THE CHEMISTRY OF LlGNOSULPHONATE AND THE EFFECT ON

PERFORMANCE OF LlGNOSULPHONATE BASE PLASTICIZERS

AND SUPERPLASTICIZERS

Kre Reknes*, Borregaard Ind. Ltd., LignoTech, Norway

29th Conference on OUR WORLD IN CONCRETE & STRUCTURES: 25 - 26 August 2004,

Singapore

Article Online Id: 100029055

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THE CHEMISTRY OF LlGNOSULPHONATE AND THE EFFECT ON

PERFORMANCE OF LlGNOSULPHONATE BASE PLASTICIZERS AND
SUPERPLASTICIZERS
Kare Reknes*, Borregaard Ind. Ltd., LignoTech, l\Iorway

29th Conference on OUR WORLD IN CONCRETE & STRUCTURES: 25 - 26 August 2004,

Singapore

Article Online Id: 100029055

The online version of this article can be found at:

http://cipremier.com/100029055

Thisarticleisbroughttoyouwiththesupportof

SingaporeConcreteInstitute

www.scinst.org.sg

AllRightsreservedforCIPremierPTELTD

YouarenotAllowedtoredistributeorresalethearticleinanyformatwithoutwrittenapprovalof
CIPremierPTELTD

VisitOurWebsiteformoreinformation

www.cipremier.com
 29th Conference on OUR WORLD IN CONCRETE & STRUCTURES: 25 - 26 August 2004, Singapore

THE CHEMISTRY OF LlGNOSULPHONATE AND THE EFFECT ON

PERFORMANCE OF LlGNOSULPHONATE BASE PLASTICIZERS

AND SUPERPLASTICIZERS

Kare Reknes*, Borregaard Ind. Ltd ., LignoTech, l\Iorway

Abstract
The most used material for formulation of plasticizers and superplasticizers for
concrete is lignosulphonate. Most of the lignosulphonate used in concrete admixtures
is consumed in the plasticizer range, but there are also lignosulphonate with
superplasticizer performance.

The chemical and physical difference in lignin from hardwood and softwood is
discussed in this paper. These differences are discussed with respect to performance
differences and modifications. It is demonstrated the in spite of the big differences
between hardwood and softwood lignin it is possible to produce lignosulphonate with
the same performance in concrete. The chemical and physical data of these
Lignosulphonates are very different. This is often leading to confusion with respect to
the performance of these products.

The structure of the lignin molecule is discussed and compared to that of linear
polymers. Typical linear polymer is NSF. This has impact on the understanding of the
behaviour of the polymer and the way lignosulphonate should be handled.

Keywords : lignosulphonate, concrete admixture, plasticizer, superplasticizer

1. Source of lignosulphonate
The raw material for production of lignosulphonate is trees . Trees can be grouped as softwood and
hardwood. The wood substance on trees is composed of different cells, which give the mechanical
strength to the trees. The wood cell consists mainly of cellulose, hemicellulose and lignin. A simplified
picture describes a skeleton of cellulose surrounded by other substances functioning as matrix
(hemicellulose) and encrusting (lignin) materials. Wood can be separated into two categories of
molecules: macromolecules and low molecular weight substances . Macromolecular substances:
Cellulose (45 %)
Hemicellulose (20-25 %)
Lignin (softwood 27-37 %, hardwood 16-29 %)
The properties and chemical composition of lignin and hemicellulose differ in softwood and hardwood,
while the cellulose is a uniform component of all wood. Low molecular weight substances:
Extractives (terpenes , alcohols, aliphatic acids, aromatic compounds, ... )

433
 Mineral components (K, Ca, Mg, Si, ... )

2. Lignin
The word lignin is derived from the Latin word "lignum" meaning wood . Lignin forms an essential part of
the wood stems. It does not only act as an "encrusting" material or as a binder of some secondary
nature, as is often misleading stated, but performs multiple function that are essential to the life of the
plant: transport of nutrition and durability of the wood. Lignin imparts rigidity to the cell walls and acts as
a binder between wood cells, creating a composite material that is outstandingly resistant to impact,
compression and bending.

