Cargo Tank Coatings

School of Marine Science and
Technology
Cargo Tank Coating for Chemical Tankers
By: Neofytos Giannakopoulos

Student No.: 027022476
Responsible Supervisor: A. P. Roskilly
Dissertation submitted to the
School of Marine Science and Technology
in partial fulfillment of the requirements for the degree
of Master of Science (MSc)
In Marine Engineering
Newcastle upon Tyne

Summer 2003
Cargo Tank Coatings for Chemical Tankers
Table of contents
INTRODUCTION .....................................................................................................................3
Chapter 1
WORLD FLEET OF CHEMICAL CARRIERS .......................................................................7
Chapter 2
STRUCTURE OF TRANSPORT SYSTEM.............................................................................8
Chapter 3
SHIP DESIGN AND ARRANGEMENTS..............................................................................10

3.1 Number of tanks.................................................................................................................11
3.2 Vertical Bulkheads.............................................................................................................11
3.3 Loading/Discharging System.............................................................................................13
3.4 Tank ventilation .................................................................................................................13
3.5 Cargo heating .....................................................................................................................14
3.6 Tank cleaning System ........................................................................................................14
Chapter 4
MECHANISMS OF CORROSION.........................................................................................15
Chapter 5
THE ROLE OF COATINGS ...................................................................................................18

Chapter 6
COATING COMPONENTS ...................................................................................................21
6.1 Pigment ..............................................................................................................................21
6.2 Resin ..................................................................................................................................21
6.3 Solvent ...............................................................................................................................21
Chapter 7
COATING SYSTEMS AND TYPES......................................................................................23
7.1 Zinc Silicates......................................................................................................................23
7.2 Epoxy coatings...................................................................................................................26
7.2.1 Pure Epoxies .................................................................................................................27
7.2.2 Epoxy Phenolics............................................................................................................29
7.2.3 Epoxy Isocyanates ........................................................................................................30
7.2.4 Cyclosilicon Epoxies ....................................................................................................31
Chapter 8
Mechanical properties of coatings ...........................................................................................33

8.1 Flexibility...........................................................................................................................33
8.2 Toughness ..........................................................................................................................34
8.3 Adhesion ............................................................................................................................34
8.4 Hardness.............................................................................................................................35
1
8.5 Abrasion.............................................................................................................................35
8.6 Slip .....................................................................................................................................36
8.7 Internal Stresses .................................................................................................................36
Chapter 9
MAINTENANCE AND REPAIR ACTIONS.........................................................................37
9.1 Surface pre-treatment.........................................................................................................38
9.1.1 Metal works ....................................................................................................................38
9.1.2. Sand blasting................................................................................................................39
9.2 Abrasives............................................................................................................................41
Chapter 10
COATING APPLICATION ....................................................................................................45

Chapter 11
T he role of ventilation and dehumidification..........................................................................53
1.1 Ventilation during Blast Cleaning .....................................................................................53
1.1.2 Ventilation during Application and Curing ..................................................................55
1.1.3 Dehumidification ..........................................................................................................57
Chapter 12
ABSORPTION – DESORPTION COATINGS CHARACTERISTICS.................................59
Chapter 13
CLEANING CARGO COMPATIBILITY..............................................................................67
Chapter 14
ECONOMIC COMPARISON BETWEEN COATED MILD STEEL AND
STAINLESS STEEL .....................................................................................................................70
Chapter 15
Statistical Analysis of measurements.......................................................................................74
15.1 Histograms and mean values ...........................................................................................74
15.1.2 Results analysis...........................................................................................................80
15.2 3D Representation of d.f.t................................................................................................81
15.2.1 Results of 3D d.f.t. representation ..............................................................................85
15.3 Conclusions and proposals (recommendations)...............................................................85
Abbreviations
Appendix
Glossary
References
2
INTRODUCTION
During the 19 th and early 20 th century, the manufacture of synthetic organic

chemicals depended principally on coal, limestone, cellulose and molasses. However,
early in this century more attention was given to petroleum because it was found to be
cheap, plenty and a rich source of elements required in chemical industry. [Corkhill
M. Fairplay Publ.,1981]
Following the tremendous growth of chemical industry in our days, the
chemical shipping industry carries more than 50,000 different chemical substances
and taking into account that the world petrochemical demand will have a growth of
80% by 2010, it is obvious that the demand for more sophisticated and efficient
chemical tankers will be increased too.[Advanced Polymer Coating,2002]
Furthermore, the seaborne trade in liquid cargoes can be broadly segregated
into three main sections as the following fig.1 show’s:
Fig.1: Seaborne trade in liquid cargoes, Source: International Coatings

Ltd,2003
We can see that approximately 30% of liquid trading cargoes (chemicals and
chemical products) is carried by chemical carriers.
3
A chemical tanker is defined as a tanker, which carries liquid cargoes except

crude oil and cargoes requiring no significant cooling or pressure tanks. The range of
cargoes carried by these ships is vast and includes not only chemical products but,
commodities such as vegetable oils, animal fats, molasses, wine, solvents and some
clean petroleum products and lubricants. Additionally a chemical tanker can carry
inorganic substances like sulphuric acid, phosphoric acid and caustic soda.
The first chemical tanker was built in the early 1960s and since then they have
become a fast growing sector of shipping industry.
Those ships can be categorised into three types:
• Parcel Tankers, which have been described as “liquid cargoes” are built
up to 40,000 dwt and are able to carry up to 50 different consignments.
• Bulk Chemicals Carriers, they have similar size to the Parcel Tankers but,
they have fewer tanks and they usually carry smaller number of cargoes
simultaneously, mainly easy chemicals like vegetable oils or acids.
• Small Chemical Tankers, generally they are under 10,000 dwt and used in
short sea trades. Despite their size these ships can also be highly complex
and expensive to be built.[Corkhill M., Fairplay Publ.,1981]
The chemical tanker is a very special type of ship due to the complexity and
the particularity of the cargo. And that’s because the cargo is extremely corrosive like
methanol, sulphuric acid, caustic soda, acetic acid and virgin naphtha. So most of the
times, much attention is given to the cargo tanks and to their ability to ensure the
integrity and the purity of the cargo.
Many times chemical tanker owners have invested large amounts of money
building ships with stainless steel cargo tanks. In general stainless steel is considered
to be the ideal material of construction, being non corrosive and easy to clean.
However, not all cargoes can be carried in stainless steel tanks. So many vessels
carrying chemical substances have cargo tanks made of mild steel coated with special
coatings systems able to prevent corrosion of the steel and protect the cargo from
contamination by contact with the steel. Of course the coatings cannot stand forever,
so a periodically survey and maintenance should be carried out.
4
Cargo tank coatings can be categorized into two main groups:

a) Inorganic coatings – zinc silicates and ethyl silicate types
b) Organic coatings- epoxy and modified epoxy systems
Each of them has good and bad characteristics:

Inorganic coatings are one-layer coatings, comprising of inorganic silicates
pigmented with high percentage of zinc powder. The paint film is porous so the cargo,
after the discharge of the ship, can be completely removed from the coating by
evaporation but it cannot be happened the same with high-density cargoes like lube
oils. Generally the life of those coatings is proportional to the thickness of the coat.
Organic coatings consist of an organic resin system which when is mixed with
a hardener it forms a cross-linked array of chemical bonds between the resin
molecules. Those types of coatings have the ability to resist in more strong acids or
alkalies than inorganic coatings and they tend to absorb significant quantities of cargo
and contamination problems can still occur.[Jones D., 2002]
Today’s state of coatings can be categorized as:
• Pure epoxy
• Epoxy phenolics
• Epoxy isocyanates
• Alkaline zinc silicate
• Ethyl zinc silicate
• Cyclosilicon epoxy [Ackermann N.,1998]
One important factor, which determines the performance of coating, is the curing
process and the adhesion of coating on the metal surface. Curing is done in ambient
temperature or with high velocity hot air applied into the tanks. Very important factor
regarding curing is the time and relative humidity.
If we consider a coating system as an epoxy/amine coating where the epoxy is the
first component of the coating and the amine is the curing agent, then the epoxy and
the amine will react together. As the curing continues the molecules will become
greater and they will continue to grow until a “gel” is formed. When the “gel” is
5
formed, the epoxy molecules cannot be more soluble to the solvent. This means that
the molecules do not move free as previously.
When the greatest amount of reaction has taken place and the biggest amount of
the solvent has escaped the system then the system can be consider to be cured.
The coating system can be further be cured in order to achieve better properties of
the coating by increasing the “environment” temperature. In this way we obtain to
assist further the molecule mobility and thus further reaction between epoxy and
amine molecules. At the end most of the solvent has escaped the system. This heat
treatment is known as the “post-curing” and the final film has better properties than
the simple cured film.
Many case studies have been made about the cost of building a chemical tanker
with stainless steel or building it with coated mild steel. The results show that a vessel
with mild steel tanks costs almost the half and further more applying the latest coating
technology, the income could greater than the one with stainless steel cargo tanks. But
the final decision is up to the ship owner to choose the most suitable-reliable coating
system for each cargo type. [Advanced Polymer Coatings,2002]
At the second part of this project, a statistical analysis of the dry film thickness
has been made. The purpose of this analysis was to explain any irregularities of the
final d.f.t. by using the given data. This analysis is composed by calculation of mean
values of d.f.t of each surface and understanding of the distributions of measurements.
Also a 3D representation of d.f.t. has been done for each surface of the tank in
order to specify the variation of coating thickness with respect to the distance of
measurements
The coating applied on a chemical’s tanker cargo tanks (not a modified chemical
tanker), which were constructed of flat welded plates and corrugated bulkheads.
A three layer epoxy coating system was applied on a blasted metal surface with a
roughness profile of 60-80 microns. The air temperature into the tank was 37 C for the
first layer, 34 C for the second and 36 C for the third. The values of relative humidity
were 33%, 40% and 24% respectively. The data, measurements were provided by a
subcontractor. The specified d.f.t according manufacturer’s specifications was 300
microns. The maximum allowed diminution was 10% or 290 microns.
6
Chapter 1
WORLD FLEET OF CHEMICAL CARRIERS
As the demand for chemical commodities keeps growing every year, the
number of new building chemical carries starts growing too. Thus the number of
trading carries has risen from 1859 ships to 2534 into one decade (1992-2002), which
corresponds to an increase of 36%. And taking into account that the world
petrochemical demand will have a growth of 80% by 2010, it is obvious that the
demand for more sophisticated and efficient chemical tankers will increase too.
At the following graph 1 this increase can be illustrated:
No. of ships
3000
2500
No. of ships
2000
1500
1000
500
0
1990 1992 1994 1996 1998 2000 2002 2004
Years
Graph 1.1:World chemical carrier fleet, Source: World Fleet Statistics
7
Chapter 2
STRUCTURE OF TRANSPORT SYSTEM
The structure of the transport system can be represented by the following fig .2.1
Fig. 2.1:Chemical carriers transport system structure, Source: Stopford,2003
On the right side are listed the commodities which appear to be carried by parcels of
under 10,000 dwt. On the left there are three fleets which transport these parcels. The
fleet of small tankers in which each vessel has a dwt. under 10,000 tones, the fleet
with vessels of dwt. between 10,000-20,000 tones and the parcel tanker fleet in which
each vessel has a dwt. range between 10,000 tones to 50,000 tones.
The parcel tankers are often operated by big companies and offer liner services
for large parcels. They arrange transport on a contract of affreightment in order to
meet the needs of the trade. However, they also take cargoes from the spot market
when the destination fits in the operating pattern and the freight rate is satisfactory.
8
The medium size vessels operate on the spot market, grouping together several
spot parcels on a voyage basis.
Finally the smaller tankers operate on the spot market, picking up whatever
parcels are available. These small tankers tend to operate particularly in the region of
Europe and Asia. [Stopford, 2003]
9
Chapter 3
SHIP DESIGN AND ARRANGEMENTS
The design of a chemical tanker is regulated by the IMO Convention on the

