Cement & Concrete Composites ! 6 (1994) 73-81 1994 Elsevier Science Limited Printed in Great Britain.

. All rights reserved 0958-9465/94/S7.00

ELSEVIER

Microstructure, Chloride Diffusion and Reinforcement Corrosion in Blended Cement Paste and Concrete
E S. Mangat,* J. M. Khatib* & B. T. Molloy
Department of Engineering, University of Aberdeen, Kings College, Aberdeen, UK (Received 8 March 1993; accepted 6 December 1993)

Abstract
This paper presents some results from a wideranging investigation of porosity and pore-structure, chloride-diffusion, and reinforcementcorrosion studies in blended cement paste and concrete. The cement-replacement materials used were pfa, slag, and microsilica. Mercury-intrusionporosimetry experiments were carried out on pastes with w/c of 0.45. Chloride-diffusion studies and corrosion investigation on rebars were carried out by using concrete mixes of proportions by weight 1:2.5:1.2 and w/c of 0.58. In all these experiments, initial curing for at least 14 days was under relatively low-humidity environments instead of idealised wet curing. The results show that microsilica cement pastes have a larger pore volume than other pastes used in the investigation. The chloride penetration, however, is the minimum in silica-fume concrete. The chloride-binding capacity of pfa concrete is less than that of normal concrete in the surface zone, but, at a greater depth (> 20 mm), the binding capacity of pfa concretes exceeds that of plain concrete. The results generally indicate a higher corrosion activity of reinforcement with increasing chloride concentration in the pore fluid. Microsilica was by far the most effective cement-replacement material in increasing the corrosion resistance of reinforcement in concrete.

Key words: blended cements, corrosion, concrete durability, porosity, chloride diffusion, corrosion potential, fly ash, slag, silica fume, mercury porosimetry.
INTRODUCTION Cement replacement materials are known to improve the durability of concrete. Porosity is deemed to be reduced and pore size to be refined, which thus hinders the movement of aggressive substances such as chloride ions and carbon dioxide, which are responsible for the corrosion of reinforced-concrete structures. A considerable amount of work has been conducted on the influence of cement-replacement materials on the durability of blended cement systems.l, 2 It is reported by some researchers that 30% replacement of cement with pfa resulted in a higher intruded pore volume but that the poresize distribution was finer. Similar results were obtained at 20% replacement level) ,4 Others have reported that a 30% replacement level of pfa increases the pore volume at the age of 28 days, but a similar volume to that of ordinary cement paste was obtained at the age of one year. 5 Ground granulated blast-furnace slag at a replacement level of 40% reduces the pore volume and pore size compared with paste without slag) Adding microsilica (0-16%) to a cement paste leads to a refinement of pore structure. 7 Most research work carried out on porosity and poresize distribution of cement paste and blended paste has adopted curing methods that allow the maximum hydration to take place. 4 Adopting other initial-curing methods by exposing specimens to relatively low relative humidity can greatly affect the porosity and pore structure of the paste) 73

*To whom correspondence should be addressed at: School of Construction, Sheffield Hallam University, Pond Street, Sheffield S 1 1WB, UK. ~Department of Civil Engineering, Glamorgan University, Pontypridd, UK. ~Mentor Project Engineering, Blackness Road, Aberdeen, UK.

