Pergamon

Cementand ConcreteResearch,Vol.24, No. 2, pp. 361-370. 1994 Copyright 1994ElsevierScienceLtd Printedin the USA.AUrightsreserved 0008-8846/94 $6.00+ .00

EFFECTS OF FLY ASH AND SILICA FUME ON THE RESISTANCE OF MORTAR TO SULFURIC ACID AND SULFATE ATTACK

Kazuyuki Torii and Mitsunori Kawamura Department of Civil Engineering, Kanazawa University, 2-40-20 Kodatsuno, Kanazawa, Japan
(Refereed)

(ReceivedApril20; in finalformDec.ember13, 1993) ABSTRCT Changes in physical and chemical properties in the mortars with different replacements by fly ash and silica fume when immersed in 2 % H2SO4, 10 % Na2SO4 and 10% MgSO4 solutions for 3 years were investigated. The long-term exposure test data showed that the replacement of portland cement by fly ash and silica fume effectively improved the resistance of the mortar to the sulfuric acid and sulfate solution attack. However, the replacement percentage by fly ash and silica fume necessary to prevent the sulfuric acid and sulfate solution attack varied significantly depending on the type of sulfuric acid and sulfate solutions. Introduction It is well known that concrete containing a good-quality pozzolan such as fly ash, blast-furnace slag and silica fume provides a satisfactory resistance to sulfate attack in the sea water or in other surroundings. In the standards of many countries, the partial replacement of portland cement by pozzolans and/or the use of low C3A portland cement have been recommended in order to improve the chemical resistance of the concrete to sulfate attack. However, the deterioration of concrete due to the sulfate attack is considered to be a complicated phenomenon of physical and chemical process. It has been suggested that the influence of sulfate ions on the deterioration of concrete may vary depending on the type of cation ( e.g. Na +, Ca 2+ and Mg 2+ ) as well as the concentration of sulfates in the solution (1). Again, the influence of sulfuric acid solution on the deterioration of concrete has also been examined by a number of investigators, and found to be very severe compared to sulfate attack. It is normally believed that the increased resistance of concrete containing pozzolans to the sulfate attack results from its finer pore structure and the reduced content of calcium hydroxide in the cement paste. Furthermore, the sulfate-related deterioration of concrete is found to be mainly due to the formation of expansive reaction product being ettringite, but the mechanism of deterioration associated with the formation of reaction product is not still fully understood (2, 3). Whether or not gypsum formation is expansive is a subject of controversy (4). This paper presents the data on the long-term resistance of the mortars with and without fly ash and silica fume to sulfuric acid and sulfate attack. Changes in physical and chemical properties in the mortars with different replacements by fly ash and silica fume when immersed in 2 % H2SO4, 10 % Na2SO4 and 10% MgSO4 solutions for 3 years are comparatively investigated.
361

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Experimental Materials and Mix Prooortion An ordinary portland cement with the specific gravity of 3.13 and the Blaine fineness of 3250 cm2/g was used. An ASTM type F fly ash with the specific gravity of 2.27 and with the Blaine fineness of 3390 cm2/g was discharged from Takasago power station in Kanagawa prefecture in Japan; a commercial grade silica fume with the specific gravity of 2.33 and with the BET specific surface of 24.2 m2/g was supplied in a dry, uncompacted form from Norway. Their chemical compositions are tabulated in Table 1. The mortars were prepared according to JIS R 5201 ; the cementitious material : Toyoura standard fine sand ratio was 0.5. Replacements of cement by fly ash were 10, 30, 50 and 70 % ; those by silica fume 5, 10, 20 and 30 %. The water-cement ratio of plain mixes was selected at 0.55 and its flow value was 185 mm. For fly ash mixes, the water content of the mortar was determined so as to obtain the same flow value as plain mixes; the higher the replacement percentage by fly ash, the lower the required water content. A highrange water reducing agent was also added only for silica fume mixes in order to improve the consistency of the mortar. TABLE 1 Chemical compositions of portland cement, fly ash and silica fume used (%). Ig. loss Portland cement Fly ash Silica fume 1.6 1.9 1.8 SiO2 A1203 Fe203 1.9 7.4 3.6 CaO 63.4 8.9 0.3 MgO 1.3 1.8 0.4 Na20 K20 0.5 0.7 0.2 0.3 0.6 0.8 SO3 2.1

