Colloids and Surfaces A: Physicochem. Eng.

Aspects 282–283 (2006) 489–497

Physicochemical characterization of calcium

lignosulfonate—A potentially useful water reducer
Xinping Ouyang a , Xueqin Qiu a , P. Chen b,∗
aSchool of Chemical and Energy Engineering, South China University of Technology, Guangzhou 510640, PR China
b Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ont., Canada N2L 3G1
Received 3 October 2005; received in revised form 12 December 2005; accepted 12 December 2005
Available online 6 May 2006

Dedicated to Professor Ivan B. Ivanov (LCPE, University of Sofia) on the occasion of his 70th birthday.

Abstract
In order to use lignosulfonates, a byproduct of pulp and paper processes, as an effective water reducer, the physicochemical properties of calcium
lignosulfonate (CL) with different molecular weights were investigated. It was found that the adsorptive capacity on the surface of cement particles,
surface activity and foam production of CL increase with increasing its molecular weight; however, the zeta potential and hence surface charge of
the cement particles show highest values at the CL lower molecular weight fraction (5000–10,000). The physicochemical properties were related
to some of the most important concrete performance properties. When the dosage of CL is less than 0.5 wt.% of the cement, the CL fraction with
a molecular weight of 10,000–30,000 gives a maximum fluidity in the cement paste. The CL fraction of a high molecular weight has a stronger
air-entraining effect, and hence decreases the compressive strength of concrete.
Because there exist intrinsic limitations with CL as a water reducer (none of CL fractions can give good results on both fluidity and compressive
strength), the original CL was further chemically modified into GCL1 by increasing its sulfonic groups, resulting in an average molecular weight
around 10,000. This new compound gives to an increase in its charge density, and hence a higher zeta potential in its absolute value. Compared with
CL, the surface tension of GCL1 solutions is lower, indicating possibly stronger wetting capability. GCL1 also has a larger adsorption capability
on cement particles, and produces more hydrated ettringite needles in its microstructure. Furthermore, GCL1 shows comparable fluidity and
compressive strength data to formaldehyde condensates (FDN), a gold standard of water reducer materials. This modified CL may be a potentially
very useful water reducer.
© 2005 Published by Elsevier B.V.

Keywords: Lignosulfonate; Superplasticizer; Water reducer; Surface activity; Dispersibility

1. Introduction
Concrete is an indispensable component in modern architec-
tural industry. The properties of concrete in use are characterized
mainly by its flow behavior and mechanical strength. The flow
behavior is mostly controlled by the dispersion of cement par-
ticles, while the mechanical strength is determined by the ratio
of water to cement during the concrete preparation [1]. Water
reducers are such a substance that increases fluidity of concrete
without adding additional water, or reduces the water content
and hence water to cement ratio (in order to increase concrete
∗ Corresponding author. Tel.: +1 519 888 4567; fax: +1 519 746 4979.
E-mail address: p4chen@uwaterloo.ca (P. Chen).
strength) for a given fluidity [2]. High quality concrete cannot be
made without using a water reducer. Water reducers are known
as the fifth component of concrete, besides cement, sand, stone
and water.
According to CEMENTBUREAU [3], the amount of concrete
produced was about 6.4 billion m3 worldwide in 1997. If we
suppose that on average 250 kg of cement are used to produce
1 m3 of concrete, with the dosage of water reducer of 0.3 wt.%
of cement, one can calculate that the demanded water reducer
will be about 4.8 million tons, which provides a large market of
water reducers used for concrete preparation alone.
One of the widely used water reducers is naphthalene sul-
fonate formaldehyde condensates (FDN). It has been reported
that this admixture exhibits a good dispersing effect in con-
crete, and can reduce water demand by up to 20% while still

0927-7757/$ – see front matter © 2005 Published by Elsevier B.V.