74

P. S. Mangat, J. M. EI-Khatib, B.

11

Molloy

A considerable volume of research has been conducted in recent years to study the resistance of hydraulic-cement-based materials to chloride d i f f u s i o n . 2,9-12 This research has adopted both accelerated forms of testing by means of diffusion-cell techniques9,"~ and longer-term testing involving the use of more realistic chlorideexposure environments.~ 1.t2 Tests on samples that were cured for 60 days at 22C in saturated air, to allow full hydration of the cement-blending materials, have shown the potential of pfa and slag as a means of reducing chloride diffusionY. "1 Initial air curing after casting for fourteen days to simulate more practical curing conditions, however. resulted in higher chloride uptake when 26% of cement was replaced with pfa. ~t Some recent work demonstrates the increased corrosion resistance of reinforcement in concretes containing pfa or microsilica.2,13 The work is often conducted on mixes in which pfa is used to obtain the same strength as for the control mix. This leads to a lower water/(cement + blend) ratio of the pfa mix, relative to the control plain-concrete mix. The porosity and pore structure of concrete will influence directly the diffusion characteristics of chlorides and other corrosion-inducing substances, and consequently it will control the initiation and rate of reinforcement corrosion. There is, however, little work done to confirm this relationship in Portland-cement concretes and in concretes containing blended cements. In the case of blended cements, the effect on chloride diffusion of a cement-replacement material is not simply the result of its effect on the physical properties but also includes the chemical combination of chloride ions with the blended-cement material. There is information available on the chemical effects, 14 but little work has been reported to correlate the porosity and pore structure of the paste to chloride diffusion in concrete and hence to reinforcement corrosion. This paper investigates this relationship between microstructure, chloride diffusion, and corrosion resistance of reinforcement.

T a b l e t . Details of paste mixes for p o r o s i m e t r y study

Proportion (by weighO (%) Mix OPC* Pfa Microsilica Slag Water/ Superplasticiser binder+ %
PA PB PC PD 100 78 91 60 -22 ----9 ----40 0'45 0-45 0"45 0"45 1"2 1-2 1"5 1"2

* O r d i n a r y Portland c e m e n t . t B i n d e r (cementitious material) consisting of O P C c e m e n t - r e p l a c e m e n t material.

and

specimens, and PB, PC, and PD, which contained pfa, microsilica, and ground granulated blastfurnace slag, respectively. The water/cementitious materials ratio was kept constant at 0.45. Superplasticiser SP2000 was added to all pastes, which is based on the sodium salt of a copolymer of an unsaturated carboxylic acid and its alkyl ester.15 It conformed to Type F and G materials of ASTMC494. Cubes (100-ram) of paste shown in Table 1 were cast in steel moulds at a room temperature of 20C and relative humidity of 55%. Just before water on the top face (trowelled face) had evaporated, the surface was sprayed with a curing compound, Curex 90, according to the manufacturer's recommendations.~ After 24 h, specimens 5 were demoulded and the other five faces of each cube were moistened before applying the curing membrane. The specimens continued to be cured in air at 20C and 55% r.h. for a total period of 28 days. At the end of this curing period, samples for mercury-intrusion-porosimetry testing were taken from the middle of the side face of each cube. The weight of each test sample ranged between 0.8 and 2.5 g. The mercury-intrusionporosimetry technique was employed to measure the porosity and pore structure of the various pastes. Data were computed by using the following Washburn equation t6 to determine the pore diameter: D = (46 cos

O)/p

EXPERIMENTAL PROGRAMME Porosity and pore structure Four different pastes were employed to investigate the porosity and pore structure of blended cements, details of which are given in Table 1. The pastes were PA, in which ordinary Portland cement was used and which formed the control

where D is the pore diameter, p is the applied pressure, 6 is the surface tension, which was taken as 486 dyn/cm, and 0 is the contact angle, which was taken as 142 . Further details of the mercury-intrusion porosimetry tests are given by Mangat and E1-Khatib. s Cube strengths of the pastes were not determined, but concrete cubes made with the same

