CEMENT and CONCRETE RESEARCH. Vol. 19, pp. 327-332, 1989.

Printed in the USA

0008-8846/89. S3.00&O0. Copyright (c) 1989 Pergamon Press plc.

CHEMICAL COMPOSITION OF CEMENT PORE SOLUTIONS

K. Andersson a, B. A l l a r d b, M. Bengtsson a, B. Magnusson c

aDept of Nuclear Chemistry, Chalmers U n i v e r s i t y of
Technology, S-412 96 G~teborg, Sweden
bDept of Water in Environment and S o c i e t y ,
Linkdping U n i v e r s i t y , S-581 83 L i n k ~ p i n g , Sweden
CDept of A n a l y t i c a l and Marine Chemistry,
U n i v e r s i t y of Gdteborg, S-412 96 Gdteborg, Sweden

(Refereed)
(Peceived Nov. 15, 1987; in f i n a l form Dec. 31, 1988)

ABSTRACT

The chemical compositions of the pore s o l u t i o n s e x t r a c t e d

from seven d i f f e r e n t cement pastes (one Swedish and one
French standard Portland cement, s u l f a t e r e s i s t a n t , blast-
furnace slag, f l y ash, s i l i c a , and high alumina cement) have
been determined. Analyses covered Na, K, Ca, Mg, AI, Fe, and
Si as well as pH and Eh (redox p o t e n t i a l ) , l o n i c s t r e n g t h s in
the range 0.03-0.29 M and pH-values in the range 12.4-13.5
were o b t a i n e d . Only the pore s o l u t i o n s from the slag cement
and the French Portland cement were reducing ( n e g a t i v e Eh).
The dominating c a t i o n s of standard P o r t l a n d , s u l f a t e r e s i s -
t a n t , slag, s i l i c a and f l y ash cement pore s o l u t i o n s were Na
and K, and in s u l f a t e r e s i s t a n t cement also Ca. The main com-
ponents in the pore s o l u t i o n s of aluminate cement were Na and
AI. The Si and Fe c o n c e n t r a t i o n s were low in all pore solu-
tions.

Introduction

The pore solution chemistry is of prime importance for the under-

standing of trace element mobility and migration processes in ce-
ment. Trace components that may be of interest for migration studes
include chloride from e.g. sea water in connection with corrosion
studies and radionuclides (actinides and fission products) from nu-
clear fuel reprocessing and reactor operations in connection with
storage of radioactive waste embedded in concrete.

Important parameters of the cement pore solution chemistry are the

ionic strength (affects ion exchange reactions with the solid
phases), pH (determines the degree of hydrolysis for hydrolyzable

327
328 Vol. 19, No. 3
K. Andersson, et al.

i o n s ) , Eh (the redox p o t e n t i a l ; determines the o x i d a t i o n s t a t e for

m u l t i v a l e n t elements), and the c a t i o n composition (presence of "com-
p e t i n g " ions with s i m i l a r c h e m i s t r y ) .

The r e a c t i o n s and e q u i l i b r i a in cement are complicated and not well

d e f i n e d . Many d i f f e r e n t s o l i d phases are formed during the h y d r a t i o n
of cement and these phases are changing with time. The pore water is
o f t e n o v e r s a t u r a t e d with respect to calcium hydroxide ( i ) . A t h e o r e -
t i c a l q u a n t i t a t i v e e s t i m a t i o n of the pore s o l u t i o n composition at a
given time is thus i m p o s s i b l e . Experimental i n v e s t i g a t i o n s of pore
s o l u t i o n s from cements have p r e v i o u s l y been performed f o r Portland
and slag cements by Longuet et a l . ( 2 , 3 ) . In t h i s paper a study of
pore s o l u t i o n s from pastes using seven d i f f e r e n t cement types is re-
ported.

Cement types

Samples of cement paste, u s u a l l y with a water/cement r a t i o (w/c) of

0.5, were prepared f o r the pore s o l u t i o n analyses:
Standard Portland cement, (SPP); from Cementa AB, S l i t e , Sweden
Portland cement, CPA 55, (CPA); a French product, provided by
SKBF/KBS, Stockholm
S u l f a t e r e s i s t a n t cement, (SRP); from Cementa AB, S l i t e , Sweden
B l a s t f u r n a c e slag cement, (MP); from Cementa AB, S l i t e , Sweden
High alumina cement, Secar 80, (ALP); from Lafarge Fondu I n t e r n a -
t i o n a l , provided by T i t a n AB, Upplands Vasby, Sweden
Fly ash cement, (FAP); prepared from standard Portland cement with an
a d d i t i o n of 30% f l y ash.
S i l i c a cement, Densit, ( S I P ) ; prepared from standard Portland cement
by a d d i t i o n of 20% s i l i c a fume and 3.2% organic p l a s t i c i z e r according
to recommendations from the Swedish Cement and Concrete Research In-
s t i t u t e (CBI) ( 4 ) .
The chemical composition of the cement pastes are given in Table 1
and of the f l y ash and s i l i c a fume used in the f l y ash and si ica
cement, r e s p e c t i v e l y , in Table 2.

