CHEMISTRY AND PERFORMANCE OF DIFFERENT

LIGNOSULFONATES

K. Reknes*, Borregaard LignoTech R&D, Norway


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28
th
Conference on OUR WORLD IN CONCRETE & STRUCTURES: 28 - 29 August 2003, Singapore
CHEMISTRY AND PERFORMANCE OF DIFFERENT
L1GNOSULFONATES
K. Reknes*, Borregaard LignoTech R&D, Norway
Abstract
Lignosulphonate from different sources is being used in concrete admixture
formulations in Asia. The properties of the different lignosulphonate can vary, as the
lignosulphonate are different both in chemistry and in performance in the concrete.
Lignosulphonate produced in China, Norway and South Africa were compared in an
investigation including chemical analysis and concrete performance testing. The
purpose of the investigation was to correlate some of the differences in chemical
composition, with the concrete performance of the materials.
There are performance differences between the samples investigated. The molecular
weight is the highest for Borresperse CA and the lowest for the Chinese samples. All
the three Chinese samples have the same molecular weight distribution. The
Chinese samples are Mg lignosulphonate and the Borresperse samples are Ca
lignosulphonate. The Chinese I sample contain a high amount of insoluble. The air
entrainment is the lowest with Borresperse CA-SA and the highest with the Chinese
samples. The air entrainment affects the compressive strength. The compressive
strength is lower with the admixture samples entraining the most air than with the
admixture samples entraining the least air. The Chinese samples contain chloride in
high concentration and are thus not suitable for formulation of concrete admixtures.
Keywords: lignosulphonate, concrete, water reducing admixture
1 Introduction
Lignosulfonate has been used in chemical admixture for concrete since the 1930-ties. The probably
most important single group of materials used in chemical admixture for concrete was and still is
lignosulfonate. The way lignosulfonate is being modified and altered has changed since the beginning
in the 1930-ties. During the 20
th
century, a wide range of new materials found their way into the
formulations of chemical admixture for concrete. The use of gluconate started in the 1940-ties. PNS
(naphthalene sulfonate) were developed and introduced in the early 1970-ties. Melamine sulfonate
(MS) were introduced around 1980, poly vinyl copolymers (VC) around 1990 and the poly carboxylic
copolymer (PC) around 2000. As new materials have been added to the range of raw materials, new
formulations have been developed with combinations of these materials and lignosulfonate.
Lignosulphonate from different sources is being used in concrete admixture formulations in Asia.
The properties of the different lignosulphonate can vary, as the lignosulphonate are different both in
chemistry and in performance in the concrete. Difference in chemical composition can have big impact
on the performance of the lignosulfonate in concrete 11, 2/. These differences can be overcome by
different ways of modifying the lignosulfonate to results in the same performance in the concrete.
These differences do also have impact on the formulation of the concrete admixture. Lignosulphonate
439
produced in China, Europe and South Africa were compared in an investigation including chemical
analysis and concrete performance testing. The purpose of the investigation was to correlate some of
the differences in chemical composition, with the concrete performance of the materials. The results of
the investigation are reported here.
2 Experimental
2.1 Samples
The samples used in the experimental work are described in Table 1. The three Chinese samples
were provided from Korea. The origin is not known to us. They are expected to be sodium
lignosulphonate. Borresperse CA-SA is a hardwood lignosulphonate. Borresperse CA is a softwood
lignosulphonate.
2.2 Concrete testing
The samples were tested on performance in concrete. concrete mix proportion is
according to the European standard EN 480-1 and is shown In Table 2. The aggregate particle size
distribution is composed according to the European standard EN 480-1.
-8mm
8-11 mm
1116mm
Admixture
The following concrete properties were determined:
slump: initial and after 15 minutes and 30 minutes when possible,
air content and fresh density,
set time by measurement of the temperature increase in isolated box and
compressive strength and density after 24 h, 7 days and 28 days.
3 Results and discussion
The results of the chemical analysis conducted are shown in Table 3. The molecular weight of the
Chinese Iignosulphonate samples is low, and lower than that of Borresperse CA-SA. The molecular
weight distribution of the samples is shown in Figure 1. The weight average molecular weight (Mn) of
the Chinese and the Borresperse CA-SA is the same, but there is difference in the weight average
molecular weight (Mw). The molecular weight of Borresperse CA is much higher that that of the other
samples. This is valid for both Mn and Mw.
The amount of reducing sugar is slightly different in the samples. The Borresperse CA-SA
sample contains 2.0 % reducing sugar, while the other samples contain 5-6 % reducing sugar. The
total sugar content of the samples is low, as the term reducing sugar also includes other reducing
components than only sugar, i.e. reducing sugar is equal to reducing matter. The content of reducing
I % sbwc = % solids by weight of cement
440
sugar or reducing mater is determined by determining the amount of aldehyd groups present. Aldehyd
groups are also present not only on sugars but also on hem i-cellulose and other low molecular weight
components.
Both Borresperse CA-SA and Borresperse CA are produced from Ca intermediate
lignosulphonate origin from the calcium sulphite pulping process. The Ca content of these samples is