Propertiesof cement-replacernentmaterials
water/cementitious materials ratio of 0.45 were tested after curing in water at 20C for 28 days and for 23 weeks. The mix proportions, by weight of cement :fine aggregate:coarse aggregate were 1:2.0:3.43, with a cementitious content of 350 kg/m 3. The strengths after 28 days' curing for mixes with cement-replacement levels of 0%, 22% pfa, 40% slag, and 9% microsilica were 48, 36, 41, and 48 N/mm 2, respectively. The corresponding values after 23 weeks' curing were 53, 47, 54, and 62 N / r a m 2, respectively.
Chloride diffusion The mixes used for the chloride-diffusion investigation are given in Table 2. The control mix D1 was of proportions by weight 1:2.5:1.2 (cement:fine aggregate:coarse aggregate) with a water/cement ratio of 0.58. The cement content was 430 kg/m 3, and no cement-replacement materials were incorporated. In mix D2, cement was partially replaced by 20% pfa. In mix D3, 10% of cement was replaced by microsilica, whereas, in mix D4, 40% of cement was replaced by blast-furnace slag. The cementitious content (OPC +blending material) was kept constant at 430 kg/m 3, and the water/cementitious ratio was 0"58. The compressive strengths of these mixes, after curing under marine-spray cycles for 520 days, are listed in Table 2. These are similar except for the slightly higher value for the microsilica mix. Prism specimens of 100 x 100 500 mm were cast in steel moulds and were covered with a polythene sheet. The specimens were demoulded after 24 h and were left to cure under uncontrolled conditions of temperature and humidity in the laboratory air for fourteen days. The entire surface of the prism was coated with bituminous paint, apart from one 100 x 500-ram side face to allow for chloride penetration during exposure to a chloride environment. The bituminous paint
Table 2. Details of mixes used for chloride-diffusion and

75

effectively sealed the surfaces against chloride penetration. After fourteen days of initial curing, specimens were transferred to a laboratory seawater spray chamber, which provided two wet and two dry cycles in every 24 h, simulating tidal-zone exposure. After 520 days of marine cycles, the chloride contents at different depths into concrete specimens were measured by using two techniques: dry drilling to obtain powder samples, which were analysed chemically, their chloride concentration being referred to as acid-soluble chloride, 11 and chemical analysis of pore fluid expressed from concrete under high pressure and referred to as free-chloride concentration. 17 Further details of the test procedure and of acidsoluble-chloride analysis are given in Ref. 11. The chloride was extracted from powder samples by heating in dilute nitric acid. On cooling, the solution was filtered, and a Mohr titration was carried out. The chloride concentration was determined from the following expression: ~l %C1- 35.453vN 10w

where N is the normality of AgNO3, v is the volume of A g N O 3, and w is the mass of the powder sample in grams. The test procedure for pore-fluid extraction and its chemical analysis are described in Ref. 17. The small quantity of extracted pore fluid was analysed by microtitration. A solution of dilute pore fluid, potassium dichromate indicator solution, and borax was titrated against 0"ls A g N O 3 to determine the free C1- concentration of the
pore fluid. 17

corrosion-resistance studies

Mix

Binder content (kg/m-~)

430 430 430 430

Cementreplacement material (%)

-Pfa (20%) Microsilica (10%) Slag (40%)

Water/ binder
0-58 0-58 0-58 0.58

Compressive strength (N/mm 2)

35 36 40 36

D1 D2 D3 D4

*Equivalent cube strength after 520 days of marine-spraycycle curing.

Corrosion resistance Mixes D1, D2, D3, and D4, which were used to study chloride diffusion, were also employed to study the corrosion resistance of steel reinforcement in these mixes. The same initial-curing method (a fourteen-day air-curing) as in the previous section was used in this case. The specimens were then exposed to up to 1200 marine cycles in the seawater spray chamber over 600 days. One prism specimen of dimensions 100x 100 x 370 mm was cast for each of the above mixes, with three replicate rebar electrodes positioned at a cover of 10 mm from the side face of the prism relative to its casting position as

76

P. S. Mangat, J. M. EI-Khatib, B. T. Mollov

shown in Fig. 1. This side face of the prism was kept unsealed during its period of marine exposure, whereas the remaining faces were sealed with a bituminous paint. The electrodes were labelled T (top), M (middle), or B (bottom), referring to their position relative to the top face of the specimen during casting. Deformed reinforcement bars of 12-mm diameter were used as electrodes in 360-mm lengths. Further details of the specimens are given in Ref. 12. Corrosion potential, Ec, and polarisation resistance, Rp, were measured by using a potentiostat apparatus. Details of test procedures are given in Ref. 18.

