Materials and Structures/Mat6riaux et Constructions, Vol.
33, July2000, pp 363-369
Slump improvement mechanism of alkalies in PNS
superplasticized cement pastes
B.-G. Kim, S. P.Jiang and P.-C. A[tcin
Department of Civil Engineering, Universityof Sherbwoke, Sherbrooke, QC, Canada,J1K 2RI
Paperreceived:June25, 1999; Paperaccepted:November5, 1999
A B S T R A C T
Some cement/superplasticizer combinations which
result in rapid slump loss can be improved by the addi-
tion of alkali sulfates when using polynaphthalene or
polymelamine sulfonates (PNS or PMS). It seems that
for a given cement there exists an optimal content of sol-
uble alkalies with sulfonated based superplasticizers. The
major effect of the alkalies is to reduce the adsorption of
PNS or PMS molecules by providing the necessary SO 4-
2 ions that are necessary to neutralize the active sites of
the interstitial phase of the cement. The second effect of
the addition of alkalies is to increase the pH of the inter-
stitial solution of the mortar or of the concrete which
seems to favor the non-adsorption of the superplasticizer
molecules on the C3A.
1. I N T R O D U C T I O N
Nowadays, the construction industry mostly uses com-
mercial superplasticizers based on polynaphthalene sul-
fonate (PNS) or polyrnelamine sulfonate (PMS). The addi-
tion of these superplasticizers to Portland cement concrete
usually greatly increases the fluidity of fresh concrete.
However, the dispersing effect of these superplasticizers
can be of short duration and can result in a rapid slump loss
depending on the particular combination of cement and
superplasticizer used. Recently, a practical method, con-
sisting in an addition of alkali sulfate, has been found effi-
cient to solve slump loss problems in some superplasticized
high-performance concretes [1, 2]. It has also been seen
that there seems to be an optimum soluble alkali content in
cements, i.e. 0.4-0.5 Na20 eq. in terms of slump and
slump loss of cement pastes [3]. The effect of alkali sulfate
on the fluidity of cement pastes has been explained in the
literature [4-8] advocating that alkali sulfate inhibits the
adsorption of PNS superplasticizer on the interstitial
1359-5997/00 9 RILEM
R !~ S U M I~
Certaines combinaisons ciment/superp!ast~'ant qui
pre'sentent des pertes d'affaissement tr& rapides peuvent
&re corrig&spar des additions d'alcalins clans le cas oh l'on
utilise des polynaphthal?nes ou polymdlamines sulfonates
(PNS ou PMS). II semblerait qu'il existe d'ailleurs une
teneur optimale en alcalis solubles clans le cas oh I'on uti-
lise un P N S ou un PMS. L'effet principal des alcalis
serait de rdduire l'adsorption des mol&ules de P N S ou
P M S en foumissant les ions S 0 4 -2 n&essaires a la neu-
tralisation des sites actifs de la phase intersticielle du
ciment. Un second effet de l'introduction de ces alcalis est
d'augmenter aussi le p H de la solution intersticielle du
mortier ou du bdtonfrais qui favorise aussi la non-adsorp-
tion des mol&ules de superplas@'ant sur le C3A.
illilli!!iiii{{i~
phases by rapidly producing sulfate ions, and then effec-
tively reducing the positive zeta potential of C3A and
C4AF by competition of sulfate ions and the sulfonate
group of PNS superplasticizer [4-8]. In addition, the role
of free PNS remaining in solution and its contribution to
fluidizing of cement pastes has been explained [8].
On the other hand, some interesting results have been
found in the literature by Luke et al. [9] showing that the
amount of PNS superplasticizer adsorbed by a
C3A/Gypsum system is significantly reduced in an alka-
line solution (0.25 M KOH, 0.025 M NaOH). At 5 min-
utes, the amount of PNS superplasticizer adsorbed is
reduced to 50% of that measured on a pure water system.
However, the effect of alkaline solution on the fluidity of
cement pastes was not investigated in the above study.
The aim of this study is to elucidate how alkalies
influence the PNS adsorption and the fluidity of super-
plasticized cement pastes. Furthermore, this paper will
discuss the slump improvement following the addition of
alkalies in superplasticized cement pastes.
363
Materials and Structures/Mat~riaux et Constructions, Vol. 3 3 , July 2000