A l l samples were moulded in c y ] i n d e r s of s u i t a b l e dimensions for pore

water pressing and stored under water u n t i l the time of a n a l y s i s .

TABLE i

Chemical Composition of the Cement Pastes ( i n Weight %)

SPP CPA SRP MP ALP FAP SIP

CaO 63.4 60.3 65.1 47,5 18.2 46.6 50 7

SiO 2 20 6 25.8 22.9 28.5 - 29.2 35 7
Al203 4 2 6.8 2.3 7.8 80.5 10.6 3 4
Fe203 2 1 2.6 3.6 1,4 - 3.7 1 7
MgO 3 4 1.5 3.4 6.9 3.1 3 4
K20 1 1 0.25 - 1.1 - 1.4 0 9
Na20 0 2 - 0.6 0.3 0 2
SO3 3 2 3.0 2.7 4.3 - 2.5 2 6
Cl - trace 0 01
ZnO 0 07
Vol. 19, No. 3 329
PORE SOLUTIONS, CEMENTS, COMPOSITION

TABLE 2

Composition of Solid A d d i t i v e s to the Fly Ash and S i l i c a Cements ( i n

Weigtn %)

Fly ash a Silicia fume b

CaO 7.3 0.07

SiO 2 49.2 96
Al203 25.4 0.23
Fe203 7.2 0.08
MgO 2.48 0.13
K20 2.12 0.37
Na20 0.40 0.20
S03 0.90 -

a From P o l i s h coal (4)

b From Kema Nobel AB, Ljungaverk, Sweden (4)

Experimental

Pore s o l u t i o n pressin 9

The pore s o l u t i o n was obtained from the cement pastes by applying

high pressures to c y l i n d r i c a l cement samples (diametre 45 mm and
height 80 mm) according to a method f i r s t described by Longuet et
a l . (2,3). The samples were placed in a holder and a pressure of
about 375 MPa was applied on a rod that was placed on top of the
sample. The pore s o l u t i o n expelled flowed through a s l i t in the
bottom of the holder via a t e f l o n tubing into a syringe. The appara-
tus is very s i m i l a r to one described by Barneyback et al. (5). By
t h i s method 4-10 ml of pore s o l u t i o n was obtained at each pressing.
The s o l u t i o n was transferred into glass v i a l s for immediate measure-
ments of the redox p o t e n t i a l and for subsequent pH-measurement and
chemical analysis ( w i t h i n 24 h).

Cation analysis

The main c a t i o n s of the pore s o l u t i o n were determined by flame atomic

a b s o r p t i o n spectrometry using a Perkin-Elmer 2380 i n s t r u m e n t . The
f o l l o w i n g elements were determined: A I , Ca, Fe, K, Mg, Na, and S i .
The analyses were checked by a n a l y s i n g a s y n t h e t i c s o l u t i o n w i t h the
f o l l o w i n g metal c o n c e n t r a t i o n s : 3000 mg/l K and Na (added as h y d r o x i -
des), 50 mg/l Ca, i0 mg/l A1 and S i , and 0.2 mg/l Mg. The agreement
between a n a l y s i s data and added amounts were s a t i s f a c t o r y except f o r
Ca, where the a n a l y s i s gave a low r e s u l t (22 m g / l ) . This was due to
supersaturation with respect to Ca(OH)2 at the p r e v a i l i n g pH which
resulted in a c l e a r l y v i s i b l e p r e c i p i t a t e .

Redox p o t e n t i a l and pH

The redox p o t e n t i a l s of the pore s o l u t i o n s were measured d i r e c t l y

a f t e r pressing, using a combination Pt/(Ag/AgCl)-electrode. For the
pH measurement a small volume (0.2 ml) of the s o l u t i o n was d i l u t e d
330 Vol, 19, No. 3
K. Andersson, et a l .

w i t h 10 ml of d i s t i l l e d w a t e r and pH of t h i s s o l u t i o n was d e t e r m i n e d ,
u s i n g a s t a n d a r d p H - e l e c t r o d e . From t h i s the pH of the o r i g i n a l pore
solution was c a l c u l a t e d . In s o m e cases pH was also d e t e r m i n e d by
titration.