doi:10.1016/j.colsurfa.2005.12.020
490 X. Ouyang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 282–283 (2006) 489–497
Fig. 1. Typical structural unit of lignosulfonate.
maintaining the flow characteristics of concrete [4]. However,
there are several limitations with FDN, including a relatively
high cost, difficulties in preparing pumpable concrete because
of large concrete slump-loss (fluidity decrease of concrete) and a
large water bleeding rate (bleeding water per unit area of exposed
concrete) by mixing FDN, and toxicity of residual (unreacted)
monomers (naphthalene). Thus, alternative water reducer mate-
rials are sought after.
Lignosulfonate is the main component in the liquid waste
from chemical pulp mills. It is estimated that there are more than
50 million tons of industrial lignin (lignosulfonate and alkali
lignin) produced every year worldwide [5], but only 10% of
them are utilized. Unused industrial lignin should be treated for
environmental protection.
Lignosulfonate contains both hydrophilic groups (sulphonic,
phenylic hydroxyl and alcoholic hydroxyl) and hydrophobic
groups (carbon chain) [6,7] (Fig. 1). It is an anionic surfactant,
possessing a certain degree of surface activity, which may pro-
mote surface adsorption, foaming and further particle dispersion.
Lignosulfonate may be used in various industrial processes, such
as being auxiliary substance for paper coating [7] and binder [8],
additives in oil drilling [9], and in concrete preparation [10].
Lignosulphonate has been used as a water reducer in concrete
for more than 70 years [3,11]; however, its water-reducing ratio
Fig. 2. Electrostatic repulsion: a schematic representative of two cement particles adsorbed with water reducer molecules.
has been low (usually around 8%) and the mechanical strength
enhancement in concrete has been insignificant. It only can be
used as a common water reducer (water reducing ratio less than
12%) or as a component of high range water reducers (water
reducing ratio more than 12%). Thus, the application of ligno-
sulphonate has been rather limited.
From both environment and water reducer market points of
view, it is desirable to make use of lignosuphonate more effi-
ciently. Much effort has since been made towards modifications
of this molecule [12–19]. If we can modify lignosulfonate into
a high-range water reducer, possibly replacing FDN, it will
bring significant economic and environmental benefits. How-
ever, lignosulfonate derives from natural plants, possessing a
relatively complex composition and a wide range of molec-
ular weights. It becomes clear that lignosulfonate has to be
fractionated according to its molecular weights before con-
ducting any detailed studies. After the fractionation, we pro-
pose to study relationships between its structure, properties
and effectiveness as a water reducer. Up to now, the ques-
tion still remains on how to modify lignosulfonate into a high
range water reducer. In this work, we will explore a new way
to modify lignosulfonate, through oxidation and sulfonation
reactions in order to improve the charge density of lignosul-
fonate molecule, and investigate its resulting physicochemical
properties and their impact on water-reducing ratio in concrete
preparation.
Many reports showed dispersing mechanisms of water reduc-
ers [20–23]. It is often considered as follows: Water reducer
interactions with cement particles lead to the adsorption of water
reducer molecules on the cement particle surfaces. Together with
the steric hindrance, the electrical charge repulsion of adsorbed
water reducer molecules can prevent flocculation of cement
particles, promoting their homogeneous dispersion in freshly
prepared concrete (Fig. 2). It is well known that surface activity
and foaming capability of the water reducer will have a posi-
tive effect on solid particles dispersing into liquid. In order to
improve the water reducing ratio of lignosulfonate, it is proposed
to modify the lignosulfonate molecule by increasing the amount
of sulfonic group, thereby altering its surface and foaming activ-
ities. In the present study, we will study adsorption amounts on
the surface of cement particles, zeta potential of cement par-
ticles containing lignosulfonate, as well as its surface activity.
 X. Ouyang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 282–283 (2006) 489–497
These physicochemical properties will be related to concrete
performance properties.
2. Materials and methods
Calcium lignosulfonate (CL) was part of a by-product of sul-
fite pulping from Guangzhou Papermaking Co. Ltd, China; it
was composed of 70 wt.% of CL, about 10 wt.% of reductive
substances and 20 wt.% of low molecular weight organics and
inorganic salts as well as ash. This commercially available CL
was a water soluble, light yellow powder, turning to brown when
dissolved in water. The Brookfiled viscosity and specific gravity
of a 40 wt.% CL aqueous solution at 25 ◦ C are 79 cP and 1.2 (g),
respectively. Using ultrafiltration (Hangzhou Water Treatment
Center, China), the raw CL was fractionated according to its
molecular weights.
Naphthalene sulfonate formaldehyde condensates used as a
high range water reducer was obtained from Guangdong Zhan-
jiang Water Reducer Co., China.
The cement was the Wuyang Brand 42.5 R ordinary Portland
cement from Guangzhou Cement Factory, China, comprising
major components of tricalcium silicate (C3 S) at 55 wt.%, dical-
cium silicate (C2 S) at 20 wt.%, tricalcium aluminate (C3 A) at
6 wt.%, tetracalcium fluoaluminate (C4 AF) at 9 wt.% and minor
components (e.g., CaO, CaSO4 ·xH2 O, Na2 SO4 and K2 SO4 ).
2.1. Fractionation of CL via ultrafiltration
Calcium lignosulfonate was separated into five fractions
with molecular weight ranges: less than 5000, 5000–10,000,
10,000–30,000, 30,000–50,000 and more than 50,000, using