thus in the range of 5.2 % and 7.6 % respectively. The other samples have a very low Ca content. The
Na content is also very low. The Chines sample I, H and A are all Mg lignosulphonate with a Mg
content in the range of 5-6 %.
The determination of amount of insoluble in the samples showed very low amount of insoluble
in all the samples. However, the Cinese I sample had a thick layer of insoluble at the bottom of the
bottle. It was not possible to keep the insoluble in this sample in solution long enough to include them
in the determination of the insoluble. A "clean" sample was thus used for this analysis. The amount of
insoluble at the bottom of the boUle was estimated to approximately 4 % v/v (volume by volume). The
Chinese I sample thus contain a lot of insoluble. Analysis verified that the insoluble consists mainly of
calcium sulphate (gypsum) and a minor fraction of oxalate. A high amount of insoluble in the solution
can create problems and is costly: The insoluble will accumulate in the production tank at the
admixture formulating plant. The cleaning of the tank takes time and implies thus a cost. The insoluble
that has preCipitated in the production tank, might by accident be transferred to the finished formulated
product. The insoluble will then end up in the admixture tank at the concrete plant with the risk of
blocking dispensers and pipelines.
The chloride content of the Chinese samples is in the range of 1.5 to 2.1 % (Table 3). This is
extremely high and 15 to 20 times the maximum limit of the allowed chloride content according to the
European standard for concrete admixture, EN 934-2, Table 1. Chloride in the concrete can have
setting and hardening accelerating effect, but will also in very low dosages result in corrosion of the
reinforcement-steel. The speed of corrosion on the reinforcement-steel is also depending on the stress
level in the reinforcement-steel and the steel quality. To avoid or to keep the probability of corrosion of
the reinforcement-steel at the minimum, chloride should not be introduced into the concrete. This is
the reason for the limitation of the allowed chloride content in concrete admixture in Europe.
Ii bl 3 Th a e It fl' fth e resu s 0 anarysls 0 esampJes.
Sample Molecular weight RedUCing Amount of
Mw Mn sugar Ca Na Mg CI insol.
2
[%1 [%1 [%] [%1 [%1 r% v/v]
2003004-1
8700 2700 5.2 0.31 0.91 5.6 1.5 < 0.10
3
Chinese I
2003004-2
8900 2700 5.3 0.26 1.1 5.4 2.0 < 0.10
Chinese H
2003004-3
9300 2750 5.5 0.36 1.0 5.7 1.7 < 0.10
Chinese A
Borresperse
CA-SA 10500 2700 2.0 5.2 0.27 0.0 0.03 0.6
LTSA
Borresperse
CA 39600 5100 6.6 7.6 0.05 0.0 0.04 0.6
LTN
The concrete performance data are shown in Table 4. The table is divided in two parts, one showing
the results with defoaming agent (TBP) and the second showing the results of the concrete without
defoaming agent (TBP).
There is no significant difference in initial slump with the Borresperse CA sample, Borresperse
CA-SA sample, Chinese sample H and Chinese sample A. The Chinese sample I results in higher
initial slump than the other samples. This is shown in Figure 2. Figure 2 shows also that the air
entrainment is much higher with the Chinese sample I than with the other samples. The higher air
entrainment correlates with the higher initial slump. This is shown in Figure 3. The air content with the
2 Insoluble: % volume by volume
3 The sample contained a lot of insoluble. The insoluble was left in the bottle and not included in the analysis, as
it precipitated too fast to be kept in the sample taken for analysis. The total amount of insoluble in the sample
was estimated to approximately 4 % v/v.
441
Chinese sample I is 2-3 % higher than that with the other samples, in spite of the 0.8 % dosage of
defoaming agent.
The initial set time is the same for the samples of Borresperse CA, Borresperse CA-SA,
Chinese H and Chinese A up to the dosage of 0.40 % sbwc. The initial set time with the Chinese I
sample is higher than with the other samples at the 0.40 % sbwc dosage. All the Chinese samples
have approximately the same initial set time at the 0.60 % sbwc dosage. The two Borresperse
samples have much longer set time than the Chinese samples at the 0.60 % sbwc dosage. The
accuracy of the test method is approximately 0.5 hours.
A principle component analysis (PCA, mUltivariate data analysis) was conducted on the
concrete performance data from the data set with 0.8 % TBP. The PC1 and PC2, that are explaining
91 % (PC1 64 % and PC2 27 %) of the variation of the data, are shown in Figure 4. Slump (Slump_O)
and initial set time (Set) correlates with the dosage (DOS) of the admixture. This is as expected. The
air entrainment (Air) correlates with the admixture dosage on PC1, but is negatively correlated on
PC2. This can be explained by the increase in air entrainment with increasing dosage (PC1). Increase
in workability (slump) makes it easier for the entrained air to escape from the concrete. Increasing
workability is a result of increase in admixture dosage resulting in the negative correlation between air
entrainment and admixture dosage on PC2. The positive correlation between air content and slump
on PC1 implies that increased air entrainment also improves the workability of the concrete. Air
content is negatively correlated to the density of the fresh concrete (Dens-f) on both PC1 and PC2.
This is as expected: Increasing air content results in lower density. Density and compressive strength
are positively correlated on PC1 both at 24 hours (C24, 024) and at 7 days (C7, 07). The 24 hour
compressive strength is negatively correlated to the density on PC2. The 24 hours compressive
strength is negatively correlated to set time on both PC1 and PC2. Increasing set time results in
reduced 24 hours compressive strength, as expected.
-
c:::
::I
o
E

