Constntction

and Building Materials, Vol. 11, Nos 7-8. pp. 383-393, 1997
0 1997 Published by Elsevier Science Ltd
Printed in Great Britain. All rights reserved
09so-U618/97
$17.00 + 0.w

PII:SO950-0618(97)00061-5

The influence of different curing conditions on

the pore structure and related properties of
fly-ash cement pastes and mortars
C. S. Peon*, Y. L. Wong and L. Lam
Concrete Technology Group, Department of Civil and Structural Engineering, The
Hong Kong PolytechnicUniversity, Hung Horn, Hong Kong
Received 3 February 1997; revised 19 August 1997; accepted 4 September 1997
The influence of two different curing conditions (in water at 27C, and in air at 15C and 60% relative
humidity) on the mechanical and durability properties of fly-ash cement pastes and mortars are
studied. Cement pastes and mortars at two water/cement
or binder ratios were prepared in the
laboratory and tested for compressive strength, chloride and water penetration. The mercury intrusion
porosity of the samples is monitored to provide mechanistic explanations for the measured results.
The results show that fly ash has significantly different influence on the strength, porosity and
durability parameters of cement pastes and mortars when the cementitious materials are subjected to
0 1997 Published by Elsevier Science Ltd.
different curing conditions.

Keywords: cement pastes; fly ash; curing

Introduction

gel/space
ratios of fly-ash mixes estimated by the
strength data are higher than those calculated from the
water/cement
(w/c> ratios of the mixes, and he attributed it to the equivalent cementing effect of fly ash.
He concluded that the strength contribution of fly ash
is the sum of nucleation and pozzolanic factors. Marsh
et al.* found that the pozzolanic reaction of fly ash in
blended cement-pastes can cause substantial reduction
in permeability. This reduction may be as large as three
orders of magnitude when compared to an identically
cured Portland cement paste of the same water/solid
ratio.
Pore structure is considered to be one of the major
factors controlling the durability and strength of hydrated cement products. A measure of the porosity and
pore-size distribution can lead to more basic understanding of many physical and durability parameters of
the material. Feldman found that at early ages, the
porosity of fly-ash cement pastes determined by mercury intrusion porosimetry (MIP) is greater than that of
the comparable Portland cement pastes although the
pore-size distributions of the two types of pastes are
similar. Bijenj further indicated that the pore size
distribution, measured with MIP of a cement paste
prepared with ASTM class F (ASTM C618) fly ash is
more coarse than the plain cement paste at the initial
curing period, but later the opposite is the case.

Fly ash is being increasingly used as a common mineral

admixture in concrete to obtain improved properties of
the fresh and hardened products,*. The use of fly ash
modifies the composition of the cement pastes, influences the hydration and microstructure of the pastes
and mortars, and the strength and permeability of
concretes-.
Montgomery et al.4 found that the ash particles act
as nucleation sites for the hydration of cement. Wai et
aL5 stated that fly ash has retarding effects on the
hydration of cement. Xu et al.83Yindicated that fly ash
has both enhancement and retardation effects on cement hydration, and may also provide nucleation sites
for the growth of hydration products. A research study
carried out at Intron indicated that fly ash improves
the particle packing of the cementitious matrix and
contributes to the strength development even when it is
not active as a pozzolana but acting as a so-called
filler. The research also investigated the effects of the
addition of fly ash on the interfacial zone between the
aggregate and the paste, and found that the rate of the
pozzolanic reaction is faster in the interfacial zone than
in the bulk of the paste. Gopalan found that the

*Correspondence

to Dr C. S. Peon

383

384

Porestructure and related properties of fly-ash cement pastes and mortars: C. S. Poon et al.

Malami et al3 demonstrated that at a w/cc +f)