23.4 5.1 54.7 22.8 86.5 0.4

TABLE 2 Physical and chemical properties of 28-day old fly ash and silica fume mortars. Watercement ratio Plain mortar Fly ash 10%
30% 50% 70%

Compressive Total pore strength volume* (MPa) (10 -3 cc/g) 45.3 37.1
35.8 23.8 ii. 7

Amount of Ca(OH)2** (%) 4.1 3.6

2.5 1.0 O. 6

0.55 O.54
0.52 0.50 O. 48

39.8(17.6) 22.4(12.5)
44.5(15.1) 42.8(16.5) 62.1 (34.6)

Silica fume 5%
10% 20% 30%

0.55
0.54 0.54 0.53

44.4
45.1 46.6 50.2

50.7(13.8)
36.1(11.6) 29.0(20.7) 28.4(21.1)

3.1
2.3 1.3 0.8

* : Measured by MIP, which is expressed by cc per g of mortar ** : Determined by DSC-TG analysis, which is given by mass of mortar ( ) : Ratio of pore volume larger than 0.1 I.tm to total pore volume, %

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Exoerimental Procedures The mortar prisms, 25 mm by 25 mm by 285 mm, were prepared for the sulfuric acid and sulfate resistance test. The tests were performed with a concentration of 2 % H2SO4, 10 % Na2SO4 and 10% MgSO4, in which the concentration of solutions was controlled periodically by measuring pH of solutions during the test. Prior to the exposure to the sulfuric acid and sulfate solutions, the specimens were cured in water at 20 oC for 14 days and then stored at 20 C for 14 days under a sealed condition. At 28 days, the specimens were immersed completely in the sulfuric acid and sulfate solutions. Changes in length and weight of the specimens were measured at regular intervals for 3 years. Furthermore, in order to examine changes in microstructure and reaction products in the deteriorated portion of the mortars, DSC-TG analysis, X-ray diffraction analysis, and measurements of pore size distributions by mercury intrusion porosimetry were carried out at selected stages. Control samples were stored in water at 20 oC and analyzed by the same method. Further details of physical and chemical analysis are given in Reference (5). Results and D i s c u s s i o n Total Pore Volume and Amount of CafOH)2 It is well known that the sulfate resistance of concrete may be related intimately to the penetrability of aggressive sulfate ions into the concrete. Mehta has pointed out that the water permeability of cement paste increases with an increase of large pores with diameter greater than 0.1 ~m, which may represent the threshold value of continuous capillary pores (6). The authors have also suggested that it is effective in the evaluation of chloride ion permeability of concrete to categorize into large pores with diameter greater than 0. ll.tm and small pores with diameter less than 0.1 ~m (7). Another important factor determining the sulfate resistance is the Ca(OH)2 content in concrete; a reduced Ca(OH)2 content will lead to the lesser formation of the expansive reaction products with sulfate ions. Results of mercury intrusion porosimetry measurements and the amount of Ca(OH)2 determined by DSC-TG analysis at 28 days are presented in Table 2. The total pore volume of fly ash mixes increased with an increase of replacement percentage by fly ash, but within replacements up to 50 % the proportion of large pores with diameter greater than 0.1 I~m was not so significant compared to plain mixes. On the other hand, for silica fume mixes, the total pore volume decreased with an increase of replacement percentage by silica fume. It is apparent from Table 2 that the pore structure of silica fume mixes at 28 days is dense and homogeneous when compared to plain and fly ash mixes. Furthermore, the results of DSC-TG analysis confirmed that the Ca(OH)2 content in both the fly ash and silica fume mixes decreased significantly in proportion to the replacement percentage by fly ash and silica fume due to both effects of the reduced cement content and the progression of a pozzolanic reaction of fly ash and silica fume during curing. Results of mercury intrusion porosimetry measurements at 1 year of exposure to the sulfuric aid and sulfate solutions are presented in Table 3. When fly ash mixes were immersed in water for I year, a drastic reduction in large pores and an increase in small pores due to the successive progression of a pozzolanic reaction of fly ash were found even at high replacement percentages, although their total porosity was still higher than those of plain mixes. On the other hand, in fly ash mixes attacked by sulfuric acid and magnesium sulfate solution, there was a remarkable increase in large pores with diameter greater than 0.1 ~tm together with an increase in total pore volume due to the leaching out and decomposition of hydrated phases. A similar marked change in pore structure was also found in the deteriorated portion of silica fume mixes attacked by the sulfuric acid and sulfate solutions.