a hollow fibre membrane ultrafiltration apparatus (Hangzhou
Water Treatment Factory, China). The operation was under a
pressure of 1.5 MPa and temperature of less than 45 ◦ C. The
nominal cutoff ratio was more than 90%.
2.2. Surface tension measurement
The surface tension of the CL aqueous solution with differ-
ent concentrations was measured by a pulling ring (membrane)
method with a 70545 Interfacial Tensiometer purchased from
CSC Scientific Instrument Company, USA, which gave an accu-
racy within ±0.05 mN/m. The liquid to be measured was placed
in a small beaker or petri dish; a platinum-iridium ring was then
suspended in the liquid; the instrument was zeroed with the ring
below the surface of the liquid. The ring was pulled upward until
it broke free of the liquid; the dial reading at the break point was
recorded as the value of surface tension.
2.3. Foaming measurement
The foaming properties were tested by a Ross-Miles pour
foam test apparatus. The foam heights were measured as fol-
lows: 200 mL of 1 wt.% CL solution were placed in a pipette
with a 2.9 mm internal diameter orifice; the solution was allowed
to fall 90 cm onto 50 mL of the same solution in a cylindri-
cal vessel with an internal diameter of 5 cm at 40 ◦ C. The
491
height of the foam produced in the cylindrical vessel was
recorded immediately after all the solution had run out of the
pipette; the time elapsed at half the initial foam height was also
recorded.
2.4. Determination of adsorption amounts on the surface of
solid particles
The cement was weighed at 0.025 g and placed in a beaker,
and 25 mL of CL aqueous solution with a given concentra-
tion were added into it. The solution was stirred for 3 min, and
then kept undisturbed for 10 min. When the solution reached
adsorption equilibrium, the water phase was separated from
slurry in a centrifuge for 10 min. The concentration of CL in
the resulting solution was determined using a UV–vis spec-
trometer (UNICAM Company, England) at the wavelength of
280 nm [24]. The adsorption amount was calculated by the dif-
ference in the amount of CL added originally and that left in the
solution.
2.5. Determination of electrokinetic potential (␨-potential)
of cement particles
Using a JS94F micro-electrophoretic mobility detector
(Shanghai Zhongchen Apparatus Factory, Shanghai, China), the
cement was added into a water reducer solution or distilled water.
The mass ratio of cement to water reducer solution or water was
1:500. The mixture was stirred for 5 min, and then poured into
the electrophoretic cell to detect the ␨-potential.
2.6. Test of performance of cement paste and concrete
To determine the fluidity of cement paste, conforming to
the Chinese National Standard GB/T 8077–1987, 300 g of the
cement with desired amounts of water and water reducer were
mixed for 3 min. The cement paste was put into a small flow
cone mold (base diameter of 10 ± 0.05 cm, top diameter of
7 ± 0.05 cm and height of 6 ± 0.05 cm), and no external vibra-
tions were used to consolidate the fresh cement paste. Once
the test cone was lifted, the fresh cement paste collapsed and
spread. The maximum diameter of the spread d1 and the diame-
ter perpendicular to it d2 were measured. The mean value of the
diameters (d1 + d2)/2, gave a measure of the fluidity of cement
paste.
Compressive strength of the concrete was tested according
to the Chinese National Standard GB11837-89 as follows. The
mixture of concrete was prepared for 10 min in a mechanical
mixer at room temperature. The mixture was then cast into metal-
lic vials (15 cm × 15 cm × 15 cm) and compacted with an iron
rod until all entrapped air was removed apparently. The prepared
samples were placed into a fog tank at 25 ◦ C. The samples were
removed from the metallic vials after 3, 7 and 28 days of cur-
ing. At a given age, three specimens per mixture were subject
to compressive strength testing using a compression machine
(Wuxi Concrete Instrument Factory, China). The ends of these
specimens were ground to ensure that the end surfaces were flat
and parallel before testing. The strength results shown were the
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average of the three specimens with variations of less than 10%.
Relative compressive strength was obtained by the compressive
strength of concrete with water reducer divided by that of refer-
ence concrete.
Measurement of air content in concrete was done according
to the Chinese National Standard GBJ80-85: Using a pressure
type “B” meter (Wuxi Concrete Instrument Factory, China).
Fresh concrete was placed into a bowl. Using a rubber syringe,
water was injected into the bowl through one petcock until water
emerges from the opposite petcock. The meter was jarred gen-
tly until all air was expelled. The air bleeder valve of the air
chamber was closed and air was pumped into the air chamber to
obtain a stabilized reading. Then the air valve between the air
chamber and the measuring bowl was opened, and readings on
the dial of pressure gauge were recorded. The air content of a
sample was calculated as follows:
3. Results and discussion
3.1. Adsorption isotherm
Adsorption isotherm of CL with different molecular weights
on the cement particles is shown in Fig. 3, as compared with
those of the raw CL (overall composition), FDN and GCL1.
Fig. 3 suggests that adsorption amounts of CL on the sur-
face of cement particles increase with an increase in molecular
weight. From Fig. 3, we also find that adsorption amounts of
FDN on the surface of cement particles are the largest among all
substances shown. This may be because its linear structure leads
to closer or more compact arrangements of adsorbed molecules
on the cement particles. The adsorption amount of GCL1 (mod-
ified CL) is closer to that of FDN. Compared with the original
CL, there has been a 30% increase in GCL1.