Materials Ordinary Portland cement, fine aggregate of Category M of BS882, and crushed-granite coarse aggregate of nominal size 10 mm were used. Deformed high-yield-steel reinforcing bars of 12mm diameter were used, whose chemical composition is given in Table 3. Pfa was supplied from the Longannet power station near Edinburgh. Blast-furnace slag was supplied by Blue Circle Ltd. Microsilica was supplied by Elkem Chemicals Ltd in the form of a slurry of equal proportions of solids and water. The chemical composition of the cement and replacement materials is given in Table 4.

RESULTS AND DISCUSSIONS

I00x1OO.5OOmm prism mould

100,100mm /-'"~ perspex Iocators .-'" ]\\~-]~f~

. . . . . . ,,oo

electrodes

wr ~ ~-~ r .m . m . . . ~ / ie" ' , m

i

...-~/"

L (M_!~]...-/ . / ....... (B~" Y ' - . . ~ .

Ban fa e r c qr m i

(TI.T--~ ./ ...... z / -~

~
for ......

~void fi0n -i~2~j

k

we is r

Fig. 1.

Details of corrosion-test specimen.

Porosity and pore structure The intruded pore volume of the various pastes considered in this investigation is presented in Table 5. It is clear that the microsilica paste possesses the largest intruded pore volume of the pastes, the value being 0.2028 cm3/g. This is followed by pfa blended paste, which yielded an intruded pore volume of 0.1953 cm3/g. The intruded pore volume of the slag blended paste, however, is 0.1655 cm3/g, which is more than that of the control paste, which is 0.1462 cm3/g. The pore-size distribution of pastes PA, PB, PC, and PD is shown in Fig. 2. The pores are divided into large pores, whose diameter is greater than 0.1/~m, and small pores of diameter

Table 3. Chemical composition of 12-mm-diameter H.Y. reinforcing bar

Element (%)

C 0'15

Si 0'21

Mn 0"81

Ph 0-011

S 0"035

Cr 0"04

Mb 0'02

Ni 0"06

Cu 0"06

Vn 0'004

Table 4. Chemical composition of ordinary Portland cement (OPC) and cement-replacement materials

O PC

Pfa 48'0 38.2 4.5 3"3 1-5 0-3 1.7

Slag 36"0 9.0 1.0 43.0 7.0 1-0

Microsilica 92.0 (1.7 1.2 0.2 0.2 2.0

(SiO2)
(A1203) (Fe203) (CaO) (MgO) (Na20) (K20)

(%)
(%) (%) (%) (%) (%) (%) (%)

(TiO2) (s 2- )

(%) (%)

20.4 4.89 3.18 64.02 2-56 0'07 0"53

1.3 1.0
300-500 15 000-20 000

(So42-) Loss on ignition Surface area

0.44 0"98 367.76 2-3 300-600

(%) (mZ/kg)

Properties of cement-replacement materials

77

less than 0.1/~m, which are presented in Table 5. Figure 2 shows that the pfa blended paste has a coarser pore structure and a larger dominant pore size. The dominant pore sizes corresponding to the maximum incremental volume, d V, in Fig. 2 are about 0.51/am for the pfa blended paste and 0"23/am for the control paste. The proportions of large pores are 68.3% of the total intruded pore volume for the pfa blended paste and 52.4% for the control mix (Table 5). The dominant pore sizes of microsilica paste and control paste are
Table 5. Pore volume of the pastes

similar, as is the dominant pore size of the slag blended paste. The large pores occupy 70.6% and 67.8% of the total intruded pore volume in the microsilica paste and the slag blended paste, respectively.
Chloride diffusion Acid-soluble chloride-diffusion profiles for mixes D1, D2, D3, and D4 after 520 days of exposure to marine cycles are shown in Fig. 3. It can be seen that the 10% microsilica mix (D3) exhibits the

Mix Total volume

PA (control) PB (22% pfa) PC (9% microsilica) PD (40% slag) 0.1462 0-1953 0.2028 0.1655