Carriage of Dangerous Chemicals by Sea. This divides the chemical cargoes and the
cargo tanks into three categories:
• IMO Type I
• IMO Type II
• IMO Type III
The most hazardous liquids must be carried in Type I tanks. This type of cargoes,
when they are released in the sea they build up in marine environment and marine
organisms.
Tankers approved for the carriage of these chemical must have double bottoms
and be located not less than one-fifth of the ship’s breadth from the ship’s sides
measured at the water line. So most of the times the Type I tanks are located in the
centre of the ship.
Type II tanks must also have a double skin to be protected by collision. Type
III can be carried in standard tanks. [Stopford,2003]
The above arrangements are illustrated in the fig.3.1
Type I Type II Type III

Fig.3.1: Cargo tank arrangements with respect to the type of cargo, Source:
Polish Register of Shipping, 2001
10
3.1 Number of tanks

The number of cargo tanks has to be carefully evaluated so as many as
possible of them to be filled up to 98% of the volume, during the voyage.
There are limitations referring the volume of the tank with respect to the type of cargo
they are design to carry. So for a Type I the tank size should have a max. volume of
1,250 m3 and for a Type II should not exceed 3,000 m3 . However, the final dwt. of the
ship will play the most effective role in order the number of tanks to be determined.
[Corkhill M.,1981]
3.2 Vertical Bulkheads

There are four types of vertical bulkheads used in chemical tanker
construction:
1. Vertically corrugated bulkheads
This bulkhead is very efficient. They can be used to border tanks in both longitudinal
and transverse direction. However, when the length exceeds 6 m. additional
strengthening should be applied.
2. Horizontally corrugated bulkheads
This type has become common for tankers grater than 5,000 dwt. They intend to be
installed in only one direction
3. Plane with horizontal stiffeners
This type is most popular in larger tankers especially as longitudinal bulkheads with
horizontal stiffeners and vertical webs arranged on the outboard side of the bulkhead
in the wing tanks.
4. Sandwich or Double skin Bulkheads
This type has many advantages in that provides a cofferdam to segregate incompatible
cargoes and to give an effective barrier between two cargoes being carried at different
temperatures. This type is commonly used for neighbour tanks which are made of
different steel (stainless steel, mild steel).
Some of the above types are illustrated in the following fig. 3.2
11
Fig.3.2: Types of bulkheads, Source: Stopford, 2003
12
3.3 Loading/Discharging System
The loading / discharging system is consisted from cargo pipelines, pumps and
valves. Some requirements should be taken into account during the deign of a such
system.
1. The system should have minimum length of pipes
2. The charging of the tanks should be direct
3. The cargo pumps and their position should be considered
4. Closing and safety valves should be taken into account
5. The system should be easily cleaned and accessed
Also the types of materials used for the pipelines should be compatible with the cargo
type.
3.4 Tank ventilation

All cargo tanks should be provided with a venting system appropriate to the
cargo being carried and this system should be independent of the air pipes and venting
systems of all other compartments of the ship.
The tank venting system should be designed so as to minimize the possibility
of cargo vapour accumulation above the decks, entering accommodation and
machinery spaces. Also entrance of water should be avoided into the cargo tanks and
at the same time neither pressure nor vacuum created in the cargo tanks during
loading or discharging.
Two types of venting systems are used:
1. The open tank venting system. It is consisted of individual vents for
each tank
2. The controlled tank venting system. It is a system in which pressure –
vacuum relieve valves are fitted to each tank to minimize the pressure
or vacuum.[IBC Code,1998]
13
3.5 Cargo heating

For some cargoes is required to be carried at certain temperatures. For that
reason heating coils are installed in the cargo tanks to keep the cargo at a relative
temperature. The heating substance is oil or water coming from a heat exchanger, so
that the cargo will be carried at a desired range of temperatures. [ExxonMobil, 2002]
3.6 Tank cleaning System

The tank cleaning system is very important because the possibility of cargo
contamination is depended on great percentage from the cleanness of the tank. A
vessel caring two products requires only a simple system. But, a parcel chemical
tanker needs a more sophisticated cleaning system, which incorporates:
1. Tank cleaning pump
2. Tank cleaning heat exchanger
3. Tank washing machines
4. Water distribution pipeline
The washing solution might be fresh water or chemical substances suitable to clean
the tanks at relative temperatures. [Corkhill M. Fairplay Publ.,1981]
14
Chapter 4
Mechanisms of Corrosion
Corrosion can be defined as “the destruction of a metal by an electrochemical

reaction with its surroundings”. Experiments have shown that iron will not rust when
it is in dry air, nor in water which is free from dissolved oxygen so both oxygen and
water are necessary in the corrosion process. The process of corrosion will be
accelerated with the presence of an electrolyte into the solution, especially when it is
acid or base.
The chemistry of corrosion is described above.
In simple terms corrosion can be expressed by the chemical reaction
Aa+bB=cC+dD where A is the metal and B the non –metal reactant (reactants) and C,
D are the products of the reaction. In other words it is an electrochemical reaction of a
metal with its environment. What actually happens can be seen at the following fig
4.1
Fig.4.1 Corrosion kinetics. Source: http://www.marineengineering.co.uk, 2003
The iron reduces to iron ions at anode, the oxygen is reduced by combining
with water and electrons passed from the anode (by iron changing to ions) to hydroxyl
ions. The oxygen reacts with the Fe2+ to form ferrous oxides (Fe2O3, FeO), which are
a reddish brown loose deposit.
15
Generally corrosion is categorized into two groups:

• ‘Dry’ corrosion, where a reaction takes place between the metal and the gas
or vapour. The gas could be air, halogen, etc. A characteristic of this type is
that the initial oxidation of the metal, reduction of metal and the formation of
compound must occur at one and at the same place at metal/non-metal
interface.
• ‘Wet’ corrosion, which is the oxidation and reduction of the metal in a
solution. The oxidation here occurs at different areas of the metal. In this case
what happens is a transfer of electrons through the metal which is the anode
to electron acceptor reducer which is the cathode. [Shreir L.L.,1994]
There are many types of corrosion. Some of them are: atmospheric corrosion,
chemical, galvanic, stress, electrical, pitting. So corrosion may take a variety of form
that range from a uniform loss of thickness to a highly localized attack resulting in
pitting and cracking of structure.
The environment is an essential feature in determining the corrosion behaviour of
metals. Sometimes slight changes can have significant effect on corrosion
performance. The following fig. 4.2 shows the effect of PH on corrosion rate of steel.
Fig.4.2Corrosion Rate vs PH , Source: Tomashov N.D.1966
In chemical tankers most of the cargoes are organic and inorganic substances
so it is essential to coat them in order to prevent corrosion of tanks. However, due
16
to break down of coating system corroded areas and spots may be developed. The
following pictures are representative examples of corroded steel of cargo tanks of
modified chemical tanker.
Pic.4.1:Corroded metal plaques, Source: Maroudis G., 2003
17
Chapter 5
The role of coatings
Basically the main purpose of coatings used in marine environment is the

protection of hull from corrosion. In operational terms, it is a way of increasing the
“life” of a metal structure or plate.
In the case of cargo tanks the role of a coating is double. Firstly the coating
system has to generate an isolation barrier between the mild steel plaque and the
corrosive cargo substance. Secondly it must have very smooth surface to provide easy
tank cleaning. Additionally the absorption/desorption characteristics must be good
enough so that minimum cargo substance is absorbed, and this quantity should be
desorbed in its greatest percentage and the faster as possible.
Furthermore the coating system should ensure the following:
• Prevent or minimize the penetration of film coating from any element of
cargo.
• Resist corrosion products that may develop from or on the substrate
• Form full and continuous film with a high level of integrity and low levels
of moisture vapour transmission
• Performing excellent adhesion and cohesion
Although most coatings are manufactured having the above features, most of the
times fail because of several reasons like bad application or weather conditions. So
the scope is to minimize the failures and maximize the life of coatings. [Dromgool,
1996]
The coating protection mechanism is composed by three sub-mechanisms:
First mechanism:
By the barrier protection, the dried film blocks oxygen, moisture and any corrosive
environment from the metal. However, all coatings cannot prevent by 100% their
penetration by the corrosive elements and this property is called permeability. Typical
barrier coatings are two-part epoxies (e.g. epoxy amines).
18
Second mechanism:
Coatings that protect by inhibition contain special pigments to inhibit the corrosion
reactions on the steel surface.
Third mechanism:
Coatings with sacrificing action contain zinc in powder form. Zinc is more active than
steel. So if zinc is in contact with steel and this system is present into a corrosive
environment, then the zinc will corrode to protect steel. Most of the times zinc is
contained in the primer. [Barnhart R.,1997]
Depending the kind of coating we are going to use, we define the number of
layers that steel is going to be coated. For example, zinc silicate coatings are applied
as one layer while epoxies can be applied as two or three.
So if we examine a three layer coating system, then each layer will have its purpose.
The following fig.5.1 shows the coating system
Fig.5.1: Three layer coating system, Source: Caridis P.,1993
The primer is the first coat applied to the surface. It is very important because
it ensures the adhesion of coating on the surface. Surface preparation helps the coating
stick by removing contaminants that interfere with bonding and by creating a profile 19
or roughened surface. Many primers for steel also contain anti-corrosive pigments that
actively assist the control of corrosion.
The intermediate coat or undercoat, is required in many coating systems and
may provide one or all of the following functions: improve chemical resistance, serve
as an adhesion coat between the primer and topcoat when the primer and topcoat are
not compatible, and increase the thickness of the coating system.
The finishing coat is the final coat applied. Topcoats are formulated to
improve the chemical and weather resistance of the coating system, and provide
characteristics such as: colour, gloss and wear resistance.
20
Chapter 6
Coating components
Generally the coating is consisted by three components:

• The pigment
• The resin
• The solvent
Each one has its purpose and their mixture provide the final coating properties.
6.1 Pigment
The pigment is used to distinguish the types and number of coatings. Is a
relatively insoluble element of the coating system. It is well known for the colour
characteristic, which gives to the coating. Additionally, it assists corrosion resistance,
adhesion characteristics and decreases moisture permeability. They can be categorized
as inorganic and organic. They are used because they enhance the anti-corrosive
coating characteristics and for aesthetic purposes. [Weldon D., 2001]
6.2 Resin
The resin plays the most important role at the film formation. It holds the
pigment particles together and binds the coating to the metal surface. Also it has
significant effect on the durability, strength and chemical resistance of the final film.
Additionally forms the final membrane upon which depend many of its basic physical
and chemical properties. Generally the coating systems are categorized according the
type of resin. [Chandler K., 1985]
6.3 Solvent
The primary role of solvent is for application. The solvent provides the coating to be
taken out of the can and be applied on the surface, dissolves the film-forming
ingredients and provides flow out of the coating once it is on the surface and
contributes to the drying, adhesion, of the final film. Furthermore the solvent is the
main component, which helps the resin and cure agent molecules to react.
21
Additionally the solvents evaporate, in a their greatest percentage, and they are not
taken into account as parts of the dried film coating. Some times the coating system
might contain more than one solvent each of which has a certain role like to dissolve
the resin and control evaporation. [Barnhart R.,1997]
22
Chapter 7
COATING SYSTEMS AND TYPES
During the last 30 years, several types of coating have been used for tank
lining service in the sea trades. Some of these coating materials have stopped to being
used for lining materials and new more reliable and flexible in performance have been
developed. Today’s typical coating systems can be categorized as follows:
7.1 Zinc Silicates