ratio of 0.5, the additions of 4% and 15% fly ash
(ASTM class C) did not significantly influence the
porosity of the mortars, but higher percentage additions resulted in an increase of the porosity. Xu et ~1.~
indicated that equal weight replacement of cement by
fly ash lowered the total initial volumetric porosity of
the mortar. Al-Amoudi et al. presented the results of
permeability and helium porosimetry tests for concrete
mixtures at w/c from 0.35 to 0.55, and with the replacement of cement by fly ash (ASTM class F) from 0
to 40% by mass. They found that at the initial curing
period of 50-75 days, the plain cement concretes were
the least permeable and the least porous. But after 1
year of curing, the best performance was shown by 20%
fly-ash cement concrete followed by 30, 10 and 40%
fly-ash concretes.
The above studies showed beneficial effects of fly ash
on the long-term durability properties and microstructure of concrete. However, these results were usually
obtained from specimens cured in water or moisten
environments. It should be noted that the fly-ash concrete is more sensitive to the curing condition and
requires a longer curing time because its hydration rate
is slower than that of the plain concrete. The benefits
of using fly ash in concretes may be diminished due to
inadequate curing.
The authors previously studied the influence of different curing conditions on the strength of normalstrength (w/c = 0.49) and high-strength (w/c = 0.3)
fly-ash concretes . The results showed that in water
curing, direct replacements of cement by fly ash in
normal-strength concrete reduced the 28-day strength
although the long-term strength was comparable to the
plain concrete. Extra (10%) addition of fly ash in
concretes decreased the early strength but enhanced
the latter strength. The strength of the high-strength
mixes was enhanced by the extra fly ash addition irrespective to the age of curing. When cured in 15C and
60% Relative Humidity (RH), fly ash addition to concrete was shown to be detrimental to concrete strength.
It has also been shown that the main contribution of fly
ash to concrete strength at the age of 28 days was likely
due to the improvement of the bonding between the
cement paste and the aggregate, rather than the enhancement of the strength of the cementitious matrix.

Objectives
The present paper tries to determine the influence of
curing conditions on the mechanical and durability
properties of fly-ash cement pastes and mortars by a
systematic study of the pore structure and porosity of
the cementitious materials. At the same time, the relationships between the compressive strength, porosity
and two durability parameters (water permeability and
chloride penetration) are also quantified.

Experimental

Materials

The materials used were locally available ordinary

Portland cement meeting the requirements of British
Standard 12 (Green Island Cement) and fly ash meeting the requirements of British Standard 3892 (China
Light and Power), crushed granite and river sand. Table
I gives the chemical analysis of cement and fly ash
whereas Table 2 shows the properties of aggregates. A
commercially available naphthalene based super-plasticizer (RBllOO) was used for the mixes with low
water/binder ratios to give a consistent workability.

Midure design

Two series of plain cement pastes with water/cement

ratios of 0.49 (Series 1) and 0.3 (Series 2) were prepared (Table 3). Some mixtures were prepared with the
cement partially replaced by 15 or 25% of equal (direct
replacement) or extra 10% (extra addition) mass of fly
ash. The normal-strength mixtures (Series 1) are denoted by N and the high-strength mixtures (Series 2)
are denoted by H. The codes of the mixtures have
three components. For example, N-15-10 represents a
normal-strength mixture prepared with a water/binder
ratio of 0.5, with 15% of cement replaced by fly ash and
an extra 10% by weight of fly ash added. In parallel,
concrete mixtures with fly-ash/cementitious
materials
and water/cementitious
materials ratios identical to
those of the corresponding pastes were prepared. Addi-

Table

Properties

of cement and fly ash

Cement (%)
20.77
65.07
0.89
3.23
6.20
2.47
0.17
0.43
0.97
0.21
< 0.05
3519
3.15

SiO,
CaO
MgO
Fe&
AU,
SOS
NazO
K,O
LO1
Insoluble residue
Chloride
Specific surface area (g/cm)
Density (g/cm)

Table 2

Properties

Fly ash (%)

44.92
5.69

1.24
4.89
35.39
0.71
0.58
0.64
5.61
63.32
< 0.05
3860
2.3 1

of aggregates
Coarse aggregate

Relative density (S.S.D.)

Water absorption (o/o)

IOmm

20 mm

2.58
0.78

2.60
0.69

Sand

2.64
0.87

Porestructure and related properties of fly-ash cement pastes and mortars: C. S. Poon et al.

pastes and the mortars from the compression tests

were collected and immersed in acetone to stop the
cement hydration and the samples were then used for
the measurement of pore structure.

tionally, mortar samples were prepared by removing

the coarse aggregate particles using a 5-mm sieve during concrete mixing. The mixture design is given in
Table 4.

The samples were prepared, cast with appropriate

compaction, demoulded (after 24 h of initial curing)
and then cured for the specified periods (27 and 90
days). The curing conditions were either in water at
27C or in an environmental chamber at 15C and 60%
relative humidity (RH). In the latter environment, the
specimens were first placed in the environmental chamber in sealed plastic bags for 3 days and then exposed
to the chamber environment.

