 71.
[15] Teyssier J., Saenko S.V., van der Marel D., Milinkovic D. C., Nat. Com-
mun. 2015, 6, 6368.
[16] a ) Sanders J.Y., Nature 1964, 204, 1151-1153;
b) Darragh P. J. , Gaskin A. J., Terrrell B. C. & Sanders J. V. , Nature
1966, 209, 13-16; c) Darragh P.J., Gaskin A.J., Sanders J.V., 1976,
Scientific American, 234, 84-95.
[17] S töber W., Fink A., Bohn E.; Journal of Colloid and Interface Science,
1968, 26/1, 62-69.
[18] S hin-Hyun Kim, Seog-Jin Jeon, Woong Chan Jeong, Hyo Sung Park,
and Seung-Man Yang; 2008, Adv. Mater., 20, 4129–4134
[19] a ) Winkler H., Bauer J., Schneider R., Heckmeier M., Vakuum in
Forschung und Praxis 2006, 18/1
b) He X., Thomann Y. et. al., Polymer Bulletin, 2006, 57, 785-796.
c) Egen M., Braun L., Zentel R., Tännert K., Frese P., Reis O., Wulf M.,
Macromol.Mater.Eng. 2004, 289, 158-163.
[20] G u H., Rong F., Tong B., Zhao Y., Fu D., Gu Z., Langmuir 2013, 29,
7576.
E U R O P E AN CO AT I NGS J O UR N AL 2018
Head Global
R&D Decoratives,
Pigments & Func-
tional Materials
Merck KGaA
carsten.plueg@
merckgroup.com
“Research will continue to
create new and interesting
effects.“
3 questions to Carsten Plüg
Do you see any future for glass pigments or will they be entirely
replaced by alumina-based pgiments? Glass flake-based pigments
have gained significant attention in industrial and cosmetic applications,
but only limited recognition in automotive coatings so far. Due to the high
degree of transparency, the use of glass pigments is somewhat limited to
three-layer white coatings. Here, strong sparkling effects can be achieved
at high-pigment concentrations that differ from the vivid living sparkle ef-
fects of existing alumina pigments. In my personal opinion, the easy-to-use
and the large variety of effects with alumina pigments make this class
of pigments, e.g. Xirallic pigments of Merck, the first choice in achieving
sparkling effects. However, further research will continue to create new and
interesting effects in both classes of pigments.
What are the main hurdles that have to be overcome regarding
wet coated aluminum flakes? Wet-coated aluminium flakes provide
exceptional high chroma in the gold-orange-red shade area. In contrast to
dry coated aluminium pigments, particularly in red shades, more homo-
geneously coated particles produce intense and vividly deep color effects
in combination with absorption pigments. The full potential of these new
pigments remains to be explored in practical use. Current developments
are concentrating on increased hiding power while maintaining the high
chroma properties.
Are there any promising approaches that could overcome the
hurdles like colour reproductively of photonic systems? The main
hurdle when producing pigments using photonic effects is freezing the self-
assembled structures during the whole processing and lifetime of the pig-
ment. Current products that are used in non-coatings applications keep
silica beads together by sintering self-assembled structures of a fairly large
size. Therefore, research is focusing on creating assembled photonic struc-
tures, in a technically suitable size, in matrices withstanding processing
conditions in coatings. The viability of these new concepts and their colour
reproducibility still remains to be proven.
 EFFE C T P I G MEN T S 49

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SPECIAL EFFECTS!
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SPECIAL EFFECT PIGMENTS
A complete introduction to the world of
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processes, and specific applications of special
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E U R OP E AN COAT I NGS JO UR N A L 2018
50 E F F E C T P IG MENT S

SPECIAL EFFECTS
Development of new effect pigments that add more than just colour to paint. By Raimund Schmid (published in ECJ
05/2014).

The development activities of pigment producers are driven Figure 1: Unground synthetic mica is cleaner compared to natu-
by the market needs of the coatings industries. In the field ral mica
of effect pigments the main driver for ongoing innovation is
the desire of industrial paint designers to get the best tools
for exciting colour styling. Innovation in pearl pigments based
on synthetic mica, as well as iron oxide-coated silver dollars,
provide the basis for visually striking whites and other exciting
colours for paints.

T he exterior design of an item is mainly determined by shape, col-

our and haptic impression. During the first minutes of exposure
to an item customers usually decide whether they are interested. For
that reason inspiring colours – very often with special effects – are
needed in all areas.
Designers often require effect pigments that support the desire to
go for colouristic ‘extremes’, including higher chroma, higher light-
ness, most neutral and dark down-flop, higher transparency of pearl
shades, whiter whites and darker, deeper blacks. Designers also ap-
preciate sparkling appearance with vivid light reflection under direct
illumination as well as the colouristic opposite, liquid appearance. The
latter can be best described by the optical impression of a coating as
smooth as the surface of a liquid metal, such as mercury.
If everything in a store looks new, an item can attract attention by
looking totally different to anything else. For instance, the so-called

E U R O P E AN CO AT I NGS J O UR N AL 2018

RESULTS AT A GLANCE
 One of designers’ main requests are for effect pigments
that support the desire to go for colouristic ‘extremes’, includ-
ing higher chroma, higher lightness, whiter whites and darker,
deeper blacks.
 The requirements of the paint industry are driving the de-
velopment of new effect pigments with developments falling
into three main areas: new substrates / effect pigments via
crystallisation, web technologies or improved glass process-
ing. Better colouristic properties are achieved through the use
of more uniform pigment shapes or smoother flake surfaces,
for example, and new surface treatments for use in waterborne
systems.
 A series of bluish white pearl pigments based on synthetic
mica substrates allows cool white pearl shades and in combi-
nation with carbon black attractive grays and gunmetal blacks
with either silky or sparkling character.
 Iron oxide-coated Al-flakes of the silver dollar type show
much higher brilliancy and stronger lightness flops compared
to the corresponding cornflake types.
‘vintage look’ is sometimes used to enhance the value of goods. In the
industrial paint industry, the equivalent effect is achieved by coatings
with crazing, patina or rusty appearances.
Also of interest to designers are changing colours influenced by view-
ing or illumination angles, temperature, sound, electric or magnetic
fields. In the coatings area, so-called goniochromatic colours and ther-
mochromic colours can be realised.
Only an attractive colour that can be applied with ease is acceptable
for demanding industries like the automotive sector. The main re-
quests from the technical side of paint manufacturing are for effect
pigments with the following properties:
 Improved hiding of pigments
 Narrower particle size distributions
 Better mechanical stability in circulation lines
 Low abrasiveness
 Better gloss and distinctness of image (DOI)
 Improved weather fastness
 Better humidity resistance
 Consistency of quality
 Colouristic equivalence in waterborne and
solvent-borne systems
A final, important driving force for new developments is
the ‘green’ image of goods and the resulting requests for
banning of heavy metals, the reduction of volatile organic compounds
(VOCs) and for sustainable production processes.
TECHNOLOGY TRENDS IN
MANUFACTURING EFFECT PIGMENTS
The above-described requirements of the paint industry are driving
the development of new effect pigments. The main development ac-
tivities fall into three groups:
EFFE C T P I G MEN T S 51
Figure 2: Colouristic performance of a bluish synthetic mica
based pearl in a white Tricoat in comparison to a yellowish natu-
1. New substrates / effect pigments via:
Crystallisation
As an alternative to natural mica (muscovite), synthetic mica (fluoro-
phlogopite) has been developed as a substrate for pearl pigments
with higher transparency [1]. Alternatively, alumina flakes grown us-
ing a melt-and-crystallisation process provide substrates for attractive
sparkling pigments [2].
Web technologies
The coating of a moving web with silica layers, aluminium films or mul-
tilayer systems, followed by the breaking of the film into flake form,
yields interesting substrates for pigments:
Silica flakes provide substrates for subsequent oxide coatings in order
to form goniochromatic colours.
Similarly prepared aluminium films (thin Al-flakes) yield the so called
vacuum metalised pigments [3-5], which provide liquid metal effects.
The first patented, web produced multilayer pigments, consisting of
semi-transparent Al-films, transparent SiO2-films and opaque Al-layers,
provided effect pigments with strong interference colours [6]. They
were, however, never produced at commercial scale. In security inks
multilayer pigments like Cr/MgF2/Al/MgF2/Cr are in use [7].
Improved processing of glass
Recent developments in glass processing allowed access to borosili-
cate glass flakes with flake thicknesses < 1µm. Instead of breaking
glass bubbles, as previously used, the thin glass flakes are made by
using a spinning cup into which molten glass is injected [8].
2. Better colouristic properties like higher chroma, higher lightness,
goniochromaticity, sparkle, liquid metal, higher transparency can be
achieved by the use of:
thinner flakes with narrower particle size distributions
 more uniform pigment shapes
 smoother flake surfaces 
E U R OP E AN COAT I NGS JO UR N A L 2018
 52 E F F E C T P IG MENT S

 Figure 3: Colouristic performance of newly developed sparkling Table 1: Liquid metal factor of Silk White S1303V in
pigments vs. state of the art comparison to the state of the art (Test system: 90:10 black
reduction in a solventborne basecoat / clearcoat)

Fi G LMF

Glacier Ext. Silk White

18,6 3,6 5,2
S1303V

Mearlin Ext. Fine Pearl

15,5 4,4 3,5
1303V

Figure 4: Iron oxide-coated aluminum flakes of the cornflake Figure 5: Iron oxide-coated aluminium flakes of the silver dollar-
type (Paliocrom Orange) type (Paliocrom Brilliant Orange)

E U R O P E AN CO AT I NGS J O UR N AL 2018
 EFFE C T P I G ME N T S 53

 use of multilayer systems (chemical synthesis [9] or Figure 6: Colouristic performance of iron oxide-coated silver dol-
physical vapour deposition [7]) lars vs. cornflake types in orange / red metallic. Full shade and

3. New surface treatments for use in waterborne systems

In order to remove heavy metals from effect pigments, chrome free
surface treated aluminum and micas are in development. The main
technologies used as replacements for Cr-treatments are silica/silane
surface treatments.

INNOVATIVE EFFECT PIGMENTS IN PAINT DESIGN

For luxury items, the shimmering and noble gloss of pearl-based pig-
ments is very popular in coatings. Conventional pearl pigments based
on titanium dioxide-coated natural mica flakes typically show a yellow-
ish tint due to iron impurities in the natural mica. Brand owners usu-
ally wish to avoid any yellowish appearance in white colours, favouring
the more bluish ‘ice’ whites.
A recently launched new series of clean, slightly bluish pearl pigments
based on synthetic mica is now available. In contrast to natural micas,
the synthetic mica substrates are absolutely transparent and free of
coloured impurities, as shown in Figure 1. These pearl pigments allow
the formulation of neutral to slightly bluish white pearl shades. Opti-
mised tricoat formulations allow for whiter whites at all observation
angles. In combination with carbon black, cool greys and noble blacks,
(gunmetal shades) with a slightly bluish appearance, are possible.
Depending on the particle size distribution, silky, brilliant or even spar-
kling effects are possible with these new pearl pigments. The ‘silk’ white
is a bluish pearl pigment with a smooth, velvet appearance. Despite
the small particle size of 12 µm the lightness flop is pronounced. The
‘frost’ white pigment is a bluish pearl with brilliant appearance. With
a medium particle size of ~19 µm the ‘frost’ white provides a good Figure 7: Sparkling performance of iron oxide coated silver dol-
balance between lightness flop, sparkle and feasibility in demanding lars vs. cornflake types and blends of both types
applications like automotive basecoats. The ‘crystal’ white pigment is
designed for strong sparkle effects not only in gloss angle, but also at
steeper viewing angles. The typical application for these 30 µm large,
sparkling pigments is industrial coatings where a good compromise
between strong sparkle and technical feasibility is requested. Bigger
flakes usually provide stronger effects, however, in some applications
technical feasibility is lower.

THE LIQUID METAL FACTOR

QUANTIFIES APPEARANCE OF PEARL SHADES

Flop index (Fi) and liquid metal factor (LMF) are tools to characterise
modern pearl shades. A well-established formula to quantify angle de-
pendent lightness with a number called the ‘Flop index’ was published
in 1992 by DuPont [10].

Fi = 2.69•(L*15°-L*110°)1.11/(L*45°)0.86

The ‘glacier silk’ white pigment is a powerful tool if smooth pearl appear-
ance in combination with a pronounced lightness of flop is requested
by paint designers. In the face angle high lightness is required, while in
the down-flop, the maximum dark appearance is the target.
In diffuse light usually the smoothest appearance is required in the
colour styling. In terms of colour measurement a low value for graini-
ness (G) is in that case the target. The surface of a liquid metal like
mercury for example has extremely low graininess in diffuse light and
a strong lightness of flop in directed light. The LMF quantifies this ef-
fect:

LMF = Fi/G
The higher the flop index and the lower the graininess, the better the
liquid metal character of a styling will be. It is important to compare 

E U R OP E AN COAT I NGS JO UR N A L 2018

54 E F F E C T P IG MENT S

only LMF values of pigments with similar particle sizes. If effect pig- cently launched innovative pigments are bluish pearl pigments based
ments with strongly different particle sizes (e.g. d50 = 12 µm with d50 = on synthetic mica and iron oxide coated silver dollars.  
25 µm) are compared, the LMF values become meaningless.
The ‘glacier silk’ white was designed as a bluish pearl pigment with an
optimised LMF (see Table 1). Part 1 of this t wo-part paper highlights the requirements of the coat-
Typical applications for fine-sized pearl pigments are the so called ings industry, technology trends in effect pigment synthesis and effect
white tricoat systems, where a hiding white solid shade basecoat is pigment innovations based on synthetic mica and iron oxide coated
over-coated with a second layer containing the pearl pigment fol- aluminium.
lowed by a conventional clearcoat, as shown in Figure 2.
Depending on the design target, bluish white shades (blue line) or yel- Part 2 with more new effect pigments will be published in the October
lowish white pearl shades (green line) are possible. Blends of natural 2014 issue.
mica based pearls and synthetic mica based pearls give access to a
range of shades in between (eg. red line).
Coarser types of pearl pigments are used if an eye-catching sparkling REFERENCES
appearance is required in a styling. Usually in the face angle such
paints are showing strong sparkling effects. At steeper angles the [1] T eiqing L., Zongxi L., Wenyuan Z., Guangqing Y., Preparation of syn-
sparkle effect is usually weaker. Especially for bigger surfaces it can thetic mica pearly luster pigment, Journal of synthetic crystals, 1990,
be a disadvantage to have good sparkle only in the face angle view Vol. 19, pp 166-171
and low sparkle effect at all other angles. A recently introduced new [2] T eaney S., Pfaff G., Nitta K., New effect pigments using innovative
sparkling pigment based on synthetic mica – glacier crystal white – substrates, Eur. Coat. J., 1999, Vol. 4, pp 90-96
offers high sparkle intensity also at higher angles, as demonstrated [3] S eubert J., Fetz A., PVD aluminium pigments: Superior brilliance
in Figure 3. for coatings & graphic arts, Paint & Coatings Industry, June 2000,
The sparkling area value (S_a) is related to the number of light re- available online
flections for a given surface area, while the sparkling intensity (S_i) is [4] U S Patent 3,949,139
quantifying how intense the corresponding light reflections are. For [5] U S Patent 4,321,087
normal coarse micas the red line is characteristic. In 15° illumination [6] US Patent 3,438,796
angle both values Sa and Si are high. At higher illumination angles [7] US Patent 5,135,812
both values are lower. The ‘crystal’ white pigment behaves differently: [8] EP 0289240
higher illumination angles, which correspond to down-flop show high- [9] S chmid R., Mronga N., Radtke V., Seeger O., Luster pigments with
er sparkling intensity. This makes the new pigment interesting for ap- colour variable properties, Eur. Coat. J., 1997, Vol. 7, pp 702-705
plications where strong sparkle intensity at all angles is required, for [10]  R odriguez A., JOCCA, 1992, Vol. 4, pp 150-153
example in decorative wall coatings or in powder coatings for facade [11]  O stertag W., Mronga N., Hauser W., Eisenoxidbeschichtete Alu
elements. miniumpigmente, Farbe und Lack, 1987, pp 973-976
[12] E P 033457
IRON OXIDE COATED SILVER DOLLARS WITH HIGH BRILLIANCY [13] E P 338428
[14] M ronga N., Radtke V., Baumann B., Paliocrom lustre pigments – their
More than 20 years ago iron oxide-coated aluminium flakes of the production, properties and application, 3rd Nürnberg Congress
cornflake-type were introduced to the coatings market, as shown in 1995, paper 18
Figure 4. Depending on the thickness of the iron oxide film on the [15] U S 7,387,669W
aluminium surface golden, orange and red interference colours are
possible [11-13]. The unique combination of high chroma, gloss and
hiding provided by iron oxide coated aluminium flakes allowed hiding
automotive effect shades with a so far, unmatched, brilliancy [14].
Recently iron oxide-coated aluminium flakes of the silver dollar type
were introduced in order to further improve the performance of auto-
motive coatings [15]. The perfectly light reflecting surfaces of the iron
oxide coated silver dollar substrates further boost the brilliancy of red
metallic, as shown in Figure 5.
The colouristic potential of iron oxide coated aluminium flakes can be
fully exploited by combining them with transparent perylene- or DPP-
pigments (diketopyrrolo-pyrole), as shown in Figure 6.
Iron oxide-coated silver dollars typically show stronger sparkle effects
than corresponding cornflake types. Cornflake-substrates are thinner
and for that reason their appearance is smoother. Having both pig-
ment types available in the same colour allows paint designers to eas-
ily adjust the desired degree of sparkle, like in Figure 7.

SUMMARY

The main requirements of the coatings industry are effect pigments

which allow higher brilliancy and chroma, stronger sparkle and cool
white and black shades. Besides improved colouristic properties
there is an ongoing demand for further improvements in technical
feasibility of colour shades, especially for better hiding basecoats. Re-

E U R O P E AN CO AT I NGS J O UR N AL 2018
 W O R LD O F C O L O UR 55

Source: joegast - Fotolia

A NEW LOOK
9,460 litres of paints were
needed for the refurbish-
ment of the Queen Mary 2.
The new paintjob was part of
a larger remodelling project
in 2016, including e.g. new
furniture and art as well as a
machinery overhaul.