2. MATERIALS AND TESTS Table 1 - Chemical and phase composition of the cements
Chemical Cement
2.1 Portland cement Composition (%) E F L N

The chemical/phase compositions and fineness of the SiO2 20.39 20.6 19.93 21.14
cements used in this study are presented in Table 1. AI203 5.02 4.2 4.76 5.23
Cements E and F are CSA Type 10 (ASTM Type I with Fe203 2.20 3.1 3.23 2.04
a 5% max. limestone filler content), while Cements L CaO 62.30 61.5 64.95 64.6
and N are ASTM Type I. These four cements present a MgO 2.49 2.6 1.37 2.75
wide range of C3A composition, their C3A contents SO3 2.90 3.4 2.67 2.95
vary from 6% for Cement F up to 11% for Cement N, K20 1.05 0.80 0.25 0.21
according to Bogue composition. The form of C3A is Na20 0.22 0.21 0.18 0.18
only cubic for Cements E, F, and N while a mixture
Na20 eq. 0.92 0.74 0.35 0.31
form of cubic and orthorhombic for Cement L has been
Na20 soluble eq.* 0.57 0.72 0.07 0.06
found by XRD analysis. The Na20 equivalent contents
of these cements vary from 0.31% for Cement N to C3S 53 51 69 56
0.92% for Cement E. C2S 18 20 5 17
C3A 10 6 7 11
C4AF 7 9 10 6
2.2 Superplasticizer Blaine (m2/kg) 370 410 380 380

A pure sodium salt of polynaphthalene sulfonate
(PNS) superplasticizer was used in this investigation. It is
an aqueous solution having 41% solids. Its pH (10%
solution) is 7.85; its sulfate content is 1.08%; its viscosity
is 65 cps (22~ and its specific gravity is 1.21.
2.3 Paste mixing procedure
The cement pastes were prepared at a constant
water/cement ratio (W/C) of 0.35. Superplasticizer w a s
added to the mixing water, then the solution was added
to the cement. The cement pastes were mixed manually
for 1.5 minutes, then with a high-speed hand-held mixer
for 2.5 minutes in order to obtain a well-dispersed paste.
The mixing procedure was carried out under controlled
temperature of 25 _+ I~ The superplasticizer dosage is
expressed as dry weight (weight of PNS superplasticizer
solids relative to the weight of cement): 0.6% for'
Cement E, F, and L; 1.0% for Cement N.
2.4 Mini slump
The mini-slump test [10] was used to assess the effect
of the different PNS superplasticizers on cement-paste
fluidity. The procedure involves transferring the cement
paste in a minicone, then lifting the cone smoothly and
quickly. The area of the paste spread on a polyethylene
plate is measured and expressed in cm 2.
2.5 Filtering system
A pressure filtering system was applied to extract the
interstitial solution from cement pastes. Nitrogen gas
pressure of 345 kPa (50 psi) and a membrane of 0.45 btm
diameter were applied in the filtering process. Samples
were taken at different times (2, 5, 15, and 30 minutes).
*Measured by ICP at W/C=0.35 at 30 minutes after mixing.
2.6 Measurement of pH
After the filtering process, the pH was directly mea-
sured by putting the sensor of an Orion pH meter in the
filtrate. The pH meter was calibrated by using t w o
buffer solutions at pH 10 and 13.
2.7 Adsorption measurement
PNS adsorption on the surface of cement particles
was evaluated by measuring the amount of PNS in the
solution extracted from the fresh c e m e n t pastes,
expressed as a percentage (mass of PNS present in the
extracted solution relative to the mass of added PNS
superplasticizer). The original filtered solution was
diluted with deionized water to obtain adequate PNS
concentration. The PNS concentration in solution was
measured at the peak absorbance wavelength between
276 and 294 ,with a Hewlett-Packard diode array UV-
visible spectrometer.
2.8 Measurement of sulfate ion concentration
in solution
The total ionic sulfur (from the sulfate ions in
cement and the sulfonate ions of the PNS) concentration
in solution in fresh cement pastes was measured using
the ICP (Inductivity Coupled Plasma) spectrometry.
The measurements were carried out 30 minutes after
mixing. The original filtrate solution obtained by the
system described above was diluted to 1:150 with 5%
HC1. The sulfate ion concentration from the cement is
calculated by subtracting the ionic sulfur from the PNS
superplasticizer.