Water permeability and chloride penetmtion. The water

permeability test was performed on concrete cylinders,
200-mm diameter x 220-mm long, using an automatic
permeameter at a constant water pressure of 2.0 &-0.05
MPa. The rate of chloride ion penetration into concrete was tested on 150-mm cubes. Separately prepared
150-mm cubes after the specified curing were immersed
either in (i> a 5 M sodium chloride solution which had
been saturated with calcium hydroxide, or (ii) a control
solution containing saturated calcium hydroxide only,
for 28 days. Powdered samples were obtained by drilling
to different concrete depths (25 mm, 50 mm and 75
mm). A mixture of 5 g of the powdered sample and 100
ml of diluted nitric acid (10 ml of nitric acid + 90 ml of
distilled water) was digested in a 300-ml beaker on a
hot plate for 15 min. The mixture was filtered through
a fast ashless filter paper. The chloride ion concentra-

Test procedures
Compressiue strength. Compressive strength tests of the
paste and the mortar samples were performed on 70.7mm cubes and that of the concrete was performed on
lOO-mm cubes using a Denison 7231 compression testing machine. The results of the concrete strength have
been reported previously I7, The fracture pieces of

Table 3
Paste
series

1 (normal
strength)

2 (high
strength)

Table 4

Mixture

2 (high
strength)

of pastes
Mixture

Notation

Water(w)

proportion

Cement

cc>

(g)

Ratios

Fly ash (f)

w/cc

+f)

f/cc

Super-plasticizer
[ml per 1000
g (c +fI

+f)

a N-O-O
N-15-0
N-25-O

49
49
49

100
85
75

0
15
25

0.49
0.49
0.49

0
0.15
0.25

0
0
0

b N-0-10
N-15-10
N-25-10

49
49
49

100
85
75

10
25
35

0.44
0.44
0.44

0.091
0.227
0.318

0
0
0

a H-O-O
H-15-0
H-25-O

30
30
30

100
85
75

0
15
25

0.30
0.30
0.30

0
0.15
0.25

5
5
6

b H-O-10
H-15-10
H-25-10

30
30
30

100
85
75

10
25
35

0.27
0.27
0.27

0.091
0.227
0.318

8
9
10

Mixture

Concrete
series

1 (normal
strength)

proportion

proportion

of concretes
Mix proportion

Notation

(kg/m31

Fly ash Coarse

w/cc

aggregate

+f)

Sand

Superplasticizer
(I/m)

Water

Cement

(w)

(c)

(f)

10 mm

20 mm

N-O-O
N-0-15
N-25-O

220
220
220

450
383
338

0
67
112

357
357
357

713
713
713

398
575
561

0.49
0.49
0.49

b N-0-10
N-15-10
N-25-10

220
220
220

450
383
338

45
112
157

357
357
357

713
713
713

546
523
509

0.44
0.44
0.44

H-O-O
H-15-0
H-25-O

168
168
168

560
476
420

0
84
140

357
357
357

713
713
713

643
615
597

0.3
0.3
0.3

2.73
3.64
3.27

H-0-10
H-15-10
H-25-10

168
168
168

560
476
420

56
140
196

357
357
357

713
713
713

578
551
532

0.27
0.27
0.27

5.18
5.82
6.36

385

Porestructure and related properties of fly-ash cement pastes and mortars: C. S. Poon et al.
tion of the sample solution was determined using an
ion selective electrode (Orion). The chloride content of
the powdered sample was calculated and expressed in
mg of chloride per g of sample.

used. A cylindrical pore geometry and a contact angle 8

of 140 were assumeds*19. The mercury intruded pore
diameter d at a pressure of P was calculated by
d = - 4y cos 8/P, where y = 0.483 N/m, the surface
tension of mercury 19.

Mercury porosimetry. The cement

paste samples after

the specified curing ages were first broken into smaller
pieces and immersed in acetone for not less than 7
days. The samples were then dried at 105C for 24 h. A
micromeritic mercury intrusion porosimeter (MIP) with
a maximum mercury intrusion pressure of 210 MPa was

Table 5

Compressive

strength

of pastes

Compressive

Results and discussions

Compressive strength of cement pastes and mortars
Table 5 gives the compressive strength values of (i) the

and mortars

strength

Compressive

of pastes

Cured in water
at 27C
28 days

N-O-O

Cured in water
at 27C
(28 days)

Cured in air at 15C

and 60% RH

90 days

strength

of mortars

(N/mm*)

(N/mm*)

28 days

90 days

Cured in air at
15C and 60%
RH (28 days)