Zinc silicates are generally a two system formulations, consisting of zinc
powder which has particles size of 5~9 microns and inorganic or organic binder. The
zinc powder may be blended with lead and iron oxides to provide improved spray
application properties.
The silicate binder may be water based with potassium (inorganic) silicate
blend or alcoholic (organic solvent) solution, in order curing take place.
Post-cured silicates normally have an aqueous base and require application of
a chemical curing solution to harden properly. Self- cured silicates may be aqueous or
solvent -based and do not require application of curing solutions.[Goldie H.,1973]
Most of the times are applied as one coat, which acts as a barrier between steel and
corrosives. However, they are not resistant to strong acids and bases. This means that
in practice these coatings are suitable only for cargoes, which have PH range of 5.5-
10. [Haga Per Roar ,1983]
Zinc silicates are unusual coatings, are one of the few coatings which are
designed so that all of the solid pigment particles are not coated with polymer and all
of the gaps between particles are not filled with polymer, i.e. they are designed to be
porous films.
23
Fig.7.1 Zinc Silicate coating system, Source: Mitchell M. & Summers M.,2002
At the following fig 7.2 we can see that as the percentage of solid zinc is increased the
percentage of gaps is decreased.
Fig.7.2 Zinc Silicate coating system with respect the zinc percentage, Source:
Mitchell M. & Summers M.,2002
It is obvious that the best performance in chemical resistance will be achieved with
the maximum zinc percentage.
Coatings, which are water based are the Alkaline Zinc Silicates, they may be
composed of water-dissolved sodium silicate, potassium silicate or lithium silicate.
The curing of coating occurs by the reaction between the zinc powder (pigment) and
the binder silica gel (binder). The binder is supposed to react also with the steel
substrate, forming a chemical form that results in outstanding adhesion. This chemical
bonding to steel surfaces avoids undercutting of coating.
The curing mechanism and coatings formation is supposed to occur in three
stages:
24
1. Initial reaction involves concentration of the components by water

evaporation. This brings the zinc and silica into close contact, providing a
moist coating on the substrate. During this stage, wetting agents in the paint
enhance contact of the coating film with the steel surface.
2. At the second stage insolubilisation of the coating film, caused by the reaction
of zinc ions with the silicate, and formation of the initial zinc silicate will
occur. After this reaction a solid coating on the metal surface has formed. The
mechanical and chemical properties are acceptable but the film has a porous
structure.
3. The third stage of reaction is composed by the action of carbonic acid formed
by the carbon dioxide and moisture on the coating surface. The carbonic acid,
when penetrates the coating film reacts with the free zinc particles completing
the formation of a dense zinc silicate matrix.
Curing or hardening of the coating takes place by hydrolysis of the soluble

silicate followed by interaction with the zinc to form an insoluble zinc/zinc silicate
complex. For self -cure formulations only atmospheric moisture is needed to complete
the chemical reaction since atmospheric CO2 creates carbonic acid with moisture. On
the contrary, at the cure of post- cure types, hydrolysis requires application of an
acidic solution by spraying it on the coating. The acidic solution (acid phosphate) is
sprayed after evaporation of water and forms insoluble silicates and phosphates. The
excess acid is removed from the surface.[Jones D.,1992]
Generally, the curing depends on the silica to alkali ratio (the higher the ratio
the faster the curing), the type of alkaline metal (lithium silicates offer the earliest
insolubilisation) and the size of zinc particles (finer particle sizes may cause cracks).
Ethyl Zinc Silicates are solvent borne coatings consisting of ethyl silicate and
zinc powder. The curing procedure is similar to the Alkaline Zinc Silicates but now
instead of water, solvent is evaporated.
Despite there are similarities in coating formation there are differences at
application.
25
So Alkaline Zinc Silicates, cannot be applied by airless spray equipment due

to high content of metallic zinc powder, dehumidification and ventilation during the
drying and curing stages 1&2 are critical, they are applied in a single coat with a
range of 75~125 microns due to crack formation.
On the other hand, Ethyl Zinc Silicates can be applied by airless spray since organic
zinc silicates have lower content of zinc powder, the drying conditions are less critical
with relative humidity be greater than 60%. The main problem is the difficulty of
respraying low dry film thickness areas since adhesion problems may occur at the first
coat.[Ackermann N.,1998]
Although the physical properties (i.e. hardness and abrasion resistance) vary
according to the type of silicate used, chemical resistance and cargo compatibility are
very similar. These coatings are normally applied as a single coat of 75~125 microns
to a blast clean metal surface. They are sensitive to quality of surface preparation and
blast cleaning to a white metal finish is necessary (Sa3).[Rogers J.,1971]
Generally, the above coatings have an extremely high resistance and tolerance
to aromatic hydrocarbon solvent such as benzene and toluene, alcohols and ketones.
They are not resistant to acids or alkalis, including sea water which has a slow
deteriorating effect. Vegetable oils and animal fats are unsuitable but halogenated
compounds are suitable provided that tank surfaces are free of moisture. Any moisture
will react with the cargo and release acids, which will damage the coating. Also the
cargo should not contain any moisture for the same reason.
So it is important that both tanks and cargo will be free of moisture. [Corkhill M.
Fairplay Publ.,1981]
7.2 Epoxy coatings

Epoxy coatings are generally suitable for the carriage of alkalis, glycols,
seawater, animal fats and vegetable oils but, they have limited resistance to aromatics
such as benzene and toluene, alcohols such as ethanol and methanol. In other words
are blends of polymers of varying molecular weights. They contain curing agents in
order to cure fast and they are 75~90 % solids by volume. They have very good
chemical resistance and they applied as two or three layers.[Salem Linda S,1996]
26
These coatings have a tendency to pick up slight traces of the product carried,
especially those chemicals which have only a limited suitability. Alcohols, esters,
ketones have a tendency to soften the coating and in this condition the coating is more
likely to absorb small amounts of cargo. A “fingernail test” can be used to establish
the hardness of the coating. If the fingernail is able to penetrate the coating, it is still
considered to be soft, in that case the tank is vented thoroughly before water washing
is carried out.
Generally these coatings are suitable for the carriage of animal and vegetable
oils provided the acid value does not exceed 10 (i.e. free fatty acid content of 5%).
However, oils or fats with acid value between 10 and 20 may be acceptable for
limited time of carriage. Molasses is acceptable in epoxy provided the PH is above 4,
although dilute solutions may become acidic and attack the coating. Such situation is
remedied by adding an alkali to keep PH in acceptable level. [Corkhill M. Fairplay
Publ.,1981].
Epoxy coating can be categorized according to the resin that they will be
mixed as follows:
7.2.1 Pure Epoxies

Pure epoxy coatings are based on bisphenol and epichlorhydrin resins
reacting, through their terminal epoxide groups, with hardeners having polyfunctional
–NH2 groups which are called polyamines.
H2N-CH2 CH2-NH- CH2- CH2NH2
[Source: Rogers J., 1971]
These reactions allow chain extension and/or crosslinking to occur without the
elimination of small molecules such as water. Therefore epoxy resin products have
lower curing shrinkage than many other types of thermosetting plastics. There is a
wide range of epoxy resins and a great diversity of crosslinked products can be
obtained. The chemical structure of epoxy resins consists of epoxy and non-epoxy
parts. The non-epoxy part may be aliphatic, cycloaliphatic or highly aromatic
hydrocarbon. In practice the reaction products of bis-phenol A and epichlorohydrin
dominate the commercial market. The epoxy is a highly reactive functional group and
27
can be crosslinked to form a network structure in the presence of curing agents or

hardeners[ Virt-u,2003]. The properties of cured pure epoxy products depend on:
• The type of epoxy

• The type and quantity of hardener
• The degree of cross-linking
• The nature and quantity of additives Z Y
Chemical resistance and mechanical properties of epoxy coatings may vary.

The factors which, influencing these properties are the molecular weight of resins, the
type of hardener (curing agent) and the pigmentation and solvent mixture.
Low molecular weight epoxy resins results in coating films with a higher
density of three-dimensional crosslinkings as well as a lower number of hydroxyl
croups. Therefore, low molecular weight epoxy resins offer better chemical and water
resistance than medium molecular weight epoxy resins, which, on the other hand offer
better mechanical resistance and flexibility.
The most valuable property of epoxy resins is their ability to transform from
the liquid state to tough, thermoset solids. The conversion is accomplished by the
addition of a chemical compound, the curing agent. Depending the type, curation may
occur at ambient temperature or may require post heating.
Amine cured agents provide good chemical resistance to epoxy coatings,
while polyamide-cured epoxies show more surface tolerance and better mechanical
properties. The later are more preferable because they offer superior solvent
resistance.
Generally this type of coating is used because of its versatility, resistance
range and application properties. A pure epoxy coating can be applied by airless spray
at medium to high dry film thickness without sagging, cracking or pinholing.
However, the maximum overcoating intervals are relatively short (three to five days),
requiring a tight application schedule.[Ackermann N.,1998]
28
7.2.2 Epoxy Phenolics

They are multifunctional epoxy resins made by the epoxidation of phenolics
resins with epichlorhydrin. This type of amine-cured resins result’s in polymers with
very high crosslink density, offering outstanding chemical resistance. However, most
epoxy phenolic coatings require heating to 50 ~70 C for four to five days to reach
their full resistance range.
Generally, the chemical resistance of heat-cured epoxy phenolics against
strong solvents and fatty acids is better than pure epoxies. From practical point of
view, however, heat post-curing poses several problems. To keep the cargo tanks at
the required temperature, they must be loaded with an inert cargo (i.e. lube oil) and
heated with the heating coils. This procedure is usually insufficient to reach 50~70 C
in areas such as deck –heads and bulkheads, requiring the use of auxiliary heaters in
the double skin compartments as well as the construction and heating of provisional
air casings (void spaces made of staging which trap into blown hot air) on the deck
areas above tank ceilings. Today the heating can be easily achieved by blowing hot air
into the tanks but it is quite difficult to ensure that all tank areas are kept constantly
and uniformly at the required temperature for long periods.
It has been observed that without heat treatment, the chemical resistance of
epoxy phenolics improves after a service tome of at least three months if only
moderately aggressive cargoes are carried, but it does not acquire the full resistance
range of heat –cured coatings.
Properly formulated epoxy phenolics coatings have application properties
similar to pure epoxies but usually longer overcoating times, making recoating less
critical. On the other hand, they may create more overspray due to their stronger
solvents, which are evaporated faster. A coating system with a dry film thickness of
more than 700~ 800 microns, which may occur at critical areas such as angular
welding seams on bottoms and ceilings may cause cracking through the whole coating
film. Usually this phenomenon appears only after a salt-water test and cannot be
detected during application. [Ackermann N.1998]
29
7.2.3 Epoxy Isocyanates

Higher molecular weight epoxy resins can be crosslinked with polyisocyanate
with polyisocyanate compounds. This reaction occurs at room temperature and the
isocyanate reacts with the hydroxyl groups of epoxy resin. So a densely crosslinked
structure with excellent chemical resistance is obtained.
Cured epoxy isocyanates offer a resistance range similar to heat-cured epoxy
phenolics, the only exception is that cannot carry alkaline cargoes with high
concentrations. Most cargoes can be carried after a curing of ten days. Very
aggressive cargoes such as methanol can be carried after a three-month service period.
It has been mentioned the cure occurs at ambient temperature however, epoxy
isocyanates are more difficult to apply than pure epoxies or epoxy phenolics and they
have more critical application properties. For example, because they need rapidly
evaporated solvents, overspray may be a problem and they are sensitive to
overthickness. So the dry film thickness of the whole system is small and crack may
occur at 150 microns. Most of the times the crack can be observed with naked eye
after drying, however some times it is visible only with magnifying lens because the
crack does not split the whole coating film. Therefore, it will not result in rusty spots
during the salt-water test. [Ackermann N.,1998]
Areas usually affected by cracking are angular welding seems and corroded
spots (pitting). Stripe coated areas, if overcoated before they are completely dry, can
cause cracking or blistering. To eliminate this problem, each coat must be inspected
for cracking and defected areas should be repaired. Paint defects such as sagging and
orange peel must be also eliminated because they are associated with cracking.
These application problems as well as health problems are the main reason for
reduced usage of epoxy isocyanates. However, if they are used they can offer
excellent resistance to aggressive cargoes, especially in the case of newbuildings. In
the case of repair they may not be recommended because at heavily corroded steel it
will be difficult to avoid overthickness on pitted areas.
30
7.2.4 Cyclosilicon Epoxies