Chinese
t
Chinese
Chinese
/ Borresperse CA
Borresperse CA-SA
Molecular weight
Figure 1 Molecular weight distribution for all samples used in the investigation.
The normal probability plot of the air content of the fresh concrete is shown in Figure 5 and of
the initial set time in Figure 6. Some of the samples are not following the normal distribution fully. The
scores and correlation loadings from the PCA are shown in Figure 7. The scores plot show that the
Chinese I sample is grouping differently from the other samples. The other samples are grouping very
similar to each other indicating that they are not very different.
442
443
(Control 22,9 0,5 53,7 1,0 68,2 O,7( 2426 11 2443 9 2440 51
The compressive strength development at the different dosages used is shown in Figure 8 and Figure
10. The main factors affecting the compressive strength are as follows:
initial set time affects the 24 hours compressive strength and
air content affects the 7 days and 28 days compressive strength.
The 24 hours compressive strength is reduced with increasing set time (Figure 9). The
compressive strength at 7 days is mainly affected by the air entrainment. Increasing air entrainment
reduces the compressive strength.
The concrete performance was also determined without addition of defoaming agent (TBP). The
data of this data set is shown in Figure 11. The air entrainment of the Chinese samples is higher than
that of the Borresperse samples. Borresperse CA-SA has a much lower air entrainment than the other
samples. The need for defoaming agent needed to control the air entrainment is thus the lowest with
this material.
The difference between the set time with the different samples is in the data set without defoaming
agent reduced relative to the data-set with 0.8 % TBP, The initial slump is lower with the Chinese
samples than with the Borresperse samples.
444
200r--------------------------------,

E
..
Q.

iii


0,00 0,10 0,20 0,30 0,40 0,50 0,60 0,70
Dosage rio sbwc)
30,0 -,----------------------------------,
25,0 +--------------------------/------\
20,0 t-------------::::t===----1
c.
..
!i 15,0 +----------------;;"-,.-:iis;;,...-e!'-'-----------\

I/) 10,0
5,0 .",=--------------------------------1
0,0 __ ----.__--_,_----!
5,0
4,5
4,0
3,5
"0

3,0
... 2,5
c
8 2,0
..
C
1,5
1,0
0,5
0,0
0,00 0,10 0,20 0,30 0,40 0,00 0,60 0,70
Dosage rio sbwc)
T
---r
../"
J..