N-15-0
N-25-O
N-0-10
N-15-10
N-25-10

67.8
59.4
55.2
71.0
58.2
49.8

72.4
63.6
74.8
88.6
84.8
74.8

49.4
39.2
33.2
52.1
39.7
30.9

47.5
34
31.2
46.9
37.6
34.4

54.2
52.5
48.4
60.6
56.3
47.9

46.3
44.6
38.0
51.5
40.8
29.5

H-O-O
H-15-0
H-25-O
H-0-10
H-15-10
H-25-10

115.7
115.5
106.0
122.2
117.6
98.5

115.0
115.2
119.5
135.1
134.5
108.9

86.9
77.2
66.6
92.4
81.5
68.6

89.3
80.4
71.8
88.5
79.8
66.7

93.8
94.5
83.0
98.3
105.3
100.5

79.1
73.5
61.9
83.8
72.3
61.3

Table 6

Results

of water permeability

test of concrete

samples

Water permeability
Cured in water at 2PC
90 days

28 days
N-O-O
N-l 5-O
N-25-O
N-0-10
N-15-10
N-25-10

Table 7

1.02
9.89
1.08
8.62
8.50
9.00

Results

E-l 1
E-l 2
E-l 1
E-12
E-l 2
E-12

of chloride

(m/s)
Cured in air at 15C and 60% RH

5.00
3.91
3.92
1.63
1.03
1.43

ion penetration

Concentration

28 days

E-12
E-12
E-12
E-12
E-12
E-12

of concrete

of chloride

5.08
5.11
5.51
4.59
5.07
5.48

E-10
E-10
E-10
E-10
E-10
E-10

2.73
3.12
3.43
2.27
2.78
2.89

E-10
E-10
E-10
E-10
E-10
E-10

samples

penetrated

at different

Cured in water at 27C

28 days

90 days

Cured

90 days

depths (mg/g)

in air at 15C and 60% RH

28 days

90 days

25 mm 50 mm 75 mm 25 mm 50 mm 75 mm 25 mm 50 mm 75 mm 25 mm 50 mm 75 mm

1.44

N-O-O
N-15-0
N-25-O
N-0-10
N-15-10
N-25-10

3.23
3.26
3.43
2.62
2.67
2.72

0.55
0.69
0.78
0.39
0.40
0.54

0.46
0.52
0.53
0.30
0.38
0.40

2.03
2.01
2.02
1.01
0.87
0.91

0.27
0.33
0.36
0.19
0.19
0.21

0.22
0.25
0.26
0.15
0.18
0.19

11.78
11.57
12.30
9.88
9.84
11.11

1.85
2.48
3.8
1.85
1.84
2.12

1.03
1.03
1.42
0.68
0.59
0.82

8.07
9.02
8.33
5.88
5.93
7.13

1.69
2.55
1.23
1.20

1.43

0.74
0.73
0.97
0.45
0.35
0.55

H-O-O
H-15-O
H-25-0
H-0-10
H-15-10
H-25-10

1.61
1.16
1.43
0.75
0.88
1.14

0.39
0.13
0.21
0.1
0.1
0.12

0.29
0.08
0.14
0.02
0.07
0.07

I .09
0.52
1.02
0.24
0.23
0.27

0.18
0.05
0.11
0.03
0.02
0.03

0.10
0.03
0.08
0.01
0.01
0.01

4.76
3.98
4.54
1.47
1.52
2.38

0.68
0.19
0.34
0.10
0.11
0.20

0.31
0.13
0.14
0.05
0.11
0.12

2.53
4.07
4.64
1.58
1.00
3.09

0.37
0.62
0.76
0.19
0.21
0.53

0.25
0.44
0.56
0.12
0.16
0.38

46.9
48.3
44.8
45.9
45.8
43.1

20.74
22.91
22.66
22.57
22.87
23.97

H-O-O
H-15-0
H-25-O
H-0-10
H-15-10
H-25-10

38.8
29.1
26.2
33.9
26.1
23.4

45.2
46.7
57.9
44.3
40.0
51.0

16.58
16.65
17.27
15.74
15.3
16.75

H-O-O
H-15-0
H-25-O
H-0-10
H-15-10
H-25-10

30.8
26.9
26.6
27.9
26.3
23.2

Average pore
diameter (nm)

Cured in air at 15C and 60% RH

N-O-O
28.84
N-15-0
29.81
N-25-O
31.4
N-0-10
27.4
N-15-10
30.26
N-25-10
31.53

24.68
25.45
26.61
22.25
26.3
27.4

Porosity (p)
(% v/v)