SETTING SAIL
The Queen Mary 2 is one of
the largest ocean liners and
was christened in 2004. The
ship, which houses 1.310 ca-
bins, has an overall lenght of
345.03 m and moves with a
maximum speed of 30 knots
(56 km/h).

E U R OP E AN COAT I NGS JO UR N A L 2018

56 E F F E C T P IG MENT S
SPECIAL EFFECTS – PART 2
New effect pigments achieve effective aged and weathered appearances for coatings. By Raimund Schmid (published
in ECJ 10/2014).
Today patina effect constitutes an important tool in industrial
design. Apart from the aesthetic appearance and practical pro-
tection of patination, an object is perceived as having greater
value if it looks as if it has aged slowly and well. In the interior
design industry there is a demand for objects that appear to
have a long history or which represent long time periods. Dec-
orative coatings providing patina effect, antique appearance
or a weathered look are becoming increasingly popular.
The second half of this t wo-part paper highlights new special effect pig-
ments for antique effects and patinated surfaces in decorative coatings
and also discusses new interference pigments that exceed the currently
achievable chroma limits. Part 1 of this paper was published in the May
edition of European Coatings J OURN AL [1].
W hen metals are exposed to air and humidity over a long time they
acquire the so-called antique or patina look, which is related to
changes in surface texture, haptic behavior and colour. In colouristical
terms patina or patination can be described as a reduction in gloss and
an inhomogeneous colouristic appearance. Haptic properties and sur-
face texture also change, because the patina layers might show a dif-
ferent porosity and heat conductivity compared to the original surface.
The chemical process by which patina is formed takes place over a long
period of time. This type of patina is called ‘acquired patina’, such as:
E U R O P E AN CO AT I NGS J O UR N AL 2018
 The green patina that forms naturally on copper and bronze, usually
consists of a mixture of copper chlorides, sulphides and carbonates
and can form on pure copper objects as well as on copper-containing
alloys, such as bronze or brass. Such a patina layer takes many years
to develop under natural weathering conditions.
 Rusty surfaces also belong to the group of patinated surfaces. For
example in construction a special type of weathered steel is used,
purely for exterior applications. This decorative effect results from
an iron oxide layer formed by a corrosion process which does not
affect the tensile strength of the steel itself.
For industrial design the time to produce the patinated effect is often
the limiting factor. Usually, a designer cannot wait the necessary time
for the effect to form. Generally they would like to align shape and
colour in a short time period. So-called ‘applied patina’ is of higher
industrial importance, describing:
 Use of chemicals (chlorides, sulfides, acids) to speed up the patination
process. The disadvantage of all these chemical approaches to modify
or patinate surfaces is that they require the handling of chemicals,
which are inconvenient or even dangerous and can also damage the
structural integrity of the article itself.
 If you consider coatings, which provide the desired patina appear-
ance, spray application or brushin techniques are state-of-the-art.
They allow a higher degree of control both for the appearance of
the effect and the standardisation of the colour.
Applied patina colours based on pigments which provide silver and
 EFFE C T P I G MEN T S 57

Figure 1: Left side: Concrete plates with plaster and the new
type of pigment coating on top; hidden surface structure. Right
RESULTS AT A GLANCE side: Concrete plates with plaster and conventional coating
based on iron oxide-coated mica; clearly visible structure
űű This paper follows the first half that was published in the
May edition of the European Coatings Journal, which discussed
the requirements of the coatings industry, technology trends in
effect pigment synthesis and effect pigment innovations based
on titanium dioxide coated synthetic mica and iron oxide coated
aluminum.

űű A new type of effect pigment for decorative coatings with

rust or patina effect has been highlighted to meet the interior
design industry’s demand for antique or weathered objects and
looks.

űű The new series of effect pigments in question is able to pro-

vide a matting effect, ‘rusty colours’, good hiding and subtle spar-
kle all within one pigment class. Besides the desirable colouristic
of rust the haptic sensation of patinated surfaces is also provided.

űű A new series of interference mica pigments is further expand-

ing the boundaries of high chroma. Formulators have the choice
to go for extremely chromatic shades or to keep existing chroma
levels and improve other coating parameters by using smaller
amounts of high chroma interference pigments.
Figure 2: Rusty wall with surface structure. Haptics, colour and
the subtle sparkle of rust are perfectly mimicked by the coating
based on the new advanced pigments

copper patina effects have been described in earlier publications [2].

Of the same high importance in interior design are rusty surfaces.
Rust, the patina of iron containing steels, consists of yellowish to blu-
ish red and even black iron oxide colours. While the original steel sur-
face is glossy the rust layers impart a matte appearance combined
with a subtle sparkle in direct light. Conventional iron oxide pigments
can be used to obtain the typical rust colors, however the matte and
subtle sparkling character is missing.

NEW EFFECT PIGMENTS FOR A RUSTY LOOK

A new series of effect pigments unify the following features in one Figure 3: Imitation of a rusty steel surface. Glossy, gunmetal-
pigment: type coating based on new pigment techniques and carbon
ąą typical rust colours (yellow, bronze, copper, russet) black, overbrushed with colours based on the advanced pig-
ąą matting properties providing in coatings the tactile sensation of ments discussed in the paper
rust
ąą soft sparkling effect
The basis of this series of pigments is special glass flakes which are
coated with thin films of titanium and iron oxide. By increasing the
thickness of the iron oxide layers the colours gold, bronze, copper
and russet are possible in a similar way to iron oxide coated micas.
However mica/iron oxide-based coatings show high gloss and light-
ness, while in interior design, especially when coating larger areas, the
opposite effect is required. In other words, walls with a strong light
reflective behaviour are not perceived as ‘cosy, relaxing or laid back
enough’, such as one would desire for a living room.
Figure 1 shows the difference between conventional iron oxide-coated
micas (right hand side) and the new type of effect pigment with matte
and soft sparkle appearance (left hand side).
All the samples shown in Figure 1 use the same concrete substrate,
to which a structured plaster has been applied. It can be clearly seen


E U R OP E AN COAT I NGS JO UR N A L 2018

 58 E F F E C T P IG MENT S
 that the mica-based wall coating reveals the surface structure of the
substrate, while with the left hand side coatings, the structure is much
more subdued. This property enhances the robustness of the applica-
tion process, as the wall paint based on such effect pigments is more
forgiving of application mistakes, while paints based on iron oxide-
coated micas show lightness differences caused by surface structures
or irregular brush strokes.
For simulated rusty surfaces several paints with different colours have
to be combined side by side. The best and most economical way is to
apply the coating in two steps, first by applying a base colour and then
brushing or stippling on top 2–3 other yellow to red shades containing
the new type of effect pigment, as shown in Figure 2.
Sometimes a metal surface with the first onset of rust has to be imitated.
In such cases metallic finishes based on aluminium flakes or pearl pig-
ments in combination with carbon black are used as a first coating. After
drying, ’overbrushing’ with a paint containing the new type of effect pig-
ment coating can be used to create this early rusting effect.
Figure 3 shows such an effect, by using as a base, a glossy, silver blue
metallic shade, based on a bluish pearl synthetic mica pigment/carbon
black combination described in part one of the present publication [1].
NEW MICA-BASED INTERFERENCE PIGMENTS
ACHIEVE OUTSTANDING CHROMA
Interference pigments are typically based on transparent substrates like
natural mica flakes, which are coated with one or more layers of thin,
Figure 4: Three generations of bluish interference pigments with
increasing chromaticity from generation to generation
E U R O P E AN CO AT I NGS J O UR N AL 2018
highly refracting metal oxides like titanium dioxide. There is an ongoing
demand for improvements in chromaticity for such pigments. Recent
R&D activities yielded higher chromaticity by optimising the particle size-
and thickness distributions. In combination with an optimised pigment
design the access to so far unreachable levels of chromaticity is now
possible. Figure 4 shows chroma and hue graphs for various blue shade
interference pigments comparing state-of-the-art products from ap-
proximately ten years ago with the latest and best performing genera-
tion of interference pigments.
The stronger the performance of the interference pigment in terms
of chroma, the more vivid the colour that can be realised. This is
achieved in the blue colour area by combining TiO2-coated micas with
transparent phthalo- or indanthrone blues.
In addition to the design target for ‘maximum chroma’ the high poten-
tial chroma of the latest range can be used in existing colour shades
to formulate better hiding basecoats which allow the use of lower film
weights on application to achieve the same opacity. If, for example,
in a black reduction based on a state-of-the-art blue interference pig-
ment, the blue interference pigment is replaced by the new interfer-
ence pigments, more carbon black can be used to achieve the same
level of chroma. This strongly improves hiding and as a result thinner
basecoats can be applied, as shown in Figure 5. The resulting lower
lightness values resulting from the higher content of P.B.7 can be
corrected by adding small amounts of a fine aluminum flake. A posi-
tive consequence of thinner basecoats is an improved appearance in
terms of DOI-values.
Figure 5: Chroma and hue of a 95:5 black reduction of a stand-
ard blue interference pigment in comparison to black reductions
with advance pigment technology
 EFFE C T P I G ME N T S 59

COPPER COLOURED PIGMENTS WITH CHROMA AND SPARKLE Figure 6: Colouristical performance of highly chromatic copper micas

Also in the copper colour area the achievable chroma has been ex-
ceeded by redesigning pigment structures and further optimising the
flake geometry. The copper pigment is an intense, semi-transparent,
copper shade, mica-based effect pigment, which allows formulators
to style colours with tremendous impact in the copper, orange and
red colour area.
In a black reduction, shown in Figure 6, the pigment is about 25 points
stronger in chroma compared to state-of-the-art copper micas. In ad-
dition to the high chroma the total sparkle value S_G is ~60 % higher
than the comparative example. High chroma and good sparkle also
make this pigment an alternative to expensive iron oxide coated alu-
mina flakes. 

REFERENCES

[1] Schmid R., Special effects, EUROPEAN COATINGS JOURNAL, 2014,

Vol. 5, pp 33 -37.
[2] Seibel B., Savar N., Schmid R., Patinated surface effects, PPCJ, April
2011 p. 24; Savar N., Seibel B., Schmid R., Patina mit Stil, FARBE UND
LACK, 2012, Vol. 7, p. 19.

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E U R OP E AN COAT I NGS JO UR N A L 2018

 60 I NT E R F E C E NCE P IGME NT S
Source: Andrea Lehmkuhl - Fotolia.com
A MORE INTENSE COLOUR
FOR ALL SYSTEMS
Coated aluminium flake interference pigments are highly stable. By Gerhard Pfaff and Kirsten Fritsche (published in ECJ 11/2014).
Metal oxide coated aluminium pigments have been produced
by a new synthesis method. These pigments carry a passiva-
tion layer and an iron oxide layer on thin aluminium flakes.
They show good stability and exposure performance in both
solventborne and water-borne coatings and allow highly satu-
rated coloured effect coatings to be obtained.
E ffect pigments differ from conventional pigments in their special
geometric and optical properties. They can also be used together
with other colourants in a wide range of applications, many in auto-
motive and industrial coatings, cosmetics, printing inks and plastics.
Effect pigments can be divided into two basic classes: special effect
pigments, the most important examples of which are pearlescent pig-
ments, and metallic effect pigments. All effect pigments are charac-
terised by platelet-shaped particle geometry. The platelets generally
have diameters in the range between 5 and 200 µm and a thickness
below 1 µm. The aspect ratio can therefore reach values of up to 200.
Metal effect pigments are formed as thin opaque metal platelets (typ-
ically aluminium and copper-zinc alloys) leading to metallic gloss and
brightness flop effects in the application system. In contrast, pear-
lescent and other special effect pigments are partially transparent.
Therefore the platelet surface of these particles reflects some of the
light, while some passes through the particles. The reflection of the
light results in a pronounced lustre effect, which is softer than that of
metallic pigments and appears to come from the depth of the coat-
ing medium.
E U R O P E AN CO AT I NGS J O UR N AL 2018
THE GENERAL NATURE OF EFFECT PIGMENTS
Traditional pearlescent pigments consist of high refractive index metal
oxide layers deposited onto a transparent, low refractive index, plate-
let-shaped substrate such as natural or synthetic mica, alumina, silica
and glass. Various effects ranging from satin to pearl lustre, from spar-
kle with high chromaticity to angle-dependent colour appearance, can
be achieved.
By the deposition of thin metal oxide layers (such as titanium diox-
ide and iron(III) oxide) on the substrate platelets, the layer-substrate
principle is used to form transparent and semi-transparent pigments
showing interference colours from silver-white to yellow, red, blue and
green. The iron oxide types result in deep chromatic lustre effects [1-
4].
Metal effect coatings containing sufficiently high concentrations of alu-
minium flakes are characterised by high opacity, a sparkle to satin fin-
ish and a high level of brightness with neutral colours and a brightness
flop. All such effect pigments act like very small mirrors within the paint
film, the reflection of which depends on their shape.
Cornflake types have an irregular shape, whereas ‘silver dollar’ types
are rounded with smooth edges. In addition there are very thin alu-
minium flake pigments manufactured by a Physical Vapour Deposition
(PVD) process.
These variations of shape and particle size lead to differences in appear-
ance and performance in the paint. The flatter and more oriented the
pigment particles are, the more specular reflection and stronger ‘flop’ can
 I N T ER FE CENCE P I G MEN T S 61

Table 1: Colour data for styling with “Taklamakan Gold” and

RESULTS AT A GLANCE “Iriodin 9307 SW” at 45°/as 15°

 Traditional effect pigments are either essentially thin flakes

of metal (usually aluminium) or pearlescents, formed by depos- Styling pigment Hue (u’,v’) Su’v’ Y
iting layers onto transparent flake substrates.
“Taklamakan Gold” 112.4 1.17 35.6
 More recently, interference colour pigments have been de-
veloped, made by depositing very thin layers of metal oxides
onto aluminium flake substrates. “Iriodin 9307 SW Star Gold” 127.2 1.17 26.2

 An improved version of this technology involves first pas-

sivating aluminium flakes, then depositing a metal oxide layer
to impart interference colour and finally applying a protective
surface treatment to improve weathering performance and al- Table 2: Colour data for the styling with “Wahiba Orange WNT”
low use in waterborne coatings.

 High stability has been found in both ageing tests on the

Styling pigment Hue (u’,v’) Su’v’ Y
stored paint and exposure tests on applied panels.

 The three pigments so far developed allow highly saturated “Wahiba Orange” 13.3 3.0 9.9
colour effect coatings to be obtained in the green, gold and red

“Iriodin 9508” 14.3 2.5 7.4

be expected. The contrast in brightness between the pigments and their Figure 1: Process scheme for aluminium pigments coated with a
vicinity under different viewing angles is desired in many cases, but there passivation layer and with iron oxide
are also limitations when used in combination with strongly scattering and
absorbing pigments.
Special passivation process
(closed dense passivation layer)
COATED METAL FLAKES ADD COLOUR TO EFFECTS
Passivated
Aluminium flakes aluminium flakes
The combination of metal flakes and metal oxide layers was first de-
scribed in the 1980s and 1990s [5-7]. Metal flakes, in particular alu-
minium platelets, can be coated with iron oxide using the Chemical
Vapour Deposition (CVD) process. Aluminium is particularly appropri-
ate because of its availability and low density, a feature which is ad-
vantageous in view of the large surface area of the platelets relative
to their weight. FeCl 3 NaOH
Iron oxide coated aluminium pigments are manufactured by fluidising
aluminium flakes at 450 °C in an atmosphere of nitrogen in a fluid-
ised bed reactor. The reactants – iron pentacarbonyl and oxygen – are Iron oxide coated aluminium flake

streamed into the reactor together with the agitated aluminium flakes.
Iron oxide is formed and deposited on the aluminium as hematite.