Lignin , a natural polymer made up of phenylpropane units, is a major component of vascular plants.
After polysaccharides, lignin is the most abundant organic polymer in the plant world . Whereas the lignin
content within a species is reasonably constant, there may be considerable variation among species.

2.1 Biosynthesis of lignin precursors

In nature every plant uses carbon dioxide (C0 2 ) from the air in the photosynthesis to produce plant

material. This is also the start of the production of lignin. The photosynthesis is transformation of CO 2 to

carbohydrates (sugars) using light as the energy. As a result of different enzymatic reactions in the

plant, glucose is through different complex steps transformed into other chemical components, which

could be called the phenylpropane lignin precursors. These are shown in Figure 1. The precursors are:

- p-Coumaryl alcohol,

- Coniferyl alcohol and

- Sinapyl alcohol.

Lignin in wood is mainly composed of combinations of coniferyl alcohol and sinapyl alcohoL

1. 2. 3.

Figure 1 Lignin precursors: (1) p-Coumaryl alcohol, (2) Coniferyl alcohol, (3) Sinapyl alcohol.

2.2 Formation of lignin macromolecules

The biosynthesis of lignin from the monomeric phenylpropane units can be generally described as a
dehydrogenative polymerisation. The first step of the biochemical pathway for building up lignin
macromolecules is the enzymatic dehydrogenation of the precursor alcohols yielding mesomeric ring
systems with a loosened proton.

The polymerisation of the monomer precursors takes place by random coupling reactions, which is the
start of building a complex lignin macromolecule as shown in Figure 2.

These random coupling reactions of the radicals result in a three-dimensional, amorphous polymer,
which, unlike cellulose and proteins, lacks regular, ordered repeating units. Lignin is the most complex
natural polymer with regard to structure and heterogeneity. Because of this, no definite structure is
possible to describe, although numerous models, representing an "average" structure, have been
proposed.

434
Figure 2 Structural scheme of spruce lignin

"Nature" uses different phenyl propane precursors (Figure 1) as monomers for the production of lignin in
different plants. For softwood the monomer is predominantly coniferyl (2) alcohol, for hardwood a
mixture of coniferyl (2) and sinapyl (3) alcohol and for annual plants, like grass, it is a mixture of
coumaryl (1) and coniferyl (2) alcohols. The result of this is differences in the lignin, degree of
crosslinking etc., which is of importance when looking at the different lignins as raw material for
lignosulphonates. These differences have, as it will be demonstrated below, impact on the properties of
the lignosulphonate and also on the performance of the lignosulphonate in concrete.

2.3 Structure of lignosulphonate

Because it is not possible to isolate native lignin from wood without degradation, the true molecular
mass of lignin in wood is unknown. It is important to keep in mind , however, that the term "lignin" or
"Iignosulphonate" normally refers to a mixture of substances having similar chemical composition but
structural differences. The sulfonate groups (S03 .) that are introduced during the pulp cooking, i.e.
dissolving the lignin from the wood.

Lignosulphonate can be classified as hydrophobic polyelectrolytes. This description refers to the fact
that the polymer is dependent on its ionised groups for water solubility. Lignosulphonates are in that
respect similar to sulfonated synthetic polymers used as water reducing admixtures, e.g . sulfonated
naphthalene formaldehyde condensate (SNF) and sulfonated melamine formaldehyde condensate
(SMF), which also are intrinsically hydrophobic polymers. Compared to common linear polymers there is
a significant complexity inherent to the chemical structure of lignosulphonate. Figure 3 illustrates that
molecular mass distribution and charge density may capture the essential characteristics of a linear
polymer, while a much larger set of parameters is needed to describe a given lignosulphonate. Most
lignosulphonate also contain additional non-lignin organic components, and this of course complicates
the picture further.

435
 D :mono!ller

o0 :fllncioll,~ group
Figure 3 Illustration of the complexity of the chemical structure of a branched polymer with several
functional groups vs. a linear polymer with one type of functional group only.