Pore volume (cm3/g) Large pores (> 0"1 ktm)

0.0767 0.1334 0"1432 0-1122

Pores (%) Small pores (< 0.11zm)

0.0695 0.0619 0.0596 0.0533

Large (>-0"1 I~m)

52.4 68.3 70.6 67"8

Small ( < O.1/zm)

47-6 31.7 29.4 32.2

0.055 0.05 _0-045 0"04 0-035 =~ 0.03" =

m

O.OSS 0.05 PA (control) 0.045 0"04

0.03S PC ( 9 % micrositica)

0.03

0025.
0.02" 0.015. 0.010.005 0-0

>o 0.025

g o-o2
E

= 0-015-

\
1~o lO
1

0.Ol 0.005 -

1000

o'i

O.bl

00 0-001 1000 100

Hean pore diameter (urn)

0-055 -

10 1 0"1 Mean pore diameter (urn)

0"01

0.~)01

0.055 0.05

0.05

0.045 "~ 0.04.a "

0-035 -

PB(22% pfa)

O.O~S

PD (40% slag)

0-04 ~a 0-35

0.03-

0.03
O

o> 0-025

> 0.025
to

5_ o-o2 ~
~ 0.0150.01 O.OOS -

c
E

0.02 0.015 0"01

0-0O5

0.0 1000

1~o

lO

~.1
Fig. 2.

o!ol

if001

0.0 1000

I00

Mean pore diameter (urn)

10 I 0.1 Mean pore diameter (urn)

0.01

0~

Pore-sizedistribution of different pastes.

78
"~ E "6 3 \ ~

P. S. Mangat, J. M. El-Khatib, B. T. Molloy

Ol ~ Control D2 o PFA(20%)
D3 o Micrositica (10%) Dr, ~' Slag (40%)

Etectrode ISymbotl

.~

:3l', '

(al

Mi,

oi

\ \

..........
. -500~ ":#~. . . . . . . .... .~ ........... . . . . ,~. -600 / 0
, 100 , 200 , 300
Time(days)

I Bo.0m I
-.......... o
~ 400 , 500 ..... "~ 600

-4O0] 10 20 30 40 Depth (mm) SO

(b} Mix D2 (20%pfa)

...................
60 70
-600-t '~ .............. ". . . . . . . . . . . . . .

Fig. 3. Acid-soluble chloride-concentration profiles for mixes D1, D2, D3, and D4.
3000
E

100

200

300 4O0 Time(days)

5O0

600

-300- ~ (c) Mix D3 {10% microsit.ica) t ......... -tO0- ~', Ol x Confrot Oz o PFA (20%) D3 u Micrositica (10%) D(, ~ Stag (60%)
0 0

g = 2000
c

-'s- "ii i/ "600- ",-:

-700','~:: o....

~"

"

...... ..................

==5;

./O~ o 1000
i

-B00 -900 0

#l 2

160

200

300
Time(days)

/*bO

S00'

600

u_

10

20

30 40 Depth (mm)

510

iO

7'0

~00- I ,,~. (d) Mix D4 (40% stag) o-" "c{

-500

Pore-fluid chloride-concentrationprofiles for mixes Fig. 4. D1, D2, D3, and D4. lowest chloride ingress at all depths compared with the control mix (D1) and the other mixes (D2 and D4), although the pore volume of the silicafume paste was found to be greater than that of the control paste (and all other pastes) as seen in the preceding section. The 20% pfa mix (D2) exhibits a higher chloride concentration at the concrete surface than the control mix (D1) up to a depth of about 9 mm from the concrete surface. At greater depths, the chloride content of mix D2 is lower than that of the control mix. The 40% slag mix (D4) shows a similar trend to the 20% pfa mix, the chloride contents being higher than for the control mix up to a depth of about 15 mm. Beyond this depth, the chloride contents are lower in mix D4 than in mix D1. Chloride concentration in pore fluid for mixes D1, D2, D3, and D4 is shown in Fig. 4. The microsilica mix (D3) shows the lowest chloride concentrations of the four mixes at all depths. Higher chloride concentrations are obtained for the pfa blended mix and for the slag blended mix than for the control mix up to a depth of about 15
ram.