These coatings are based on a new resin, which is essentially a cyclic silicon
structure with five epoxidised phenol groups, that are cured by means of catalyst to
give a highly crosslinked polymer. In other words these coatings are a two-component
paint based on Siloxirane, a patented polymer with an organic/inorganic matrix.
More precisely Siloxirane consists of SiO- rings as a backbone forming a
homopolymerized thermoset (heat cured) coating resin with high chemical resistance
and good mechanical properties. [Advanced Polymer Coatings,2002]
The homopolymerized thermoset resin has an oxygen to carbon linkage with high
dense and cross-linked molecular structure. Also the absence of –OH eliminates the
failure of building other types of polymers. [Keehan Don,2001]
Polymerization occurs with transformation of epoxy groups into ethers
resulting in this way and after curing in strong ether (carbon-oxygen -carbon) linkages
without hydroxyl or ester groups. So in this way we avoid the attack of acid or
hydrolysis to the coating system.
The combination of a very densely crosslinked structure and strong chemical
bonds makes the resin to perform excellent resistance to penetration by the most
aggressive solvents, acid and alkaline cargoes.
In contrast to the other coatings, cyclosilicon coatings are much more resistant
because of the two following main reasons:
1. The higher bond strengths of the Si-O bond, which form the backbone of
the inorganic polymer chain make them more resistant compared to the C-C bond
strength of the organic polymer chain.
2. The Si-O bonds are already oxidised making them resistant to atmospheric
oxygen and most oxidising chemicals. [Andrews Adrian F.,2002]
3. The measured internal stresses give very low values when compared to high
solid epoxies. This could be due to the lack of diluents which are often found in
epoxies. [Mitchell M. & Andrews A.,2002]
31
Manufactures claim that cyclosilicon coatings can resist up to 98% of the sea-
trade cargoes, including cargoes which are unsuitable for stainless steel. Additionally
these coatings have very low absorption characteristics. As a result they can offer
significant advantages over conventional coatings regarding the cargo range, cargo
handling and tank cleaning.
The coating is applied as a two-component paint. It can be applied like a
conventional organic coating with partial curing taking place at room temperature,
then the curing time will range from four to five days. However, for the full chemical
resistance range, heat curing at 80 C for at least eight hours with hot air is necessary.
Moreover, the coating system is sensitive to overthickness. Maximum dry film
thickness should not exceed 500 microns because of the risk of solvent entrapment or
cracking. Also overthickness could be a problem when recoating older tankers with
corroded structures since the barrier of 500 microns could be exceeded.
The coating systems can be summarised at the following table7.1:
Coating Systems for Cargo Tanks
Surface Coating System Minimum Number of
Preparation DFT stripe Coats
ISO 8501-1 Sa 2.5 Epoxy primer 100 microns 2
Epoxy undercoat 100 microns
Epoxy finish 100 microns
ISO 8501-1 Sa 2.5 Epoxy phenolic primer 100 microns 2
Epoxy phenolic undercoating 100 microns
Epoxy phenolic finish 100 microns
ISO 8501-1 Sa 2.5 Epoxy isocyanate primer 90 microns 2
Epoxy isocyanate undercoating 90 microns
Epoxy isocyanate finish 90 microns
ISO 8501-1 Sa 2.5 Zinc Silicate 80 microns 1
ISO 8501-1 Sa 2.5 Cyclosilicon epoxy 150 microns 1~2
Cyclosilicon epoxy 150 microns
ISO 8501-1 Sa 2.5 : Preparation of steel Substrates before application of paints and
related products-Visual assessment of surface cleanliness.
Table 7.1. Coating Systems for Cargo Tanks: Source: Ackermann N.,1998
32
Chapter 8
Mechanical properties of coatings
Generally, the performance of a coating describes how well it is carrying out

its function in service. No matter how, good the chemical properties of a coating are,
in order to fulfill its function, has also to provide adequate mechanical properties.
The mechanical performance of a coating describes how it responds to stresses and
strains imposed during service. The main mechanical properties of coating can be
categorized as :
8.1 Flexibility
Flexibility is the ability of a coating to be bent or flexed in forming operations
without cracking, losing adhesion, or failing in some other manner
In the case of a ship the whole structure, including cargo tanks, are subjected to
deformations during service. Additionally, stresses on the structure are appeared
during the loading of ship or when close tanks are charged with different kind of
cargoes. The following fig.8.1, show’s the elastic deformation of a chemical tanker’s
structure due to uniform loading.
Fig.8.1:Deformed plot, uniform loading, Source: Lloyd’s Register Technical

Association, 1995
33
So the coating should have a degree of elasticity to remain on the steel surface
without any crack to occur.
The same elastic behaviour of coating system should be provided during plastic
deformation of tank components.
The following picture 8.1, show’s that no crack of coating has occurred during the
plastic deformation of a stiffener.
Pic 8.1:Un-cracked coating after plastic deformation, Source APC, 2002
8.2 Toughness
Toughness can be defined as the ability of a coating to withstand an impact without
cracking or breaking. It is dependent on the nature of coating used and on adhesion.
8.3 Adhesion
The importance of adhesion is the ability of a coating to resist removal from the
surface to which it is applied. Such adhesion can be between substrate and coating,
between a primer coating and a top coating or between coatings applied to an existing
coating. In addition, the coating must adhere under various weathering and cleaning,
usually aqueous, conditions. The mechanism of adhesion problems can be represented
on the following fig.8.2
34
Fig.8.2: Adhesive and cohesive failure of coatings, Source: Caridis, 1993
8.4 Hardness
Coating hardness is the ability to resist permanent indentation, scratching, cutting, and
penetration by a hard object. Different methods of evaluating hardness yield different
results because they measure different qualities of the material. There is no absolute
scale and each method has its own scale of defined hardness.
8.5 Abrasion
Abrasion resistance is the ability of a coating to resist having its original appearance
and structure altered when it is subjected to the influence of erosion, rubbing,
scraping, or other ablative action. Both temperature and environment can have an
effect on abrasion resistance, but the relationship between these factors and
interrelated mechanical properties is not simple. For example, hardness and modulus
increase with decreasing temperature, and this may be detrimental to abrasion
resistance if the coating loses flexibility or toughness. Increases in humidity around an
object or subjecting an object to a moist environment as in washing a wall can soften
a coating and alter its resistance to abrasion. [ Koleske J.,1997]
35
8.6 Slip
Coatings are said to have good slip when they have a low coefficient of friction and
poor slip when they have a high coefficient of friction. Slip indicates the ease with
which two contacting surfaces can move by each other. Coatings are said to have slip
when they have a tack-free surface and behave as if they were lubricated. Slip is an
important characteristic of coated tanks for it is the property that allows easy removal
of cargo during tank cleaning.
8.7 Internal stresses
When a solid coating film forms, a liquid is changed into a solid. While the film is
liquid, the coating is mobile and volume contraction takes place. As a solid coating
film forms, contraction continues but is restricted by adhesion. As a result of this
restriction, tensile stresses develop within the coating. However, as soon as stress
develops, the molecules seek to relieve the stress and a relaxation process begins.
Therefore, as film development continues, stresses within the film can increase,
decrease, or remain constant depending on the rate of stress development and of stress
relaxation. It should be noted that stress development begins when the glass transition
temperature (Tg) of the changing system is reached.[Marrion A.,1994]. Tg is the
temperature where a polymer changes phase from soft form to glassy form
36
Chapter 9
MAINTENANCE AND REPAIR ACTIONS
Before each maintenance and repair action takes place, it is essential to ensure
safety of people on board the ship. So the owner has to deliver each tank in a clean
and gas free condition, the shipyard or the subcontractor should fit explosion-proof,
low voltage lighting so that good working light is achieved in all parts of tank during
work operations and inspections. Additionally, shipyard should supply and maintain
at all times adequate ventilation and proper dehumidification during all phases of
blasting, coating and curing.[Advanced Polymer Coatings,2002]
In order to eliminate every possibility of damage on steel or on coating the
following considerations must be taken into account.
Only combination “pipe and cable ladder-type” with expanded metal grate
staging, suspended from specially fitted stainless steel overhead lugs or rigid knock
down pipe staging, is acceptable.
A representation of the used staging can be seen at the below picture 9.1
Pic. 9.1 : Scaffolding erection, International- Marine coatings, 2002
All pipe ends shall be fitted with plastic plugs to prevent grit accumulation
within the pipe. Staging is to be of such construction that it can be disassembled and
removed from the tank without damage the lining. [Devoe Coatings,1993]
37
Items not to be blasted and coated such as heating coils or pumps should be
removed from the tank or protected against over-blast and over-spray by covering-
wrapping. During the blasting process the best protection is offered by a wrapping in
heavy duty rubber or plastic with overlaps and joints on the underside of the coils to
prevent dust and blast media collecting in the wrapping. During application the
covering should be made of paper material. [Hempel,2002]
Finally, suitable protection from water should be provided above the hatch
openings of all tanks, which will be lined. So water guards are to be installed to
prevent rainwater from draining into the tank.
9.1 Surface pre-treatment
9.1.1 Metal works

The highest level of possible surface preparation is strongly recommended in
all tank lining work and that’s because the effective life of any tank lining system
largely depends on how the surface of the steel has been prepared prior to application
of the paint.
Before abrasive blast takes place, all sharp edges and welds must be ground to
a smooth finish of radius of 2 mm and all traces of rust and dirt to be removed as the
following fig 9.1 shows
Fig. 9.1:Sharp edges, Source:International-marine coatings,2002
38
Weld metal should be of good quality free from pores, undercuts and notches in order
to avoid pinholes and surface irregularities.
Fig.9.2: Undercuts, International-marine coatings,2002

Of equal importance is the removal of surface laminations, which may be present in
the steel plate.
Fig.9.3: Plate defects: Source: International-marine coatings,2002
9.1.2 Sand blasting

During blast cleaning, a large number of small metal or mineral particles
impact the steel surfaces that are being cleaned at high speed. There are several ways
of achieving a clean surface with blasting whose differences lie in the size of particles
used, the manner of “transportation”, (e.g.air), and in the type and kind of mechanical
equipment required. The choice of method depends on the kinds of dirt present and
the various types of old, worn, and damaged protective coatings. For cargo tanks, the
abrasives are forced on the metal surface by air. The resulting surface should not be
excessively smooth but rough enough to achieve satisfactory adhesion of the paint to
the metal surface.[Caridis P., 1993]
The compressed air used for abrasive blasting should be oil free, be cooled
after compression and must not have higher temperature and humidity than the air fed
into the tanks by the dehumidifiers. By balancing the ventilation of the tanks,
oxidation of the blasted surface is effectively prevented.
The abrasive should to be used should be dry, sharp, of good quality with a
content of soluble salts which should not exceed a specific limit.[Carboline Int.,1995]
After the end of blasting an inspection of steel roughness is done by using
specific tools and standards. There are many test methods to measure roughness of the
39
surface. Among the most suited for the field are the comparators.
In ISO 8503, two comparators are specified, one with profiles corresponding to blast-
cleaned surfaces using grit abrasive (reference comparator G) and one corresponding
to blast-cleaned surfaces using metallic shot abrasives (reference comparator S).
The nominal values for these profiles identify the limits of the three grades fine,
medium and coarse.
The following stage is the inspection for contamination of the metal surface by
oil, grease or salt substances, which may lead to early lining failure due to osmotic
blistering. To detect water soluble salts, the most user-friendly method available today
is to dissolve the salts being present at the surface and to measure the conductivity of
the water sample. Conductivity is an indication of how well a liquid solution will
conduct electricity and is measured in micro-Siemens (µS). The conductivity can
through calculation be converted to a corresponding salt content on the surface.
[Jotun, 2003]
The procedure can be seen at the following fig. 9.4
Fig.9.4: Contamination test, Source: Forsgren A.,2000
First we attach the patch on the metal surface, after that we use a needle to inject
deionised water into the patch and finally we measure the solution conductivity.
An easy test for detecting oil/grease on a surface is the "water break method",
where a drop of water is added on to the prepared surface. The drop will spread out
rapidly on the surface if no oil/grease is present, but will remain on the surface in a
40
drop-shaped form in the presence of oil/grease. This method is not a standard. [Jotun,
2003]
The type and the size of abrasive are important to the work. The abrasive
should produce the profile shape and height required to ensure acceptable lining
adhesion to the substrate (metal).
After the finish of blasting we use suitable industrial-type of vacuum cleaners
in order to remove residual grit and dust from surfaces. Also the staging should be
vacuum cleaned.
Since we have ensure that the metal surface is completely clean and the
temperature and humidity of air into the tank the most appropriate we can start apply
the coating keeping these conditions constant at the same time.
9.2 Abrasives
Abrasives should be chosen with characteristics that minimize shattering and
embedment into the metal, which is the most important. Many of the heavy angular
grits, particularly the steel grit, can damage an old lining but their disadvantage is that
they may embedded in the substrate.
Usually for marine applications we use non-metallic abrasives because of their
low dusting, low fragmenting and ability not to penetrate the substrate.
The most effective abrasive is the one, which produces uniform, jagged tooth
with the greatest increase in effective surface area but with a height, which is
approximately to 30 % of the final dry film thickness.[Dromgool M.,1996]
A projection of a blasted and coated surface can be seen at the below fig.9.5
41
Fig. 9.5 : Blasted and coated surface profile, Source:Rogers J., 1971
However, the quality of blast-cleaning can vary widely depending on types of
abrasives, air pressure, distance and angle of nozzle from metal surface and speed of
blasting.
The following fig.9.6 show’s the usage of several types of abrasives on metal surfaces
and the impact direction
Fig. 9.6: Abrasive types, Source:Caridis P., 1993