364
Kim, Jiang, Aftcin

3. RESULTS adsorbed is not significant. On the contrary in the case

of Cement L, the amount of PNS adsorbed continously
3.1 Effect of alkalies addition on mini slump increases as a function of time in the absence of alkalies.
The tendency of PNS adsorption is not changed by the
It is clearly seen in Fig. 1 that cements E and F are addition of alkalies in both cements as shown in Fig. 3.
compatible with the PNS superplasticizer while cements These results seem to be related to the form of C3A as
L and N are incompatible when considering mini- well as the amount of C3A and C4AF in cement. It has
slump measurements and as shown in another paper by
the Marsh cone test [2]. These results show that the
cement pastes made with cement E and F including a a)
given dosage of PNS superplasticizer have a high initial 250
mini-slump value and maintain this high value for 90
_0.8 %. .Na2SO
. . . . 4. . . . .
minutes. On the contrary, in the case of cement L, the
initial slump is maintained for 15 minutes but the slump
~ 200
.4 ~i
rapidly decreases thereafter. The cement paste made 150
. . . . . . . . . . . . .

with cement N has a relatively low slump even at 2 min- 0.2 %

utes although the dosage of superplasticizer is higher 100
than that of the three other cements.
In order to investigate the effect of an addition of alkali 50
hydroxide on the fluidity of cement pastes made with Reference " 1.
cements N and L, mini slump tests were done on grouts I I I I
where the amount of NaOH was increased and the results
were compared with the addition of alkali sulfate and 0 20. 40 60 80 100
hemihydrate, as presented in Figs. 2a and 2b. The com- Time (min)
parison shows that sodium hydroxide is as effective to
reduce the slump loss as sodium sulfate. Moreover, a rela-
b)
tively small amount of sodium hydroxide influences the
fluidity of cement pastes more than sodium sulfate, 250 ,a ~ . _ / 0.2 %. .
although the mole amounts were considered. As shown in
Figs. 2a and 2b, the addition of hemihydrate is less effec- 200 [-~- - -~- ~- . . . . . " . . . . . . .

tive to increase the fluidity of cement pastes.

The amount of PNS adsorbed was measured as a O.-! % NaOH . . . .
function of time in the absence or presence of alkalies
and the results are presented in Fig. 3. First of all, in the
absence of alkalies, the amount of PNS adsorbed in
Cement N rapidly increases up to 70 % at 2 minutes,
100

50
Reference
iiiiiii " #
but after 5 minutes, the increase in the amount of PNS
t I I I

0 20 40 60 80 100
200
Time (min)
Cement F
160 c)
250
Cement E
~ 120 200
e,
Cement L o
so 150
o
<
100
. CementN..-'~. ~
40
_

E
50
0 I I I I
Refere'nce #
I I I I
0 20 40 60 80 100
0 20 40 60 80 100
Time (min)
Time (min)
Fig. 1 - Mini-slump of superplasticized cement pastes vs hydra-
tion time. The dosage of superplasticizer: 0.6 % for cement E, F, Fig. 2a - The effect of additives on the mini-slump of Cement N.
and L; 1.0 % for cement N. a) Na2SO4, b) NaOH, c) CaSO 4 1/2H20 addition.