A s = A1 − G 3.2. Zeta potential

where As is air content of concrete, A1 is apparent air con-
tent of sample, and G is air content of aggregate (sand and
stone).
2.7. Modification of calcium lignosulfonate
In order to break up the three-dimensional structure of CL
molecules and to increase its chemical reaction activity, an oxi-
dation reaction was chosen at a temperature of 60–80 ◦ C as the
first step of the CL modification, where 0.1 wt.% Fe2+ + Cu2+
were used as a catalyst, and 5%wt. H2 O2 as an oxide agent.
Then, a process of sulfonation reaction with 8 wt.% sulfite was
conducted at 90 ◦ C and pH 9 to increase the number of sul-
fonic groups on the molecule. At the end of this reaction, the
temperature was adjusted at 80 ◦ C, followed by a condensa-
tion reaction for 1–2 h with an addition of 5 wt.% formalde-
hyde to adjust the molecular weight of the product. The mod-
ified lignosulfonate was obtained, as an intended high range
water reducer (GCL1). The characteristics of the molecular
structure before and after the CL modification are shown in
Table 1.
Table 1 indicates that the amount of sulfonic groups of GCL1
increased as compared with that of CL, and after the modification
the average molecular weight also increased from ∼7000 of
original CL to ∼10,000 of GCL1 using formaldehyde.
The zeta potential of cement particles containing water reduc-
ers is shown in Fig. 4.
The adsorption of water reducer on the surface of cement
particles is mainly due to electrostatic attractive forces between
negative charged sulfonic groups and positive charged cement
particle surfaces. After the CL modification, there will be more
negative charged sulfonic groups in GCL1 molecules, and this
leads to larger attractive forces between the adsorbate and the
cement particle. As a result, a larger zeta potential value of
around 30 mV was obtained with GCL1, compared to that of
CL. In general, the higher the adsorption amount on the surface
of cement particles, the higher the zeta potential (in absolute
values) is. However, comparing Fig. 3 with Fig. 4, it can be
found that the zeta potential increases with decreasing adsorp-
tion amounts, with an exception of the fraction of molecular
weight less than 5000. The reason for this is that CL fraction
with a molecular weight from 5 to 50 kDa tends to have a char-
acteristic high charge density and hence contributes to the zeta

Table 1
Structural characteristics of CL (with an average molecular weight of ∼7000)
before and after modification
Average molecular Relative absorbance
weight, Mw A1040 /A1509 a
Sulfonic group