42
Standards of blast-cleaning are described in various specifications laid down

by different authorities. For example, the steel preparation according the Swedish
Standards Association is:
Sa 1: Light blast cleaning
When the surface is examined using the naked eye, it has to seen to be free of traces
of oil, grease, dirt and lightly attached mill scale, rust, old layers of protective
coatings and other bodies.
Sa 2: Thorough blast cleaning
When the surface is examined using the naked eye, it has to be seen to be free of
traces of oil, grease and dirt and of the greater part of attached mill scale, rust, old
layers of protective coatings and other bodies. Any remaining dirt has to be well
attached to the surface.
Sa 2.5: Very thorough blast-cleaning
layers of protective coatings and other bodies. Any attached dirt has to have the form
of light stains in the form of narrow strips or points.
Sa 3: Blast-cleaning to visually clean steel
layers of protective coatings and other bodies. The surface should have a metallic
shine.
In the shipbuilding industry, we often encounter an initial condition A (good
condition) or B (rust condition), whereas the required preparation grades are,
according to regulations Sa 2, Sa 2.5 and Sa 3. Preparation grade Sa 3 is desirable but
requires expensive cleaning installations whereas at the same time it produces an
increase in surface roughness beyond the desired level. Thus, in superstructures a
43
preparation grade of Sa 2 is often sufficient whereas for underwater regions of the hull
and the inner structure of compartments a preparation to grade Sa 2.5 is required.
Table 9.1 that follows includes the preparation grades of steel surfaces using
blast- cleaning methods, and the symbols used in four different regulations.
International British Standard Steel Structures National

Standards BS 4232-1967 Painting Council, Association of
Organisation USA Corrosion Eng.
ISO 8501 -1 (1998) NACE TM-0 1 -70
Swedish scale
SS 05 59 00-1988 2
German scale
DIN 5592 1977
Sa 1 SSPC-SP7 Brush off NACE No. 4
blast -cleaning
Sa 2 Grade 3 SSPC-SP6 NACE No. 3

Commercial-blast
cleaning
Sa 2.5 Grade 2 SSPC-SP5 Near-white NACE No. 2
blast-cleaning
Sa 3 Grade 1 SSPC-SP4White metal NACE No. 1
Table 9.1: Blasted surface Standards, Source: Caridis P., 1993
44
Chapter 10
Coating application
Regardless of the coating material that is finally chosen the correct implementation of
coating is extremely important.
It has been mentioned previously that steel temperature and relative air
humidity in the tank are the two basic factors, which ensure the correct application of
coating.
Steel temperature, can be measured by a contact thermometer. It is an electronic
instrument to measure the steel temperature. When steel temperature is measured and
we have found the dew point, we can determine if it is possible to start the paint
application. The steel temperature should always be 3 C above the dew point.
A contact thermometer can be seen at the below picture 10.1
Pic. 10.1: Contact thermometer, Source: Jotun, 2003
The dew point is the highest temperature at which moisture will condense
from the atmosphere. The dew point is essential to determine if the climatic
conditions are acceptable for paint -work. The calculation, can be done from tables or
by a so-called dew point calculator. There are two slightly different types available
today. They are based on similar principles and consist of two seals, which are set
against each other, so that the required information can be read. When you have
measured the dry and wet bulb temperature, the dew point and relative humidity can
be read from the dew point calculator.
45
Pic. 10.2: Dew point calculator, Source: Jotun, 2003
The relative humidity is measured with a sling hygrometre. The sling

hygrometre, picture 10.2, consists of two thermometers, one dry and one wet (wet
cotton wool wrapped around the sensor). On rotation, the water in the cotton wool
will evaporate, thus cooling the thermometer in ratio to the dry one, which measures
the temperature of the air. From the temperature readings, the relative humidity can be
calculated
Pic. 10.2: Sling hygrometre, Source: Jotun,2003
In our days, the use of dehumidification (DH) and temperature control systems
has been shown to provide a number of benefits during surface preparation and
coating/lining operations in a variety of ambient conditions. For example, by creating
air dew points well below surface temperature, thus reducing relative humidity at the
surface, properly employed DH systems can prevent the development of rust during
and after surface preparation and prior to coating application. Properly sized DH
46
equipment can also improve worker health and safety conditions by providing
increased air flow and oxygen levels, and lower explosive limits and toxicity levels
within storage vessels and other closed areas.[SSPC,2003]
Since all conditions are satisfied the application of coating may start. The
lining material, which is stored under controlled temperature is mixed and thinned in
the correct proportion before use, and after mixing must be used within the specified
“pot life” set by the manufacturers. To avoid errors in mixing ratios the components
are supplied appropriately sized containers.
The application of coating starts from the bottom of the tank to the ceiling,
because during application the evaporated solvents go to the bottom of the tank. So
the air in the tank is both renewed and dehumidified to keep clean atmosphere and
steady temperature and humidity conditions.
The used equipment is an air-less spray system, as shown in the following fig.10.1
Fig 10.1: Air-less spray system, Source : Perez A., 2003
The advantages of air-less spray include the provision of a smooth paint film
with less change of air entrapment, greater versatility for the operator, less turbulence
in the spray pattern and greatly reduced risk of contamination with moisture and oils
from improperly cleaned compression equipment.[Goldie H.,1973] The following
picture 10.3 shows the coating application.
47
Pic.10.3: Application of coating, Source: PCE,2000
Also important role play’s the sequence of coating application. A brief

representation of coating sequence can be seen at the following fig. 10.2
Fig. 10.2: Coating application sequence, Source: Perez A.,2003
If we consider a coating system of two parts (2 coatings), then we apply the

first coating to all tank surfaces for a specific dry film thickness. At this stage, as we
approaching the ceiling we must cover the tank bottom to avoid any overspray.
After the first coat is sufficiently dry the tank should be inspected and any
uncoated spots should be coated.
However, there are some critical areas where due to their structure it is
impossible to achieve the appropriate dry film thickness. For that reason stripe coats
are applied with roller or brush. Typical stripe coat areas are: 48
• backs of stiffeners
• cut outs i.e. scallops, etc
• welds
• areas of difficult access (corners etc)
• ladders and hand rails
• areas of properly prepared pitting
Some of these areas are show at the following fig.10.3
Fig 10.3:Key areas for stripe coat applications, Source: International-

marine,2003
Some stripe coatings can be seen at the following picture 10.4
49
Pic. 10.4: Stripe coatings Source: Maroudis G.,2002
As the stripe coatings have been applied and inspected we apply the second
coating, which has different color from the first, using the air-less equipment.
When the coating system has adequately dried then dry film thickness
measurements are done using appropriate instruments like the one at the following
pic.10.5
Pic. 10.5: Instrument for d.f.t. measurement, Source: Jotun,2003
At the same time hardness of the coating are taken using a hardness-pen and
inspection for any uncoated areas is done for the whole tank.
The following pictures show how a coated tank looks like.
50
Pic.10.6Coated cargo tank of modified chem. Tanker, Source: Sigma Coatings

Marine,2003
Pic.10.7: Coated cargo tank of a chemical Tanker, Source: APC2003
The tanks may be charged with sea -water and then discharged in order any
uncoated areas to be discovered. These areas will be corroded by the sea -water.
At the last stage all heating coils and pumps are fitted on their initial places.
Hot air is applied into the tank continuously to enhance curing of coating. This
procedure is called post-curing and it can be done even while the ship is in service
51
with these tanks empty. The curing time depends on temperature as the following
graph show’s.
Cure Schedule @ Different Ambient Temperatures
50
(C)
40
Temperature
30
20
10
0
3 4 5 6 7 8
Cure Time (Days)
Graph 10.1: Cure time with respect toTemperature, Source:

International-marine,2003
52
Chapter 11
T he role of ventilation and dehumidification
It has been stressed previously that in order to be a coating system efficiently

applied air temperature and humidity should be under control, the same controlled
conditions should be achieved during blasting. Temperature determines the maximum
amount of moisture which air can hold. When warm air is trapped in the tank, it is
cooled by contact with the cold structure of the vessel so the relative humidity level
rises until the dew point is reached and water droplets begin to form on the cold
surfaces. So in order to avoid the above mentioned phenomenon we try to keep steel
temperature few degrees of C above the air tank temperature.[ Doughty P.,1998]
There are three primary purposes for ventilating tanks and enclosed areas
during cleaning and coating operations:
- operator’s health and safety
- operator’s visibility
- curing of coating. [Appleman B.,2000]
Ventilation is required during each stage of the process: blast cleaning,

application of coating, and curing of coating. It can be described in terms of airflow
and the exchange of clean incoming air and dirty outgoing air. The balancing of
incoming and outgoing air is an important feature of a ventilation system. If a high
volume of clean air is blown into the tank while a lower volume of dirty air will be
extracted then air turbulence will be created.
11.1 Ventilation during Blast Cleaning

During abrasive blasting, the air is filled with dust from the abrasive material,
which breaks down as it hits the rust-coated surface and from the surface that is being
cleaned. The dust creates visibility problems for workers as well as risks to their
respiratory systems and to their eyes. In addition, dust that settles on the surface after 53
blasting, effect’s the proper adhesion of the coating system. The amount of ventilation
or the number of complete exchanges of incoming and outgoing air required during
blast cleaning depends primarily on the volume of the tank. Other important factors
are the number of blast operators, the amount of corrosion on the tank’s surface, the
characteristics of abrasive and surface material, which will be removed.
The following fig.11.1 show’s the arrangement for the tank blasting
Fig.11.1:Set-up of blasting equipment, Source: Appleman,2000

There are no specific rules for required air changes. However, some
ventilation requirements have been adopted from experience. Some characteristic
figures are pointed below.
• Spaces of 2,000 ft3 (60 m3) and less shall have an air change every minute.
• Spaces from 2,000 ft3 to 30,000 ft3 (60 m3 to 850 m3) shall have an air change every
three minutes.
• Spaces from 30,000 ft3 to 100,000 ft3 (850 m3 to 2,800 m3) shall have an air change
every five minutes.
• Spaces over 100,000 ft3 (2,800 m3) shall have an air change every ten minutes.
[Appleman B.,2000]
54
11.2 Ventilation during Application and Curing