Results and d i s c u s s i o n

The r e s u l t s of the pore w a t e r a n a l y s e s are g i v e n in Table 3. The main

c a t i o n s in t h e cement pore w a t e r were Na, K, and Ca. When comparing
the concentrations of t h e s e ions in the pore s o l u t i o n from the same
s t a n d a r d P o r t l a n d cement b a t c h , i . e . s t a n d a r d P o r t l a n d , s i l i c a cement
and f l y ash cement, l a r g e d i f f e r e n c e s were f o u n d . The s i l i c a cement
pore w a t e r had much l o w e r Na and K c o n t e n t s and lower pH than t h e
o t h e r s , w h i l e t h e f l y ash cement pore w a t e r had the l o w e s t Ca-con-
t e n t . However, the w/c r a t i o of s i l i c a cement was lower due to the
special formulation of t h i s cement. The French P o r t l a n d cement had
similar Na and K c o n c e n t r a t i o n s in the pore s o l u t i o n , although the
w/c was even lower f o r the French cement. Low c o n c e n t r a t i o n s of Na
and K but v e r y h i g h C a - c o n c e n t r a t i o n were found in the pore s o l u t i o n
of the s u l f a t e resistant cement. The l o w e s t C a - c o n c e n t r a t i o n was
found f o r t h e high a l u m i n a cement pore s o l u t i o n , and was e x p e c t e d
since this cement is based based on aluminum compounds i n s t e a d of
c a l c i u m compounds.

TABLE 3

Data f o r t h e Pore Waters (Ion Concentrations in m g / l ) .

SPP CPA SRP MP ALP FAP SIP

Volume a 8 4 9 9 7 8 4
Age b i0 4 9 i0 i0 i0 i0
w/c 0,5 0.36 0.5 0.5 0.5 0.5 0.35

Na 1500 1800 600 3200 4200 1600 300

K 6300 5700 600 6000 100 7500 700
Ca 90 20 470 50 i 15 130
Mg 0,2 0.1 0.2 0.1 0.06 0.15 0.1
Al 5 30 5 5 2800 15 5
Si 6 6 6 6 6 6 6
Fe 0,5 0.5 0.5 0.5 0.9 0.7 0.5
Icalc c 0,23 0.22 0.04 0.29 0.18 0.26 0.03

Eh d 139 -196 84 -377 131 106 134

pH 13.4 13.2 13.1 13.5 13.3 13.4 12.4

a Volume of pore w a t e r p r e s s e d from 0 . 2 kg s o l i d , ml

b Age of cement p a s t e sample b e f o r e pore w a t e r p r e s s i n g and a n a l y s i s ,
months
c C a l c u l a t e d a c c o r d i n g t o I= 0 . 5 ~ C i Z i 2, M
d in mV
Vol. 19, No. 3 331
PORE SOLUTIONS, CEMENTS, COMPOSITION

The Mg c o n t e n t was low in a l l pore w a t e r s , u s u a l l y 0.2 mg/l or l e s s .

The main d i s s o l v e d component in the high alumina cement pore s o l u t i o n

was A I , besides Na. For the o t h e r coments the c o n c e n t r a t i o n s were
u s u a l l y 5 mg/l or less w i t h the e x c e p t i o n f o r f l y ash cement (15
m g / l ) and the French P o r t l a n d cement (30 m g / l ) .

The Si c o n t e n t was below the d e t e c t i o n l i m i t (6 m g / l ) f o r a l l samples

but f o r the pore s o l u t i o n of the French P o r t l a n d cement, where i t was
6 mg/l.

The Fe c o n c e n t r a t i o n s were also low, a l l below 1 m g / l . The t o t a l

chemical analyses of the s o l i d s showed l i t t l e d i f f e r e n c e in the i r o n
c o n t e n t between the cements. No attempts were made to analyze the
Fe(ll)/Fe(lll)-ratio.

A pH-range of 12.4 to 13.5 was observed f o r a l l the samples. No o b v i -

ous c o r r e l a t i o n of pH w i t h the chemical c o m p o s i t i o n s of the s o l i d s
c o u l d be observed.

The redox p o t e n t i a l s were p o s i t i v e f o r a l l pore s o l u t i o n s ( r o u g h l y

corresponding to systems in e q u i l i b r i u m with air as given by
Eh=O.9-O.06 pH, V) except in the pore s o l u t i o n s of the b l a s t f u r n a c e
s l a g and French P o r t l a n d cement ( g i v i n g a r e d u c t i o n of the p o t e n t i a l
by 0 . 3 - 0 . 5 V). Reducing c o n d i t i o n s have p r e v i o u s l y been found in slag
cement by o t h e r i n v e s t i g a t o r s ( 2 , 3 ) . The French P o r t l a n d cement seems
to d i f f e r significantly from the Swedish P o r t l a n d cement, a l t h o u g h
t h e r e were no l a r g e d i f f e r e n c e s in the t o t a l chemical a n a l y s i s , c . f .
Table i . There are, however, i n d i c a t i o n s of a c e r t a i n slag c o n t e n t in
the French cement ( 4 ) .