-l
- ---
F

.:.:..: ---- '--
--
0,00 0,10 0,20 0,30 0,40 0,50 0,60 0,70
Dosage rio sbwc)
Borresperse CA
____ Borresperse CA-SA
--t--- Chinese Sample I
--* --Chinese Sample H
- -lI( - Chinese Sample A
Borresperse CA
____ Borresperse CA-SA
--t--- Chinese Sample I
-. * . -Chinese Sample H
- -lI( - Chinese Sample A
Borresperse CA
____ Borresperse CA-SA
--t--- Chinese Sample I
. -* . -Chinese Sample H
- -lI( - Chinese Sample A
Figure 2 The concrete performance as function of dosage for all samples with 0,8 % defoaming agent
(TBP). The slump is shown at the top. The set time is shown in the middle and the air content of the
fresh concrete is shown at the bottom.
445
250 -r-----------------,. 4,5
4,0
200 3,5
3,0
E
g
i 100 2,0 g
o u
1,5
50 -/-,:-"=---------------'1 1,0
0,5
o -1---.---.-----,--__,.-__ --_--+ 0,0
0,00 0,10 0,20 0,30 0040 0,50 0,60 0,70
Dosage [% sbwc]
-+--BspCA (S)
----BspCA-5A (S)
-I--CJ(S)
- - -- - - BspCA (A)
- . Q - . BspCA-SA (A)
- - + - -CJ (A)
Figure 3 The initial slump and the air content of the fresh concrete as function of dosage for the
Chinese I sample and the Borresperse CA and Borresperse CA-SA samples .
10
. . LosdingS.f?<1.. .
05
.05
.1.0
PCt
.1.0 .0.5 0.5 1.0
RESULT2. Xexpl: 64%.27%
Figure 4 The result of principle-component analysis of all the concrete performance data with
defoaming agent (TBP). (OOS = dosage, S/ump_O = initial slump, Set = set time, Air = air content,
OensJ= fresh density, 024 = density at 24 hours, C24 = 24 h compressive strength, 07 = density at 7
days, C7 = 7 days compressive strength)
96.88
90.63 .. 561
8438
7813
7188
65.63
59.38
53.13
46.88
4063
34.38
28.13
21.88
15.63
938
3.13
1.0 15 2.0 25 3.0 35 40
Figure 5 Normal probability plot of air content of fresh concrete with 0.8 % defoaming agent (TBP),
446
96.88 > : SA
90.63
84.38
78.13
71.88
65.63
59.38
53.13
46.88
40.63
34.38
28.13
-' .
21.88 ..,. ,
15.63

9.38
3.13
-
5 10 15 20 25 30
Figure 6 Normal probability plot of set time of concrete with 0.8 % defoaming agent (TBP).
PC2
.,
.,
.,
RESULT2.X.eJIi 64'1,,2PJ.
Scores
.,
peA 1 2 ... X-ex lained: 64 %. 27 %
Correlation Loadin
1.0 PCZ
05
10
Fef
.10
RESU.T2. X-flJ;lt 64'1t..21'1.
0.5
Figure 7 Scores and loadings calculated for the concrete performance data of the concrete with 0.8 %
defoaming agent (TBP). Outliers are eliminated from the data set.
"iii'
D-