3.1
4.3
4.6
3.6
3.5
3.6

6.1
7
5.1
5.9
7.9
6.1

4.5
9.7
11.4
6.1
12.7
12.5

6.4
11.2
10.3
16.3
12.3
14.1

< 10 nm

72.5
57.2
57.2
65.7
63.8
65.4

45.9
38.2
29.5
47.3
44.5
33.6

85.3
75.6
72.2
73.9
71.3
72.3

79.2
76.0
74.7
72.4
75.4
77

lo-100

nm

24.4
38.5
38.2
30.7
32.7
31.0

48
54.8
65.4
46.8
47.6
60.3

10.2
14.7
16.4
20.0
16.0
15.2

14.4
12.8
15.0
11.3
12.3
8.9

>lOOnm

% Pore fractions in total pore volume

28 days

Results of mercury intrusion porosimetry test for pastes at 28 and 90 days

Cured in water at 27C

N-O-O
N-l 5-O
N-25-O
N-0-10
N-15-10
N-25-10

Table 8

20.14
23.11
22.13
21.15
23.52
24.29

29.53
30.56
33.75
27.71
31.43
32.51

13.05
13.6
15.6
13.3
14.45
16.66

22.29
21.47
22.45
18.62
23.07
23.10

Porosity(p)
(% v/v)

90 days

54.7
55.6
47.0
54.1
50.9
44.6

58.1
75.2
78.1
62.0
56.5
65.6

35.0
27.1
27.0
30.9
26.4
23.1

28.0
23.6
19.6
22.7
24.8
24.8

2.3
3.3
3.5
2
2.8
3.1

3.5
2
3.2
3
3.5
2.9

4.5
13.5
10.8
6.5
11.6
17.1

8.5
13.9
18.7
14.7
11.8
13.5

67.2
54.0
64.1
66.5
61.3
64.1

30.5
42.7
32.4
31.5
35.9
32.8

59.2
65.1
70.0
59.5
56.2
64.8

15.7
16.6
19.4
15.4
21.4
20.1

79.8
69.9
69.8
78.1
67.0
67.8

37.3
32.9
26.8
37.5
40.3
32.3

15.7
11.4
12.6
11.3
16.7
16.0

75.8
74.7
68.7
74
71.5
70.5

Average pore % Pore fractions in total pore volume

diameter (nm)
< 1Onm
lo-1OOnm
> 1OOnm

388

Porestructure

of fly-ash cement pastes and mortars: C. S. Poon et al.

and related properties

pastes at 28 and 90 days and (ii) the mortars at 28 days.

The results show that with 27C water curing, replacement of cement by equal weight of fly ash reduced the
28-day strength for both the pastes and the mortars. At
28 days, extra addition of fly ash increased the strength
of the mortars but decreased the strength of the pastes.
At 90 days, all the fly-ash mixtures exhibited strength
values comparable to or higher than the control plain
cement mixes.
Air curing at 15C and 60% RH had the negative

Table 9

Results

of mercury
Cured

N-15-0
N-2.5-O
N-O-IO
N-15-10
N-25-10
H-O-O
H-15-0
H-25-O
H-0-10
H-15-10
H-25-10

Water permeability and rate of chloride penetration

The results of the water permeability test on concrete

cylinders are given in Table 6 and the rates of chloride
penetration expressed as the chloride concentrations at

porosimetry

test for mortars

at 28 days

Cured in air at 27C and 60% RH

in water at 37C
Average

Porosity
(% v/v)

N-O-O

intrusion

effect of fly ash on early strength more significant.

Contrary to the case of water curing, the extra addition
of fly ash did not improve the strength of both the
mortars and the pastes.

pore diameter
(nm)

Porosity
(% v/v)

Average

pore diameter
hm)

21.63
17.21
21.62
17.81
17.75
20.45

37.6
30.6
28.7
32.8
28.4
26.0

23.04
19.52
23.57
19.22
22.27
22.19

48.7
51.4
61.4
44.2
69.1
78.8

14.03

38.6
28.6
25.6
33.5
29.3
21.6

14.25
14.86
17.56
14.68
15.83
17.21

41.8
48.2
43.1
44.7
49.7
65.9

11.01
13.88
10.97
10.70
10.51

-Serkla

20 /
10

20

30

40

Fly ssh to totnl ccmentitiotrr mstcrial ratio

W)

10

20

30

/
40

Fly uh to total cnnentitiola material ratio

W

b. Pastes with extra fly ash

a. Pastes without extra fly ash

la

-Serbs

20,
0

-Serieslb
-\

_.-._Series2e

_.-._Sdss2b

\
\
\

*t
\ .