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T A B L E 3 Total pore v o l u m e o f fly ash and silica f u m e mortars w h e n i m m e r s e d in sulfuric acid and sulfate solutions for 1 y e a r ( 10 -3 cc/g).

Water

2% H2SO4

10% Na2SO4

10% M g S O 4

Plainmortar Fly ash 10% 30% 50% 70% Silicafume 5% 10% 20% 30%
(

33.8(22.1) 26.3(34.6) 33.2(15.4) 38.6(13.2) 58.5(10.6) 30.1(11.6) 44.7(22.6) 33.8(17.8) 17.8(36.5)

47.0(45.7) 32.2(22.7) 50.8(16.7) 88.3(72.1) 98.5(78.6) 57.2(43.3) 66.7(40.5) 21.1(32.2) 26.7(33.7)

94.8(83.3) 28.7(20.9)

46.8(24.6) 27.2(31.2)

25.2(36.1) 25.8(32.9) 22.9(38.4) 19.9(42.7) 43.5(19.5) 45.6(28.9) 22.4(21.4) 55.7(57.6) 68.6(87.5)

) : Ratio o f pore v o l u m e larger than 0.1 ~tm to total pore v o l u m e , %

T A B L E 4 R e a c t i o n products identified by D S C - T G and X R D analysis in fly ash and silica f u m e mortars w h e n i m m e r s e d in sulfuric acid and sulfate solutions for 1 year.

Et

2 % H2SO4 G p Ch M h

Et

10% N a 2 S O 4 Gp Ch Mh

Et

10% M g S O 4 G p Ch M h

Plain m o r t a r F l y ash 10% 30% 50% 70% Silica f u m e 5% 10% 20% 30%

++ + +

++ ++ +++ + +++ + +++ +++ +++ + +++ + +++ +++

. . .

+ -

++ ++ + + . . . + ++ + . . . . . .

+ + +

. . .

+ -

+ +

++ ++

+ + + +

+ + + + ++ + ++ + ++ + + ++ +++ -

Et : Ettringite, G p : G y p s u m , Ch : C a l c i u m hydroxide, M h : M a g n e s i u m h y d r o x i d e Intensity o f p e a k ( + + + : V e r y strong, ++ : Strong, + : W e a k , - : Not detected)