Figure 2: Bright-field microscopic images (optical magnification 200 x) of the orange, gold and red pigment particles in a masstone
coating (pigment content = 3.68 wt%, coating thickness 15 µm, on a black substrate)

E U R OP E AN COAT I NGS JO UR N A L 2018

 62 I NT E R F E C E NCE P IGME NT S
 The resulting pigments display golden and orange effects with high
colour brilliance. The layer thickness of the iron oxide determines its
interference colour, which together with the absorption colour pro-
duces the desired colour effects.
INTERFERENCE COLOURS WITH IMPROVED PIGMENT STABILITY
Several years ago, Merck began investigating another technology that
could be used for coating aluminium flakes with metal oxide layers. The
objective was to develop improved and new effect pigments based on
the layer-substrate principle with metal oxides as the layer and alumin-
ium as the substrate.
The technology should allow the synthesis of such pigments with vari-
ous structures and effects, also allowing their use in waterborne paints.
The intention was to deposit metal oxides such as iron oxide, titanium
dioxide, tin dioxide and silicon dioxide on passivated aluminium flakes.
The pigments thus formed should exhibit the well-known advantages
of other effect pigments, for example good application properties in a
variety of binder systems, environmental compatibility and simple han-
dling together with a high stability and the possibility of achieving unique
optical effects.
The newly developed technology is rather unique, combining key steps
from different effect pigment technologies. This includes the passivation
of aluminium flakes with special layers, the deposition of colouring metal
oxides on the passivated flaky particles, conditioning, thermal treatment
and surface treatment. Pigments manufactured by using these sub-
steps are mostly based on aluminium flakes of the silver dollar type.
However, other types of aluminium flakes can be used for the synthesis.
The flakes are first coated with a passivation layer by a wet chemical
route. The second step consists of depositing metal oxide layers on the
passivated flakes by precipitation. After conditioning and heating up, a
surface treatment is applied to the pigment as the last layer to improve
the weathering performance of the pigments and make them adaptable
to different binder systems.
Figure 1 shows the process for the manufacture of a pigment contain-
ing iron oxide schematically. The layer structure of a pigment particle
consisting of an aluminium flake coated with iron oxide formed by the
process described is shown at the end of the process scheme.
Figure 3: Colour properties of the orange, gold and red effect pigments in a masstone coating (measured with 45 °/as 15 ° geometry
on masstone sample with 18 wt% pigment concentration and layer thickness of approximately 15 µm on a black substrate)
“Meoxal F120-30 CWT Taklaman Gold” “Meoxal F120-58 CWT Wahiba Orange”
0.6 “Meoxal F121-51 CWT Atacama Red”
0.5
0.4
v’
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6
u’
E U R O P E AN CO AT I NGS J O UR N AL 2018
COLOURS AND PERFORMANCE OF THE NEW PIGMENTS
These effect pigments are finally wetted with a solvent chosen for opti-
mum universal use (diethylene glycol monoethyl ether, also known as
carbitol). The solvent choice also provides a decreased tendency to ag-
glomeration in package storage, ease of use and removes the risk of
dust explosion. The passivation technology is unique. It is the basis for
the further manufacturing steps and makes the final pigments suitable
for use in waterborne systems.
These pigments, branded “Meoxal”, can be used in both solventborne
and waterborne systems, which eliminates the need for separate
products for different formulations. The process of pigment incorpo-
ration in a paint system runs very easily as well as the formulation of
new colour variations together with other colorants.
The pigments obtained by this route exhibit the following values:
 Chromatic metallic effect with excellent colour saturation
 Elegant sparkle effect of individual particles
 High brightness coupled with strong depth
 Easy to use in solventborne and waterborne systems
 Good storage stability in paints
 Superior shelf life
Three types of these pigments are already on the market:
 Orange type (“Meoxal Wahiba Orange”)
 Gold type (“Meoxal Taklamakan Gold”)
 Red type (“Meoxal Atacama Red”)
All three types are based on silver dollar aluminium flakes coated with
a passivation layer, an iron(III) oxide layer and a surface treatment.
They are delivered as pigment pastes consisting of carbitol and 70
% pigment. Carbitol does not affect the performance properties. The
special surface treatment developed for this new class of effect pig-
ments allows high demands for outdoor applications such as automo-
tive industry and other high-end applications to be met.
Figure 2 shows a bright-field microscopic image of the three alumini-
um-based pigments in a mass tone coating. The single pigment par-
ticles exhibit a uniform orange, golden or red colour with almost no
tendency to agglomeration. The colour properties of these pigments
can be seen in Figure 3. A very high luminance occurs, especially at the
specular angle, together with a high saturation.
Pigment Hue(u’, v’) Su’ v’ Y
“Taklamakan Gold” 57.6 1.13 141
“Wahiba Orange” 23.4 2.14 62
“Atacama Red” 18.2 2.4 30
 I N T ER FE CENCE P I G MEN T S 63

Figure 4: (a) Styling with “Taklamakan Gold” (left) and “Iriodin 9307 SW” (right); (b) Enhancement of Y / The particle size distribution of the orange
S[u’,v’] by using the new gold pigment; measurement position varies from -15, +15, 25, 45, 75 to 110 pigment, as an example, with a volume av-
° at a constant illumination angle of 45 ° erage diameter range Dv(0.1) of 10.4 µm,
Dv(0.5) 18.1 µm and Dv(0.9) 30.9 µm, satisfies
45 the requirements for use in high-end applica-
tion systems. The same applies to the other
40 two effect pigments of this series.
35
30 Y HIGHLY SATURATED
COLOURS CAN BE ACHIEVED
25

Y 20 These pigments offer unique styling possibili-

15 ties which cannot be achieved with other com-
mercial pigments. The strong advantage of the
10
Gold, for example, is the extreme luminance
– Styling with “Taklamakan Gold” 5 Y in the face angle in combination with a high
– Styling with “Iriodin 9307 Star Gold”
0 saturation S over all viewing angles. The colour
0 0.5 1 1.5 hue angle (u’,v’) of 58 ° (aspecular viewing at 15
S ° over black) allows exciting green as well as
gold and orange stylings to be produced.
As an example, a green styling with the gold is
Figure 5: (a) Styling with “Wahiba Orange” (left) and “Iriodin 9508 SW” (right); (b) shown in Figure 4a in comparison to the same
Enhancement of Y/S[u’,v’] by using the new orange pigment; the measurement angle styling with a semi-transparent mica pigment.
varies from -15, +15, 25, 45, 75 to 110 ° at a constant illumination angle of 45 ° The corresponding colour data (Table 1 and
Figure 4b) show the strong enhancement of the
luminance by using the gold.
12
The advantage of the orange effect pigment is
Y the strong colour saturation over all viewing an-
10
S gles. The hue of 23  ° (as 15 ° over black) allows
red colours to be created with high saturation
8
and luminance, which are impossible with oth-
er commercial pigments. Figure 5a shows a red
y

6
styling with the orange in comparison to the
4 corresponding styling with the mica pigment
“Iriodin 9508 SW”. The clear advantage for the
2 orange related to the saturation of the styling
is obvious and also confirmed by the corre-
– Styling with “Wahiba Orange” sponding colour data (Table 2 and Figure 5b).
– Styling with “Iriodin 9508” 0
0 0.5 1 1.5 2 2.5 3 3.5 The red pigment is naturally even more reddish
S than the orange one and offers new styling pos-
sibilities in the area of deep red colours, which
cannot be reached with commercial pigments
so far. Also the red offers a high saturation over
Figure 6: (a) Styling with “Atacama Red” (left) and “Wahiba Orange” (right). (b) Shift of all angles. Due to its more bluish character, the
the hue (u’,v’) from red to bluish red at the same saturation S(u’,v’) level by using the styling with this pigment shows a reduced light-
red. With decreasing S, the measurement position varies from 15, 25, 45, 75 to 110 ° ness compared to that with the orange.
at constant illumination angle of 45 ° The difference between the orange and the red
in a styling in combination with organic red pig-
ments and carbon black is shown in Figure 6a.
3.5
The visual impression is confirmed by the col-
our measurements depicted in Figure 6b.

3
HIGH STABILITY AGAINST BOTH STOR-
AGE AND EXPOSURE
s

2.5
The combination of passivation technology with
surface treatment ensures very good stability
of the pigment paste itself and good stability in
2
paint systems, even waterborne ones. For both
– Styling with “Wahiba Orange” the gold and the orange, the pigment paste has
– Styling with “Atacama Red” been proved to have a shelf life of two years.
1.5
-6 -4 -2 0 2 4 6 8 10 12 The pigments were tested in an automotive
Hue (°) coating system (black reduction) for colour
changes. The results achieved for the orange 

E U R OP E AN COAT I NGS JO UR N A L 2018

64 I NT E R F E C E NCE P IGME NT S

pigment are shown as an example in Figure 7a-c. No significant colour shift Figure 7: Colour shift of a coating (black reduction of “Wahiba Or-
is observed after the orange pigment was stored at room temperature ange”) within 27 months storage of the pigment paste (for each
for 27 months. panel the paint was freshly prepared using the same pigment
The surface treatment improves the incorporation of the pigments into batch); (a) Lightness L*, (b) Chroma C*, (c) Hue H*
many paint systems, especially waterborne ones. Dispersion is easy and
can be achieved in liquid systems using a dissolver. However, a circum-
60 20
ferential speed of 4 m/s should not be exceeded. Triple roll mills, bead
mills or other machinery with high shear forces should not be used. Pre- 18
wetting the pigments with solvent is recommended to avoid agglomera- 55

L*45*/as45*
L*45*/as15*
tion. Well-dispersed pigments show excellent storage stability. 16
For use in waterborne paint systems, aluminium pigments must show 50
gassing stability. The gassing test ensures this type of pigments can be 14
safely used in waterborne paint without an excessive amount of hydro- 45
12
gen being generated during a period of 30 days at 40 °C. It is considered
as acceptable if the gas amount is less than 25 ml from 300 ml paint
40 10
prepared with 4 % pigment. The results for the orange and gold in this 12 21 24 27
test are summarised in Table 3. They were achieved without any addition
of stabilising agents. 90
39
Good weatherability is essential for use in automotive coatings. Ac- 85
37
celerated weathering results (using a xenon arc tester) for the orange 80

C*(a,b)45*/as15*

C*(a,b)45*/as45*
35
pigment are shown as examples in Figure 8. Similar good weathering 75
results have been measured for the Gold and the Red. These results 33
70
are also confirmed by visual evaluation. Visually, no significant colour 31
65
shift is detected. Florida exposure for all three pigments is ongoing.  29
60
27
55
25
REFERENCES 50
12 21 24 27

[1] Pfaff G., Perlglanzpigmente, Chem. unserer Zeit, 1997, Vol. 31, pp 6-16. 56
[2] Pfaff G., Special effect pigments, in Industrial Inorganic Pigments, 54
ed. G. Buxbaum, G. Pfaff, 3rd edition, Wiley-VCH Verlag GmbH & Co.
52
KGaA, 2005, pp 230-252.
H*(a,b)

[3] Pfaff G., Reynders P., Angle-dependent optical effects deriving from 50
submicron structures of films and pigments, Chem. Rev., 1999, Vol. 48
99, pp 1963-1981.
46
[4] Pfaff G., Optical principles, manufacture, properties and types of
special effect pigments, in Special Effect Pigments, ed. G. Pfaff, 44
Vincentz Net work, Hannover, 2008, pp 16–91. 42
12 21 24 27
[5] Ostertag W., Mronga N., Hauser P., Eisenoxidbeschichtete Alumini-
umpigmente, FARBE UND LACK, 1987, Vol. 93, pp 973-976. time/months
[6] Ostertag W., Effektpigmente, Nachr. Chem. Tech. Lab., 1994, Vol. 42,
– 45°/as 15°
pp 849-854.
– 45°/as 15°
[7] Ostertag W., Mronga N., Properties and application of luster pigments,
Macromol. Chem. Macromol. Symp., 1995, Vol. 100, pp 163 - 168.

Figure 8: CIELab colour shift of the masstone and a black reduc-

Table 3: Gas generation of orange and gold effect pigments in a tion of “Wahiba Orange” after 4000 hours SAEJ 2527 exposure
waterborne paint after 30 days at 40 °C at different aspecular viewing angle

Sample pH Gas volume collected ml 2,5

dL*
2
dC*
1,5 dH*
L*, C*, H*(a,b)

Blank 8.0 0 1
0,5
0
“Wahiba Orange” 7.9 6
-0,5
-1 15° 25° 45° 75° 110° 15° 25° 45° 75° 110°
full shade black reduction
“Taklamakan Gold” 7.8 6 “Meoxal Wahiba orange CWT” “Meoxal Wahiba orange CWT”

E U R O P E AN CO AT I NGS J O UR N AL 2018
 HOW TO EFFICIENTLY
USE TIO2 PIGMENTS

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Jochen Winkler
TITANIUM DIOXIDE
Everything about titanium dioxide in a single
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properties, working mechanisms, and possi-
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C OATINGS library
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 66 P E R L E S C E NT P IGMENT S
Source: Punto Studio - Fotolia.com
IN SEARCH OF THE
PERFECT BLACK PEARL
Darker colour enhances tinting options in powder and liquid coatings. By Jonathan Doll, Aaron Hollman,
and Adam Andreas (published in ECJ 12/2015).
A new black pearlescent pigment has been developed that
offers excellent lustre, jetness and sparkle. It can be used in
masstone or as a tinting agent in both liquid and powder coat-
ings. Notably, the new pigment shows no problems with charg-
ing or separation in powder coating applications.
P earlescent pigments are a special type of effect pigment that
exhibit colour through the constructive and destructive interfer-
ence of light. The colour perceived is determined by a combination
of the pigment’s physical structure and the absorbance of its com-
ponents.
Because the colour of pearlescent pigments is structurally generated,
the colour perceived shows a dependence on the viewing angle. This
angle-dependent colour is described as iridescence or lustre and is
characteristic of pearlescent pigments.
Structurally, pearlescent pigments are all similar. They comprise a
platelet-shaped substrate that is coated with one or more layers
of a metal oxide such as titanium dioxide (TiO2), iron oxide or silicon
dioxide, among others. Most pearlescent pigments are white and trans-
parent, only displaying colour when viewed over a black background.
E U R O P E AN CO AT I NGS J O UR N AL 2018
HOW COLOURED PEARLESCENT PIGMENT ARE PRODUCED
Traditional pearlescent pigments can be grouped into ten basic col-
ours. Six of these are produced by coating a transparent substrate
with TiO2: silver/white, interference gold, red, violet, blue and green.
The colour is mainly dependent on the thickness of the coating, as
shown for one particular pigment in Table 1.
The range of colours can be extended to metallic gold, bronze, copper
and red russet by using iron oxide and/or iron oxide-TiO2 coatings.
The first such pigments were based on coating natural mica, a low-cost
material which readily forms thin flakes. Its limitations include a faint
greenish-yellow colour due to impurities in the crystal lattice and slight
variations of thickness even within individual flakes. For this reason,
substrates such as synthetic mica, borosilicate glass and alumina have
increasingly been used to produce pigments of higher optical quality.
Because iron oxide is coloured, pearlescent pigments coated
with a layer of iron oxide will also have an absorption compo-
nent to the perceived colour. Besides pure colours, pearles-
cent pigments can have a range of special effects related to
the size and type of the substrate ranging from satin finishes

RESULTS AT A GLANCE
 Black is a popular colour for many consumer goods, but it
has so far proved difficult to produce a deep black pearlescent
pigment. A new effect pigment has now been developed that
offers excellent lustre, jetness and sparkle.
 The pigment can be used in masstone or as a tinting agent
in both liquid and powder coatings across a range of applica-
tions.
 Tinting in powder coatings becomes apparent at 0.25%
loading or less, while the sparkle effect is visible at loadings of
1.0% and upwards.
 The new pigments do not show any problems with charging
or separation in powder coating applications, so they can be
used either by dry blending or bonding.
(< 15 micrometre substrates) to high sparkle (> 250 micrometre). Ex-
panding the pearlescent pigment colour gamut beyond the basic ten
allows formulators to produce unique designs.
WHY IT IS HARD TO PRODUCE BLACK PEARLESCENTS
One of the most sought after pearlescent colours is black. Black is one
of the most popular colours for most consumer products, from cars
to fashion. Despite this inherent demand, producing a black pearles-
cent effect presents many challenges due to the nature of the colour
black.
Figure 1: Masstone in a liquid coating for the new pearlescent pigment (pearl A) compared to three other black pearl pigments (B-D).
A B
P ER LE S CENT P I G MEN T S 67
Black is defined physically as the absence or minimisation of
light reflection at all visible wavelengths. It is the ultimate result of
subtractive colour blending and is characterised by absorption across
all wavelengths.
Pearlescent pigments, on the other hand, tend to generate colour
through interference and not absorption. The colour perceived from
blending pearlescent pigments is therefore additive, and blends of
several pearlescent pigments will produce a ‘whitening’ of the overall
appearance. Making a pearlescent pigment black will reduce the per-
ception of colour travel and sparkle because most of the light incident
on the pigment is absorbed instead of reflected.
Despite these difficulties, there are black pearls available on the mar-
ket. However, in many cases, these pigments are not truly black. Most
can be described as gun-metal grey (too high a lightness or L* value)
or black olive (too high a chroma or C* value). True blacks are achro-
matic and have low L* and C* values. Some examples of true black
pearls exist on the market. However, these pearls lack the sparkle ef-
fect that is typical of traditional pearlescent pigments.
In this article, a new development in the area of black pearlescent pig-
ments is described. This pigment has exceptional lustre, sparkle and
jetness when compared to traditional commercially available black
pearlescent pigments. These new pigments can be incorporated into
many different applications, such as liquid and powder coatings, with
no reduction in the perceived effect. Additionally, they can be used to
tint powder coatings to obtain a range of colours that display excep-
tional sparkle and lustre effects.
NEW BLACK PEARL SHOWS IMPROVED VISUAL PROPERTIES
To demonstrate the uniqueness of the new black pearlescent pig-
ment, Figure 1 shows a masstone comparison of a drawdown of the
new black pearl (pearl A) to typical black pearls (pearls B-D) at 10%
loading by weight in a clear acrylic paint. The pictures were all taken
under identical conditions under D65 illumination.
Of all of the black pearls on display in Figure 1, only pearl A has the de-
sirable combination of high jetness, lustre and sparkle. The remaining
pigments either do not have appreciable lustre (pearls B and C), or they
are more blue (pearl D) when compared to pearl A. None of the com-
parative pearls display the characteristic, attractive sparkle of pearl A.
The flop index (F.I.) and jetness (Mc) of pearls A-D were measured
in order to quantitatively understand their colour. The displays from
Figure 1 were used to measure these values. The flop index was cal-
culated from colour data obtained using an X-Rite “MA-98” multi-angle
spectrophotometer. Mc was calculated from colour data obtained
from a Datacolor “SF600 plus” spectrophotometer using a diffuse re- 
C D
E U R OP E AN COAT I NGS JO UR N A L 2018
 68 P E R L E S C E NT P IGMENT S

 flection sphere. F.I. and Mc were calculated using Equations 1 and 2, the sparkle effect, flop and jetness creates an effect unlike any of the
respectively, and are reported in Table 2. other pearlescent pigment in this study, demonstrating the unique-
ness of the pigment.

(1) A VERSATILE PIGMENT FOR TINTING POWDER COATINGS

A key application for pearl A is to use it as a tinting agent in powder

(2)
Where L15*, L45* L110* are the brightness values measured at 15°, 45°
and 110° from the specular reflection angle (at 45° incident light). Xn,
Yn and Zn are the tristimulus values of the incident light source and
X, Y and Z are the tristimulus values of the reflected light, and are
defined by:
(3)
coatings. Because powder coatings are, by definition, dry paint systems,
traditional tinting pigments such as carbon black are difficult to disperse
and use universally across all powder coating base types.
To overcome this limitation, black pearlescent pigments are typically 
Table 1: Dependence of interference colours on coating film
thickness for titanium dioxide applied to glass
Coating thickness/nm Reflected colour Transmission colour

(4) 60 Silver Silver

80 Yellow Blue
100 Red Green
120 Blue Yellow
(5)
140 Green Red

The flop index can be used as a measure of the overall lustre and travel
seen by the pearl, because it takes into account the brightness at three
different viewing angles. A higher flop index will correspond to a lustrous Table 2: Flop index (F.I.) and jetness (Mc) of the five pearlescent
appearance when the sample is viewed by an observer. The jetness is a pigments studied
measure of how black the pigment appears. Higher Mc values mean that
Sample F.I. Mc
the pigment is more black or jet.
Table 2 shows that pearl A, the new black pearlescent pigment, has a Pearl A 7.41 361.92
good balance of jetness and flop. Pearls B and C have good jetness Pearl B 5.43 375.10
but poor colour flop and pearl D has the worst jetness, but high flop. It
would appear that pearl A offers the best balance of properties. Pearl C 5.83 372.66
In addition, the masstone pictures in Figure 1 show that pearl A has a Pearl D 16.58 348.58
sparkle effect which is not observed in pearls B-D. The combination of

Figure 2: Masstone spray panels showing the difference be- Figure 3: Loading ladder of pearl A in a green-tinted powder
t ween pearl A and pearl B; the much more intense sparkle effect coating base, with loading increasing from 0.0% to 8.0% when
of pearl A can be seen. going from left to right.