10

-_._

20

30

40

FIy a_&tototal ccmentitiolrs material ratio

W

c. Mortars without extra fly ash

Figure 1

Average

pore diameters

of water-cured

samples

at 28 days

10

20

30

40

Fly ash to total ccmentitiour mtierial ratio

W)

d. Mortars with extra fly ash

Porestructure and related properties of fly-ash cement pastes and mortars: C. S. Poon et al.
different concrete depths are given in Table 7. For the
normal-strength
water-cured specimens, when compared with the control mix (N-O-O), mixes with direct
replacement of cement by fly ash (N-0-10, N-15-10 and
N-25-0) showed equivalent and lower water permeability coefficients at the ages of 28 days and 90 days,
respectively, but slightly higher rates of chloride penetration at both ages. However, mixes with extra fly ash
(N-15-10 and N-25-10) showed consistently lower water
permeability coefficients and rates of chloride penetration at both ages.
For the water-cured high-strength concretes, only
the results of the chloride penetration test are available, because the water permeability was too low to be
measured by the available equipment (the test nevertheless showed that the air-cured samples had consistently higher water permeability than the water-cured
samples).
With water curing, most normal- and high-strength
fly-ash concretes had lower rates of chloride penetration than the control mixes (N-O-O and H-O-O) at both
curing ages, especially for those with extra fly ash
addition. For both the normal- and high-strength mixes,
when the fly-ash concrete samples were cured in air at
15C and 60% RH, addition of fly ash to concrete did
not show significant improvement of concrete performance in terms of water permeability and chloride

.o

penetration. It can also be noted that the water permeability of the concrete samples with inadequate curing
is two orders of magnitude higher than that with water
curing.
Pore structure

The results of the MIP test for the cement pastes are
summarized in Table 8 and those for the mortars are in
Table 9. Both tables give the total mercury porosity and
the average pore diameters. In Table 9, the pore fractions with diameters < 10 nm, 10-100 nm and > 100
nm are also given.
Porosity and average pore diameter. For a specific w/cc

+f) ratio, the porosity and the average pore diameter

varied with the fly-ash contents and curing conditions.
In 27C water curing, the addition of fly ash reduced
the average pore diameter of the pastes and the mortars at 28 days (Figure I). However, it can also be
observed in Figure 2 that the addition of fly ash up to a
level of 25% of the cementitious materials increased
the porosity of the pastes but reduced the porosity of
the mortars. When cured in air at 15C and 60% RH,
the addition of fly ash increased the porosity and the
average pore diameter of both the pastes and the
mortars (Tables 8 and 9).

30 7

30

25

25 --

_Series
20

la

s
e

_Serieslb

-._._saries2b

_._._Sar@s2a
.I

_-._._.-_-----

E
15

2o
15 --

-T

10;
0

lOI
10

20

30

Fly ashto total cemclltitiousmated

40
ratio

w9

a. Pastes without extra fly ash

10

10

20

30

-Serissla

-Series
_.-._Serk2b

20

40

Fly ash to total cemcntitiousmaterialratio

C4

_._._Sarii2a

30

40

Fly ash tototal cemcntitiousmaterialratio

W)

Figure 2

b. Pastes with extra fly ash

51
0

c. Mortars without extra fly ash

Porosity of water-cured samples at 28 days

389

51
0

10

20

lb

30

40

Fly ashto total cemcatitiou, material ratio

cr.)

d. Mortars with extra fly ash

Porestructure and related properties of fly-ash cement pastes and mortars: C. S. Poon et al.

390

120
t

Lbear regression:

loo -.

I_

.ia
f

80..

w
y=303.34(1-X)"W

y =I)._

R=O.9741

R=0.8218

40 --

20
t
OJ

1-I:

t----t--i
0

0.1

0.05

0.15

02

0.3

0.25

0.35

0.05

Water

permeability

0.1

0.15

POrOSity

Figure

Compressive

strength

Figure

25m

5omlK
10

Compressive

strength

of mortars

l
.

2
---I

0.15

0.2

0.25
0

c__
0

,
0.05

0.1

vs. porosity

The increase in porosity of the fly-ash pastes might

be due to the higher water/cement
ratio and lower
gel/space ratio when cement was partially replaced.
This is in agreement with Feldmani and Malami et aL3
The decrease in porosity of the water-cured fly-ash
mortars might be due to the better filling effect of the
fly ash in the mortars. This observation supported the
theory that fly ash improves the interfacial bonding
between the paste and the aggregate in concreteio9.
It can be observed from the regression analysis (Figures 3-6) that the MIP porosity correlated well with
the strength, permeability and rate of chloride penetration values. With respect to strength, there are a number of expression used to relate the porosity and the
strength of porous solids, such as):
a,(1 -p>

or
u=

A75mn

Figure

CT=

00

rnsm

Porosity

Figure

.25m

y=185.~."'