~.~:.=:~'~:,~,:.-.--.:=:====,=_.
......

100

; ....... 7. ...... : .......

200 300 Time(days)

4O0

5O0

600

Fig. 5. Corrosion potential with time for mixes D1, D2, D3, and D4.

slag blended mix show negligible chloride content after a depth of 35 nun from the concrete surface, whereas the control mix exhibits a considerable chloride content, even after a depth of 65 mm. Similar observations of greater depths of chloride penetration into normal concrete have been made by other researchers, who have stated that detrimental amounts of chloroide reach embedded steel even through high-quality concrete when ordinary Portland cement is used in the mix without cement-replacement material.19
Corrosion potentials, E c

Figures 3 and 4 show negligible chloride concentration (acid-soluble and pore-fluid) after a depth of 25 mm from the concrete surface for the 10% microsilica mix. The pfa blended mix and the

Corrosion potentials of the three electrodes in the control-mix (D1) specimen are plotted against exposure time in Fig. 5(a). Similar plots for 20% pfa mix (D2), 10% microsilica mix (D3) and 40% slag mix (D4) are plotted in Fig. 5(b), (c) and (d). The long-term electrode potentials of the pfa mix (D2) are more negative than those of the control mix, which indicates more corrosion activity in the pfa mix. In the 10% microsilica mix (D3), the potentials at an early stage, up to 100 days, are much more negative than those of the control mix and the other mixes (D2, D4). The long-term

Properties of cement-replacement materials

potentials of mix D3, however, show less negative values than the control mix (D1). On the other hand, the long-term potentials of the 40% slag blended mix show similar corrosion potentials to the control mix, although previous researchers have indicated a slower progression to active potentials for rebars in slag c o n c r e t e . 19

79

Polarisation resistance, Rp
The polarisation resistance, Rp, which is measured by using a potentiostat apparatus, was converted into the corrosion rate by using Faraday's law. Details of the equations used are given in Ref. 18. The average long-term polarisation resistances for rebars embedded in specimens of mixes D1, D2, D3: and D4 and the corresponding corrosion rates are listed in Table 6. The pfa mix (D2) yields the lowest g p v a l u e and therefore the highest corrosion rate. The corrosion rates were 0"018 mm/year and 0.00754 mm/year for the pfa mix and the control mix, respectively. The microsilica mix shows a corrosion rate of 0.0047 mm/ year, which is the lowest value of those obtained for the four mixes. The slag blended mix yields a corrosion rate of 0.0054 mm/year.

Further discussion
Paste specimens, which were cast for mercuryintrusion porosimetry, were initially membranecured in air at 20C and 55% r.h. Previous work has shown a poor performance of the curing membrane used in the investigation,8 so the membrane-curing was considered to be identical to air-curing. In order to compare the various aspects investigated in this study, the acid-soluble chloride and pore-fluid chloride-concentration values at 10 mm from the concrete surface were obtained from Figs 3 and 4 and are listed in Table 6. The 10-mm depth represents the cover to the reinforcing bars used in the corrosion experiments. It can be observed from the results obtained that the intruded pore volume of the microsilica