For some of the listed lignosulphonate parameters (Figure 3) one may predict the resulting polymer's
properties. For the branched polymer skeleton, for instance, we know that condensed morphologies and
relative small effective size in solution can be expected. High molecular mass lignosulphonate is due to
this often said to behave like nano-spheres in solution. In generallignosulphonate samples tend to have
a greater polydispersity than synthetic polymers produced by condensation reactions. The polydispersity
make the lignosulphonate less well defined since, not only are there several functionallignosulphonate
groups, the content of these groups is also depending on the lignosulphonate molecular mass (Mw). An
example of such a dependency is shown in Figure 4 for standard softwood lignosulphonate, where it is
seen that the relative number of sulfonate and phenolic groups increases with decreasing Mw of the
lignosulphonate.

The role of the relative content of different functional groups is more difficult to predict than
configurational differences, and the effect of which may be expected to differ from system to system. An
important phenomenon for the function of lignosulphonate in cementitious systems is that a low ratio of
sulfonate to phenolic and carboxylic groups leads to a reduced stability of lignosulphonate in alkaline
solutions rich in calcium ions. Because of this effect precipitation of Ca-lignosulphonate complexes in
alkaline solution occur with several families of sulfonated lignins, including oxylignins, kraft lignins, and
some hardwood lignins.

3. Production of ligno5ulphonate
Pulp has basically been produced from wood. Pulp is predominantly used for papermaking but also
processed to various cellulose derivatives. The main purpose of the pulping processes is to liberate the
fibres, which can be accomplished either chemically or mechanically or by combining these two types of
treatments. Only the chemical pulping processes will be treated here, since they are the basis for
Borregaard LignoTech's raw material and thus also the basis for production of lignosulphonates.

The principal behind the chemical pulping processes is to liberate the cellulose by dissolving other
macromolecules like hemicellulose and lignin into the cooking liquor.

Conditional typical of acid sulphite pulping (140 DC, pH 1-2) results in effective delignification. Ca
hydrogen sulphite is the cooking chemical in the Borregaard process. Since Ca is the base all salts
produced are Ca salts. Other bases used in sulphite pulping are Mg, Na or NH 4 .

436

 1000 10 000 100 000 HXXHXlO

Molecular weight (Mw)
-803
-ph-OH

Figure 4 The tentative number of -S03 and -PhOH groups per aromatic unit as a function of HPLC-Mw.
Data obtained from analysis of gel column fractions of standard softwood LS.

Two reactions during the sulphite cook are of importance in the formation of lignosulphonate:
fragmentation and sui phonation. These reactions are the main reaction, but there will also be other like
condensation. The result of the reactions is water-soluble sulfonated lignin (Iignosulphonate). The
hemicellulose (sugar polymer) will under the acidic sulphite conditions be hydrolysed to monomeric
components like D-mannose, D-glucose, D-xylose, L-arabinose, D-galactose and L-rhamnose (reducing
sugars) in the cooking liquor. This means that the lignosulphonate intermediate (the liquor after removal
of the pulp) contains sulfonated lignin fragments of different molecular size (the lignosulphonates), sugar
monomers, inorganic salts and small amounts of extractives from wood.

3.1 Composition and properties

The typical differences in composition of lignosulphonate intermediate and black liquor are shown in
Table 1.

Table 1 Typical composition of different liquors.

Softwo()d Hardwo()d
Lignosulphonate 58% 55 %
Hexoses 20% 7%
Lignosulphonate
Pentoses 8% 20%
intermediate
Organic acids 6% 10 %
Ash 8% 8%

The variability of lignin composition is much greater in hardwood than in softwood trees. The reason is
that hardwood lignin is made from both coniferyl and sinapyl alcohol precursors, creating syringyl and
guaiacyl structures in the lignin in different ratios for different hardwood trees. This means that
lignosulphonates produced from hardwood and softwood trees are different, but also that
lignosulphonates made from hardwood trees like Aspen and Eucalyptus may have different properties.
The differences can be a result of differences in molecular weight distribution, degree of cross-linking
and thereby differences in conformation in solution ("spherical" or more "Iinear"). This will have an effect
on rheology properties, dispersing properties etc.