A B
0. 0% 0. 25% 0. 5% 1. 0% 2. 0% 4. 0% 6. 0% 8. 0%

Increased loading of pearl A

E U R O P E AN CO AT I NGS J O UR N AL 2018
 P ER LE S CENT P I G MEN T S 69

“The critical pigment

volume
concentration is
72.29%.“ Jonathan Doll
Sun Chemical Performance Pigments
T +1 513 6815950-4364
jonathan.doll@sunchemical.com

3 questions to Jonathan Doll

Could you explain in more detail with which kinds of black pearls you compared your pig-
ment in figure 1 & 2? Without providing competitor brand names, Pearl B and Pearl C in Figure
1 were natural mica coated with iron (II, III) oxide. Pearl D was a natural mica coated with titanium
dioxide and iron (II, III) oxide. In Figure 2, Figure B is another example of Pearl B in Figure 1 and it is
a natural mica coated with iron (II, III) oxide.

Which loading do you recommend for a sufficient sparkle and a dark black colour? For
powder, the recommendation for sufficient sparkle is at 1.0% and a dark black color at 6.0%. For
liquid, the recommendation for sufficient sparkle is at 1.0% and a dark black color at 5.0%.

What is the critical pigment volume concentration in your case? The critical pigment volume
concentration is 72.29 %.

 used as they provide a high degree of workability and an acceptable
amount of tinting. Figure 2 shows a side-by-side comparison of the
masstone of pearl A versus pearl B when sprayed in a clear polyure-
thane powder coating base at 6 % loading. Pearl A and B have similar
jetness and opacity; Pearl A, however, shows the unique polychromat-
ic sparkle effect that is uniform and homogeneous.
It is worth noting at this point that the new black pearl pigments do not
show any issues with charging or separation in powder coating appli-
cations. Powder coating bases can therefore be loaded with the black
pearlescent pigment by either dry blending or bonding.
In both cases, there are no observed issues with charging and/or sep-
aration, which lead to problems such as surging, spitting or agglom-
eration when they are being sprayed. It has also been discovered that
the black pearlescent pigment works in both high and low gloss bases,
and in addition can be used to tint textured powder coating bases.
The use of the new black pearl allows for greater flexibility in tint-
ing, and can lead to shades that have greater appeal and lustre than
standard black pearls. Figure 3 shows a picture of a stainless steel
floor panel that has been sprayed with a tinting ‘ladder’ that uses pearl
A to tint a green shaded clear powder coating base.
As the loading of the new black pearl pigment is increased from
0.25 % to 8.0 % by weight, the shade of the powder coating
gradually darkens and the sparkle effect becomes more promi-
nent. It is remarkable that a significant shift to a darker shade
is observed even at low loadings of pearl A. Finally, at about
1.0 % loading, the sparkle effect becomes readily apparent and in-
creases with loading.
ENHANCED EFFECTS FOR MASSTONE AND TINTING
In conclusion, a new black pearlescent effect has been developed for both
liquid and powder coatings that shows exceptional sparkle and jetness. In
comparison to other black pearlescent pigments, the new pigment shows
the right balance of lustre and jetness, as well as a unique sparkle.
The new black pearl is readily incorporated into powder coatings both as
a tinting agent and in masstone with little issues associated with powder
coating charging and separation.  

E U R OP E AN COAT I NGS JO UR N A L 2018

 70 P IG M E N T C H EM I S TRY
Source: rdnzl - Fotolia
LEAD IS DEAD
Maintain opacity and durability and expand the colour range with new pigment chemistries. By Mark Ryan,
The Shepherd Color Co (published in 03/2013).
A new pigment chemistry, niobium tin pyrochlore yellow, has
been developed that expands the envelope of durable colours
available in paints and coatings. It has the chromaticity and
brightness of organic pigments and the opacity and durability
of inorganic pigments. The new yellow is complemented by im-
provements in rutile tin zinc to increase its red value. Together
these pigments provide an alternative to lead chromate pig-
ments and expand the envelope of durable colours in the yel-
low and orange colour space.
M arket demands and regulatory requirements have placed pres-
sure on coatings formulators and chemists to find alternatives
to lead chromate pigments. This middle-yellow colour space can be ad-
dressed by a number of different pigmentations that are a balance of
performance and cost for a given colour. Organic pigments offer high
chromaticity, but less than desired durability and opacity. They are of-
ten a compromise of performance that requires the use of special col-
oured primers, and multiple coats of low opacity and even clear coats
to reach desired levels of weathering performance. Inorganic pigments
have opacity and durability, but alone currently lack the ability address
all the colours desired by the marketplace.
Niobium tin pyrochlore (NTP) yellow is a new, patented pigment chem-
istry that addresses the need for bright chromatic colours that are
highly durable. It is an inorganic pigment that had been given the Col-
E U R O P E AN CO AT I NGS J O UR N AL 2018
our Index (C.I.) Pigment Yellow 227 designation (called PY 227 in this
article). It is a bright yellow similar in shade to middle-chrome yellows
(PY34) with excellent opacity, chromaticity, tint strength and inertness.
To complement this development, advances have been made to in-
crease the red tone of PY216 rutile tin zinc (RTZ) orange pigment chem-
istry. The result is a pigment with a bright, chromatic-orange masstone
and high tint strength. This tinting ability, especially the RTZ orange’s
red value, makes it very valuable in blends with the PY 227 to provide
chromatic, all-inorganic matches to a number of colours from middle
yellow to red shade yellow to orange. Both pigments also complement
other organic and inorganic pigments to meet a wide range of colours
and improve coatings properties such as opacity and durability.
In order better to understand the significance of the two new materials, it
is instructive to position them in relation to other pigments. A plot of hue
angle and chromaticity is a convenient way of showing how colours relate
to one other. In Figure 1, the horizontal axis represents the hue angle of
a pigment with redder pigments on the right hand side and greener pig-
ments on the left hand side. The vertical axis represent the chromaticity
of a pigment with less chromatic colours towards the bottom the plot
and higher chroma colours towards the top.
Figure 1 illustrates the relationship between PY53 (nickel titanate) and
PBr24 (chrome titanate). As can be seen, PY53 (nickel titanate) is in the
lower left corner and PBr24 (chrome titanate) to the right. However, both
are at the bottom of the graph. These two important titanate pigments
 P I G MEN T CHEM I S T RY 71

Table 2: Inorganic pigment formulation

RESULTS AT A GLANCE
 PY 227 and RTZ orange pigments have durable colour and Inorganic Formula percent [wt.]
chromaticity which widens the colour envelope
PW6 Titanium dioxide 0.5
 Their physical properties are very positive
PY227 NTP yellow 77.8
 They exhibit excellent weathering properties and high sta-
bility in difficult conditions
PBr24 Chrome titanate 12.7

 The pigments are also inherently safe; however, the NTP PY

PY53 Nickel titanate 9.0
227 and RTZ orange have obtained regulatory approvals

 They demonstrate that a colourant that cannot only have ex-

cellent properties, but can also be used in sensitive applications.
Table 1: Organic pigment formulation
 The two new pigment chemistries provide high-perfor-
mance, high-durability colour envelope expanding tools for the Organic Formula percent [wt.]
coatings chemist and paint formulator

PY154 Benzimidazolone 55.20

 They can be used in high durability systems such as coil and
extrusion, powder, silicate-based paints and coatings for the
architectural, ACE, automotive, signage and corporate colour PW6 Titanium dioxide 33.50
marketplace.
Monoazo/
PY181 11.20
Benzimidazolone
 They provide viable alternatives to lead chromate pigments in
high-value systems where the highest performance is expected. PG7 Phthalocyanine 0.10

are standard components in high-durability systems, but are fairly low in
chroma. PBr24 is redder than PY53. Higher up near the upper left corner
of the graph, PY184 (bismuth vanadate) is to be found. It is a very green
shade, chromatic pigment. Arrayed in an arc to the right are several of
organic pigments ranging from green shade yellows (PY54), oranges, to
bright reds (PR254). Along this arc is PY34 (lead chromate). This repre-
sents a middle-chrome pigment with a reddish-yellow shade. Its chro-
maticity, opacity and economics made it a standard pigment until regula-
tions and market pressure necessitated looking for alternatives.
HIGHER CHROMA
As can be seen, PY 227 is very close to the lead chromate colour space
and has much higher chroma than standard high-durability inorganic
pigments such as the titanates mentioned earlier. Due to the need to
move away from lead chromates, the PY 227 provides a bridge between
inorganic and organic pigments in chromaticity, opacity and durability.
PY 216 can be found in the lower right quadrant of the graph. The
increase in the redness of the latest product can be seen by the offset
to the right of PY 216. This increase in redness produces a more an
orange colour which is more in demand than previous offerings seen
to its left. Besides this pleasing masstone, the RTZ Orange makes an
excellent adjunct to other pigments and makes it possible to offer
redder tones than have been available to date with organic pigments.
Until the redder shade of RTZ pigments were developed, a chromat-
ic red-shade yellow was made from purely inorganic highly durable

Figure 2: A hue v. chromaticity graph comparing the addition of

Figure 1: A plot of hue angle and chromaticity RIO or RTZ Orange to BiV

E U R OP E AN COAT I NGS JO UR N A L 2018

 72 P IG M E N T C H EM I S TRY
 pigments. A common option would have been to start with a green-
shade bismuth vanadate (PY 184) and add red iron oxide (PR 101) to
make the colour redder. Figure 2 is a more selective chroma and hue
angle plot which illustrates the colours of this combination with the
line labelled ‘blends of BiV-RIO’. The iron oxide shifts the yellow from
its green-shade to redder shades, but there is a loss of chroma. If
the bismuth vanadate is instead blended with the RTZ orange to shift
to colour redder, the resulting colours are represented by the line
marked ‘blends of BiV-RTZ’. These colours shift redder as with the red
iron oxide blends, but they are more chromatic. The area between
the two lines represents the increase in colour space available to col-
our formulators if the desire to stay with all inorganic colourants for
durable colours.
As can be seen in Figure 3, PY 227 can also be blended with the bis-
muth vanadate and the RTZ orange pigments to make a wide range
of colours. They are represented by the lines labelled ‘blends of BiV-
NTP’ and “blends of NTP-RTZ. The difference between these two lines
and the ‘blends of BiV-RTZ’ in Figure 2 represents the increase in col-
our space available to colour formulators for highly durable colours
through the use of the PY 227.
This increase in the colour envelope available with all inorganic pig-
ments represents a very popular and useful colour space. As is appar-
ent from Figure 4, it includes a number of the highly popular RAL 1000
Figure 3: A comparison of the effect of blending RIO rather than
RTZ Orange with BiV
Figure 5: A comparison of contrast ratio v. film thickness for inor-
ganic and organic pigment matches
E U R O P E AN CO AT I NGS J O UR N AL 2018
series of colours. RAL 1003 is a very common colour and it can be
matched in a number of ways.
The two formulations are based on either inorganic or organic pig-
ments. While they give the same colour, they have different costs and
performance characteristics. One of the most apparent properties in
bright yellow colours is opacity. The two pigment formulations were
used with an acrylic binder at a pigment volume concentration (PVC)
of about 22 %. Due to the large difference in the specific gravity of the
two pigment formulations, the pigment-to-binder ratio was 1.2 for the
inorganic and 0.4 for the organic. Both represent fairly high loadings of
pigment as illustrated in Tables 1 and 2.
The acrylic paints were then drawn down at various thicknesses and
the opacity of the films recorded and plotted. Figure 5 clearly shows
that the inorganic based match to the RAL 1003 made mainly of PY
227 has much higher opacity at a lower film thickness than the organic
pigment based match. This relationship holds for other bright yellow
colours.
EXPANDING COLOUR ENVELOPE
PY 227 was incorporated into a polyester resin in a 23-micron film over a
chromate primer on a steel substrate. When standard organic pigments
are used to try to match the PY 227 panel, they do not keep enough of
Figure 4: hue v. chromaticity for RAL colours inside the envelope
Figure 6: A comparison of the opacity of PVDF/acrylic coatings
as the pigment-to binder ratio of different

their chromaticity due to lack of opacity to hide the substrate and reach
the colour. However, the combination of PY 227 and RTZ orange dra-
matically pushes the edge of the durable colour envelope when it comes
to thin film applications.
The inherent advantages in opacity over even other inorganic pigments
can be seen in Figure 6 that shows the opacity of PVDF/acrylic coatings
as the pigment-to binder ratio of different pigments is increased. PY
227 has much higher opacity than the organic alternatives. A plot of the
opacity of a coating made with bismuth vanadate is used as reference.
While PY 227 does not compete directly with bismuth vanadate, be-
cause of the relative prices, performance and hue it has higher opacity
than the bismuth vanadate.
Besides the appearance properties of colour and opacity, the NTP and
RTZ pigments have other desirable properties. They have excellent UV
stability, weathering resistance in accelerated tests and acid/alkali resist-
ance. In addition they have a range of advantageous physical properties.
The pigments are dense because of their inorganic metal-oxide structure
and a particle size of around 1 micron. Like many inorganic pigments,
they have low surface areas and oil absorption for easy incorporation as
well as the potential for high pigment loads for increased opacity or higher
loading levels in dispersion bases. The pigments have listed heat stabilities
of 320 °C, however this is system dependant. The pigments themselves
do not react with molten resins in the way that pigments like BiV do. In
Figures 7: Tint colour stability of various pigments
Figure 8: Tint gloss change of various pigments
P I G MENT CHEM I S T RY 73
fact, if the pigment can be protected from oxygen, it can survive much
higher temperatures than those listed. An example of this would be in a
silicate system based system cured at 500 °C for 10 minutes. PY 154 and
a PY 184 undergo a significant colour change due to the temperature and
high-pH of the system, but the PY 227 retains its colour.
Aside from the performance in a basic system, the periodic Kesternich
acid stability test was run on cured masstone and tint PVDF/acrylic pan-
els. After seven cycles, the PY 227 had similar colour and gloss reten-
tion properties when compared to a PY 53 (nickel titanate), the standard
CICP green-shade pigment.
ACCELERATED WEATHERING TESTS AVAILABLE
When exposed to UV light, the pigment’s high opacity protects sensitive
substrates and primers. At the same time, the UV light that it does ab-
sorb is not released as a free radical, rather it is dissipated by a vibration
mechanism (heat) that is negligible in a paint film exposed to sunlight.
The NTP yellow and improved RTZ Orange are still being tested in re-
al-world situations. This will be reported in the future, but accelerated
weathering results are already available.
When NTP yellow is incorporated into a PVDF/acrylic film over a chro-
mate based primer on a steel substrate, excellent EMMAQUA weather-
ing results are obtained. Most notable feature of the masstone colour
change and gloss loss graphs in Figures 7 and 8 is that the PY 227 weath-
ers very similarly to the green-shade standard pigment for highly dura-
ble systems, PY 53 (nickel titanate). PY 227 also performs better than PY
184 (bismuth vanadate) and PY 139 (isoindoline).
Using the above resin system and tinting with TiO2, the PY 227 performs
very well in the same accelerated weathering testing. It has excellent col-
our retention, especially compared to the organic pigment. It loses gloss,
but as can be seen in comparing the masstone and tint gloss change
data, the major driver in the gloss change is the TiO2, even though a
highly durable grade was used.
The new RTZ orange show excellent accelerated QUV masstone weath-
ering comparable to the red-shade standard, high-durability pigment
PBr 24(chromium titanate) –see Table 3.
CONCLUSION
Together the new NTP yellow and improved RTZ orange pigments pro-
vide high-performance, high durability colour envelope expanding tools
for the coatings chemist and paint formulator. Their high opacity and
chromaticity increase the colours that can be obtained in thin film coat-
ings while pushing the edge of the colour envelope in high durability
systems like coil and extrusion, pwoder, silicate-based paints and coat-
ings for the architectural, ACE, automotive, signage and corporate colour
marketplace. They also make alternatives to lead chromate pigments in
Table 3: QUV masstone weathering performance with PBr 24
and PY 216
Masstone PVDF/acrylic QUV testing
1000 2000 3000
hrs hrs hrs
D60° D60° D60°
Description DE* gloss DE* gloss DE* gloss
Yellow 29 (PBr 24) 0.7 0.5 0.8 -1.0 0.9 -2.0
Orange 10C341 (PY
1.0 1.0 1.0 0.0 0.8 -4.0
216)
E U R OP E AN COAT I NGS JO UR N A L 2018
 74 I R O N O X I D E P IGMENT S
Source: Matthias Haas - Fotolia.com
COLOUR CHART
Establishing the causes of colouring in iron oxide pigments. By Peter Köhler and Jürgen Kischkewitz (published in ECJ 01/2014)
Synthetic iron oxides are an important group of inorganic col-
our pigments, with annual consumption around one million
metric tonnes. But even though these products have been
used extensively their colouring mechanism (causes of colour-
ing) has not been described sufficiently to date. Detailed de-
scriptions of colouring for red, yellow, orange and black iron
oxides is provided and explained, using structural features of
each and findings from ligand field and molecular orbital (MO)
theory.
IRON OXIDE RED PIGMENTS
C olouring inorganic pigments is commonly produced by a com-
bination of light absorption and diffusion in the visible spectral
range. The tests performed were carried out on phase-pure iron ox-
ide pigments that are grouped together with selected properties in
Table 1.
a-Fe2O3 pigments have the crystal structure of the corundum and
contain only octahedrally coordinated Fe(III) ions in a high-spin state,
i.e. all five 3d electrons are unpaired, which is particularly important
for the electron structure and thus the colouring.
The products exhibit a virtually isometric habit (spherical to cube-
shaped). Average particle diameter varied in a range from around
0.08 to 1.0 µm.
The smallest unit in oxidic iron(III) materials is formed by regular Fe(III)
O6 octahedra, each with six identical Fe-O distances of around 2.05 Å.
E U R O P E AN CO AT I NGS J O UR N AL 2018
Fe2O9 double octahedra with common faces are present in the he-
matite lattice, with the Fe(III) ions occupying only 2/3 of the available
octahedron positions, while the oxygen lattice section is full. As a
result of the unoccupied Fe(III) positions, a deficit in positive charge
is produced that is compensated by moving the Fe(III) ions from the
centre of the octahedra. This leads to pronounced distortion for the
two individual octahedra (trigonal components). As a result, the Fe-O
distances vary greatly (3 x 2.12 Å and 3 x 1.95 Å in the respective indi-
vidual octahedron) and the Fe(III)-O-Fe(III) angle is approximately 85°.
LIGHT ABSORPTION AND COLOURING
When considering a hematite single crystal and a powder a-Fe2O3 pig-
ment, in both cases the green and blue spectral ranges of the incident
light are absorbed selectively. The unabsorbed proportion of visible
light (600 – 720 nm) causes the red colour impression.
To investigate selective light absorption without influence from light
diffusion, the absorption spectrum of a hematite single crystal was
first recorded at room temperature (RT) and is shown in Figure 1. [2]
The x axis shows the wave number (in cm-1) and wavelength (in nm)
and provides the energy positions of the absorption bands.
The y axis shows extinction E and enables quantitative data relating to
the intensities of the absorption bands. (The scale is logarithmic, i.e.
there is a difference of 104 between E = 0 and E = 4.)
The correlation
E = log I0/I = e ∙ d
 I R O N O X I DE P I G MEN T S 75

applies to absorbance, with I0 indicating the intensity of the incident

RESULTS AT A GLANCE
 Colouring inorganic pigments is commonly produced by
a combination of light absorption and diffusion in the visible
spectral range. Tests performed were carried out on phase-
pure iron oxide red, yellow, orange and black pigments using
structural features of each and findings from ligand field and
molecular orbital (MO) theory.
 For iron oxide red pigments rises in absorption become
much less intense as particle size increases, and the steepness
is reduced. A slight shift toward lower wave numbers also oc-
curs. These changes result in a distinct bluish cast and a dirtier
colour impression compared to the red pigments I, II and III.
light and I the intensity of the transmitted light.
ε describes a solid’s absorption properties and d expresses the single
crystal’s layer thickness.
Bands I (11,600 cm-1 (approximately 860 nm), intensity of approxi-
mately 10) and II (15,700 cm-1 (approximately 635 nm) as a shoulder
with an intensity of approximately 12) of the absorption spectrum are
due to the two initial electron transitions of the d5 electron system of
the iron(III) ions in octahedral oxygen coordination.[3]
The sharp and intense rise in absorption with a wide plateau extend-
ing up to the UV range (from 16,800 cm-1 (approximately 595 nm) with
Table 1: Tested iron oxide pigments with selected properties