paste is the largest of the pastes studied, although the microsilica concrete has the lowest chloride concentrations (acid-soluble and pore-fluid) and the lowest corrosion activity. One possible explanation for the lower chloride ingress despite the greater pore volume in microsilica concrete may be the improved matrix-aggregate bond that has been observed in concretes containing microsilica as partial cement replacement. Other research has shown that, in concrete with more than 7.5% cement replacement by microsilica, aggregate failure leads to compression failure, whereas, in similar non-microsilica concrete, bond failure at the matrix-aggregate interface occurs at the compression-failure stage. This superior interracial bond may be responsible for hindering chloride penetration into microsilica concrete. The intruded pore volume of the pfa paste is higher than that of the control paste, although the acid-soluble chloride in the pfa concrete mix was found to be lower than that in the control mix, as shown in Table 6. The chloride concentration of the pore fluid in the pfa concrete, however, was larger than that in the control mix up to a depth of about 20 mm. These results show that the capacity to combine chemically (bind) chloride ions in the matrix is lower in pfa concrete than in non-pfa concrete at relatively low depths from the concrete surface. The specimens of this investigation were exposed initially to air-curing for fourteen days. The surface zone of concrete was more susceptible to the poor curing that did not allow full hydration of pfa particles and therefore led to a higher chloride concentration of the pore fluid. But, at depths beyond 30 mm, in pfa concrete, the pore-fluid chloride concentration decreased relative to the acid-soluble chloride concentration, which thus indicated a superior chloride-binding capacity of the matrix at greater depths, where the effect of low-humidity curing is less critical. The high concentration of chloride in the pore fluid (free chloride) in the pfa concrete at a 10-mm depth is accompanied by a higher corrosion rate

Table 6. State of rebar corrosion and chloride concentration at 520 days of marine exposure

Mix

Rp (ohm cm 2)

Corrosion rate (mm/year)

0.00754 0.018 0.0047 0.0054

E c (m V SCE)

Chloride concentration at lO-mm depth Acid-solub&

~)

Pore-fluid
1200 1325 750 1250

~mM/~tre)

D1 D2 D3 D4

4 104 1.7 104 6-3 x 104 5"6 104

-450to -580to -440to -540to

-550 -690 -480 -560

2-0 1-8 1.3 2.1

80

P. S. Mangat, J. M. El-Khatib, B. T. Mollov

than in non-pfa concrete, although the acid-soluble chloride is lower in pfa concrete at the same depth relative to the control mix D 1 and the slagconcrete mix D4. This indicates that the concentration of chloride in the pore fluid is responsible for determining the corrosion rate. The intruded pore volume of the slag blended paste is found to be larger than that of the control paste. Slightly higher concentrations of chloride (acid-soluble and pore-fluid) are obtained at the concrete surface up to a depth of about 20 mm. The corrosion potentials of the reinforcement electrodes embedded in the slag blended concrete are similar to, or slightly more negative than, those of the control mix at various periods of marine exposure (Figs 5(a) and 5(d)), which thus indicates similar progression to active corrosion potentials. The corrosion rate of 0.0054 mm/year for the reinforcement in slag concrete (Table 6) is lower than the value for the control specimen. Results of other researchers indicate a slower progression to active potentials for rebars in BFS concrete.2.2~