During painting operations in tanks, the air becomes laden with paint overspray
and solvent vapour. Like dust from abrasive blasting operations, airborne overspray
particles can create respiratory risks for workers. In addition, overspray particles that
settle on the surfaces, which are being coated can interfere with the adhesion of the
coating. Solvent vapors can pose health risks. They can also create fire and explosion
atmosphere. The health and safety hazards presented by these conditions dictate that
ventilation requirements must be carefully calculated and that the air inside the space
should be subsequently monitored throughout the painting operation.
The ventilation rate should sufficient to dilute solvent vapour to 10% or less of the
lower explosive limit (LEL) of the specific solvents being sprayed. LEL is the lower
limit of flammability or explosiveness of a gas or vapour at ordinary ambient
temperature. It is expressed in percent of the vapor in air by volume.
Additionally we force the solvents to leave the coating system so that molecules
can move easily and further hardening reaction take place.
Proper ventilation is obtained with equipment for moving air, directing the air, and
the efficient set-up of the equipment. The major air movement components of a
ventilation system are fans, ducting, and system layout. A typical ventilation system
during coating application and curing is represented below.
55
Fig.11.2:Set-up of ventilation during painting and curing, Source: Appleman

B.,2000
The reason of setting the suction pipes near the bottom of the tank is because dust
particles and vapour solvents are heavier than air they concentrate at the lower tank
height. Additionally as both blasting and painting are applied from the tank bottom to
the top, we keep the atmosphere for workers clean.
56
11.3 Dehumidification
Dehumidification may be required or desired for three reasons. One reason is that
a coating specification may require a maximum relative humidity (RH) that is below
the ambient RH of the tank. For example, U.S. Navy specifications allow a maximum
RH of 50% during application and cure of solvent-free epoxies. For most shipyards in
the USA, Europe, and Asia, the ambient RH will normally be higher than 50%, so
dehumidification is needed to meet the specification.
A second reason for requiring dehumidification is to prevent condensation on a
steel substrate. Condensation will occur when the dew point is at or above the surface
temperature. Most coating specifications require the surface temperature to be at least
3 degrees C above the dew point temperature. If these conditions are not met,
dehumidification can be used to lower the dew point. These conditions will then allow
blasting and painting to proceed. Some shipyards prefer a spread of 6 or 8 degrees C,
especially for tanks. In many locations, the surface temperature is less than 3 degrees
C above the dew point temperature, so without dehumidification, there would be a
substantial risk of condensation.
A third reason for requiring dehumidification is that it can create working
conditions that can improve productivity. Dehumidification can raise or lower the
ambient temperature while reducing the RH in a tank. Coating work on tanks under
dehumidification can continue despite cooler ambient temperatures and high RH.
Dehumidification can also lower the ambient air temperature, so it can reduce hot and
humid conditions inside a tank that make the workers tired.
A dehumidification system can be characterized by the following parameters:
• volume of airflow
• air velocity through the dehumidifier
• power requirements
• external static pressure
• moisture removal capacity
• initial and final temperatures.
A typical dehumidification system is shown at the following fig.11.3
57
Fig 11.3 Dehumidification system, Source: Appleman B.,2000
58
Chapter 12
ABSORPTION – DESORPTION COATINGS CHARACTERISTICS
Generally the coatings are porous, this means that cargo can physically
penetrate the film and be captured into it. The sequent of this behaviour is the possible
reaction between the previous and the following cargo, which might lead to cargo
contamination. The potential of cargo contamination exists with all types of coating
and the rules of Food & Drug ministries of several counties are quiet severe regarding
tests for extractable constituents in paint film. [Jackson P.R, 1996]
Regarding inorganic coatings (i.e. zinc silicate coatings), very volatile cargoes
can be easily removed using evaporation-ventilation techniques from the coating
because this type of coating does not absorb large quantities of cargo. However,
“heavier” cargoes like lube oil cannot be easily removed from the film. That might
cause contamination of the next cargo, especially when the next cargo is a “good”
solvent. [Jones D., 2002]
The following fig.shows the condition of a zinc silicate coating before and
after the cargo storage:
Fig 12.1: Advanced Polymer Science. Absorption characteristics of Zinc Silicate

coatings,2002
59
The organic tank coatings, despite they are more resistant to corrosive
environments they tend to absorb greater quantities of cargo than zinc silicate.
The following fig. 12.2 show’s the condition of an epoxy coating before and
after the cargo storage:
fig.12.2 : Absorption characteristics of Epoxy coatings, Advanced Polymer

Coatings 
Despite the fact that organic coatings absorb and desorb cargoes is not new only the
last years few projects have been done related to this attitude of the coatings.
The main factors influencing absorption-desorption characteristics are:
• Coating thickness
• Temperature
• Tank cleaning
Also some coating absorption/desorption characteristics are influenced by water.
Some coatings have considerably lower rate of absorption when they are saturated
with water.[Woods W.,1994]
At the following pictures we can see the difference between a new coating and
a coating breakdown.
60
Pics 12.3 &12.4 : New and old coating, Source: Trevor P.,1998
The coating breakdown has a form of blistering, which increases the tendency of the
coating to absorb cargo.
It has been observed that the absorption rate of a substance into a coating film
is rapid and increases in a linear way and then falls to zero when the film becomes
saturated. In other words no more cargo is absorbed by the coating. On the other hand
the desorption rate is rapid too, at the first stages, and at the end it falls to a steady
value. That means than the absorbed substance has not fully escape the film. .[CWA
Consultants Ltd, London, 2002]
The following fig.12.4 shows the absorption/desorption characteristics of an
organic tank lining.
Fig.12.4 :Absorption/Desorption characteristics, By David R. Jones, Oil &

Chemical Dept., CWA Consultants Ltd, London
61
It can be seen that absorbed cargo quantity becomes maximum during the first
three days and until the 13th day the absorption rate relatively does not change. By the
13th day desorption occurs, and lasts four days. As we can see the desorption rate does
not change during the last two days (17-19), which means that an amount of absorbed
substance will retain into the coating.
If we make a comparison between different types of coatings and one type of
carried cargo we can see that different types of coatings show a variation in
absorption/desorption characteristics.
The following fig. 12.5 shows those variations between pure epoxy, phenolics
epoxy and epoxy isocyanate coating
Fig.12.5: .[Absorption/Desorption characteristics, By David R. Jones, Oil &

Chemical Dept., CWA Consultants Ltd, London]
One of the methods which has been used in order to measure the adsorption
and desorption was similar to the Standard Test Method for Water Absorption of
Plastics, ASTM D570.
According this method coated test panels were immersed into cargo
substances. The panels were initially blasted cleaned to Sa 3 roughness level and then
62
were coated with appropriate thickness, the coatings were cured according to
manufacturer’s instructions.
Before the immersion, measurements of panels weight were taken. Thus
observing the panel weight change as the panel was immersed, conclusions were
made about when the absorption has stopped. Similar conclusions about the
desorption were made about the desorption which occurred at 25 C and relative
humidity (RH) 50%.
The results shown that:
• For several types of coating in various types of cargoes that
absorption/desorption curves follow the above mentioned format.
Fig12.6
• Cargoes having small molecules are able to penetrate organic coatings
easier than those cargoes with greater molecules. For this reason
methanol is one of the most aggressive cargoes.
• Each coating has different performance at different type of cargo. For
that reason careful examination of coating performance should be
carried out before the choice of coating.
Fig 12.6: Parry Trevor, Absorption/Desorption Characteristics of Organic Tank

Lining Systems
63
It has to be stated that during the above experiment the temperature was
constant. For variations of temperature the coating performance is expected to change
too. [Parry T. Dec.1998]
After some years in service (i.e. 5~10), depending the type and the sequence
of cargo, the coating stops having its protective characteristics. The following picture
shows the condition of an epoxy phenolic coating used to protect tanks from
methanol.
Picture 12.3:Christopoulos N., General Shipping, Destroyed protective coating

of a chemical tanker
64
The latest technology coatings claim’s outstanding performance. They prevent

the film penetration and desorption of absorbed cargo is very small. The molecular
size is smaller and the density of links is grater. .[Advanced Polymer Coatings,2002]
This can be shown to the following fig.12.7
Fig.12.7: Chemical characteristics and absorption of coatings,Source:Advanced

Polymer Coatings,2002
Due to high cross-linked molecule structure of coating the percentage of adsorbed
cargo is reduced. Fig 12.8
  
NOTE: Percent absorption in parenthesis (0.18%)
 
Fig.12.8Chemical characteristics and absorption of coating, Source:Advanced
Polymer Coatings,2002
65
So the general considerations, which should be taken into account can be

summarized as follow:
• The absorption/desorption characteristics of the paint systems differ significantly.
Some paints absorb less amount of cargo than others and desorb the cargo more
efficiently. The selection of such coating system reduces the risk of contamination.
• Allow coatings to desorb as long as possible. The rate of desorption increases as the
tank temperature increases. An important point is that continuous ventilation of tank
is not as effective as the increased air temperature in the tank.
• Avoid the stowage of “sensitive” cargoes such as ethanol, methanol, isopropanol
etc., in tanks where incompatible cargoes have been previously stowed.
66
Chapter 13
CLEANING CARGO COMPATIBILITY
It is often necessary to clean or ventilate cargo tanks when changing cargoes

in order to prevent undesired interactions between cargo residues and the next cargo.
Such interactions can form substances that may attack the coating system, enhance
danger of steel corrosion and contaminate or discolour the next cargo.
For example, when residues of a cargo, which contains ester groups in its chemical
composition, may create acetic acid by hydrolysis. Hydrolysis will take place as soon
as the residues of a cargo will come in touch with water molecules. This reaction will
cause corrosion and may attack the coating. The same will happen when, cargo
residues, contain chlorinated hydrocarbons. They can form hydrochloric acid upon
contact with water or water containing cargo.
To avoid such interactions, all esters and chlorinated hydrocarbons must be
transported in dry cargo tanks. Methanol cargoes can be especially problematic.
Besides having a softening effect on organic coatings, methanol residues in a coating
can cause water vapour permeability, causing osmosis between coating and steel
substrate. In addition, methanol can extract residual solvent and low molecular weight
materials from the coating. This induces stresses in the coating that can lead to
cracking. Only highly crosslinked coatings are resistant to methanol. Most coatings
suppliers do not allow transportation of water-containing cargoes after transportation
of methanol. [ Berendsen A.M.1998]
Additionally cargo-compatibility tables result of collaboration of chemical
companies and organizations are available to ensure the cargo purity and corrosion
steel prevention. The following table 13.1, has been created by US coast guard and
chemical companies:
67
Table 13.1: Cargo Compatibility, Source: Corkhill M. Fairplay Publ.,1981
68
Commodity lists from coating manufacturers commonly indicate which

cargoes may be transported in tanks coated with their systems and under what
conditions (e.g.,cargo temperatures, transport times, and types of subsequent cargoes).
The following Table 13.2, shows the type of cargo according to IMO standards and
the temperature range that cargo should be carried
IMO Product Cargo / Temperature

Code Code Product Rating
8 ACETONITRILE A
9 ACETOPHENONE (PHENYL METHYL KETONE) A
488 ACETOXYETHANE A
3 1344 ACETOXYETHYLENE,1- A
891 ACETOXYPROPANE,1- A
645 ACETOXYPROPANE,2- A
3510 ACETYL CHLORIDE A
2 5 ACETYL OXIDE A
229 ACETYL TRIBUTYL CITRATE A
9 ACETYLBENZENE A
10 ACETYLENE DICHLORIDE A
1 2728 ACETYLENE GAS A
3 1246 ACETYLENE TETRACHLORIDE A
3511 ACID MIXTURES (NITRATING ACID) A
2729 ACIDULATED OILS (SOAP STOCK) A (80)
11 ACIDULATED VEGETABLE OILS A (80)
2730 ACINTOL A
1370 ACRALDEHYDE A
3 12 ACROLEIC ACID A
1370 ACROLEIN A
Table 13.2: Cargo/Product- Carriage Temperature range. Source APC,2003

Guidelines for tank cleaning procedures when changing cargo should be followed
carefully to ensure that cargo residues are sufficiently removed before loading a new
cargo. Organic tank lining systems can absorb materials from cargoes, and the
amounts after different time periods are not well defined. Variable and unpredictable
absorption/desorption characteristics are found not only among different coating types
but also within the same generic type of coating from different manufacturers. In
69
addition, different rates of absorption/desorption are found among different cargoes.