R=0.8334

R-O.9419

of pastes

6 ._

y =214.96(1-x)".m

0.1

vs. porosity

75mny=7&939x'-

0.05

0.35

y =429,32x""g

R=0.8574

mwerregrersinn:

of concretes

R=O.&315

12 1

0.3

0.25

PWCdy

of pastes vs. porosity

I4T

200

0.2

a, - kp

where p is the porosity, a0 is the strength at zero

porosity and n or k are empirical constants.
For the range of porosities covered in this paper, a
linear expression is thought to be more appropriate
(see Figures 3 and 4). Also, the power regression analysis of the porosity against the permeability and the rate
of chloride penetration values shown in Figures 5 and 6
indicate good correlation.

Chloride

penetration

0.2
0.15
m=lty

concentrations

0.25

0.3

0.35

vs. porosity

On the contrary, the average pore diameter appears

not to be correlated with the strength and permeability
values.
Pore-size distribution. The results in Table 8 indicate

that the water-cured fly-ash pastes have larger pore

fractions with diameters < 10 nm (gel pores) when
compared with the water-cured plain cement pastes,
indicating the fly-ash pastes had smaller average pore
sizes. Also, the pore sizes were influenced significantly
by the curing conditions. When exposed to air at 15C
and 60% RH, the pore fractions with diameters > 100
nm were increased by several times.
The pore-size distribution of the pastes and the
mortars are further characterized by expressing the
relative volumes as dV/d logD, the differential increment in pore volume with respect to the pore size. The
results are plotted against the pore diameter in Figures
7-10. The pore-size distribution curves show that the
water-cured plain pastes and mortars at the age of 28
days had peaks between 10 nm and 100 nm (Figure 7).
The addition of fly ash shifted the peaks to the left
along the x-axis indicating a reduction in pore size. For
the high-strength mixes, this effect was more significant
(Figure 8).

The pore-size distribution curves of the air-cured

pastes and mortars samples were very different from

Pore structure and related properties of fly-ash cement pastes and mortars: C. S. Poon et al.

N-25-O

-H-o-o

0.2

+J_

9
6

H-250

+l+O-10

0.15

H-25-10

_&_

391

0.1

i
-:

0.05

t
0

100
Porn diamtcr

IOW

IOWLl

(am)

Pore damter

(am)

a. pastes
a

Pastes

0.12
=r

3
6

-N-o-a

1
0.09

_o-

N-25-O

_&_

N-25-10

h
J

0.06

i
8.
-:
P

0.03

0
lb

Pore diamtcr

b. Mortars
Figure 7 Pore-size
water at 27C

-1WWJ

100

(nm)
100

distribution

of normal-strength

samples

cured

Pore dhmter (nm)

in

those of the water-cured specimens as shown in Figures

9 and 10. Curing in air shifted the peak to the right of
the lOO-nm mark. The addition of fly ash, whether as a
direct replacement or as an extra addition, further
increased the pore size and the peaks at approx. 1000
nm became significant for both the high- and normalstrength mixes. It should also be noted that the lOOO-nm
peaks of the mortars are much larger than those of the
pastes. This might be due to the presence of larger
pores between the paste and aggregate interface when
the mortars were subjected to drying shrinkage.

Conclusions
The above study indicates that the fly ash being studied
has significantly different infh_rences on the strength,
porosity and durability parameters of cement pastes
and concretes when the cementitious materials are
subjected to different curing conditions. Other fly ashes
from different sources might show similar or different
results and warrant additional study.

1000

b. Mortars
Figure 8 Pore-size
water at 27C

distribution

of high-strength

samples

cured

in

than 80% of the pore volume comprised of pores with

diameters smaller the 100 nm. The addition of fly ash
increased the porosity of the pastes but reduced the
porosity of the mortars at the age of 28 days. But
adding fly ash rendered the pore size of both the pastes
and the mortars smaller. This observation explains the
different effects of fly ash on the strength performances of cement pastes and concretes and supports
the theory that fly ash improves the interfacial zone
between the pastes and the aggregates.
The addition of fly ash substantially reduced the
water permeability and the rate of chloride penetration
of the water-cured concrete specimens. The effect was
not significant for normal-strength concretes [w/cc +
f) = 0.491 with only direct fly-ash replacement at 28
days. In contrast, the effect of extra addition of fly ash
was significant for normal- and high-strength concretes
[w/cc +f> = 0.44 and 0.271 at the ages of 28 and 90
days.
Air-cured at 15C and 60% RH

Cured in water at 27C

In water curing, the pastes and mortars had the most
probable pore sizes between 10 and 100 nm, and more

When compared with the results of the samples after

water curing, the exposure in air considerably increased
the pore size and pore volume of the pastes and the

Porestructure and related properties of fly-ash cement pastes and mortars: C. S. Poon et al.