 For iron oxide yellow pigments, as a result of these different Chemical composi-
Structural
ligand field parameters, the high-intensity absorption bands III Pigment type* tion and oxidation Lattice type
features
to VI for α-FeOOH are positioned much more in the short-wave level of the iron
range, with the result that the rise in absorption that deter-
mines colour also undergoes a significant UV shift. Fe2O9 double
Iron oxide red -Fe2O3 Corundum
octahedra with
(hematite) (Fe(III) ions) ( -Al2O3)
 For iron oxide orange pigments, the calculation of electron common faces
transitions I to IV provides a very good correlation with the
Edge-sharing
measured band positions I to IV, as shown in Figure 7, and thus Iron oxide yellow -FeOOH Diaspore
FeO3(OH)3
explains the colour change from yellow to orange. (goethite) (Fe(III) ions) ( -AlOOH)
octahedra

 For iron oxide black pigments, at RT, the octahedrally co- Iron oxide
-FeOOH Boehmite
Edge-sharing
ordinated iron ions have an average valence of + 2.5, which orange FeO3(OH)3
(Fe(III) ions) ( -AlOOH)
Mössbauer spectroscopy also demonstrates with a signal split (lepidocrocite) octahedra
as a sextet, as the “Fe2.5+ ions” couple magnetically with the Fe(II)/Fe(III)
Fe3O4
tetrahedrally coordinated iron(III) ions. Iron oxide black octahedra
(Fe(II) Inverse spinel
(magnetite) Fe(III) tetrahe-
and Fe(III) ions)
drons

Figure 1: Single crystal absorption spectrum of α-Fe 2O 3 Figure 2: Absorption spectrum of iron oxide red III

E U R OP E AN COAT I NGS JO UR N A L 2018

 76 I R O N O X I D E P IGMENT S

 Table 2: Properties of α-Fe 2O 3 pigments with different particle sizes

Inflection points IP
Product Average Intensity i Intensity (L64,
Rise in absorption b*
name particle size (µm) Band II Rise in absorption pure tone)
(cm-1)

Red I (yellowish cast) Approx. 0.08 0.20 17,600 2.05 24.1

Yellow shift
Red II (yellowish cast) Approx. 0.15 0.30 17,300 2.25 23.7

Red III Approx. 0.25 0.42 17,100 2.40 20.5 –

Red IV
Approx. 0.70 0.50 16,700 8.3
(bluish cast)

Blue shift
Red V (strongly bluish
Approx. 1.0 0.50 Approx. 16,500 0.70 5.5
cast)

Figure 3: Absorption spectrum of α-Fe 2O 3 and comparison with a Figure 4: Absorption spectrum of α-FeOOH and comparison with
cadmium red pigment a cadmium yellow pigment

Figure 5: Absorption spectra of α-FeOOH and comparison with a Figure 6: Simplified electron structures of hematite and goethite
α-Fe 2O 3 pigment

E U R O P E AN CO AT I NGS J O UR N AL 2018

an intensity of around 10,000) is caused by a large number of other
electron transitions of the d5 multiple electron system. [3]
The very high intensities are caused by the particular spin-spin inter-
actions of the unpaired 3d electrons of two iron(III) ions in the double
octahedra by way of the bridging oxygen anions (Fe-O-Fe angle ap-
proximately 85°). [4]
The intensity of this absorption range is increased further by the rise
to the first electron transfer band (transfer of an electron from the
O2- ligand to the iron(III) central atom), which is widest in the range
from approximately 30,000 cm-1 to 35,000 cm-1 and also exhibits very
high intensity. The precise band position can be calculated using MO
theory. [5]
A quantitative evaluation of all electron transitions of Fe(III)O6 octa-
hedra is possible using ligand field theory and provides the electron
structure of a-Fe2O3 in the d5 multiple electron system. Figure 6 shows
the simplified term structure with the measured (I and II) and calcu-
lated (III to VI) electron transitions in the visible spectral range. [6]
Unlike single crystals, both absorption and scattering properties need
to be taken into account to explain colouring for powder iron oxide
red pigments. When measuring pigment powders, the part of the
light that provides colour (red spectral range) is first scattered several
times on the pigment particles and then enters the spectrometer (in-
tegrating sphere) as diffused light.
To obtain the absorption spectrum from the remission spectrum thus
measured, the measured remission values R (υ, l) need to be con-
verted using the Kubelka-Munk equation
K (1–R∞)2
–– = –––––––––––
S 2R∞
and plotted against the wave number / wavelength as K/S.
K is the absorption coefficient of the red pigment and correlates with
the extinction (absorbance) E of the single crystal through the rela-
tionships
K = 2.302 ∙ e ∙ d and E = e ∙ d.
With the exception of the factor 2.302, single crystal and pigment
powder have comparable dependencies in terms of absorption prop-
erties.
S is a pigment’s scattering coefficient and is essentially dependent on
particle size and the refractive index n.
Figure 2 shows the absorption spectrum of a red pigment with an aver-
age particle size of
approximately 0.25 µm (red III). Bands I and II have virtually the same
energy positions as for measurement of the single crystal, as shown
in Figure 1. This is logical given the identical electron structure of the a-
Fe2O3 materials. The correct magnitude of intensities is only obtained
by measurement of the a-Fe2O3 single crystal.
The absorption spectrum of a saturated cadmium red pigment (Cd-
SxSe1-x mixed phase), as shown in Figure 3, features a very steep, sud-
den rise in absorption that is caused by direct electron transitions
from the valence band (VB) to the conduction band (CB). In the case of
a-Fe2O3 pigments, the rise in absorption is less steep (angle of inclina-
tion a at the turning point TP is approx. 80° compared to 85° for the
cadmium red pigment) and the steepness is also reduced by band II
at approx. 15,500 cm-1.
These differences lead to the a-Fe2O3 pigments being much less satu-
rated and exhibiting much lower colour purity.
The influence of particle size on pigment colouring properties is well
known. To also investigate this spectroscopically, red pigments of vari-
ous particle sizes from magnetite precursors were produced using
the Laux process (characterisation in line with Table 2.) and investi-
gated spectroscopically.
If considering the red pigments I to V, red III represents the reference
point (average particle size approximately. 0.25 µm). With increasing
I R O N O X I DE P I G MEN T S 77
fineness, the colour shifts toward more yellowish products (red I and
red II). When the pigment particles are increased, a significant blue
shift occurs (red IV and red V).
In the transition from red III to red pigments II and I (increasing fine-
ness), the profile of the absorption spectra is very similar (same posi-
tions for bands I and II). However, a difference exists for the intensities
of band II, as decreasing particle size is accompanied by a reduction,
shown in Table 2, which results in the somewhat greater colour satura-
tion for the finer pigments. If we consider the rises in absorption, it is
possible to observe a shift toward the short wave from red III to red
II and red I (see inflection points in Table 2), which explains the yellow
tinge of the finer red. The intensities for the finer pigments are also
slightly lower than for red III.
In the transition from red III to the red pigments IV and V (increasing
particle size), the energy positions of bands I and II in the absorption
spectra are also comparable to red III, while the intensities of band II
are slightly higher, which Table 2 shows.
The rises in absorption become much less intense as particle size
increases, and the steepness is reduced. A slight shift toward lower
wave numbers also occurs. These changes result in a distinct bluish
cast and a dirtier colour impression compared to the red pigments
I, II and III.
IRON OXIDE YELLOW PIGMENTS
Iron oxide yellow (goethite, a-FeOOH) has the crystal structure of dia-
spore (a-AlOOH) and contains only Fe(III) ions in an octahedral coordi-
nation. The pigments exhibit a needle-shaped habit, with a length-to-
width ratio of around 5 : 1 predominating.
The smallest structural units for aFeOOH are FeO3(OH)3 octahedra,
where the iron(III)-ion is coordinated asymmetrically by three oxygen
(O2-) and three hydroxyl (OH-) ligands.
This distortion of the individual octahedra becomes clear if we look at
the Fe-O and Fe-OH distances:
Fe-O with 1 x 1.89 Å and 2 x 2.02 Å
Fe-OH with 1 x 2.05 Å and 2 x 2.12 Å
In the crystal lattice of the goethite, these FeO3(OH)3 individual octa-
hedra form double chains through shared edges and these chains are
linked to each other via corners, thus creating tunnel-like cavities [1].
There are also hydrogen bonds between the double chains, with the
hydrogen atoms being located essentially in the “tunnels” of the crystal.
ABSORPTION SPECTRUM AND COLOURING
At 21,500 cm-1 (band III) and 24,000 cm-1 (band IV), the absorption
spectrum of a yellow pigment, shown in Figure 7, exhibits two intensive
absorption maximums that determine colouring.
The high intensity of the two bands is due to electron transitions with
particular spin-spin interactions of the five unpaired 3d electrons of
two adjacent Fe(III) ions in the crystal lattice, with the rise in absorp-
tion adding additional intensity to the first electron transfer band from
the O2-/OH- to the Fe(III) cation. A disadvantage for the saturation and
colour purity of the a-FeOOH pigments is the relatively flat rise in the
range from 18,500 to 20,500 cm-1 (angle of inclination a at the turning
point TP of approx. 64°). In contrast, the rise in absorption of the bril-
liant cadmium yellow pigment is much steeper (angle a approx. 84°,
as shown in Figure 4)
The two wide and low-intensity bands at 10,850 cm-1 (I) and 15,500
cm-1 (II) have no significant impact on colouring of a-FeOOH pigments.
Although the electron structures of red and yellow are very similar, a dis-
tinct short-wave shift in the rise in absorption of around 2,100 cm-1 can
be detected when comparing the absorption spectra, which is shown
in Figure 5.
An explanation for this is provided by ligand field theory in conjunction 
E U R OP E AN COAT I NGS JO UR N A L 2018
78 I R O N O X I D E P IGMENT S

with the structural differences of the two pigments. Figure 7: Absorption spectra of α-FeOOH and γ-FeOOH compared
Fe2O9 double octahedra with common faces are present in the α-
Fe2O3, while edge-sharing FeO3(OH)3 individual octahedra can be ob-
served in the α-FeOOH.
In accordance with ligand field theory, the OH- ion is a stronger ligand
than the O2- ion [3,5], with the result that a much higher ligand field
strength ∆ is calculated for α-FeOOH than for α-Fe2O3 following evalu-
ation of the two absorption spectra (∆α-FeOOH = 13,600 cm-1 and ∆α-
Fe2O3= 11,300cm-1). The covalence parameter B was fixed at 580 cm-1
(α-Fe2O3) and 630 cm-1 (α-FeOOH), i.e. the Fe-O bonds in the α-Fe2O3
exhibit higher covalence components.
As a result of these different ligand field parameters, the high-intensi-
ty absorption bands III to VI for α-FeOOH are positioned much more
in the short-wave range [6], with the result that the rise in absorption
that determines colour also undergoes a significant UV shift.

IRON OXIDE ORANGE PIGMENT

Lepidocrocite (γ-FeOOH) has a boehmite structure (γ-AlOOH). The

smallest structural units are FeO3(OH)3 octahedra that have three dif-
ferent Fe-O distances with 2 x 1.93 Å, 2 x 2.05 Å and 2 x 2.13 Å.
In the crystal lattice of the lepidocrocite, these individual octahedra
form double chains through shared edges, these chains developing
slightly waved layers at the b/c level of the elementary cell with further
double chains.[1] The individual layers are finally bonded by means of
hydrogen bonds, similar to α-FeOOH.

LIGHT ABSORPTION AND COLOURING

The absorption spectrum of γ-FeOOH is very similar to that of α-
FeOOH, which is shown in Figure 6.
The rise in absorption for band III exhibits a steepness that is compa-
rable with that of band III for α-FeOOH, but the position of this rise for
γ-FeOOH has been shifted around 600 cm-1 in the long-wave direction,
shown in Figure 7, which causes the colour shift to orange.
This longer-wave position of bands III and IV for γ-FeOOH can be ex-
plained using ligand field theory if the differences in the hydrogen
bonds are also taken into account. In the case of γ-FeOOH, these hy-
drogen bonds are less pronounced due to the differing linking of the
octahedron chains, so that a somewhat stronger ligand field results
for the Fe(III) ions, which leads to a higher ∆ value (14,000 cm-1 as op-
posed to 13,600 cm-1 for α-FeOOH). The covalence of the Fe-O bonds
is comparable in the two pigments due to the calculated B values of
630 cm-1.
On this basis, the calculation of electron transitions I to IV provides
a very good correlation with the measured band positions I to IV, as
shown in Figure 7, and thus explains the colour change from yellow to
orange. [6]
the tetrahedrally coordinated iron(III) ions. Further evidence for the
indistinguishability of iron ions in octahedron positions is provided by
neutron diffraction with an Fe-O distance of only 2.06 Å. [7]
REFERENCES
[1] Wells A. F., Structural Inorganic Chemistry, 1975, Oxford.
[2] Single crystals were prepared and measured in the working group
under Prof. R. Glaum, University of Bonn, Inorganic Institute.
[3] Schläfer H. L., Gliemann G., Einführung in die Ligandenfeldtheorie,
1967, Akademische Verlagsgesellschaft, Frankfurt/Main.
[4] Sherman D. M., Physical Chemistry of Minerals, 1985, Vol. 12, p 161-175.
[5] Duffy J. A., Bonding, Energy Levels and Bands in Inorganic Solids,
1990, John Wiley, New York.
[6] Köhler P., Eigene Berechnungen mit den d5-Energiematrizen in Oh-
Symmetrie.
[7] Day P., Verbindungen mit gemischter Valenz, Endeavour, 1970, p
45-49.

CAUSES OF COLOURING IN IRON OXIDE BLACK PIGMENTS

The chemical composition and distribution of Fe(II) and Fe(III) ions in

the spinel lattice can be described as follows:
Fe(III)tet [Fe(II) Fe(III)]oct O4
Ideally, the ratio of Fe(II) and Fe(III) ions to octahedron positions is 1
: 1, with the respective octahedra being linked via shared edges. At
RT, the two octahedron positions cannot be distinguished, with the
result that a fast electron transition from Fe(II) to Fe(III) can occur that
requires only minimal excitation energies. This energy is ≥ 1,000 cm-1,
i.e. the entire visible light and part of the infrared light are absorbed
virtually completely, thus forming the black colour of the magnetite.
At RT, the octahedrally coordinated iron ions have an average valence
of + 2.5, which Mössbauer spectroscopy also demonstrates with a
signal split as a sextet, as the “Fe2.5+ ions” couple magnetically with

E U R O P E AN CO AT I NGS J O UR N AL 2018
Source: ShanePhoto - Fotolia.com W O R LD O F C O L O UR 79

ANCIENT PAINTS
Popular pigments used for
cave paintings were iron oxi-
de, maganese oxide and char-
coal, mixed with water, spit or
fat. Researchers assume that
other raw materials were ore,
feldspar, blood, limestone, re-
sin, milk and herbal juices.

FROM BRUSHES TO
SPRAY PAINTING
The paint was applied with
branches, stamps or
fingers. In addition to this,
paints were also spray
painted using pipes made
from bone.

E U R OP E AN COAT I NGS JO UR N A L 2018

80 I R O N O X I D E P IGMENT S

Source: Stefanie Ortanderl - Fototlia.com

STRUCTURE
DETERMINES
SHADE
How the crystal lattice of iron spinels affects their
appearance. By Peter Köhler and Jürgen Kischkewitz.