Deterioration o f Mortars I m m e r s e d in 2 % H2SO4 Solution C h a n g e s in l e n g t h and w e i g h t o f fly ash and silica f u m e m i x e s w h e n i m m e r s e d in a 2 % H 2 S O 4 solution are s h o w n in Figs. 1 and 2. U n d e r a v e r y l o w p H o f 2 % H 2 S O 4 solution, all hydrated p r o d u c t s , h y d r a t e d s i l i c a t e a n d a l u m i n a t e p h a s e s and c a l c i u m h y d r o x i d e , c a n e a s i l y be d e c o m p o s e d , r e s u l t i n g in a s e v e r e d i s i n t e g r a t i o n o f the m o r t a r matrix. Plain mixes were m a r k e d l y a t t a c k e d by a 2 % H 2 S O 4 s o l u t i o n w i t h i n 1 m o n t h o f e x p o s u r e t o g e t h e r w i t h a s i g n i f i c a n t w e i g h t loss d u e to the p e e l i n g - o f f o f s u r f a c e l a y e r , l e a d i n g to the c o m p l e t e d e c o m p o s i t i o n at 7 m o n t h s . O n the o t h e r hand, fly ash m i x e s m a i n t a i n e d r e a s o n a b l y g o o d e x t e r n a l shape in a 2 % H 2 S O 4 w i t h i n 1 y e a r o f e x p o s u r e , e s p e c i a l l y at h i g h r e p l a c e m e n t p e r c e n t a g e s o f m o r e than 30 %. H o w e v e r , it s e e m e d apparent that e v e n in fly ash m i x e s with

Vol.24, No. 2

FLYASH,SILICAFUME,SULFATEATTACK,ACIDRESISTANCE

365

~ O.bt'04t0.~ f

__[

[ ~

19F

I I I I oPlain mortar vFly ash 5 0 % aFly ash 10% . F l y ash 7 0 % . ~ l y as. ~,,'~ _

t.l~,
15'-"

_ -__at A ....~_ _A---A.--A-----~

I
-

/
-o--a--

/
---~--g--

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-

"-" 10g~ ~' AI'- \

"-'-"*----.

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2% H2804

Time of immersion (Months) [ 0.51,% 04[O',~L

o~l ~
0.11.~

FIG. 1 Length and weight changes in fly ash mortars when immersed in 2% H2804 solution.
I II

IoF

f /

9
-" ~ t / ~ ' F

oPlain mortar aSiliea fume 20%4 aSiliea fume 5% "Silica fume 30%-] ASiliea fume 10%
-

"t_~a~:~-o-..~--~-,-,--o~,--o C ~'~s~~--~
I I

~
I

-~ _ - - ~ - - - a - - - ~ .
. ....~r -

? ~*a --10
"~:
-';'7

=t-'-t:nt:::=t:~-'-a--a ~I

I-

g, , off ~ / .i0 ~

" dr~e~~zz:m--~:=::~

""o
I ~r
6

"zx.-~x...~
l
12 18

2% H2804

_
- -

24

30

I-

I 36

Time of immersion (Months) ^.l U~:~-04~o3t-

FIG. 2 Length and weight changes in silica fume mortars when immersed in 2% H2804 solution.

I ,~F ~" /
/

t
/

I I I 0 Plain mortar-~xF Z~Fly ash 10% - ,ny ash 30% -

()2[-"
"=
"~

o11- ~ /
= 1~.....
-

C~

.~

/~

o Fly ash 50%

-Fly ~sh 70% _

----w -I: : ~ -I -

T-"--T
F

" " T:~:~

_.-.~F

-5-

-1(3

10% Na2SO4-Time of immersion (Months) FIG. 3 Length and weight changes in fly ash mortars when immersed in 10% Na2SO4 solution.