365
Materials and Structures/Mat~riaux et Constructions,Vol. 33, July 2000

a) Table 2 - Solubility of additives

250 Product Solubility (g/L) at 25~
Sodium Sulfate 279
200 Sodium Hydroxide 500
Hemihydrate c~(Ca S O 4 9 1/2H20) 6.20
150 Hemihydrate [3 8.15

100

Futhermore, when compared to hemihydrate, alka-

50 . . . . o_ 0.2 > lies such as sodium sulfate and sodium hydroxide, signif-
icantly reduce the amount of PNS adsorbed on cement
I I I I
particles, probably because of much higher solubility of
0 20 40 60 80 100 alkalies as shown in Table 2.
Time (min)
3.2 Effect of SO 3 ion concentration on the
b)

iaO"
250
amount of PNS adsorbed on cement particles
0.2%
As shown in Fig. 4, an inverse relationship between
200
E the SO 3 concentration and the amount of PNS adsorbed
"
at 30 minutes was found in both cements. It has been
150 found that sodium sulfate rapidly dissolves sulfate ions,
O
< which increase w h e n the dosage of sodium sulfate
m. 100 increases. However, calcium sulfate does not decrease
significantly the amount of PNS adsorbed because it
50 does not rapidly increase the concentration of SO42-
ions. In the case of alkali hydroxides such as sodium
hydroxide and potassium hydroxide, it has been found
0 20 40 60 80 100 that they also increase the 8042-concentration. It seems
that the addition of alkali hydroxide increases the solu-
Time (rain) bility of calcium sulfate present in Portland cement [12].

c)
250 3.3 Effect of alkalies addition on pH of
cement pastes
" 200
In order to see the pH difference in compatible
t~ 150 (cement E and F) and incompatible (cement L and N)
O
cements, the pH was measured with or without PNS
100 superplasticizer as shown in Fig. 5. These results show
'E that compatible cements (cement E and F) have higher
50 pH values than incompatible cements (cement L and N)
Reference v v
because of their higher alkalies content [13]. The differ-
I I I I
ence in pH between compatible and incompatible
cements is about 0.5-0.6. in the cement pastes under
0 20 40 60 80 100 study. In all of these, the pH increases with time. The
Time (min) addition of PNS superplasticizer does not affect the pH
of the cement pastes because its pH is already neutralized
Fig. 2b - The effect of additives on the mini-slump of Cement L. at 7.85.
a) Na2SO 4, b) NaOH, c) CaSO 41/2H20 addition. The effect of alkalies on pH of cement pastes was
investigated and the results presented in Fig. 6. It was
been found by Nawa et al. [4] that the adsorption rate of found that the measured pH value depends not only on
C4AF is lower than that of C3A. Moreover, the cubic the type of addition but also on its amount. The effect of
form of C3A is more reactive than the orthorhombic additives on the pH value is as follows: 0.8 % NaSO 4
form [11]. The tendency of adsorption in Cement E and (NS) > 0.2 % NaOH (NH)> 0.8% C a S O 41/2 H 2 0 (CS)
F is similar to that of Cement N although the magnitude for both cement pastes. The relationship between the pH
of the amount of PNS adsorbed in Cement E and F is and the amount of PNS adsorbed at 30 minutes following
lower than in Cement N. the addition is presented in Fig. 7. A close inverse rela-