Iron oxide pigments are used on a very large scale in many α-Fe2O3, α-FeOOH and γ-FeOOH is relatively well known, yet there re-
industries. The ways in which the structure of a major group mains a need to explain the absorption properties of these products.
of these pigments (the spinels) affects their colour is explored In particular, an answer is provided for the fundamental question of
in detail. The absorption spectrum of some of these pigments why α-Fe2O3 is red and why a colour shift to yellow or orange occurs
was studied and related to their crystal structure and the elec- for α-FeOOH and γ-FeOOH.
tron orbital transitions that can occur. These aspects are examined in detail based on structural and elec-
tronic properties of synthetic iron oxides and a relationship is estab-

W ith an annual demand of almost one million metric tons, syn-

thetic iron oxides are the World’s most widely used colour pig-
ments. They also feature a highly versatile range of properties.
lished with colour quality and changes in colour.

TWO GROUPS OF COLOURED IRON OXIDES COMPARED

Although these products have long been used as pigments, the ques-
tion of what causes their colouration has yet to be explained ade- The focus theme Iron Oxide Pigments – the creation of colour (Eisen-
quately. The influence of particle properties on the colour quality of oxidpigmente – die Entstehung der Farbe) in FARBE UND LACK [1] set

Figure 1: Structural features of the spinel lattice AB 2O 4.

a) isolated tetrahedrons b) linking of octahedra about c) linking of tetrahedrons and octahedrons

common edges about common corners

Grey balls: A (Zn 2+)

Green balls: B (Fe 3+)
Red balls: O 2-

E U R O P E AN CO AT I NGS J O UR N AL 2018

RESULTS AT A GLANCE
űű Iron oxide pigments are used on a very large scale in many
industries. The ways in which the structure of a major group of
these pigments (the spinels) affects their colour is explored in
detail.
űű In general, iron spinels have two cations and two possible
crystal lattice arrangements – tetrahedral and octahedral. Zinc
ferrite generally has a ‘fixed’ structure with the zinc ions in a
tetrahedral arrangement and the iron ones in octahedral struc-
ture. However, in other spinels the distribution is more complex
and in magnesium ferrite depends on the synthesis conditions.
űű The absorption spectrum of some of these pigments was
studied and related to crystal structure and the d-d electron
orbital transitions that can occur in these structures.
out how the colours red, yellow, orange and black of the iron oxides
hematite, goethite, lepidocrocite and magnetite arise. These materials
are used as pigments on an industrial scale.
The spinel pigments containing iron(III) - zinc ferrite, magnesium ferrite
and maghemite – however, are dominated by the colour brown with a
wide range of variations from yellow-brown to dark brown tones.
This wide range of colours is primarily due to the distribution of the
iron(III) ions in the spinel lattice and leads to special absorption spec-
tra that can be explained using ligand field theory.
These spinel pigments may not be as important commercially as the
iron oxides already mentioned, yet Zn- and Mg- ferrite frequently find
interesting applications in particular areas of the plastics and the
coatings industries thanks to their exceptional thermal stability, while
maghemite is used due to its special magnetic properties.
STRUCTURAL ASPECTS OF THE ZINC FERRITE SPINEL LATTICE
Iron(III) spinels have the general formula AIIB2IIIO4, in which the cations
A(II) and B(III), with the oxidation states +2 and +3 respectively, can oc-
cupy both tetrahedral sites (coordination number 4) and octahedral
sites (coordination number 6) according to a specific pattern. This dis-
tribution is substantially determined by the site preference energies
(Ev values) of the cations involved (see Table 1) [2].
As a result, zinc ferrite has a chemical composition of ZnIItet [FeIII2]octO4,
i.e. the Fe(III) ions are located exclusively in octahedral sites when slow
cooling to room temperature takes place after high-temperature syn-
thesis.
These predictions have been confirmed by the Mössbauer spectrum
of nuclear interactions, as only one doublet is measured, which shows
that there is no magnetic coupling between Fe(III) ions in tetrahedral
and octahedral sites. This is also in agreement with the paramagnetic
properties of the zinc ferrite at room temperature and is an unam-
biguous indication of a normal spinel [3].
I R O N O X I DE P I G MEN T S 81
MORE COMPLEX CATION DISTRIBUTION IN OTHER SPINELS
The cation distribution is more complicated in the case of magnesium
ferrite, as the Mg(II) ions preferentially occupy the octahedral sites
(see Ev values in Table 1) and so force the Fe(III) ions to also occupy
tetrahedral sites. The chemical composition with a temperature-inde-
pendent occupancy factor λ (a measure of the degree of inversion) is
(MgII1-λFeIIIλ)tet [MgIIλFeIII2-λ]octO4. An ideal inverse spinel has λ = 1, which
is to be expected according to the Ev values (Table 1).
The proof of this Fe(III) distribution is again provided by the Möss-
bauer spectrum, which exhibits a symmetrical sextet arising due to
the antiferromagnetic coupling of the Fe(III) ions in octahedral and
tetrahedral sites.
Depending on how high the synthesis temperature is and the cooling
conditions, λ can also take on values less than 1, i.e. the Mg(III) ions
are in part located in tetrahedral sites, which indicates a statistical dis-
tribution of the Mg(II) and the Fe(III) ions [4]. This possible variation of
the cation distribution affects the colour and its reproducibility.
Maghemite (γ-Fe2O3) presents a special case of the spinel pigments,
as it forms a defect structure of the formula FeIIItet [FeIII5/31/3]octO4. The
octahedral sites are not completely occupied by Fe(III) ions (where
1/3 = unoccupied octahedral sites), which causes a slight distortion of
the FeO6 octahedrons. [4]
The FeO4 tetrahedrons in all spinel variants (normal, inverse, and defect)
are isolated from one another, while the FeO6 octahedrons are joined
by common edges. All of the tetrahedrons are joined to the octahe-
drons by common corners, which is important for the magnetic prop-
erties of the spinels (Figure 1). Increasing occupancy of the tetrahedral
sites by Fe(III) ions causes a colour change from brown-yellow to brown.
COLOURATION AND ABSORPTION SPECTRUM OF ZINC FERRITE
To determine the origin of the colour, the absorption spectrum of a
pigment in powder form is measured at room temperature (Figure 2)
and evaluated for octahedrally coordinated Fe(III) ions using ligand
field theory. The absorption spectrum initially shows the lower intensi-
ty d-d electron transitions in the octahedral structure, O1 and O2, which
due to their low wave number have no effect on the colouration.
The increase in absorption that determines the colour starts in the
region from 16,000 cm-1 to 17,000 cm-1 and has its point of inflection
Wp at approx. 18,800 cm-1. The slope is relatively steep, and the sub-
sequent absorption plateau (from 20,000 cm-1) is formed from further
high-intensity electron transitions of the FeO6 octahedrons, which lie
relatively close to one another (Table 2).
A pronounced shoulder is visible in the region from 16,000 cm-1 to
18,500 cm-1. This prevents a steeper rise at the start of the increase
in absorption.
This is the first pair excitation (1st PE) of adjacent FeO6 octahedrons in
the spinel lattice. The five unpaired d electrons of the Fe(III) ions can
couple with one another via the oxygen ligands (O2-) and thus create
a higher-intensity transition. The result is a loss of saturation and a
yellow pigment with a pronounced brown cast.
Comparison of the Zn ferrite with the orange-coloured γ-FeOOH (lepi-
docrocite) shows that while the a* (red-green axis in colour space) val-
ues in the coating system are practically identical (21.1 and 21.0), b*
values (yellow-blue axis) show a pronounced deviation (40.4 to 45.9).
The absorption spectrum of lepidocrocite does not show a shoulder
at around 17,500 cm-1, as its first PE is located at about 21,000 cm-1
and the absorption can rise more steeply as a result [1].
COLOURATION OF MAGNESIUM FERRITE
The Fe(III) ions in this spinel are also located on tetrahedral sites,
which have a substantial effect on the absorption spectrum (Figure 3a,
E U R OP E AN COAT I NGS JO UR N A L 2018
82 I R O N O X I D E P IGMENT S

measured on powder at room temperature). Compared to Zn ferrite,
two additional absorption bands with relatively higher intensity occur
at approximately 16,500 cm-1 (T1 = first d-d electron orbital transition
of the Fe(III) tetrahedrons) and at approx. 19,500 cm-1 (T2 = second d-d
transition of the Fe(III) tetrahedrons).
The first high-intensity PE is located at around 19,500 cm-1 and, with
further d-d transitions of the FeO6 and FeO4 polyhedrons, contributes
to the rise in absorption with a maximum in the region of approx.
21,000 cm-1 (Table 3).
In addition, the O2 transition of the Mg ferrite is displaced to higher
wavenumbers (13,800 cm-1 as opposed to 12,500 cm-1 in the case of
Zn ferrite), which initiates the less steep increase in absorption in the
Figure 2: Absorption spectrum of Zn ferrite (1:10 in BaSO 4) [8]
visible region of the spectrum. An explanation of this band shift will be
provided near the end of this paper.
These spectroscopic differences with respect to the Zn ferrite lead
to a significant colour change from a brownish yellow to a medium
brown in the case of the Mg ferrite.
COLOURATION OF MAGHEMITE
The absorption spectrum of the γ-Fe2O3 (Figure 3b, measurement of
powder at room temperature) shows a similar curve to that of Mg
ferrite, whereby all visible d-d transitions (O1 to O3 and T1 to T3 re-
spectively) and the first PE are displaced to a higher wavenumber in
comparison to the Mg ferrite (Table 3).
Due to the defects in the octahedral partial lattice of the γ-Fe2O3,
these sites offer greater scope for the FeO6 octahedrons to expand,
resulting in greater Fe-O distances. This leads to reduced ligand field
strength ∆ in the case of γ-Fe2O3 and causes the observed band shifts
to higher wavenumbers.

COMPARISON AND DISCUSSION OF

THE ELECTRON STRUCTURES

The calculation of the energy levels of the d5 multi-electron system

(high-spin state, five unpaired d electrons) was accomplished using li-
gand field theory, providing the electronic ground state GS and the ex-

Table 1: Site preference energies E v of cations in the spinel lattice.

Al 3+ - 10.5 Exclusively O sites
Mg 2+ - 20.9 Mostly O sites
Al 3+
- 55.7 Both T and O sites
Mg 2+ -132.3 Exclusively T sites

O = octahedral sites, T = tetrahedral sites

Figure 3a: Absorption spectrum of Mg ferrite [8]. Figure 3b: Absorption spectrum of γ-Fe 2O 3 (1 : 10 in BaSO 4) [8].

E U R O P E AN CO AT I NGS J O UR N AL 2018
 I R O N O X I DE P I G MEN T S 83

cited states O1 to O5 for octahedral symmetry and T1 to T5 for tetrahe-
dral symmetry [5]. The ground state is set to zero as a reference point
so that the excited states take on positive energy values (Figure  3).
The d-d transitions in the excited states O1, O2 and O4 and T1, T2 and
T4 depend on the ligand field strength ∆ and on the electronic inter-
action parameter B, and can be quantitatively characterised using
energy equations. The transitions O3 and O5 and T3 and T5 are de-
pendent only on B and possess their own individual energy values,
i.e. the parameter B (a measure of the covalency of the Fe-O bonds)
thus has the same values for Fe(III) octahedrons and for the Fe(III)
tetrahedrons.
The edge coupling of the FeO6 octahedrons leads to a Fe-O-Fe an-
gularity of approximately 90 ° and permits cooperative interactions
of the unpaired d electrons between adjacent Fe(III) ions via the O2-
ligands. This electronic coupling creates additional transitions in the
visible region of the spectrum, which are designated as PE [6] and are
coupled with the d-d transitions of the FeO6 octahedron as follows:
1. PE = O1 + O1
2. PE = O1 + O2 Increasing energy values
3. PE = O2 + O2
4. PE = O1 + O3
Charge transfer transitions, i.e. the transport of an electron from the
O2- ligand to the central Fe(III) atom within the Fe(III) oxygen polyhe-
dron, are a further aspect in understanding the electron structures of
Fe(III) materials.
The first high-intensity charge transfer transition (CT1), has a wide ab-
sorption maximum in the region of 35,000 cm-1 that can be calculated
using molecular orbital (MO) theory and is important for the coloura-
tion [7]. The rise to this absorption maximum lies partially in the vis-
ible region of the spectrum and adds additional intensity to the d-d
transitions starting from 20,000 cm-1.
ELECTRON TRANSITIONS IN ZINC FERRITE
the 1st to the 3rd PE in the absorption spectrum (Table 2).
As has already been briefly discussed, the relatively steep and high-in-
tensity rise in absorption in the region from 17,000 cm-1 to 20,000 cm-1
is responsible for the colouration of the Zn ferrite. The high intensi-
ties of the participating transitions (2nd PE, O3, O4 and O5) result from
the cooperative spin-spin interactions, which significantly increase the
probability of these transitions. Furthermore, the rise to CT1, the first
charge transfer transition, adds additional intensity.
The 1st PE at approx. 17,500 cm-1, which as a pronounced shoulder
in the adsorption spectrum prevents a steeper start to the rise of the
absorption, is disadvantageous in terms of colouration.
DIFFERING ELECTRON TRANSITIONS IN MAGNESIUM FERRITE
The electron structure of the Mg ferrite is shown in Figure 4b and also
exhibits the d-d transitions T1 to T5 of the FeO4 tetrahedrons so that a
large number of electronic transitions of different intensities are reg-
istered in the region from 15,000 cm-1 to 25,000 cm-1. This does not
Table 2: Characterisation of absorption spectrum from Zn ferrite
(octahedral sites).
O1 approx. 8,500 1st d-d transition (∆- and B-dependent)
O2 approx. 12,500 2nd d-d transition (∆- and B-dependent)
approx. 17,500
1st PE
(shoulder)
1st pair excitation 2 x O1 = 17,000 cm-1
2nd pair excitation O1 + O2 =
2nd PE approx. 21,000
20,500 cm-1
O3 approx. 21,250 3rd d-d transition (B-dependent)

approx. 23,500
The complete electron structure of the Zn ferrite is shown in Figure O4
(calculated)
4th d-d transition (B-dependent)
4a and is formed from the excited states O1 to O5 (d-d transitions)
and the four excited pairs (1st PE to 4th PE). The d-d transitions O1, approx. 24,500
O5 5th d-d transition (B-dependent)
(calculated)
O2 and O3 are clearly visible as bands in the absorption spectrum
(Figure 2) and, via the energy equations, provide the ligand field 3rd PE approx. 25,000 3rd pair excitation 2 x O2 = 25,000 cm-1
strength ∆ = 15,500 cm-1 (average of the calculations from O1 and O2)
O = octahedral sites, T = tetrahedral sites
and the electronic interaction parameter B with 600 cm-1 (calculation
from O3).
In the case of the pair excitations, the calculation used the absorption
bands of the d-d transitions O1 and O2 and confirms the energies of
Table 3: Ligand field parameters of the Fe(III) spinels (O = octa-

Figure 4: Electron structure of Fe(III) spinels.

Spinel Zn ferrite Mg ferrite Maghemite

O1 (cm ) -1
8,500 9,500 11,300

O2 (cm ) -1
12,500 13,800 15,500

T1 (cm-1) - 16,500 17,250

T2 (cm-1) - 19,500 20,000

1st PE (cm-1) 17,500 19,500 23,500

(measured) (measured) (measured)
17,000 19,000 22,600
(calculated) (calculated) (calculated)
O3 (cm-1) 21,000 21,000 21,000

Formal octahedral [FeFe] [FeMg] [Fe5/3 1/3]

sites
∆oct (cm-1) 15,500 13,850 12,650

E U R OP E AN COAT I NGS JO UR N A L 2018

84 I R O N O X I D E P IGMENT S

“Zn-ferrite pigments exhibit

a much greater thermal
stability than pure goethite pigments.“

Dr Jürgen Kischkewitz

Contact:
3 questions to Dr Jürgen Kischkewitz Christoph Schmidt
Head of Global Brand Management
Iron(III) spinel pigments are discussed in depth. Please explain the pigment choice to the Lanxess AG
formulator and what must be considered when choosing them. christoph.schmidt1@lanxess.com
Spinel pigments basically behave comparably to pure iron oxide pigments during processing, as
these also undergo intensive grinding. There are differences in thermal stability. Zn-ferrite pigments
exhibit a much greater thermal stability than pure goethite pigments.

What does a formulator who wants to use these pigments have to consider?
Mg- and Zn-ferrite pigments exhibit a high thermal stability that is particularly well suited for the
coloration of plastics and for use in more thermally-demanding coating processes. Maghemite is not
as thermally stable and upon exposure to extreme heat can transform to the more stable hematite
modification and change colour. What makes maghemite special are its magnetic properties.

How do the results of this research impact practical applications?

The research results explain the fundamental crystallographic cause of colour in the spinels investigat-
ed. The facts described make it clear that in the case of Mg-ferrite, for example, the colour of the pig-
ment may fluctuate due to the possible variations of the iron(III) ion distribution in the crystal lattice.

permit a rise in absorption as in the case of Zn ferrite, and causes the
change in colouration from yellow to brown.
The short-wave shift of the O1, O2 and 1st PE transitions relative to the
Zn ferrite is noticeable, while the d-d- transition O3 (only dependent
on B) of the two spinels has the same energy (Table 3).
As Mg(II) and Fe(III) ions each occupy 50 % of the octahedral sites of
Mg ferrite and Mg(II) has an approximately 9 % larger ionic radius,
these sites are further apart than in the Zn ferrite, so that greater Fe-O
bond lengths are possible. This leads to a smaller ligand field strength
∆ for an Mg ferrite (Table 3) giving the short-wave shift of O1, O2 and
the 1st PE (Table 3).
The electron structure of the γ-Fe2O3 is in principle comparable to
that of the Mg ferrite; however, the octahedral d-d transitions O1 and
O2 and the 1st PE are located at even shorter wavelengths (Table 3).
Due to the empty sites in the octahedral lattice, the FeO6 octahedrons
have even more space for expansion, which reduces the ligand field
strength ∆ in γ-Fe2O3 even further (12,650 cm-1 as opposed to 13,850
cm-1 in the case of Mg ferrite).
As the B values for all spinel pigments are comparable (600 cm-1, cal-
culated from O3), the displacement of the transitions O1, O2 and 1st PE
are exclusively based on the different ∆ values. The positions of the
tetrahedral d-d transitions T1 and T2 only change by a moderate
amount (Table 3), as the isolated FeO4 tetrahedrons in the spinel
lattice react less to the expansion effect.  
REFERENCES
[1] Eisenoxidpigmente – die Entstehung der Farbe [Iron Oxide Pigments
– the creation of colour], focus theme, FARBE UND LACK, Jan. 2014.
[2] Weiss A., Witte H., Kristallstruktur und chemische Bindung, Verlag Chemie,
1983.
[3] Wells A. F., Structural Inorganic Chemistry, Oxford, 1975.
[4] Krebs H., Grundzüge der Anorganischen Kristallchemie, Enke Verlag,
Stuttgart, 1968.
[5] Own calculations with the d5 energy matrices for Oh and Td symmetry.
[6] Sherman D. M., Physics and Chemistry of Minerals, 1985, Vol. 12, pp.
161–175.
[7] Duffy J. A., Bonding, Energy Levels and Bands in Inorganic Solids,
John Wiley, New York, 1990.
[8] The absorption spectra were measured by the research group of
Prof. Glaum, University of Bonn.