366

K. Torii and M. Kawamura

Vol. 24, No. 2

high replacement percentages, it was impossible to effectively prevent the sulfuric acid attack during the long-term exposure. On the other hand, the progress of deterioration in silica fume mixes immersed in a 2 % H2SO4 solution varied widely depending on the replacement percentage by silica fume; at high replacement percentages of 20 and 30 %, the mortars expanded at early stage of exposure and a deep longitudinal cracking was observed at comers, while at the low replacement percentage of 5 %, the substantial weight losses due to the scaling were found after 4 months of exposure. From the data on the long-term resistance of silica fume mixes to the sulfuric acid solution, the 10 % silica fume mix was found to be most effective in preventing the sulfuric acid attack. Hydrated phases identified by DSC-TG and XRD analysis and the amount of Ca(OH)2 determined by DSC-TG analysis in the mixes at 1 year of exposure to sulfuric acid and sulfate solutions are tabulated in Table 4 and 5. DSC-TG and XRD analysis showed that in the deteriorated portion of the mortars exposed to a 2 % H2SO4 solution, the principal hydrated phase was gypsum (CaSO4o2H20), and that calcium hydroxide in the matrix was decomposed and disappeared. SEM also showed that large amounts of gypsum, which was the bundle of rodlike crystals of several hundred micron in length, precipitated in voids or cracks, and that no ettringite and calcium hydroxide were present in the matrix ( Photo. 1 (a)). It appears that in the sulfuric acid attack, the early decomposition of calcium hydroxide and the subsequent formation of large amounts of gypsum are attributed to the progressive deterioration accompanied by the scaling and softening of the matrix. TABLE 5 Amount of Ca(OH)2 determined by DSC-TG analysis in fly ash and silica fume mortars when immersed in sulfuric acid and sulfate solutions for 1 year (%). Water
Plain morxar Fly ash 10% 30% 50% 70% Silicafume 5 % 10% 20% 30% 4.1(8.0) 3.3(7.4) 1.2(5.2) 0.2(4.4) 0 (3.2) 3.3(6.6) 1.6(7.2) 0 (6.8) 0 (5.4)

2% H2SO4
1.6(6.8) 1.2(7.2) 0.2(5.7) 0 (6.9) 0 (7.0) 1.2(8.6) 0.4(7.2) 0 (6.5) 0 (8.1)

10% Na2SO4 10%MGSO4

1.6(5.9) 1.6(5.4) 0.8(6.0) 0.1(5.8) 0 (4.6) 1.6(5.4) 1.0(5.0) 0 (6.7) 0 (5.1) 2.5(7.0) 1.9(5.3) 1.0(6.4) 0.1(6.2) 0 (6.6) 2.3(7.6) 1.2(5.4) 0 (7.1) 0 (9.8)

) : Weight losses in TG curves between 20 and 600 C, %

Deterioration of Mortars Immersed in 10 % Nag$Qa Solution Changes in length and weight of fly ash and silica fume mixes when immersed in a 10 % Na2SO4 solution are shown in Figs. 3 and 4. Plain mixes expanded and deteriorated after 5 months of exposure to a 10 % Na2 SO4 solution, leading to the failure at 7 months. DSC-TG and XRD analysis indicated that the expansion of plain mixes were associated with the formation of both ettringite and gypsum ( Table 4 ). SEM observation showed that in deteriorated plain mixes, plenty of microcracks occurred within the matrix and fine needle-like crystals of ettringite of 1 to 31.tm were formed ( Photo. l(b) ). On the other hand, all fly ash mixes showed a good resistance to a 10 % Na2SO4 solution at an early stage of exposure up to 1 year since the replacement by fly ash reduced the calcium hydroxide and alumina-bearing hydrates which are most vulnerable to the sulfate attack. However, the 10 % fly ash mixes started to expand

Vol. 24, No. 2

FLY ASH,SILICAFUME,SULFATEATrACK,ACIDRESISTANCE

367

~" 0.5~'

IoFI
/ ] / -/~3

!o
"

041"" O31-" '~L rz 0.11--

Or'lain /' Silica -Silica uSilica mSilica

_.

I mortar I
fume fume fume fume

o ~ ~

_-~--,_~,-~oz- _o-ore_ -I

"-~ 5% --~ 10%..4 20%1 30% - 1

I{

-q

-101"
Time of immersion OF#~34~ ~.'J
/ I I I t

10% Na2SO4 FIG. 4 Length and weight changes in silica fume mortars when immersed in 10% Na2SO4 solution.

(Months)
I t o Plato mortarLxFIy ash 10%.