GCL1 10010 5.13

CL 7008 3.12
a Relative absorbance was obtained by the intensity of adsorption peak of
sulfonic group at the wave number of 1040 cm−1 in infrared spectrum divided
by adsorption peak of aromatic ring exists in the CL structure unit at the wave
number of 1509 cm−1 . Fig. 3. Adsorption isothermal of water reducer.
 X. Ouyang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 282–283 (2006) 489–497
Fig. 4. zeta potential of cement particles containing a water reducer.
potential (in absolute values) more effectively. As for the fraction
of molecular weight less than 5000, which has the lowest zeta
potential (in absolute values), more inorganic components exist
in this fraction which compresses the electrical double layer
above the particle surface. Fig. 4 shows that the zeta poten-
tial for cement particles without adsorbing any water reducer is
around 10 mV, indicating that the surface of cement particle is
charged positively. With an increase in water reducer concentra-
tion, the zeta potential decreases, passing over the value of zero,
at which no electrostatic repulsion exists among the cement par-
ticles and the cement dispersion becomes unstable. After that
point, the zeta potential will change to a negative value and
the absolute value increases, up to a plateau value with further
increasing water reducer concentration. With CLs, the maximum
zeta potential is around −20 mV; while with adding GCL1 into
the cement water system, the zeta potential can reach −30 mV.
This means that GCL1 adsorption may impose stronger electro-
static repulsive forces among cement particles than simply CL
adsorption.
3.3. Fluidity of cement paste
Many references suggest that the water reducing effect is
dependent on electrostatic repulsive forces among cement par-
ticles adsorbed with water reducer molecules [25]. In order to
evaluate the effect of electrostatic repulsive forces on water-
reducing and dispersion effects of CL on cement particles, we
have determined the fluidity of cement paste blended with CL of
different molecular weights. The mass ratio of water to cement
is 0.35:1. The results are shown in Fig. 5.
When the dosage of CL is less than 0.5 wt.% of dry powder
of cement, the fluidity of cement paste blended with different
molecular weight CL does not change in any pattern with the
change in molecular weight of CL. The addition of CL molec-
ular weight of 10,000–30,000 seems to give a largest fluidity of
493
Fig. 5. The relationship between fluidity of cement paste and dosage of CLs.
the cement paste. When the dosage of CL is larger than 0.5 wt.%
of cement, the fluidity of cement paste increases with increas-
ing CL molecular weight. In this situation, excessive amounts
of CL exist and adsorb onto the cement particles, forming steric
hindrance. It is easy to understand that a substance with a high
molecular weight has a stronger effect of steric hindrance. How-
ever, actually it is never used in practice with a dosage of CL
more than 0.5 wt.%, because of excessive retarded setting times
(the curing time of cement paste).
It is obvious that the dispersing effect of water reducers
cannot be explain only by electrostatic repulsive forces among
cement particles only because Fig. 4 exhibits CL with a molec-
ular weight of 5000–10,000 contributes to strong electrostatic
repulsive forces among cement particles, but CL with molecu-
lar weights of 10,000–30,000 contributes to a better fluidity of
cement paste when the dosage is less than 0.5 wt.% of cement.
3.4. Surface tension of CL solutions
Fig. 6 shows the surface tension of aqueous solutions of CL
with different molecular weights. We can find that the effect
of CL with a low molecular weight on the reduction in surface
tension is not strong. In accordance with the results observed
by Rojas and Salager [25], lignosulfonate has a characteristic
of being strong hydrophilic. Its hydrophobic skeleton appears
spherical in shape, so it cannot form a regular arrangement
at the interfacial phase. This is common with certain surfac-
tants of low molecular weights. Fig. 6 also indicates that the
surface tension of CL solutions decreases with increasing molec-
ular weight. This may be related to the fact that the charged
hydrophilic groups decrease, relatively, with a molecular weight
increase. The static repulsive forces between hydrophilic groups
at the solution surface weaken; as a result, CL molecules of
a high molecular weight form a dense adsorption layer (cf.
Figs. 3 and 6). The adsorption amount thus increases, leading to
that CL with a high relative molecular weight has higher surface
activity, i.e., lower surface tension.
494 X. Ouyang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 282–283 (2006) 489–497

Table 3
Effect of CL with different molecular weight on air content and relative com-
pressive strength of concrete
Molecular weight Air content of Relative compressive
of CL concrete (%) strength (%)
3-day 7-day 28-day

Reference 0.5 100 100 100

Less than 5000 3.5 101 109 119
5000–10,000 3.9 98 105 115
10,000–30,000 4.9 95 98 102
30,000–50,000 5.7 92 91 89
More than 50,000 6.8 86 83 81

The dosage of CL is 0.25% wt. dry powder of cement.