E U R O P E AN CO AT I NGS J O UR N AL 2018
 W O R LD O F C O L O UR 85

Source: Dieter Hawlan - Fotolia.com

A GRUESOME TREND
During the 16th and 17th
century a pigment entitled
„mummy brown“ was popu-
lar, especially among pre-ra-
phaelite painters. One of the
main ingredients were re-
mains of Egyptian mummies,
mixed with pitch and myrrh.

SUBSTITUTES
During the early 20th century,
production decreased due to
exhaustion of the supply of
available mummies. Today,
the pigment is a mix of kao-
lin, quartz, goethite and he-
matite. It varies from yellow
to red and dark violet.

E U R OP E AN COAT I NGS JOU RN A L 06 – 2016

86 P H Y T H A L O C YAN I NE P IGMENT S
FAST FADING BLUES:
THE INSIDE STORY
Indoor durability of phthalocyanines can be worse than expected. By Roberto Mazzari. Umberto Dainese and Giovanni
Marsili (published in ECJ 02/2014).
Copper phthalocyanine pigment blues show good light and
weather fastness in exterior paints, but rapid fading has some-
times been observed ininterior applications. Light levels, bind-
er type and the photoactivity of titanium dioxide appeared to
have no significant effect. However, ozone in theair was shown
to degrade the chromophore groups in the pigment.
C opper phthalocyanine (CuPC) blue pigment is widely used for col-
ouring decorative coatings, both for interior and exterior applica-
tions. It is known to have good resistance to light and weathering [1]
but sometimes it reveals some limitations.
One representative example is the evident and unexpected colour
fading observable in certain blue coloured interior waterbased paints,
which may happen in a surprisingly short period of time. Indeed it is
detectable within a few months after initial painting and can be ob-
served by just moving an element of protection such as a picture (see
Figure 1). Conversely, when using an inorganic cobalt blue pigment
instead of CuPC the fading does not occur at all.
The purpose of the present work is to examine the indoor colour fad-
E U R O P E AN CO AT I NGS J O UR N AL 2018
ing of CuPC pigment in waterbased paints. Whereas exterior durability
of the pigment has been extensively studied in scientific literature,
researches on interior fastness are scarce.
TEST FORMULATIONS AND APPLICATION PROCEDURE
In order to determine the causes of the interior fading, an experi-
mental process was designed around six test paints made up using
each of three binders (acrylic, styrene-acrylic, vinyl-versatate) at two
different PVC levels (see Table 1). These were tinted with eight com-
mercial colourant pastes using four different forms of CuPC (Colour
Index classifications PB 15, PB 15:1, PB15:3 and PB15:4) along with
a control sample of cobalt blue (PB 28) tinting paste.
1 % by weight of each blue paste was added to the test paints. Alto-
gether the test system represents a matrix of 54 possible combina-
tions. In sample preparation, two layers of each blue paint were ap-
plied by brush on gypsum board, then dried for one week at room
temperature and, just before starting the exposure, CIE L*a*b* col-
our values were taken by means of a portable spectrophotometer.
The aim of the experiment was to recreate conditions that are the

RESULTS AT A GLANCE
űű Copper phthalocyanine blues are widely used in architec-
tural coatings. Their exterior durability has been extensively
studied, showing good light and weather fastness. However,
there are few studies on interior durability, but on occasions
very rapid colour fading has been observed in interior water-
borne paints.
űű The interior colour fading of waterbased paints containing
phthalocyanine pigment blue was therefore investigated. Nei-
ther light levels nor the photoactivity of titanium dioxide signifi-
cantly affect fading. Although some dependence was found on
PVC, binder type also had little significant effect.
űű Fading was correlated to the presence of ozone in the am-
bient air. An accelerated ozone test also showed rapid colour
fading, with a direct correlation between accelerated test and
natural exposure. XPS analysis showed how ozone interacts
with the pigment leading to chromophore group depletion.
same as an ordinary room at home. Therefore panels were placed
vertically in a part of a building well lit by both natural and artificial
light, with a normal rate of indoor air exchange (test room). Then
the CIE L*a*b* data was collected regularly and the degradation
results after seven months of exposure are shown in Figure 2.
INITIAL RESULTS REVEAL SOME CLEAR TRENDS
The initial results show a number of very clear trends.
ąą Firstly, only organic blue CuPC pigments show colour fading,
while the inorganic cobalt blue pigment shows no significant vari-
ation.
ąą All CuPC pigments have a large variation in terms of ∆E. The rate
of the phenomenon is relatively fast and can be observed in few
Figure 1: An originally blue wall paint (colour still visible in
square areas originally covered up) has completely changed
colour after a few months
P HYT HA L O CYAN I N E P I G ME N T S 87
months.
ąą CIE L* a* b* data reveal that the major variation is in the ∆b*
value, signifying that the tints have become less blue.
ąą The b crystalline form (PB 15:3) shows better resistance than the
others.
ąą The influence of the type of binder is negligible, though paints
with a lower PVC have better performance than those with a
higher PVC.
In conclusion, the tests show how different organic CuPC pigments,
considered in the present work, have slightly diverse behaviours
and the binder type has no influence, but lower PVC leads to better
resistance.
These initial results are in accordance with real paint applications:
that is, in a wide range of tints containing blue CuPC pigments, a rel-
atively fast degradation of the blue tone takes place. But what is the
likely cause? There could be either endogenous causes (something
reactive in the paint formula), or exogenous causes (something ex-
ternal to the paint).
LIGHT AND PHOTOACTIVITY OF TIO2 HAVE LITTLE EFFECT
It is well known that titanium dioxide interacts with light and it
shows photo-catalytic activity, depending on the metamorphic form
of the TiO2 and treatment. It can form radicals able to react with
organic compounds [2]. So, instead of TiO2 (rutile), a reference paint
with barium sulphate white was prepared, coloured and exposed to
the same test conditions as before.
Even though the tints are altered by the pigment substitution, the
results, in terms of ∆E, are in accordance with what was verified in
the original test (see Figure 3). Thus, it appears that colour fading
does not depend on the photo-activity of titanium dioxide.
Even if the exposure takes place indoors, natural light itself should
be identified as a possible cause of degradation. Thus in order to
check the influence of light, two sets of equal test panels were pre-
pared following the previous procedure and exposed into two test
rooms, one lighted and the other completely dark.
After four months an equivalent degradation was observed (see Fig-
ure 4). Therefore, ordinary interior illumination also has no influence
on the vanishing of the blue shade.
SEALING THE TEST PANELS PREVENTS FADING
Some reactive substances are present in ambient air, among them
some radical species and mainly ozone (O3) [3] may react with pig-
ments. Therefore two series of equal test panels were prepared
following the previous procedure and exposed into the test room,
one covered and carefully sealed by thick glass and one exposed
as usual.
After four months a remarkable difference in degradation was de-
tected (see Figure 4). In fact the glass-covered sample shows practi-
cally no colour change compared to the unprotected panel, sug-
gesting that air is responsible for the degradation.
After taking this into consideration, the behaviour of the same sam-
ple exposed in the same room in different seasons was analysed.
Figure 5 shows degradation in term of ΔE* of the same paint ex-
posed at different periods of the year, where degradation is higher
in summer than in winter season. This suggests that the likely cause
should be sought in some component of the air that increases in
concentration during the warm season.
Indeed, literature studies describe a kind of interaction between
ozone and copper phthalocyanine blue colorants as the cause of
fading [4]. In accordance with the current experimental results,
ozone has higher concentrations in summer than in winter and can
be correlated to the phenomenon. 
E U R OP E AN COAT I NGS JO UR N A L 2018
 88 P H Y T H A L O C YAN I NE P IGMENT S

 Table 1: Formulas of waterborne paints with t wo different PVCs ACCELERATED OZONE TEST SHOWS RAPID COLOUR LOSS

In order to verify this hypothesis, some samples were treated with

Formula 1 % weight (PVC Formula 2% weight (PVC
Composition
58) 82)
ozone. For this purpose an ozonising instrument was used where
a fan-cooled corona-discharge (CD) tube generates 1 g/h of ozone
Water 20.5 24.2 from pure oxygen. The ozone is then carried into a closed sample
chamber.
Dispersant 0.6 0.6 By means of this accelerated test, samples were treated for 40 min-
utes with high ozone levels and the degradation values (ΔL*, Δa*,
Wetting agent 0.5 0.5
Δb*, ΔE*) were compared with samples exposed for seven months
Cellulosic thick- in the test room (see Figure 6).
0.4 0.4
ener The final results show an almost perfect relationship between the
Antifoam 0.3 0.3 accelerated and non-accelerated tests, pointing to ozone as the
cause of blue-fading.
Coalescing agent 1.5 0.8
Titanium dioxide
16 9 REACTIONS STUDIED BY X-RAY PHOTOELECTRON SPECTROSCOPY
(Rutile)
Calcium carbon- X-ray photoelectron spectroscopy (XPS) has been used to study
35 54
ate
the reaction mechanism. XPS measures the sample’s elementary
Binder 25 10 composition and chemical/electronic state with a detection limit
between 0.001 and 1 of the atomic percentage [5]. Moreover, to be
Biocide 0.2 0.2

Figure 3: Measures of ∆E after 4 months of exposure in test

Figure 2: Measures of ∆E after 7 months exposure in test room room using different blue pigments (identified by CI numbers)
and different white pigments

Figure 4: Measures of ∆E after 4 months of exposure under dif- Figure 5: Measures of differential ∆E of test sample and rela-
ferent test conditions tionship with tropospheric ozone concentration

4
ΔE*

0
Test room Dark room Covered by glass
PVC 82 styrene-acrylic binder
15:1 b 15:1c 15 15:4

E U R O P E AN CO AT I NGS J O UR N AL 2018
 P HYT HA L O CYAN I N E P I G ME N T S 89

sure of detecting a significant signal change, the analysis was car-
ried out directly on pure colorant pastes.
To do that, the 15:1 colorant was applied on a PVC sheet. Then,
when dry, it was divided into three: one piece represents the initial
reference (t0), the second treated for 40 minutes into the ozone
chamber (1 g/h O3) and the third exposed into the test room for one
month, and finally all samples were analysed by XPS.
The survey analysis was carried out between 0 - 1350 eV to identify
all detectable elements and a more detailed scan (multiplex analy-
sis) was performed to collect the spectra of significant elements.
SPECTROSCOPY CONFIRMS DEGRADATION IS DUE TO OZONE
ąą As copper blue phthalocyanine pigment is the only component in
the colorant that contain nitrogen, an evident change and breakage
of the chromophore group of the pigment occurs when treated
with ozone.
ąą The intermediate behaviour of the test room sample shows how
just 30 days of natural exposure causes
an evident change of the chromophore group of the pigment,
explaining the fading phenomenon.
In conclusion, XPS analysis shows how oxidation occurs in both accel-
erated and natural tests, and in addition the chemical shift of nitrogen
atoms leads to a substantially modified molecular arrangement in the
chromophore groups, explaining the observed colour variation.  

The key findings of the XPS analysis are shown in Figure 7 and can be
summarised as follows:
ąą An increase of the oxygen signal was found in the treated sample
compared to the untreated, as result of the oxidation reaction.
ąą A chemical shift of nitrogen, as shown by the considerable variation in
shape and position of peaks in the spectra, is due to the new chemi-
cal bonds built up among nitrogen and other more electronegative
species.
Figure 6: CIE L*a*b* data of samples exposed in test room and
ozone chamber
REFERENCES
[1] Herbst W., Hunger K., Industrial Organic Pigments, 2004, Wiley.
[2] Kobayashi M., Kalriess W., Cosmetics & Toiletries magazine, 1997,
Vol. 112, pp 83-85.
[3] Lee D. S., Holland M. R., Falla N., Atmospheric Environment, 1996,
Vol. 30 No. 7, pp 1053-1065.
[4] Fujie Y. et al, Fujifilm R&D, 2009, Vol. 54, pp 35-42.
[5] Hofmann S., Auger and X-Ray Photoelectron Spectroscopy in Mate-
rial Science, Springer, 2013

ACKNOWLEDGEMENTS

This work has been carried out thanks to collaboration bet ween the San
Marco Group’s laboratory and the University of Padua. Special acknowl-
edgment is due to professors S. Mammi and R. Bertoncello of Padua de-
partment of Chemistry and to San Marco’s team: R. Nicoletti, M. Mazzari,
F. Toneatto, M. Pettenò, D. Minto, A. Cillotto, L. Piovesan and G. Bellato.

Figure 7: XPS multiplex nitrogen and oxygen spectra

36000
Oxygen Nitrogen
30000 12000

24000
CPS

CPS

18000 9000

12000

6000 6000

522 524 526 528 530 532 534 536 538

Binding energy / eV 388 392 396 400 404 408
t=0 ozone test room Binding energy / eV
t =0 ozone test room

E U R OP E AN COAT I NGS JO UR N A L 2018

90 FL U O R E S C E NT P IGMENT S
GLOWING WITH PROMISE
Daylight fluorescent pigments for paints, PVC and PU open up new applications in packaging. By Dr. Rami Ismael (pub-
lished in ECJ 01/2015).
Daylight fluorescent pigments (DFPs) have found wide use in
warning and safety applications, while, more recently, the
packaging industry has turned to daylight fluorescent pig-
ments, as brands look for new ways to make their products
stand out on the shelf. However, solvent-resistant, strongly
fluorescent pigments have been so far only available based on
formaldehyde containing polymers.
D aylight fluorescent pigments are colourants that absorb energy
upon illumination with daylight. The invisible UV part of the day-
light is transferred into visible light. Additionally, a variable shortwave
part of the visible light is transferred into the fluorescence colour. The
light yield is enhanced at a distinct wavelength of the perceived colour
so they appear more brilliant and look more intense compared with
conventional colours and also show a strong luminosity under black
light (UV light), while conventional colours appear dull.
APPLICATIONS OF FLOURESCENT PIGMENTS
Daylight fluorescent pigments have found wide use in warning and
safety applications, as well as marking and danger identification. Typi-
cal applications are paints for rescue vehicles or safety vests in lu-
minous orange and yellow. Their use in advertising and in consumer
brands has also been rising in recent years. Neon colours are used for
E U R O P E AN CO AT I NGS J O UR N AL 2018
eye-catching fashion designs and accessories, while magazines and
advertising posters count on the impact of luminous signal colours.
The packaging industry has become increasingly interested in daylight
fluorescent pigments, as more and more brands present their prod-
ucts in a striking manner, to stand out from the competition.
The vast majority – some 99 % – of DFPs are organic fluorescent dyes,
which are bound to a carrier resin or polymer and available as stir-
in pigments, where no grinding is needed and the compatibility with
other resins is optimal. Stability and resistance properties of the pig-
ments depend mainly on the polymer technology deployed.
Solvent-resistant, strongly fluorescent pigments have been so far only
available based on formaldehyde containing polymers. Among these,
melamine-toluenesulfonamide-formaldehyde resins, as well as ben-
zoguanamine-formaldehyde resins with lower light stability [1] can be
identified. High fluorescent formaldehyde-free pigments are partially
available on the market [1] and are characterised by low solvent-re-
sistance compared with their formaldehyde-containing counterparts.
These are based on modified polyester resins and are suitable for
applications, which do not require solvent stability like waterborne
paints, crayons, paper and target coatings.
OPTIMISING SOLVENT RESISTANCE
Solvent resistance of fluorescent (and all other) pigments can be easily
tested. The pigment needs to be grinded to a median particle size of
 FL U O R E S CENT P I G MEN T S 91

Figure 1: Reflection of "AG-103 Orange" vs. Pigment Orange 73

(same concentration, same titanium oxide parts)

RESULTS AT A GLANCE
 With the new technologies, the possibility of formaldehyde-
free production of fluorescent pigments is realistic.

 Eliminating formaldehyde in daylight fluorescent pigments

is no longer combined with compromises.

 The new technologies discussed in the paper excel in all

their attributes compared with their formaldehyde-containing
predecessors.

 A similar technology will soon allow the use of fluorescent

pigments in cosmetic products. These hybrid resins will be com-
bined with cosmetic dyes such as D&C Yellow 8, D&C Red 28,
D&C Red 21, D&C Violet 2, FD&C Blue1, FD&C Red 5 and all avail- Figure 2: Test of "AG-100 Lemon", 5 % in PVC at 175 °C
able Lake-versions of these dyes.

3–10 µm. Then 1 g of the pigment is mixed with 10 ml of solvent in a test

tube and left to stand 40 minutes in a water bath at 37 °C.
Solvent-resistant pigments should float in the tube upon gentle shaking
and should not show any tendency towards gel formation. Depending
on the degree of gel formation the pigments are evaluated between 5
(no gel formation, the best) and 1 (complete gel formation, the worst).
Common solvents are mixture of methyl-ethyl-ketone with xylene
(50:50), acetone, methanol, ethanol, propanol, ethyl acetate, xylene and
their mixtures.