]
&

u..~"
02~"

~)F /== ~5/r'"

O/i /

_ . AFIy ash 30% . ~...,.~t- oFly ash 50% /" "Fly ash 70% "

o.II-

,~_~_~__~__~--~--~

15I'10-

I.F
-~3;-~

L_~___g ~ t

1-

_5 ~ "8 -15 ~:
-10

10% MgS04 --

I~Z

18

214

130
(Months)

Time of immersion
I I I
oF

FIG. 5 Length and weight changes in fly ash mortars when i m m e r s e d in 10% MgSO4 solution.

I
OPlain

I
mortar

I
-

Q5
r-,

04

j.

~ O~ ,--1
o

/ J-~F ..,af y lr~,.,~

,.,o"

~
~

~xSilica /oF -'Silica / n Silica "Silica

. . . .

fume 5%_ fume 10%_ fume 20% fume 3 0 % . _ _

~_~..4----1~---x
15 -

____.__~-

.~.F

tI

&

5
--5

~ --10 --15

10% MgS04
30

36

Time of immersion

(Months)

FIG.6. Length and weight changes in silica fume mortars when immersed in 10% MgSO4 solution.

368

K. ToriiandM. Kawamura

Vol. 24, No. 2

PHOTO. 1 Scanning electron microphotographs of deteriorated mortars when immersed in sulfuric acid and sulfate solutions. ((a) : Fly ash 50%, H2SO4, 3 months, (b) : Plain mortar, Na2SO4, 3 months, (c).: Silica fume 10%, MgSO4, 6 months, (d) : Plain mortar, MgSO4, 12 months, (d) : Fly ash 50%, MgSO4, 12 months, (e) : Silica fume 30%, MgSO4, 12 months )

Vol. 24, No. 2

FLY ASH, SILICA FUME, SULFATE ATI'ACK, ACID RESISTANCE

369

around 1 year, leading to the failure in close to 2 years, while the 30 % fly ash mixes did not expand during 3 years of exposure. Again, despite the porous pore structure of fly ash mixes with high replacements, the 50 % and 70 % fly ash mixes showed a good resistance to a 10 % Na2SO4 solution. Furthermore, all silica fume mixes did not expand independently of the replacement percentage by silica fume during 3 years of exposure. The visual condition of these silica fume mortars was also excellent. From the DSC-TG data and SEM observations, the attack on silica fume mixes in a 10 % Na2SO4 solution appeared to be limited only to the surface of the mortar due to their dense and discontinuous pore structure, resulting in reduced leaching out of calcium hydroxide and very little formation of ettringite and gypsum in the matrix ( Table 4 and 5). Deterioration of Mortars Immersed in 10 % MgSO4 solution Changes in length and weight for fly ash and silica fume mixes when immersed in a 10 % MgSO4 solution are shown in Figs. 5 and 6. It is considered that the magnesium sulfate solution attacks the cement paste more severely than other sulfate solution due to the low resolvability of magnesium hydroxide formed and the high aggressiveness against the C-S-H gel itself. Plain mixes expanded markedly after several months of exposure, resulting in the failure at 13 months. The magnesium sulfate attack was found more severe in the 50 % and 70 % fly ash mixes, resulting in a pronounced cracking and softening of the mortar within 1 year of exposure, whilst the 10 % and 30 % fly ash mixes did not expand so much during 3 years of exposure. Similarly, the 20 % and 30 % silica fume mixes deteriorated more severely at the early stage of exposure than the 5 % and 10 % silica fume mixes. In the 20 % and 30 % silica fume mixes, sharp cracks were observed at corners after several months of exposure, the development of extensive cracking leading to the failure within 2 years of exposure. From the expansion data and visual observations, it is evident that for fly ash and silica fume mixes, the magnesium sulfate attack is more severe at high replacement percentages than at low replacement percentages. DSC-TG and XRD analysis indicated that gypsum, magnesium hydroxide and ettringite were present in deteriorated mixes, but with the larger amount present in the mixes at high replacement percentages by fly ash and silica fume ( Table 4 ). These hydrated phases arise from the reaction of magnesium ions with the calcium hydroxide, calcium silicates and C-S-H gel in the matrix. It has been pointed out that in the advanced stage of magnesium-sulfate attack, the subsequent reaction of magnesium and silica gel can cause formation of non-cementitious hydrates of magnesium silicates (8). Furthermore, It has also been suggested that C-S-H gel produced by the pozzolanic reaction may behave differently and be more susceptible to a magnesium-ion attack (9). SEM observations confirmed that in fly ash and silica fume mixes with high replacement percentages, magnesium sulfate attack caused the decomposition of calcium hydroxide and C-S-H gel produced, which changed their pore structure to a porous and non-cementitious one ( Photo. 1 (c),(d),(e),(f)). Observations somewhat correlate with recent work of Boren and Cohen (10, 11).