trapped will decrease the friction among the cement particles,

Fig. 6. Surface tension of water reducer.
For the process of solid particles dispersing into liquid phases,
the first step is that the solid particle was wetted by the liquid.
The lower surface tension of the liquid solution is, the easier the
wetting of solid particles may be because this helps the cement
particles more readily disperse into water.
Fig. 6 shows that the surface activity of FDN is very low;
CL has a certain degree of surface activity when the concen-
tration is 10 kg/m3 . The CL aqueous solution surface tension
is about 44 mN/m at its minimum, but after modification, the
resulting GCL1 can have a low surface tension of 32.9 mN/m at
a concentration of 1 kg/m3 .
3.5. Foaming property
The initial foam height and foam half-life time of a CL
solution (at a concentration of 1 wt.%) were tested. They, respec-
tively, represent the foaming ability and foaming stability of CL.
The results are shown in Table 2.
The results demonstrate that the foam production and foam
stability increase with increasing CL molecular weight. This
may be due to the fact that with increasing molecular weight,
surface activity of CL solution increases, and foam formation
becomes less energy demanding. In this situation, thicker foam
films may be formed with higher molecular weights, resulting
in more stable films and therefore better foam stability.
When CL is added into the concrete mixture, it not only
adsorbs at the interface of solid-liquid, but also adsorbs at
the interface of liquid-gas; as a result, some bubbles are eas-
ily formed and can be trapped into the concrete. The bubbles
Table 2
Foam property of CL with different relative molecular weight
Molecular weight Initial foam height (cm) Half life time (min)
and therefore increase the fluidity of the concrete. Table 2 seems
to indicate that CL with higher molecular weights is more suit-
able for using as a concrete water reducer.
The effectiveness of water reducers is not only determined
by the increasing of fluidity of concrete, but also determined
by the increasing of compressive strength after adding the water
reducer. So we studied the effect of addition of CL with different
molecular weights on air content and compressive strength; the
results are shown in Table 3.
From Table 3, we can find that when the molecular weight
of CL increases, the air content in concrete increases and the
compressive strength decreases. The foaming results show that
foaming ability increases with the relative molecular weight, so
the air content in concrete also increases. The increase in air
content will surely increase the amount of pore in concrete, and
thus causes the strength to decrease.
The function of water reducers used in concrete includes two
aspects: One is to increase fluidity of concrete without supplying
additional water, so it can increase workability of concrete on
the basis of not decreasing the strength of concrete; the other one
is to reduce water consumption under the condition of the same
fluidity of concrete, so as to increase the strength of concrete.
As discussed above, when CL is applied in concrete, lower or
intermediate molecular weight fractions have a strong electro-
static repulsive force (in favor of dispersing of cement particles
once adsorbed with CL), but a lower surface activity and lower
air content (entraining). On the other hand, CL with a higher
molecular weight has a good surface activity but lower electro-
static repulsive forces, also its higher foam production will lead
to a decrease in concrete strength. It seems that CL is rather
limited in its use as a water reducer since none of CL fractions
can give good results on both fluidity and strength. The original
CL should be modified to increase its charge density (and hence
dispersion capability) and to adjust it surface activity (and hence
high air content) in order to increase its overall water reducing
capability.

Less than 5000 4.8 3. 5 3.6. Effect of GCL1 (modified CL) on concrete properties
5000–10,000 5.6 5.8
10,000–30,000 6.7 6.3 The results of fluidity of cement paste with additions of CL,
30,000–50,000 7.2 8.2
More than 50000 7.8 9.5
GCL1 and FDN are shown in Fig. 7. The mass ratio of water to
cement is 0.32.
 X. Ouyang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 282–283 (2006) 489–497 495