366
Kim, Jiang, ARcin

adsorbed is progressively
Cement N Cement L
100 100
reduced when the pH value
Ref ~ 9 of the interstitial solution
~" 80 - 0.8% ca increases through the addi-
g 80
0.2% NH tion of alkalies.
60 60 0.2%NH
40 40 o.8%~
4. DISCUSSION
20 < 20
Slump improvementmecha-
o I I I 0 i i i
nism of alkalies in super-
0 10 20 30 40 0 10 20 30 40 plasticized cementpastes
Time (min) Time (rain) In a previous study by the
Fig. 3 - Effect of additives on the PNS adsorption. NS:Na2SO4, NH:NaOH, CS:CaSO4 1/2H20.
authors [8], it was found that
incompatible cements have a
tendency to rapidly adsorb a
Cement N Cement L high amount of PNS super-
100
plasticizer, while in the case
100
of compatible cements, a
Ref%0.8% CS
90 90 high amount ofa PNS super-
0.2% NS ~ 0 . 2 % NH Ref
g 80 0.2% KH ~ ' ~ % ~ 4 o / o NS 80 0.8% CS plasticizer remains in solu-
tion after a small initial
z 70 z 70 0 . 2 % ~ 0.2% N H adsorption. For a given
0.4%NH I 1 ~ 0.2%NS ~ --~,
60 ",~ o.8%NS 60
0.4% NS,I, ~ . 4 % NH cement, it seems that the
adsorption capacity of a
50 50 o0.8%
oo,.,T',
NS cement is mainly controlled
40 40 by the soluble alkali content
30 i i J
30 i i i i when using a PNS superplas-
0 50 100 150 200 250 0 50 100 I50 200 250 ticizer. Futhermore, it was
S03 (mmol/L) S03 (mmol/L) found that the addition of
alkali sulfate was a very effec-
Fig. 4 - Relationship between the SO 3 content and the amount of PNS adsorbed at 30 minutes by tive method to reduce the
the addition of additives. NS:Na2SO4, NH:NaOH, KH:KOH, CS:CaSO 4 1/2H20.
amount of PNS adsorbed on
cement particles and to increase the fluidity of cement
13.3 pastes. However, the working mechanism of alkalies on
13.2 f } Compatible
reducing the amount of PNS adsorbed was not fully
cements
explained.
13.1 Nawa et al. [5] have suggested the 8042-/PNS com-
13 petition mechanism. That is, both the polymer anion of
the PNS superplasticizer and the 8 0 4 2 . ion have neg a-
12.9 --!1-- E-1 --Q-- E-2 tive charges, both may be adsorbed by positively charged
12.8 at F-I ~F-2 surfaces on early C3A hydration products, or incorpo-
rated into such products, almost immediately after the
12.7 +L-I --O-- L-2
beginning of hydration. This mechanism has been
# N-1 O N-2
12.6 ~ proven by experimental results [4-6] showing that the
12.5 , Incompatible
adsorption of the PNS on C3A was greatly reduced in
cements the presence of Na2804. The presence of sulfate ions,
12.4 derived from either calcium sulfate or alkali sulfate,
decreases the adsorption of PNS on C3A and C4AF but
12.3 increases the adsorption on C38 [4].
0 15 30 45 In this study, it has also been found that when the
Time (rain) concentration of sulfate ion is increased by the addition
of different alkalies, the amount of PNS adsorbed
Fig. 5 - pH vs hydration time in four different cements. decreases, as shown in Fig. 4. Moreover, alkali hydrox-
El:water+cement, E2:water+cement+PNS and the same meaning ides such as sodium hydroxide and potassium hydroxide,
in the other cements.
as well as sodium sulfate, increase the concentration of
sulfate ion by increasing the solubility of calcium sulfate
tionship between the pH value and the adsorption of present in cement.
PNS can also be established, as shown in Fig. 7. It can be On the other hand, the influence of the pH on the
seen that for a given cement paste the amount of PNS adsorption affinity of PNS superplasticizer has been

367
Materials and Structures/Mat6riaux et Constructions, Vol. 33, July 2000

of the zeta potential, i.e. pH

Cement N Cement L
= 12.2 but that it goes down
13.2 13.2
very sharply when approach-
13.1 13.1 ing the zero-point. For
13 13 example, the positive values
12.9
078% Na2SO4 12.9 of zeta-potential of C3A are
12.8 12.8 approximately 57, 50, 44, 34,