Conclusions The laboratory test data showed that the replacement of cement by fly ash and silica fume effectively improved the resistance of the mortar to the sulfate attack due to the high impermeability and low calcium hydroxide content in the mortar. However, the effectiveness of fly ash and silica fume on the resistance to the sulfate solution attack varied depending on the type of cation, Na + and Mg 2+, in sulfate solutions, which was classified into two types of processes depending on the predominant chemical reaction taking place; the ettringite-forming reaction or gypsumforming reaction. Under a very low pH of 2 % H2SO4 solution, the replacement of cement by fly ash and silica fume could not effectively prevent the acid-type deterioration involving the scaling and softening of the mortar. In the exposure to a 10 % Na2SO4 solution, the sulfate-generated expansion of fly ash mixes was reduced when the replacement percentage by fly ash was higher

370

K. Torii and M. Kawamura

Vol. 24, No. 2

than 30 %, while that of silica fume mixes was greatly reduced even at the low replacement percentage by silica fume of 5 %. However, in the exposure to a 10 % MgSO4 solution, the higher replacement by fly ash and silica fume was not necessarily effective in preventing the magnesium-ion attack since C-S-H gel produced in the process of a pozzolanic reaction was more susceptible to a magnesium-ion attack. Acknowledgment The authors are grateful to K. Taniguchi and H. Taniguchi, Hazama Co. Ltd., for their help in the experiment. Reference 1. P.K. Mehta, Proc. of Int. Workshop on the Use of Fly Ash, Slag, Silica Fume and Other Siliceous Materials in Concrete, pp. 337-351 (1988). 2. P.K. Mehta, Cement and Concrete Research, 13, pp. 401-406 (1983). 3. K. Torii, M. Kawamura and H. Taniguchi, Trans. of the Japan Concrete Institute, 9, pp.7986 (1987). 4. M.D. Cohen and B. Mather, ACI Materials Journal, 88(1), pp.62-69 (1991). 5. K. Torii, M. Kawamura and H. Taniguchi, CAJ Review of the 42nd General Meeting, The Cement Association of Japan, pp. 106-109 (1988). 6. P.K. Mehta, P.K., Proc. of 7th Int. Congress on the Chemistry of Cement, 3, pp. 1-5 (1980). 7. M. Kawamura and K. Torii, Proc. of 1988 MRS Symposium, 137, pp.411-416 (1989). 8. F.M. Lea, Chemistry of Cement and Concrete, 3rd ed., Chemical Publishing Company, New York, pp.345-350 (1971). 9. M.D. Cohen and A. Bentur, ACI Materials Journal, 85(3~, pp.148-157 (1988). 10. D. Boren and M.D. Cohen, Cement and Concrete Research, Part 1, 22(1], pp.169-180 (1992). 11. D. Boren and M.D. Cohen, Cement and Concrete Research, Part 2, 22(4), pp.697-708 (1992).