This can make it difficult to select the correct cargo tank coating system.
Chapter 14
ECONOMIC COMPARISON BETWEEN COATED MILD STEEL

AND STAINLESS STEEL
Stainless steels are good materials for chemical tanks, because of their ability
to create a passive layer on their surface. A thin, both non- penetrative and protective
film is created on the steel surface. This passive layer is mainly consisted by
chromium oxide, which is very resistant to corrosive environments.
A typical stainless steel composition illustrated in the following Table 14.1
Composition of Composition %
316LN St. steel
Chromium 17.5%
Nickel 11%
Molybdenum 2.9%
Carbon (max) 0.03%
Nitrogen 0.14%
Iron 66%
Table 14.1:compasition of St. steel
It has a relative high percentage of chromium (17.5% Cr). So when the metal
is exposure to air the chromium (Cr+3) will react with oxygen (O-2) forming the
chromium oxide (Cr2O3). The film thickness is generally 15-50 Armstrong [A] and
free from pores.[Goldie,1973] However, in some environments like strong hot acids,
chloride solutions and generally solutions which contain halogens, the passive film
can break down locally and prevention of new film formation can occur. Generally
70
the halogens block the atoms of oxygen to react with chromium. Alloys containing
molybdenum show improved performance towards this type of attack. [Sheffield A.
,2000]
However, stainless steel is an expensive metal, its quality can vary from
supplier to supplier, and special skills are necessary for constructing large volumes
tanks. Particularly special attention should be given to the welds. [Keehan D., 1996]
A case study was made for a new 37,000 dwt double hull chemical tanker in
order to determine the cost and profitability when it would have been built throughout
with stainless steel tanks or with coated mild steel.
The survey initially shown that the tanker with stainless steel tanks would cost 75
million US$, almost the double than the one with coated mild steel tanks.
Additionally some assumptions were made:
1. Both ships would operate 275 days per year.
2. The cargo would be methanol
3. The assumed interest over 20 years was 6%
4. Same operating costs of 6,162 USD
The result shown that with amortization of the financing costs, including the above
interest, the 75 million USD ship would represent a daily amortization cost of 23,433
USD, on the other hand the 30.5 million USD ship would have a daily amortization
cost of 11,810 USD.
Thus the total daily cost would be 29,595 USD for the ship with stainless steel
tanks and 17,972 USD for the ship with the coated mild steel tanks.
For the above cargo and for a freight rate of 0.69USD/dwt/day there would be
generated a revenue of 25,530 USD per day for both ships.
So finally we have a daily loss of 4,065 USD for the ship with stainless steel
tanks and a profit of 7,558 USD for the ship with the coated mild steel tanks.
A summary of the above results can be seen at the Table 14.2
71
37,000dwt double hull Stainless Steel Tanks Coated Mild Steel Tanks
chemical tanker
75M$ 30.5M$
Daily amortization 23,433 $ 11,810 $
operation 275days/year
Operating Cost/day 6,162$ 6,162$
Total Cost/day 29,595$ 17,972$
Revenue/day for 25,530$ 25,530$
methanol and 0.69$/dwt
Profit or (Loss)/day (4,065$) 7,558$
Table 14.2: Economic comparison of steels, Source: Advanced Polymer

Coatings,2002
So in order to make profit the stainless tank vessel should be ‘fixed’ at higher
freight fates. This would probably lead the vessel out of competition or to be
chartered at low freight rates caring few types of cargoes.
Finally the case study shown that in order the to generate the same operating
profit the freight rare should be increased to 1.09USD/dwt/day or 58%. [Advanced
Polymer Coatings, 2002]
72
Chapter 15
Statistical Analysis of measurements
As it has been stated at the introduction, measurements of d.f.t. have been

taken from all tank surfaces and each reading had a distance of 50 cm from the other.
According to the coating manufacture specifications, the coating should have a
specified d.f.t. of 300 microns and the minimum d.f.t. should not be below the 290
microns. In other words, the final d.f.t. should not have a diminution more than 10%
of the specified.
The tank was constructed by three corrugated bulkheads and three flat
surfaces, all welded together. (Rough drawings are given in the appendix)
The total area to be coated was 440 m2 and tank’s dimensions are given below:
Height H= 7.5 m
Length L=12 m
Breath B= 4.9 m
15.1 Histograms and mean values
Since a large number of readings were available we are able to analyze the
data by constructing a distribution histogram. This is accomplished by dividing the
horizontal axis into intervals of appropriate size and constructing a rectangle over the
ith interval with area proportional to the number of observations.[ Hunter W.,1987 ]
Also we can define the relative frequency of observation, which is given as the
fraction of observations over the population of measurements.
Fi= ni/N
Generally the higher the frequency of observations, the higher the number of
observations.
73
Based on these measurements, we obtain information about the value of mean

( µ or ). The mean value of measurements (x) is given as the fraction of summation
of all measurements over the population of measurements [Jonhson R.,1996 ]
So the results for each surface are given below:
Centreline BHD:
This surface is a corrugated bulkhead.
Distribution of measurements on CL BHD

observations
180
160
140
120
100
of
80
Frequency
60
40
20
0
290-310 310-320 320-340 340-355
Intervals
Relative
Measurement N=322 Frequency
Population N
Mean value µ=332 1st interval 0.034
2nd interval 0.108
Max value 354
3rd interval 0.52
Min value 290
4th interval 0.335
We can see that the greatest percentage of readings, which corresponds to a relative
frequency fi of 0.52, is around the mean value. This means that the biggest area of the
CL BHD surface is coated with a d.f.t. range of 320 to 340 microns. However, the
74
second biggest percentage of observations has a value of relative frequency of 0.33

for the range of 340-355 microns. The reason of this is the weld seams and corners.
As the coating dries has a tendency to become thinner due to internal stresses.
This phenomenon becomes more intense on sharp edges. For this reason we try to
have greater d.f.t. than the flat surfaces. At the corners we try to have again grater
d.f.t. than the specified, because on these areas it is difficult the coating to be applied
due to the construction.
Finally the two lower percentages express the BHD’s rounded areas, as the following
fig. 15.1 show’s, where the coating has less thickness due to the above mentioned
phenomenon of stresses.
Round areas
Fig. 15.1: Rounded areas on a corrugated bulkhead

Longitudinal BHD:
This surface is flat. The results are shown at the below graph.
Distribution of measurements on Long BHD

Frequency of observations
180
160
140
120
100
80
60
40
20
0
290-310 310-320 320-330 330-340 340-350
Intervals
75
Measurement N=322 Relative

Population N Frequency
2nd interval 0.776
Max value 349
3rd interval 0.229
Min value 294 4th interval 0.478
5th interval 0.189
Again we can see that the biggest percentage of measurements is around the mean
value and the relative frequency of this interval is 0.478.
There is a range of measurements from 340 to 350 microns, which corresponds to
weld seams and corners. The relative frequency of this interval is 0.189.
The intervals which contain values from 290 to 330 are accepted because the
specifications are satisfied.
Main Deck plating:

This is a flat surface.
Distribution of measurements on Main Deck Plating

observations
200
150
of
100
Frequency
50
0
315-325 325-335 335-345 345-355
Intervals
Measurement N=230
76
Measurement N=230
Population N
Mean value µ=341 Relative
Mean value µ=341
Frequency
Max value 356
Max value 356 1st interval 0.030
Min value 316 2nd interval 0.034
Min value 316
3rd interval 0.739
4th interval 0.195
Here, the biggest percentage of population has values from 335 to 345 microns. So the
greatest percentage of the area is coated with a d.f.t. of a range from 335 to 345
microns. Again values greater than the mean are due to corners and weld seams. Also
on the bottom tank there are some areas which are coated using brush, so the d.f.t is
increased at these points. The reason is because at these areas there were the
scaffolding foundations.
Tank Top:
This is a flat surface.
Distribution of measurements on Tank Top

observations
250
200
150
of
100
Frequency
50
0
315-325 325-335 335-345 345-355
Intervals
77

2nd interval 0.073
Max value 348
3rd interval 0.865
Min value 316 4th interval 0.030
Like the main deck, the tank top show’s a similar type of distribution, around the
mean value. As previously, there are points which have high d.f.t. due to welds and
corners.
Transverse AFT BHD:

Distribution of measurements on Transvesre AFT BHD

observations
100
80
60
of
40
Frequency
20
0
295-315 315-335 335-345
Intervals

2nd interval 0.18
Max value 345
3rd interval 0.714
Min value 294
78
The greater percentage of the area is coated with a range of d.f.t. between 335 to 345
microns. The d.f.t does not exceed 345 as in other surfaces without to exclude the
possibility of existence of these values. Values less than 335 are due to areas of
bulkhead which have been explained previously.
Transverse FWD BHD:

Dstribution of measurements on Transverse FWD

BHD
observations
100
80
of
60
Frequency
40
20
0
295-315 315-335 335-345
Intervals

2nd interval 0.13
Max value 345
3rd interval 0.825
Min value 294
Again the greater percentage of the area is coated with a range of d.f.t. between 335 to
345 microns.
79
15.1.2 Results analysis