3.2 Processing of the liquors

Borregaard LignoTech produces different lignosulphonates for different applications from
lignosulphonate intermediate. The liquor can be fermented to remove the hexoses (only softwood
liquor), purified, fractionated and chemical modified to achieve or improve special properties.

437

The lignin in the "black liquor" has to be purified by precipitation or fractionation and
sulfonated/sulfomethylated before it can be used as a dispersing agent for special applications . Kraft
lignin is not used for formulation of water reducers for concrete.

Sugar is effectively removed by fermentation. Only hexoses are treated by fermentation converting them
into alcohol. Fermentation of pentoses would produce only CO 2 , Sugars can also be converted
(reduced) at high temperature and high pH. This treatment converts sugar into sugar acid . The set
retarding effect of sugar acid is not as strong as the set retarding effect of sugar, but there is still some
set retardation caused by sugar acids. See Figure 5.

Most lignosulphonate products are made from Ca lignosulphonate intermediate. Sodium products are
made by ion exchange, adding sodium sulphate and precipitating calcium sulphate. Sugar is normally
reduced during the ion exchange process. The content of insoluble is normally lower in sodium
lignosulphonate than in calcium lignosulphonate due to the extra cleaning step during the ion exchange
process.

Calcium IIgnosulfonate Intennediate

i
i

I /fermentation decanting!

I
,~~-..
r------. --,
: I
i Borrespersa CA, Borresperse CA-SA i
!
, lion e)(ctlange
I
! lion exchange and !
I
I Fractlonatlorv'
~ e.g. sooluln ! sugar destruction! :
t surrateJ. + t
Prod uot 2 Produc1 a Product 3
Bormsperse NA Borresperse NA 246 Ultrazine CA

Figure 5 Lignosulphonate production process: most lignosulphonate products origin from Ca

lignosulphonate intermediate.

4. Performance difference between different lignosulphonates

The performance of lignosulphonate covers a wide range. The classical, normal grades of
lignosulphonate are typical water reducer or plasticizing admixture of Type A according to ASTM C494
or EN 934-2. More refined lignosulphonate have a different performance with increased water reduction
and reduced set time. These lignosulphonate have performance of Type G or F according to ASTM
C494, i.e. they are high range water reducing and set retarding admixture (Type G) or high range water
reducing admixture (Type F) .

Lignosulphonate for plasticizing admixture or normal water reducing admixture are both calcium and
sodium lignosulphonate with a moderate sugar content. The sugar has been removed by fermentation
or reduced chemically. There is no difference in performance between calcium and sodium
lignosulphonate as long as the only difference between them is the cation. Sodium lignosulphonate is
regarded as being less set retarding than calcium lignosulphonate. This can be true, but the difference is
not caused by the cation, but by the difference in sugar content. Sodium lignosulphonate that origins
from calcium lignosulphonate have lower sugar content than the calcium lignosulphonate due to some
extra sugar conversion during the ion exchange process.

Full sugar lignosulphonate with 20-25 % sugar content are used as set retarding admixture (Type B
according to ASTM C494).

Altering the chemical composition of the lignosulphonate by removing all sugars and most of the organic
acids, and increasing the molecular weight will change the performance of the Iignosulphonate strongly.
Typically, lignosulphonate that has been through this type of process has performance as high range

438

water reducing and retarding admixture. The water reduction with this type of lignosulphonate is
comparable to that of NSF. The workability retention is much longer than that of NSF, while the set time
with this lignosulphonate is longer than that with NSF.