Figure 3 (right): Stability properties of the formaldehyde-free

Table 1: Solvent resistance of AC-103 Orange (melamine-for- series AG-10 and AC-60 as compared with the formaldehyde-
maldehyde-toluenesulfonamide resin) compared with AG-103 containing series (AC-10 and AC-20)
Orange (hybrid resin)

"AC-103 "Ag-103
Solvent
orange" orange"
MEK: Xylene (50:50) 5 5
Methanol 5 5
Ethanol 5 5
Propanol 5 5
Ethyl acetate 4 5
Xylene 5 5
Acetone 3 5
Methyl-ethyl-ketone (MEK) 4 5
Cyclohexanone 3 5
3 % NaOH solution 5 5
Water + Ethanol 5 5 

E U R OP E AN COAT I NGS JO UR N A L 2018

 92 FL U O R E S C E NT P IGMENT S

 The formaldehyde containing (< 0,1 %) “Araco-10” (AC-10) series with its
pigments “AC-100 Lemon” to “AC-107 Magenta” is compared with the
formaldehyde-free pigments of the “Aragen-10” (AG-10) series (“AG-100
Lemon” to “AG-107 Magenta”).
Precursors of AG-10 series are modifications based on polyester resins.
The polyester resins are the basis for the “Araco-60” (AC-60) pigments,
which have a low solvent resistance. Modifications of the polyester res-
ins by the addition of amide units have led to good reflection, accompa-
nied by a low resistance to solvents.
Increasing the multifunctional parts in the polyester resin (pentaerythri-
tol) led to improvement in the solvent resistance, but to the cost of the
reflection.
Similar results have been found by increasing the multifunctional
parts in polyamide or polyurethane resins. The traditional formalde-
hyde-containing amine resins have been superior to other resins.
The AG-10 technology uses a hybrid polymer of the mentioned for-
maldehyde-free technologies. The solvent resistance is given in Table
1. Table 2 compares the reflection and the L*a*b* values that identify
the saturation, brightness and chromaticity differences between the
AC-10 (formaldehyde containing) and the AG-10 pigments (formalde-
hyde-free).
A CLOSER LOOK AT LUMINOSITY
To compare the fluorescence and thus the luminosity intensity, pig-
ments are mixed into acrylic paint. The typical reflection curve of “AG-
103 Orange” compared with conventional pigments (here Pigment Or-
ange 73) is shown in Figure 1. Similar comparisons can be created for
all the bright colours of the AG-10 series with conventional pigments.
The reflection of all colours is 2-3 times higher than with conventional
pigments. “AG-103 Orange” achieves in white pigment-free formula-
tions, a reflection of 233 % or more, as shown in Table 2.
LIGHT FASTNESS AND HEAT RESISTANCE

Figure 4: Left: LDPE film with 1.35 % "AP-100 Lemon and a Figure 5: In extrusion blow molding process produced HDPE bot-
layer thickness of 150 microns. Right: LDPE film with 1.35 % AP- tles with a fluorescent outer skin layer and a white barrier inside
100 Lemon and a layer thickness of 100 microns mounted on a layer
white layer of 100 microns

Table 2: Comparison of the reflection maximums and the L*a*b*-values between AC-10 (formaldehyde containing) and AG-10 series (formaldehyde-free)
in Acryl resin
Product Colour max. refl. WL/nm L* a* b*

"Araco-100" Lemon 190 520 109 -43 115

"Aragen-100" Lemon 195 520 110 -50 116

"Araco-103" Orange 235 610 82 85 92

"Aragen-103" Orange 233 600 86 74 89

"Araco-104" Orange-red 226 610 87 87 72

"Aragen-104" Orange-red 213 610 84 84 79

"Araco-105" Red 223 610 72 92 56

"Aragen-105" Red 212 610 74 87 54

"Araco-106" Pink 218 610 75 94 10

"Aragen-106" Pink 212 610 77 91 18

"Araco-107" Magenta 190 620 71 91 6

"Aragen-107" Magenta 182 620 72 88 3

WL = Wave length. Max. refl. = Maximum reflection

E U R O P E AN CO AT I NGS J O UR N AL 2018

In addition to the solvent resistance of daylight fluorescent pigments,
light fastness and heat resistance are important application criteria.
The new formaldehyde-free pigments exceed, even in these proper-
ties, their formaldehyde-containing counterparts. On the Blue Wool
Scale (BWS) “Araco-103” shows in orange acrylic paint (30 %), at a layer
thickness of 16 microns, a light fastness of 3, while “Aragen-103 Or-
ange” shows a light fastness of 4 on the BWS under the same condi-
tions. Experience shows that it is possible to use selected UV-absorb-
ers, a thickness of 100 microns and a pigment concentration of 30 %
to achieve light fastness of 6 in PVC. A topcoat with UV absorbers
helps to achieve a better light fastness.
Thanks to the good solvent resistance; light fastness and to the good
reflection the door is open for the AG-10 series in luminous paints
and spray cans.
For applications on the PVC calendar or in injection and blow mould-
ing a good or heigh level of heat resistance is required.
Mixtures of “AG-100 Lemon” respectively “AG-103 Orange” were test-
ed in soft PVC formulations at 165  °C and 175  °C over a period of
20 minutes. The pigment concentration was increased from 5 to 10 %.
The typical pigment concentration of 30  % was omitted in order to
better assess the effect of heat stress on the colour development. In
all tests, the colour development was uniform, and the fluorescence
of the PVC films consistently high. Through the influence of heat, there
were no odours or sticking of the mass on the roll, as shown in Figure
2.
To evaluate the heat resistance at higher temperatures, HDPE was
coloured with 1 % pigment and tested at various temperatures in an
injection moulding machine. Injection moulded in olefins “AG-100
Lemon” remains stable up to 240 °C and loses only on colour strength
and brilliance to 280 °C. “AC-100 Lemon” loses stability above 220 °C
and at 260 °C begins to show black combustion traces associated with
an unpleasant odour. However, plastic parts that were coloured with
“AG-100 Lemon” have been heated up to 280 °C without the genera-
tion of odours and showed no traces of burning and up to 240 °C with
the colour remaining stable.
Figure 3 provides a summary comparison of the main properties of
the traditional technologies of daylight fluorescent pigments with
the properties of the new AG-10 series. The results of the tests show
that daylight fluorescent pigments of the AG-10 series have multiva-
lent uses. They are equally suitable for the colouring of aqueous and
solvent-containing concentrates, inks, paints and coatings. Moreover,
they are suitable for the colouration of plastics such as PVC, PU, ole-
fins and some engineering plastics. The higher light resistance also
allows for a greater range of outdoor applications, but not sufficient
for use in car or construction paints.
OTHER FORMALDEHYDE-FREE TECHNOLOGIES FOR DAYLIGHT
FLUORESCENT PIGMENTS
In addition to the pigment series which retain their particle form in
the application, there are pigments which melt at a certain tempera-
ture in the application, without being soluble in it. This leads to high
migration fastness and improved colour strength. Melting daylight
fluorescent pigments (MDFP) use such a technology. Both series
“Araplast-10” (AP-10) and “Araplast-20” (AP-20) are formaldehyde-free
polyester amide resins, coloured with fluorescent dyes.
The colouring of solventbased paints or coatings is not possible with
MDFP technology, this fails in such media due to the poorer solvent
resistance.
AP-10 & AP-20 pigments already begin to melt at 100 °C and are com-
pletely melted at 140 °C. For this reason, and because they are par-
tially soluble in PVC and PU, MDFP pigments are not suitable for the
colouration of these polymers. On the other hand a high migration
fastness makes the use of AP-10 & AP-20 pigments suitable for the
FL U O R E S CENT P I G MEN T S 93
colouring of TPU and olefins (LLDPE, LDPE, HDPE, PP and cPP), while
the applications in polystyrene, polycarbonate and PET are limited.
The following properties are important for the colouring of thermo-
plastics:
ąą No sticking on the extruder screws during the master batch pro-
duction
ąą No, or very low, plate-out on the tools of injection moulding ma-
chines
ąą High heat resistance and acceptable to good light fastness
ąą Low odour
ąą Low level of residual monomers for low migration (efflorescence)
and for enabling blow moulding of thin layers or sheets
ąą Good fixation of the dyes to improve the migration properties of
the dyes
ąą High compatibility of the polymers, in order to prevent subsequent
efflorescence or bleed. High polymer compatibility is also impor-
tant for the production of thin layers, or films, by blow moulding or
rolling.
Daylight fluorescent pigments in plastic packaging are used mainly for
household cleaning products. Other methods, such as the blowing
of thin luminous PE films or bottles with fluorescent outer layer and
white inner barrier layer, have failed at production scale due to high
residual monomer content and plate-out of daylight fluorescent pig-
ments and their limited compatibility with olefins. In this context, the
AP-10 & 20 technology should be evaluated.
A 45 % master batch was made with AP-100 Lemon in LDPE. In the
final product, the master batch was reduced with LDPE to a final con-
centration of 1.35 % “Araplast-100 Lemon” in LDPE (corresponding to
3 % master batch).
First, a PE film was produced at 100 microns thickness and was then
mounted on a white sheet having a thickness of 100 microns. Another
film was produced with a layer thickness of 150 microns. The higher
layer thickness is necessary because the fluorescence effect without
the opaque, white background appears weaker. Film production went
smoothly and the resulting films were homogeneous and without
shortcomings, as shown in Figure 4.
The high compatibility of the AP pigments with olefins, the very low
plate-out and the very low content of residual monomers have ena-
bled the preparation of thin, fluorescent LDPE films. Previously, thin
fluorescent plastic films were only available with PVC or PU as a carrier
polymer or by coating procedures.
In another test, the melting pigments were tested in extrusion blow
moulding (EBM) process. Two extruders have produced two hoses,
which were combined in the injection tool to a two-layer bottle with
fluorescent, thin outer skin layer of 250 microns and a white inner
barrier layer of 500 microns, as shown in Figure 5.
In the course of the entire test, over 4000 bottles were produced.
The combination of outer fluorescent skin layer and the opaque white
inner layer resulted in higher fluorescence visibility. This technique
allows the use of daylight fluorescent pigments for new applications
in packaging. The white barrier layer prevents any migration of colour
towards the content and supports simultaneously the fluorescence
and brilliance.  
LITERATURE
[1] I smael R., Schwander H., and Hendrix P., 2013 Fluorescent Dyes
and Pigments. Ullmann’s Encyclopedia of Industrial Chemistry. 1–22.
E U R OP E AN COAT I NGS JO UR N A L 2018
 94 F OR M U L AT IO N TRAI N I NG
Source: bizoo_n - Fotolia.com
Dr Roland Somborn
is head of the vocational training centre
at Axalta’s Wuppertal site. Previously, he
was responsible for production reliability
at DuPont Performance coatings. In addi-
tion to education, his professional focus
lies on the formulation and production of
coating systems.
E U R O P E AN CO AT I NGS J O UR N AL 2018
METALLIC BASECOAT (CONVENTIONAL)
Special-effect paints enjoy uninterrupted and increasing popularity. Apart from the
conventional “silver” and “gold bronzes” which are in fact mostly aluminium and
copper pigments, the pearlescent pigments have become very important.
TASK
Develop a conventional metallic basecoat for
the decorative metal coating that meets the
requirements set out below. Prepare a for-
mulation and instructions for the coating and
use the questions to guide you. Take envi-
ronmental protection factors and health and
safety into account when selecting materials.
Prepare about 500g of the metallic base coat.
Then prepare a test metal sheet with the cor-
responding optical structure (surfacer, metal-
lic base paint, clear coat) and carry out the
appropriate quality controls. Note: You can
also tint the metallic basecoat with suitable
pigment pastes.
PROFILE OF REQUIREMENTS
 Binder system: Cellulose acetate butyra-
tenon-volatile matter (solids): w = ca. 17%
 Pigment-binder ratio 1:4 to 1:5 (mass)
 Bronze type: Non-leafing bronzes
 Flow type (flow cup to EN ISO 2431):
25-30 s to processing: 21 s
 Application: Spraying
 “Drying”: about 10 min at room
temperature
 Adhesion: good adhesion on a surfacer
 Sagging: good non-sag properties on verti-
cal surfaces sag-free up to about 20 µm
 Optical requirements: non-blooming
QUESTION 1
a. Give the chemical structure of cellulose
acetate butyrate (CAB).
b. Describe the properties of CAB.
c. What influence does the butyryl, acetyl
and OH content have on CAB properties?
FORMULATION TRAINING

This series was developed exclusive-
ly for the European Coatings Jour-
nal. The articles are based on a long-
running successful course of project
work undertaken by trainee paint
technicians at Axalta. The first part
presents new tasks while you can
find the answers to the homework
of the last issue in the second part.
QUESTION 2
With which binders can you achieve elasti-
fication and an increase in the non-volatile
content of the metallic basecoat?
QUESTION 3
Which solvents are suitable for the prepara-
tion of the metallic basecoat?
QUESTION 4
a. Describe the differences between leafing
and non-leafing bronzes.
b. Compare the advantages and disadvan-
tages of the one-coat metallic with those of
the two-coat metallic.
c. Describe the procedure involved in
bronze solubilisation.
d. What has to be taken into account when
formulating a water-thinnable metallic base-
coat regarding to the choice of bronze?
QUESTION 5
Which additives are mostly used when
formulating the metallic basecoat? Name the
groups of substances and their effect.
QUESTION 6
What has to be taken into account in pro-
duction and application of metallic coatings?
QUESTION 7
Define the following effects:
Flop effect, DOJ effect and sparkle effect
QUESTION 8
Name factors which may be responsible for
blooming and give hints on how to avoid this.

M0DEL ANSWERS
These are the model answers for the
“Metallic basecoat (conventional)” task
set as part of the “Formulation Train-
ing” in the March issue of the European
Coatings Journal.
BASIC FORMULATION
A. Bronze reaction
Provide and mix the following in the order
stated
ąą 3.5% glycol
ąą 2.0% butyl alcohol
ąą 1.0% N-methyl pyrrolidone
Whilst stirring slowly pour in and continue
stirring for 20 min.
50% aluminium bronze for water-borne me-
tallics
B. Basic coat production
Provide and mix the following in the order
stated
ąą 55.0 % polyurethane dispersion (20 %}
ąą 0.5% dimethyl ethanolamine solution
Slowly pour the bronze reaction (A) into the
preparation (B)
Pour whilst stirring
ąą 1.0 % thickening agent
ąą 15.0 % polyurethane dispersion (25 %)
Adjust the pH-value from 7.6 to 7.9 with
DMEA solution.
Adjust for viscosity
17.0 % volume units in water
Green pigment paste is used to obtain the
required colour.
MODEL ANSWERS - KEY QUESTIONS
RE 1: POLYURETHANE DISPERSION
The structure of polyurethane dispersions
is obtained by the polyaddition of diisocy-
anates and diols using dimethylolpropionic
acid (hydroxycarboxylic acid). The polyure-
thane chain thus gains a functionalisation
with a carboxylic acid group which can be
transferred into water dilutable by means of
neutralising with amines.
Special emphasis should be placed on the
following characteristics:
ąą good optical characteristics
ąą good adhesion on various substrates
ąą high water resistance
RE 2: GREEN PIGMENTS
Green pigments which might be used in the
formulation of water-dilutable metallic must
be dispersible to transparency.
Copper phthalocyanines are particularly suit-
able (= metal complex pigments).
RE 3: ADDITIVES
The following additives should be considered
when formulating water-borne metallic base-
coats:
ąą defoaming agents
ąą wetting and dispersing agents
ąą anti-Sedimentation agents
ąą rheology additives
ąą flow control agents
ąą antistatics (possibly with electrostatic ap-
plication)
RE 4: “WATER MOUNTAIN”
A peculiarity of water-based paints compared
with conventional paints is the occurrence of
viscosity anomalies. When the paints with wa-
ter-dilutable binding agents are diluted with
water there is no continuous decrease in
viscosity but a maximum viscosity is reached.
This viscosity pattern is generally referred to
as a “water mountain“ There are three dis-
tinct sections during dilution:
1. Decrease in viscosity (normal dilution ef-
fect).
2. Increase in viscosity to a maximum point.
Reason: The salt groups of the binding
agents are dissociated by water and
this causes the polar molecules of the
binding agent to associate (= increase in
viscosity ).
3. Rapid decrease in viscosity due to com-
plete solvation of the polymer molecules
=> no interaction between polymers.
viscosity
water mountain
(2)
(1)
(3)
additional water
The water mountain can be eliminated or at
least reduced by the following measures, for
instance:
ąą by adding water miscible co-solvents
ąą by varying the degree of neutralisation
ąą by lowering the concentration of ionic
groups in the polymer molecule
RE 5: SPECIAL FEATURES WHEN
PRODUCING THE COATING MATERIALS
When producing water dilutable coating
materials one must be careful about pos-
sible reactions between water and iron. For
this reason non-corroding materials such as
stainless steel must be used. Furthermore
F O R MU LAT I O N T R AI N I N G 95
the water mountain can cause such a sharp
increase in viscosity that the mixer cannot
mix sufficiently to achieve good homogenisa-
tion and permit further processing.
Water dilutable coating materials tend to
produce foam which can cause problems
(e.g. development of specks and limits to fur-
ther processing). Therefore the development
of foam has to be prevented by adding de-
foaming agents and by making adjustments
to pumping and mixing capacity.
Dispersions are not completely shear resist-
ant which should be taken into consideration
when dispersing.
RE 6: GASSING
“Gassing” occurs with water-borne metallics
as a result of the reaction of water and the al-
uminium surface. In this reaction, which can
arise in an acid or alkaline medium, hy­drogen
is accumulated. For this reason the alumini-
um particles have to be stabilised (protected)
by “corrosion inhibitors” or by special protec-
tive layers. The following possibilities can be
responsible for gassing:
ąą inadequate or no protection of the alu-
minium particles
ąą mechanical or chemical destruction of the
stabilisation.
RE 7: METAL EFFECT
The most decisive factor concerning the for-
mation of the metallic effect is the alignment
of the platelet-like metal effect pigments. In
“water-based paints” the rheology additives
cause a pseudoplasticity to form and result
in the effect pigments aligning.
RE 8: PARTICLE SIZE DISTRIBUTION
The particle size distribution in dispersions
can be deter­mined by laser diffraction pro-
viding that the dispersion is sufficiently trans-
parent. This involves passing a laser beam
through the dispersion which is to be exam-
ined. The laser beam is deviated and diffract-
ed at the particles depending on their size.
RE 9: DANGERS OF
GASSING WITH METALLICS
“Gassing“ metallics are potentially dangerous
for two reasons. Firstly, the container can
explode owing to the high pressure which
the gassing can cause to build up. This can
lead to the material splashing into the eyes.
Secondly, the hydrogen produced presents a
further danger since hydrogen forms an ex-
plosive and easily inflammable mixture when
combined with atmospheric oxygen. Contain-
ers of gassing material should therefore only
be opened with the utmost care and using
personal safety equipment. 
E U R OP E AN COAT I NGS JO UR N A L 2018