on the fluidity of cement paste is even more significant, and

Fig. 7. fluidity of cement paste for water reducer.
As shown in Fig. 7, we can see that the contribution of GCL1
to fluidity of the cement paste is much better than that of CL.
When the dosage of water reducer increases, so does fluidity of
the cement paste. The maximum fluidity of cement paste with
adding CL is only 100 mm; at the same condition, that with
adding GCL1 is 200 mm. Furthermore, we can see that when
the dosage is less than 0.5 wt.% of cement, the effect of GCL1
indeed better than that of FDN. But when the dosage is more
than 0.5 wt.% of cement, with the increase of dosage, the fluidity
of cement paste with adding of FDN will continue to increase,
while that of GCL1 increases to a less extent. These results mean
that after being modified, GCL1 has become a high range water
reducer, but it still has some disadvantages when compared with
the gold standard of FDN in concrete industry.
As mentioned above, compressive strength is one of the most
important mechanical properties of concrete; the compressive
strength of hardened concrete after using a water reducer at dif-
ferent stages was tested and shown in Table 4.
Table 4 suggests that the water reducing rate of CL is only
6.4%. When varying the dosage, the water reducing rate of CL
is always lower than 8% (data not shown). The early stage com-
pressive strength of concrete with CL is also low. But after the
modification, the water reducing rate increases to 19.5%, and
the concrete compressive strength also increases significantly
with GCL1, where its compressive strength increases by 60
and 28% at 3 and 28 days, respectively. It is obvious that the
water reducing and strength increasing of GCL1 have markedly
improved from those of CL. In fact, such improvements have
met the industrial standards of high range water reducers, with
many properties being similar to those of FDN, a widely used
water reducer in practice.

Table 4
Effect of water reducers on concrete properties
Dosage of water reducer (%) Water reducing ratio (%) Relative compressive strength (%)

3days 7days 28days

Reference concrete 0 0 100 100 100

Concrete with addition of CL 0.25 6.4 119 94 102
Concrete with addition of GCL1 0.40 19.5 160 138 128
Concrete with addition of FDN 0.40 22.1 170 140 126

Fig. 8. SEM photographs of hydration product of hardened cement paste (a) with addition of CL (b) with addition of GCL1.
496 X. Ouyang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 282–283 (2006) 489–497
Fig. 9. SEM photographs of surface morphology of hardened cement paste (a) with addition of CL (b) with addition of GCL1.
3.7. Effect of GCL1 on the structure of hardened cement
The surface morphology of the cement hydration product, i.e.,
hardened cement, with addition of CL and GCL1 after 28 days of
hydration was imaged by SEM, and are shown in Figs. 8 and 9.
Fig. 8 shows that with GCL1 as the water reducer, the prin-
cipal products of cement hydration are branched crystals, in the
form of ettringite needles; while with CL as the water reducer,
the products of cement hydration appear to be larger, but fewer in
number, ettringite crystals. This result indicates a slower hydra-
tion with CL, as compared to that with GCL1.
As shown above, GCL1 can better disperse cement particles
into water when compared with CL. During cement hydration,
with the presence of GCL1 the cement paste can generate more
nuclei and form finer ettringite needles than with the presence
of CL. Because of finer crystal structures with GCL1, the com-
pressive strength of hardened cement is also improved.
From Fig. 9, it is easy to find that there are many voids in the
hardened cement with adding CL, but fewer voids with adding
GCL1. The hardened cement with GCL1 is denser and more
uniform than that with CL. These imply that the diameter of
bubble induced by CL is bigger than that by GCL1, during the
process of cement paste preparation. The bubbles induced by
water reducers will collapse and leave behind with pores in the
hardened cement, and they are detrimental to the strength of
hardened cement.
4. Summary
In this work, we characterized calcium lignosulfonate, a
potentially useful water reducer, from a physicochemical point
of view. It was found that the adsorptive capacity on the surface
of cement particles, surface activity and foam production of CL
increase with increasing its molecular weight; however, the zeta
potential and hence surface charge of the cement particles show
highest values at low or intermediate molecular weights.
The physicochemical properties were related to some of
the most important concrete performance properties. When the
dosage of CL is less than 0.5 wt.% of the cement, the CL fraction
with a molecular weight of 10,000–30,000 gives a maximum flu-
idity in the cement paste. The CL fraction of a higher molecular
weight has a stronger air-entraining effect, and hence decreases
the compressive strength of concrete.
The original CL was further chemically modified into GCL1
by increasing its sulfonic groups, resulting in an average molec-
ular weight around 10,000. This new compound gives to an
increase in charge density, and hence a higher zeta potential
in its absolute value. Compared with CL, the surface tension
of GCL1 solutions is lower, indicating possibly stronger wet-
ting capability. GCL1 also has a larger adsorption capability on
cement particles, and produces more hydrated ettringite nee-
dles in microstructure. Furthermore, GCL1 shows comparable
fluidity and compressive strength data to those of FDN, a gold
standard of water reducer materials. This modified CL presents
a promising commercial water reducer.
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