Figure 6 shows the difference in initial slump (workability) and set time with two different sodium
lignosulphonate. Ultrazine is a purified sodium lignosulphonate that is sugar free and very low in organic
acid content. The molecular weight is increased. Borresperse is a standard sodium lignosulphonate
containing some sugar and sugar acids. It is low in insoluble. The high molecular weight lignosulphonate
that is sugar free results in the same initial workability as the normal grade sodium lignosulphonate, but
at a much lower dosage. The dosage is given as % solids of the polymer by weight of the cement. The
set time is much shorter with the high molecular weight lignosulphonate at the same dosage as with the
normal grade lignosulphonate. The total effect of the high molecular weight lignosulphonate being more
effective in terms of workability and less set retarding is, that the set time will be much shorter with the
high molecular weight lignosulphonate that with the normal grade lignosulphonate.

c..

~--t~
E
::l
us
-. - - -.-. --j---+l----~

I
Ultra~ine
Borr1sperse

Dosage

Figure 6 Slump, set time and workability retention as function of dosage for a high range water reducing
lignosulphonate and a water reducing lignosulphonate.

Figure 6 shows the difference in workability retention between these lignosulphonates, and the effect on
set retardation. The workability retention is much longer with the high molecular weight and sugar free
lignosulphonate than with the normal grade lignosulphonate.

; ! ; . ;

1,20 i--+-...;....,-+,--....,.
' -t----:-t-.,...,..---h-,-+~
'__/
____,. ~~-- . " - ~: . ~ v. "
NSF
LS: TypeG
- Poly. (NSF)
- Poly. (LS: Type G)

o% 5% 10 % 15 % 20 % 25 % 30 % 35 r.
Water reduction

Figure 7 Dosage as function of water reduction for NSF and LS (lignosulphonate) of Type G (ASTM
C494).

439
An investigation was conducted to compare the performance of a high molecular weight, sugar free
lignosulphonate with a good quality NSF. The dosage of these two materials needed to obtain water
reduction in the range of up to 32 % is shown in Figure 7. The dosage of the lignosulphonate is less
than that of the NSF, at all water reduction levels. The test was done with initial concrete slump of 88
mm. The set retardation with the lignosulphonate is becoming very long at water reduction above 25 %.

Lignosulphonate are compatible with most other materials used for formulation of concrete admixture.
They can be used alone or in formulations in combination with NSF (sulfonated naphthalene
formaldehyde condensate) or PCE (polycarboxylate) and other materials. Calcium lignosulphonate
should be used when the other materials also are based on calcium and sodium lignosulphonate should
be used when the other materials are based on sodium . Combining calcium lignosulphonate with
sodium NSF can cause precipitation of gypsum. When mixing calcium lignosulphonate with sodium NSF
gypsum is formed from the free calcium in the lignosulphonate and the excess sulfate present in the
NSF.

Good quality raw material should in general be used in formulating concrete admixture as they are low
in insoluble and consistent in quality and performance. Raw materials that are not of good, consistent
quality will cause much precipitation in the production tanks for the chemical admixture. The
performance of the formulation might vary, causing problems to the concrete. Insoluble is always a
problem as they can block dispensers and other parts of the dosing equipment at the concrete mixing
plant.

The above case demonstrates that it is possible to modify lignosulphonate to give very different
performance in concrete. The difference in chemistry between softwood and hardwood lignosulphonate
has to be dealt with in very different ways to result in products that perform in the same way in concrete,
i.e. products that have the same water reduction and set properties in concrete. The differences that
accounts for performance differences are not obvious on typical product data sheets and parameters
like sugar content does not give accurate information on the set retardation of a lignosulphonate
product.

5. Conclusion
Lignosulphonate is processed to be high performing special chemicals. Different performance in the
concrete is achieved through different processing of the lignosulphonate. Chemically different
lignosulphonate can be made to give the same performance in the concrete, through different
processing.

Lignosulphonate are compatible with most other materials used for formulation of concrete admixture.
Consistent good quality of the lignosulphonate is crucial in the formulation of good, high quality concrete
admixture.

Lignosulphonate covers the performance range from set retarding admixture, water reducing admixture
to high range water reducing admixture.

Lignosulphonate are very well suited for formulation of concrete admixtures, and especially in areas with
high ambient temperature as set retardation is needed.

440