Conclusions

The cement pore s o l u t i o n s s t u d i e d had f a r i l y high i o n i c s t r e n g t h s (up

to 0 . 3 ) , pH in the range 1 2 . 4 - 1 3 . 5 , and p o s i t i v e redox p o t e n t i a l s ,
c o r r e s p o n d i n g to o x i d i z i n g c o n d i t i o n s ( e x c e p t f o r the slag c o n t a i n i n g
b l a s t f u r n a c e slag cement and the French P o r t l a n d cement).

For s t a n d a r d P o r t l a n d , s u l f a t e r e s i s t a n t , slag, silica and f l y ash

cements the d o m i n a t i n g c a t i o n s in the pore s o l u t i o n s were Na and K.

A l u m i n a t e cement pore s o l u t i o n c o n t a i n e d m a i n l y Na and AI.

The calcium c o n t e n t s of a l l cements except f o r the s u l f a t e r e s i s t a n t

cement were below 150 mg/l and o t h e r c a t i o n s were p r e s e n t o n l y in
t r a c e amounts. For the s u l f a t e r e s i s t a n t cement the C a - c o n c e n t r a t i o n
was a l s o moderate.

The h i g h i o n i c s t r e n g t h s of the pore s o l u t i o n s would have some i n f l u -

ence on the m o b i l i t y of f o r e i g n c a t i o n s at t r a c e c o n c e n t r a t i o n s in
the cement, s i n c e the e l e c t r o s t a t i c interactions ( i o n exchange)
u s u a l l y observed f o r c a t i o n s on s o l i d s u r f a c e s (6) would be low under
these c o n d i t i o n s .

Migration/diffusion that is only hindered by g e o m e t r i c a l factors of

332 Vol. 19, No. 3
K. Andersson, et a l .

~ne cement ~ a v a ~ l a b l e s u r f a c e f o r d i f f u s i o n ) would thus be expected.

For h y d r o l y z a b l e c a t i o n s the h i g h pH may cause f o r m a t i o n of p o o r l y
s o r b i n g n e u t r a l or n e g a t i v e l y charged h y d r o l y s i s p r o d u c t s i n s t e a d of
the h i g h - s o r b i n g c a t i o n i c species observed at lower pH ( 7 ) . These
species may, however, become l a r g e and t h e i r m o b i l i t y would thus
decrease.

Measurements of t r a c e element m o b i l i t i e s in the seven cement pastes

in t h i s s t u d y and d i s c u s s i o n s of chemical e q u i l i b r i a in the pore
water systems w i l l be presented in a subsequent paper.

Acknowledgements

T h i s work, which is p a r t of a s t u d y of t r a c e element m o b i l i t i e s in

s o l i d cement paste and c o n c r e t e , i s funded by the Swedish Nuclear
Fuel S a f e t y P r o j e c t (KBS). The a s s i s t e n c e w i t h pore s o l u t i o n p r e s s i n g
by P r o f . O. Gj6rv and c o w o r k e r s , the Norwegian Cement and Concrete
Research I n s t i t u t e , Trondheim, and d i s c u s s i o n s w i t h Dr. A. Grudemo,
the Swedish Cement and Concrete Research I n s t i t u t e , Stockholm, are
gratefully acknowledged.

References

i. F.M. Lea, The Chemistry of Cement and Concrete, Edward A r n o l d

L t d . London (1970)
2. P. Longuet, L. B u r g l e u , A. Zelwer, Rev. des Mat. de C o n s t r u c t i o n
et des Traveaus P u b l i c s 676, 35 (1973)
3. P. Longuet, S i l i c a t e s I n ~ t r i e l s 7/8, 321 (1976)
4. V. L e h t i n e n , Swedish Cement and Concrete Research I n s t i t u t e (CBI),
Stockholm, personal communication
5. R.S. Barneyback, S. Diamond, Cement and Concrete Research i i , 279
(1981)
6. K. Andersson, B. A l l a r d , " S o r p t i o n of R a d i o n u c l i d e s on Geologic
Media - a L i t e r a t u r e Survey. Part I : F i s s i o n P r o d u c t s " , KBS TR
83-07, K ~ r n b r ~ n s l e s ~ k e r h e t , Stockholm (1983)
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L o n g - L i v e d R a d i o n u c l i d e s in Igneous Rock", in E n v i r o n m e n t a l M i g r a -
t i o n of L o n g - L i v e d R a d i o n u c l i d e s , IAEA, Vienna 1982, p 111.