i
c
e
Ui
ci
E
8
Figure 8 The compressive strength of the concrete with 0.8 % defoaming agent (TBP).
447
PCf
10
25,0 -.-----------------,
20,0
!.
::
g' 15,0
1:
"!
10,0
8
.c
5,0
0,0
0,0 5,0 10,0 15,0 20,0 25,0 30,0
Set time [h]
-+--Borresperse CA
--II-Borresperse CA-SA
---I-Chinese Sample I
- - -x, - - Chinese Sample H
- "* - Chinese Sample A
Figure 9 The 24 hours compressive strength as function of the set time for the concrete with 0.8 %
TBP.
4 Conclusion
There are chemical differences and performance differences between the samples investigated,
The molecular weight is the highest for Borresperse CA and the lowest for the Chinese
samples. All the three Chinese samples have the same molecular weight distribution. The Chinese
samples are Mg lignosulphonate and the Borresperse samples are Ca lignosulphonate. The Chinese I
sample contain a high amount of insoluble.
The air entrainment is the lowest with Borresperse CA-SA and the highest with the Chinese
samples, The air entrainment affects the compressive strength. The compressive strength is lower
with the admixture samples entraining the most air than with the admixture samples entraining the
least air.
The Chinese samples contain chloride in high concentration. Chloride can be harm full in
reinforced concrete and these lignosulfonates are thus not suitable for formulation of concrete
admixtures.
5 Reference
111 Gustafsson, J. and Reknes, K. Adsorption and dispersing properties of lignosulfonate in model
suspensions and cement pastes, Proceedings of the Sixth CAN M ET/AC I International
Conference on Superplasticizers and Other Chemical Admixtures in Concrete, Nice, October,
2000
/2/ Reknes, K. and Gustafsson, J. Effect of modifications oflignosulfonate on adsorption on cement
and fresh concrete properties, Proceedings ofthe Sixth CANMET/ACI International Conference
on Superplasticizers and Other Chemical Admixtures in Concrete, Nice, October, 2000
448
0.20 % sbwc
80,0
70,0
'f 60,0
::5
50,0
tj,



I'
5; 40,0

Q. 30,0
1
E
c3 20,0
IJ
10,0
0,0
0
0.40 % sbwc
90,0
80,0
'ii' 70,0
Q..
i! 60,0
.:
i' 50,0
1: 40,0
II!
30,0
c3 20,0
10,0
0,0
0
0.60 % sbwc
80,0
70,0
'f 60,0
::5
50,0
tj,
5; 40,0

7 14 21 28
Time [days]
7 14 21 28
Time [days]
--=:;::t
.. :,.:.:..- -:..::-+


//
II
Q. 30,0
20,0
!
10,0
0,0
.J

o 7 14 21 28
Time [days]
35
35
35
____ Borresperse CA
--II-Borresperse CASA
-+--Chinese Sample I
.. * .. Chinese Sample H
- "* - Chinese Sample A
----Borresperse CA
--II- Borresperse CA-5A
-+--Chinese Sample I
Chinese Sample H
- "* - Chinese Sample A
____ Borresperse CA
--II-Borresperse CASA
-+--Chinese Sample I
.. * .. Chinese Sample H
- "* - Chinese Sample A
Figure 10 The compressive strength as function of time for the concrete with 0.8 % defoaming agent
(TBP).
449
250
200
E 150
.E.
co.
E
"
100
iii
50
a
0,00
30,0
25,0
_ 20,0
=.
..

15,0
'&;
II)
10,0
5,0
0,0
0,00
10,0
9,0
8,0

0"
7,0
a

6,0

5,0
0
4,0
u

3,0
2,0
1,0
0,0
0,00
0,10 0,20 0,30 0,40 0,50 0,60 0,70
Dosage rio sbwc)
0,10 0,20 0,30 0,40 0,50 0,60 0,70
Dosage [% sbwc)
0,10 0,20 0,30 0,40 0,50 0,60 0,70
Dosage rio sbwc)
--+-Borresperse CA
____ Borresperse CA-SA
-+--- Chinese Sample I
- - .)<f - - Chinese Sample H
- "* - Chinese Sample A
--+-Borresperse CA
____ Borresperse CA-5A
-+--- Chinese Sample I
-. '* .. Chinese Sample H
- "* - Chinese Sample A
--+-Borresperse CA
----Borresperse CASA
-+--- Chinese Sample I
.. '* .. Chinese Sample H
- "* - Chinese Sample A
Figure 11 The concrete performance as function of dosage for all samples without defoaming agent
(TBP), The slump is shown at the top. The set time is shown in the middle and the air content of the
fresh concrete is shown at the bottom.
450