If we examine the formats of the first four graphs we can reach to the
conclusion that the distribution of measurements is a type of normal distribution.
However, the distribution is not symmetrical as in regular normal distribution, having
a symmetrical “Bell” shape format around the mean value, fig15.1
Fig 15.1: Normal distribution curve, Source Johnson R., 1996
The graphs have a “Bell” shape format, which is displaced to the right. This
type of distribution is called “long tail to left” or “skewed” normal distribution.
[Jonhson R.,1996]
Despite the format of the two last graphs, if we examine the mean value for
FWD BHD and AFT BHD we can see that in both cases it is 335 and 336
respectively. However, this is the lower limit of the third interval and because this
interval has the biggest relative frequency 0.71 and 0.82 respectively, the distribution
of the last two graphs is also “long tail to left” normal distribution.
Generally we can see that all graphs have a displacement to the right. The
main reason is that the average d.f.t of the whole tank, it is greater than the specified
value of 300 microns. Generally the higher the film thickness, the longer the “life”
time of a coating. So in this way we can explain the displacement of the mean from
300 to 340.
80
Also at the critical points and areas, where more attention is needed, In the
d.f.t. has to have higher values than the average to avoid or minimize the possibility of
coating failure.
One important factor, which should be taken into account regarding the
increased d.f.t. and the possibility of solvent entrapment into the film, is the climatic
conditions. The high weather temperatures and relative low values of relative
humidity decrease the solvent entrapment. The above ship’s tanks were maintained in
Greece during summer time, where the above conditions are satisfied. Additionally
these vessels are equipped with ventilation systems, so they can dry the coating while
they are in service, leaving empty the fresh coated tanks.
15.2 3D Representation of d.f.t.
The following 3D graphs show the thickness variation of the dried coating
system. The vertical axis indicates the value of d.f.t and the other two the coordinate
system of measurements. The areas coloured gray are the metal surfaces.
Centreline BHD:
D.F.T variation on CL BHD
370
350-370
Value of D.F.T.
350
330
330-350
310-330
310
290-310
290
270-290
270 250-270
250
650
50
100
150
200
250
300
500
350
400
450
500
350
550
600
650
700
750
200 Y Coordinate
800
850
900
950
1000
X Coordinate
1050
50
1100
1150
81
From the graph we can see the variation of thickness between 322 measured points on
this surface. The “valleys” which are shown on the graphs represent the rounded
points, which were explained above. The pick points indicate the weld seams and
corners. Also the thickness around the bulkhead’s surface, which is welded with the
other BHD’s and plates, is almost equal to the thickness on welds.(330~350 mic.)
Longitudinal BHD:
D.F.T. variation on Long BHD
350
340 340-350
Value of D.F.T.
330 330-340
320 320-330
310-320
310
300-310
300
290-300
290
280-290
280
650
50
100
150
200
250
450
300
350
400
450
500
550
600
250
650
700
Y Coordinate
750
800
850
900
950
50
1000
X Coordinate
1050
1100
1150
Here the pick points represent the welds on the surface. Since this surface is flat is
easier to distinguish these points. Again areas close to the welds with the other
BHD’S and welds have similar thickness to the thickness on the welds.
82
Main Deck Plating:
D.F.T variation on Main Deck Plating
360
Value of D.F.T
340 340-360
320-340
320 300-320
280-300
300
280
50
100
150
200
250
450
300
350
400
450
350
500
550
600
250
650
700
750
800
150
850
900
Y Coordinate
950
1000
50
1050
1100
X Coordinate
1150
Here the 3D surface is smoother than the other two. The main reason is that this area
is easier to be coated. However, there are some pick points.
These points are areas where have been coated with brush. At these areas there were
the scaffolding foundations, which have been removed at the last stage of coating
inspection.
83
Tank top plating:
D.F.T. variation on Tank Top
350
340
Value of D.F.T
340-350
330 330-340
320 320-330
310 310-320
300-310
300
290-300
290
50
150
250
350
450
450
550
350
650
250 Y Coordination
750
850
150
950
1050
X Coordination 50
1150
This is also a smooth surface like the main deck plating but there are no such great
picks on this surface.
Transverse AFT BHD:
D.F.T variation on Transverse AFT BHD
340-360
360
320-340
Value of D.F.T.
340 300-320
320 280-300
260-280
300
280
260
50
450
150
250
350
350
250
450
150 X
Y Coordinate
550
50 Coordinat
650
Like the CL BHD we observe valleys and picks for the reasons discussed previously. 84
Transverse FWD BHD :
D.F.T. variation on Transverse FWD BHD
350
340 340-350
Value of D.F.T.
330 330-340
320 320-330
310 310-320
300 300-310
290 290-300
280 280-290
50
150
450
250
350
350
250
450
Y Coordinate 150
X
550
650
50
Coordinate
Again we have the phenomenon of valleys and picks as it has been observed
previously on the other two corrugated bulkheads.
15.2.1 Results of 3D d.f.t. representation
Regarding the flat surfaces like main deck plating, tank top and longitudinal
bulkhead, we can see that the variation of thickness does not change a lot due to the
format of the plate. The only exception is the main deck plating where we have the
scaffolding support areas. At the weld seams, thickness is also increased to avoid
possible rapid damage of coating. The same increase is observed at the weld points
with the other bulkheads or plates.
On the corrugated bulkhead surfaces we observe the phenomenon of “valleys”
and picks. The “valleys” are explained as a result of round areas of the bulkheads,
where we have thinner coating due to internal stresses as it dries.
85
The pick points appearance is explained as a result of weld seams and weld points
with other plates or bulkheads.
15.3 Conclusions and proposals (recommendations)
By doing the above literature review we reach to the conclusion of how

important a coating system is for a chemical tanker. However, in order a coating
system to be selected many factors should be taken into account. The most important
are listed below:
 Chemical resistance of coating system
 Cargo compatibility
 Cargo sequence
 Absorption and desorption characteristics of coating system
 Mechanical properties
Also the conditions into the tank, during blasting and coating, are very critical. The
stages and elements, which need special attention are:
 Selection of appropriate abrasives with respect to tank condition

 Monitoring of air temperature and humidity into the tank during blasting
 Application of coating system and selection of sequence, with respect to time
 Monitoring of temperature and humidity into the tank during application and
curing time
 Inspection of areas and points where poor thickness is expected due to surface
irregularities and construction difficulties.
By doing the statistical analysis we come to the conclusion that in order to maximise
the life of a specific coating system we can increase the thickness. This could be done
by spraying an area more time or from a closest distance. The displacement of the
mean value to the right (see bar graphs) show’s the above mentioned increase.
86
Additionally the increase of thickness reduces the possibility of coating failure,

regarding chemical resistance.
However, by increasing thickness we increase the amount of solvent, which
will be contained into a coated area. So if we assume that we have two areas coated
with the same coating system, but different thickness, then for the same time of drying
the coating which is thinner would have better properties than the thicker due to the
greater percentage of solvent evaporation. In other words the thinner coating system
will have been better cured.
In this way we conclude that in order to achieve a better coating system with
respect to the thickness we would like to achieve, temperature and humidity are
important aspects.
An integrated temperature and humidity system could help to optimise tank
conditions. This system could also be installed on board the ship to control the above
mentioned conditions and it can be combined with the already existing ventilating
system, which is used for cargo tanks. So the ship can be in service while some of her
fresh coated tanks a will still be post-cured.
A simple drawing of the system is represented below:
87
“In” and “Out” arrows show air circulation.

Some temperature and humidity sensors can be attached on the tank plates using
magnets in order to monitor air temperature and humidity. These sensors can be
removed after the completion of curing.
The readings, which we are going to take, can be compared to the desired values and
so, the incoming air quantity, its temperature and its humidity can be steady and
optimum. The optimum conditions can be defined by the coating company taking into
account parameters like type of coating, weather conditions, size of tank.
Generally we can achieve better performance of coating since we will improve its
resistant characteristics even at the areas where the coating is poor.
88
Abbreviations
d.f.t.: Dry film thickness
RH: Relative humidity
DP: Dew point
CL BHD: Centre line bulkhead
Long BHD: Longitudinal bulkhead
AFT BHD: After bulkhead
FWD BHD: Forward bulkhead
89
GLOSSARY
ACID: Any chemical compound containing hydrogen (-OH) capable to be replaced

by positive element.
ALCOHOLS: Organic substance, which is characterized by the presence of hydroxyl
(-OH) in the chemical structure.
ALKALI: A strong base. A substance, whose water solution yields a great volume of
hydroxyl ions.
AMBIENT CURE: A curing reaction which takes place at the temperature of site.
AMINES: Substances derived from ammonia
ANIMAL OIL: Oily material deriving from animal substances.
BINDER: Component which provides the cohesion of a coating.
CROSSLINK: That part of a coating system, which links chains, often formed
previously, to one another.
CURE: The process by which a freshly applied coating becomes intractable.
DEW POINT: The temperature at which the liquefaction of a vapour begins.
ETHANOL: Organic substance, which contains on its chemical structure two
molecules of C and one –OH group.
EPOXY: Epoxide. A polymer or reactive species containing epoxy or oxirane groups
FATTY ACID: Acid which is derived from fats or oil.

HUMIDITY: The percentage of water evaporated in the atmosphere.
IBC: International code for the construction and equipment of ships carrying
dangerous chemicals in bulk.
IMO: International maritime organisation.
KETONES: A class of organic compounds produced by the oxidation of secondary
alcohols.
METHANOL: Organic substance which contains on its chemical structure one
molecule of C and one –OH group.
90
PH: An indicator which specifies the acidity of a solution. Acidous solutions have
PH<7, alkaline have PH>7 and those who have PH=7 are called neutral.
PHENOL: Hydroxybenzene
PIGMENT: A powdered material used in coating compositions to impart various
properties.
POLYMER: A high molecular weight species formed from many monomer residues.
POST CURE: A procedure of drying a coating using hot air in order to maximize the
evaporation of solvent from the coating system. The characteristics of coating are
improved.
PRIMER: A coating applied to a bare substrate to prepare it for subsequent coats.
RESIN: A film forming material, usually polymeric or oligomeric.
SOLVENT: Products used in chemical industry to dissolve other substances.
THERMOSET: A polymeric system which can undergo a chemical crosslinking
process, usually on heating.
TOP COAT: The last layer on a coating system.
VEGETABLE OIL: Oil derived from plants.
VISCOSITY: A measure of the internal friction or the power in resisting a change in
the molecular structure of a substance.
VOLATILITY: Liquids which evaporate readily are known as volatile liquids.
91
References
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469.
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performance”, International Protective Coatings, Akzo Nobel, England.
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14 ,No5, ISSN 8755-1985.
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of the hull structure using coatings and hull preparation, Witherby Publishers,1993, pg
300-331,ISBN 1856091910.
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Devoe Coatings, Devchem 253, coating specification, 1993.
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1998, pg 72. ISSN 00721-456.
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Exxonmobil service”, Exxonmobil, p 45.
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PCE, vol.5 ,No6, June 2000, pg64-66, ISSN 02453-469.
92
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7.
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cargoes”, In: MER, v 7, No13,p 46 ISSN 0067551.
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Inhibitors.1992, pg 484.ISBN 0-13-359993-0.
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95

Cargo Tank Coatings

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School of Marine Science and

By: Neofytos Giannakopoulos

Newcastle upon Tyne

SHIP DESIGN AND ARRANGEMENTS..............................................................................10

THE ROLE OF COATINGS ...................................................................................................18

Mechanical properties of coatings ...........................................................................................33

COATING APPLICATION ....................................................................................................45

During the 19 th and early 20 th century, the manufacture of synthetic organic

Fig.1: Seaborne trade in liquid cargoes, Source: International Coatings

A chemical tanker is defined as a tanker, which carries liquid cargoes except

Cargo tank coatings can be categorized into two main groups:

Each of them has good and bad characteristics:

Graph 1.1:World chemical carrier fleet, Source: World Fleet Statistics

STRUCTURE OF TRANSPORT SYSTEM

Fig. 2.1:Chemical carriers transport system structure, Source: Stopford,2003

SHIP DESIGN AND ARRANGEMENTS

The design of a chemical tanker is regulated by the IMO Convention on the

Type I Type II Type III

3.1 Number of tanks

3.2 Vertical Bulkheads

Fig.3.2: Types of bulkheads, Source: Stopford, 2003

3.3 Loading/Discharging System

3.4 Tank ventilation

3.5 Cargo heating

3.6 Tank cleaning System

Corrosion can be defined as “the destruction of a metal by an electrochemical

Fig.4.1 Corrosion kinetics. Source: http://www.marineengineering.co.uk, 2003

Generally corrosion is categorized into two groups:

Fig.4.2Corrosion Rate vs PH , Source: Tomashov N.D.1966

Pic.4.1:Corroded metal plaques, Source: Maroudis G., 2003

The role of coatings

Basically the main purpose of coatings used in marine environment is the

Fig.5.1: Three layer coating system, Source: Caridis P.,1993

Generally the coating is consisted by three components:

COATING SYSTEMS AND TYPES

7.1 Zinc Silicates

1. Initial reaction involves concentration of the components by water

Curing or hardening of the coating takes place by hydrolysis of the soluble

So Alkaline Zinc Silicates, cannot be applied by airless spray equipment due

7.2 Epoxy coatings

7.2.1 Pure Epoxies

can be crosslinked to form a network structure in the presence of curing agents or

• The type of epoxy

Chemical resistance and mechanical properties of epoxy coatings may vary.

7.2.2 Epoxy Phenolics

7.2.3 Epoxy Isocyanates

7.2.4 Cyclosilicon Epoxies

Mechanical properties of coatings

Generally, the performance of a coating describes how well it is carrying out

Fig.8.1:Deformed plot, uniform loading, Source: Lloyd’s Register Technical

Pic 8.1:Un-cracked coating after plastic deformation, Source APC, 2002

Fig.8.2: Adhesive and cohesive failure of coatings, Source: Caridis, 1993

8.7 Internal stresses

MAINTENANCE AND REPAIR ACTIONS

Pic. 9.1 : Scaffolding erection, International- Marine coatings, 2002

9.1 Surface pre-treatment

9.1.1 Metal works

Fig. 9.1:Sharp edges, Source:International-marine coatings,2002

Fig.9.2: Undercuts, International-marine coatings,2002

Fig.9.3: Plate defects: Source: International-marine coatings,2002

9.1.2 Sand blasting

Fig.9.4: Contamination test, Source: Forsgren A.,2000

Fig. 9.6: Abrasive types, Source:Caridis P., 1993