~
12.7 12.7 26, 19, 10, 0 mV at 8, 10, 11,
12.6 ~1/2H20 12.6
12.5 11.7, 11.9, 12, 12.1, 12.2 pH
12.5 values, respectively. These
12.4 12.4 results indicate that a small
12.3 ' ~ q 12.3 I I I difference of pH near the
0 10 20 30 40 0 10 20 30 40 zero-point of zeta-potential
Time(min) Time(rain) could significantly affect the
amount of PNS adsorbed on
Fig. 6 - Effect of additives on the pH in cement N and cement L. cement particles.
Experimental results
obtained in this study, pre-
Cement N Cement L sented in Fig. 6, showed that
100 100 the addition of alkalies
rapidly increases the pH of
90 Ref~N II 0.8% CS 9O
the interstitial solution. The
so " ~ 0 . 2 % N S
80 Ref ~ % C S dependency of the amount of
70 0.2% NH N,~ 0.2% KH z 70 PNS adsorbed on pH in
1~0.4% NS 0.2o/~, ~,"~ 0.2~N. solution is also well proven in
60 .4% NH 60 0.2%Ns "N 0.4%~s | Fig. 7.
-,~o.4%~q
5o 0.8% NS 50 ~ [ In conclusion, the flu-
40 40
idizing mechanism of super-
1.6% NS 9 , , I(6% NS ~ / plasticized cement pastes is
30 t I I 30 closely related to the amount
12.2 12.4 12.6 12.8 13 12.2 12.4 12.6 12.8 13
pH
of PNS adsorbed on cement
pH particles, especially on the
Fig. 7 - Relationship between the pH and the amount of PNS adsorbed at 30 minutes by the addi-
positively charged aluminate
tion of additives. NS:Na2SO4, N H : N a O H , K H : K O H , CS:CaSO 4 1/2H20. phase, because the adsorp-
tion rate of PNS on pure
C3A and C4AF was found to
advocated in the literature [14, 15]. The adsorption Of be much larger than that adsorbed on pure C3S [5, 20].
PNS on TiO 2 is strongly dependent on the pH of the Moreover, the amount of PNS adsorbed on the alumi-
suspension. For example, at pH 3, TiO 2 bears a strong nate phase is mainly determined by the alkalies content,
positive surface charge and the adsorption is maximum. especially soluble alkalies content [2] that rapidly
However, the surface charge of TiO 2 becomes negative increase not only the concentration o f sulfate ions
when.the pH is over the zero-point of zeta-potential, but also the pH value o f the interstitial solution.
and the zeta-potential depends on the pH of the cement
suspension [16-19].
As shown in Fig. 5, the interstitial solution of com- 5. CONCLUSION
patible cement pastes (cement E and F) have a higher pH
value than the incompatible ones (cement L and N). The Alkalies can be used to increase the fluidity of a
difference in pH is on the order of 0.5 - 0.6. As a mater superplasticized cement paste by decreasing the amount
of fact, the difference in pH results from the difference of PNS adsorbed on aluminate phase, allowing more
in alkali content because the alkalies increase the pH as PNS to remain in the solution. The working mecha-
well as sulfate ion concentration in cement paste sys- nisms of alkali sulfate are as follows:
tems. In order to understand the effect of the pH on 9 Rapidly increasing the pH in the interstitial solution -
adsorption, it is necessary to study it in a pure system not a small increase in pH can significantly affect the amount
including sulfate ions. Tadros et al. [18] examined, there- of PNS adsorbed because at the near zero-point of zeta-
fore, the dependence of the surface charges upon the pH potential, the zeta-potential value is significantly
using pure C3A with aqueous solutions not including changed by a small difference in pH.
sulfate ions. They have found that the surface charges 9 Rapidly increasing the concentration of sulfate ions -
and the zeta potential of the C3A is significantly depen- when they rapidly dissolve, the amount of PNS adsorbed
dent on the pH of the solution. Their study showed that is significantly reduced by being preferentially adsorbed
the zeta potential of C3A is positive above the zero-point on the positive surface, such as C3A and C4AF, and

368
Kim,Jiang,ARcin
reducing the positive zeta-potential value.
ACKNOWLEDGMENTS
T h e authors would like to thank Kyunggi Chemicals
Ind., Co. Ltd. o f Korea for its financial support and A.
Lemieux, Department of Chemistry, University of
Sherbrooke for carrying out the I C P analysis.
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