5. Higher chloride concentration in the pore fluid leads to higher corrosion activity of rebar in concrete. 6. The microstructure of paste matrix is not necessarily related to chloride diffusion and to reinforcement-corrosion rates in concretes containing different cement-replacement materials. ACKNOWLEDGEMENTS The authors gratefully acknowledge the financial support of the Science and Engineering Research Council and the University of Aberdeen for this project. REFERENCES
1. Barrow, R. S., Hadchiti, K. M., Carrasquillo, P. M. & Carrasquillo, R. L., Temperature rise and durability of concrete containing fly ash, American Concrete Institute Report SP-114, Vol. 1, 1989, pp. 331-47. 2. Berke, N. S., Resistance of mierosilica concrete to steel corrosion, erosion and chemical attack. American Concrete Institute Report SP-114, Vol. 2, 1989, pp. 861-86. 3. Day, R. C. & Marsh, B. K., Measurement of porosity in blended cement pastes. Cement and Concrete Research, 18 (1988) 63-73. 4. Shigun, L. & Roy, D. M., Investigation of relations between porosity, pore structure and CI- diffusion of fly ash and blended cement pastes. Cement and Concrete Research, 16 (1986) 749-59. 5. Manmohan, D. & Mehta, P. K., Influence of pozzolamic, slag and chemical admixtures of pore size distribution and permeability of hardened paste. Cement, Concrete and Aggregates, 3 (Summer)(1981) 63-7. 6. Roy, D. M. & Parker, K. M., Microstructures and properties of granulated slag, Portland cement blends at normal and elevated temperatures. American Concrete Institute Report SP-79, 1983, pp. 397-414. 7. Sellevold, E. J., Bager, D. H., Klitgaard, E. & Knudsen, T., Silica fume -- cement pastes: hydration and pore structure. Norwegian Institute of Technology, Trondhelm, Report BML 82.160, 1982,pp. 19-50. 8. Mangat, E S. & EI-Khatib, J. M., Influence of initial curing on pore structure and porosity of blended cement concrete. American Concrete Institute, SP, 1992. In press. 9. Page, C. L., Short, N. R. & EI-Tarras, A., Diffusion of chloride ions in hardened cement pastes. Cement and Concrete Research, 11 ( 1981 ) 395-406. 10. Byfors, K., Influence of silica fume and fly ash on chloride diffusion and pH values in cement pastes. Cement and Concrete Research, 17 ( 1987) 115-30. 11. Mangat, P. S. & Gurusamy, K., Chloride diffusion in steel fibre reinforced concrete containing pfa. Cement and Concrete Research, 17 (1987) 640-50. 12. Mangat, P. S. & Molloy, B. T., Factors influencing chloride induced corrosion of reinforcement in concrete. Rilem Materials and Structures, 25 (1992) 404-11. 13. Thomas, M. D. A., Matthews, J. D. & Haynes, C. A., Chloride diffusion and reinforcement corrosion in

CONCLUSIONS The following conclusions are based on the experimental results reported in this paper. 1. Replacing about 10% of cement with microsilica in a cement paste increases the intruded pore volume. However, both chloride penetration (acid-soluble and porefluid) and the corrosion rate of embedded steel reinforcement decrease in concrete containing a similar cement,replacement level of microsilica. 2. The replacement of cement with about 20% pfa leads to a higher pore volume and a coarser pore-size distribution in a hardened paste. It increases the concentration of acidsoluble chloride and of free chloride in the pore fluid in the concrete surface zone. At depths beyond 30 mm, the acid-soluble chloride and the concentration of chloride in the pore fluid are reduced. 3. The corrosion rate of steel in concrete containing 20% pfa is higher than that in non-pfa concrete at a depth of 10 nun from the concrete surface. 4. Replacing 40% of cement with slag increases the intruded pore volume of cement paste. The rate of corrosion of rebar embeded in concrete containing a similar replacement level of slag is, however, lower.

Properties of cement-replacernent materials

marine exposed concrete containing pulverised-fuel ash. Corrosion of Reinforcement in Concrete, Elsevier Applied Science, Barking, Essex, UK, 1990, pp. 198-214. Page, C. L. & Vennesland, O., Pore solution composition and chloride binding capacity of silica-fume cement paste, Materials and Structures, 16 (1983) 19-25. Cormix Ltd., Workington, Cumbria, UK. Washburn, E. W., Note on a method of determining the distribution of pore sizes in porous materials. Proc. Nat. Acad. Sci., 7 (1921) 115-16. Mangat, P. S. & Gurusamy, K., Pore fluid composition under marine exposure of steel fibre reinforced concrete. Cement and Concrete Research, 17 (1987) 734-42. Mangat, E S. & Molloy, B. T., Influence of pfa, slag and microsilica on chloride induced corrosion of reinforce-

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ings of 3rd International Conference on Deterioration and Repair of Reinforced Concrete in the Arabian Gulf, Bahrain, 1989, Vol. 2, pp. 299-336. 21. Keer, J. G., Chadwick, J. R. & Thompson, D. M., Protection of reinforcement by concrete repair materials against chloride induced corrosion. In Corrosion of Reinforcement in Concrete, ed ? Page, ? Treadaway & ? Bamforth. Elsevier Applied Science, Barking, Essex, UK, 1990, pp. 420-32.