392

~H-o-0

Pore diameter (nm)

a.

H-25-O

-c,-

+HOlO

Pore diamter (nm)

Pastes
a. pastes
0.12 i

9
i?

-N-O-O

0.09

+N-O-10

-5

-H-O-O
+

_.+-K2510

0.12

--Q-K250

H-25-0

-.-H-O-10

On9

H-25-1 0

-:k

0.03

-_t_------100

1Mx)

Pore diamter (nm)

100

1000

Pore diamter(nm)
b. Mortars
Figure 9 Pen-size distribution
air at 15C and 60% RH

of normal-strength

samples cured in
b. Mortars

Figure 10

Port-size distribution
air at 15C and 60% RH

mortars, particularly
for those samples containing
fly
ash. The pore size distribution
results of the mortars
indicated that the pore fraction with diameters approx.
1000 nm became significant, which is considered
to be
resulted from the drying shrinkage
at the interfacial
zone.
Subject to inadequate
curing, the water permeability
of concrete specimens were two orders of magnitude
higher than that of concrete with water curing; the rate
of chloride
penetration
was also increased
twofold.
Addition of fly ash to the concrete specimens did not
show any improved resistance against water permeation
and chloride penetration.
The porosity of pastes and mortars correlated
well
with the compressive
strength, water permeability
and
rate of chloride penetration
of the samples. On the
contrary the average pore diameter was less well correlated with strength and water permeability.

samples cured in

Malami, C., Kaloidas, V., Batis, G. and Kouloumbi, N., Carbonation and porosity of mortar specimens with pozzolanic and
hydraulic cement admixtures. Cement and Concrete Research.

Montgomery,
D. G., Hughes, D. C. and Williams, R. I. T., Fly
ash in concrete - a microstructure study. Cement and Concrete

1994, 24, 1444

Research. 1981. 11, 591

5

Wai, F. J., Grutzeck,

M. W. and Roy, D. M., The retarding
effects of fly ash upon the hydration of cement pastes: the first
24 hours. Cement and Concrete Research, 1985, 15, 174

Plowman,
hydration

C. and Cabrera, J. G., Mechanism

and kinetics of
of C,A and C,AF,
extracted from cement. Cement

and Concrete Research, 1984, 14, 238

7

Ogawa, K., Uchikawa, H. and Takemoto, K.. The mechanism of

the hydration in the system C3S-pozzolania.
Cement and Cow
crete Research, 1980, 10, 683

Xu, A., Sarkar, S. L. and Nilsson, L. 0.. Effect of fly ash on the
microstructure
of cement paste. Materials and Structures, 1993,

IO

26, 414
Xu, A. and Sarkar. S. L., Microstructural
development in highvolume fly-ash cement system. Journal of Materials in Civil Engineering, ASCE, 1994, 6, 117
Bijen, J. and Van Selst, R. F/y Ash as Addition to Concrete,
Research
Research

References
M. R. H., Fly ash as the fourth ingredient in concrete
Fly Ash, Silica Fume, Slag, atrd Natural Pozzolanics in
Comrete. AC1 SP-91, Detroit, 1986, p, 171
Ho, D. W. S. and Lews, R. K., Effectiveness of Ily ash fol
strength and durability of concrete. Cement and Concrete Research, 1985, 15. 793

of high-strength

by Intron, Institute for Material and Environmental

B.V.A.A. Balema. Rotterdam,
1992

I1

Gopalan, M. K., Nucleation and pozzolanic factors in strength

development of Class F fly ash concrete. AC1 Materials Journal.

12

Marsh. B. K.. Day, R. L. and Bonner, D. J.. Pore structure

characteristics affecting the permeability of cement paste containing fly ash. Cement and Concrete Research, 1985, 15, 1027

13

Feldman,

Dunstan,
mixtures.

1993.90,

117

R. F. and Beandoin,

J. J., Pretreatment

of hardened

Porestructure and related properties of fly-ash cement pastes and mortars: C. S. Poon et al.
hydrated cement pastes for mercury intrusion measurements.
Cement and Concrete Research, 1991,21, 297
14 Feldman, R. F., Effects of fly ash incorporation. In Cement and
Concrete, ed. S. Diamond. Mater. Res. Sot, University Park, PA,
USA, 1981, p. 124
15 Bijen, J., Benefits of slag and fly ash. Construction and Building
Materials. 1996, 10, 309
16 Al-Amoudi, 0. S. B., Maslehuddim, M. and Asi, I. M. Cement,
Concrete and Aggregates, 1996, 18, 71

17 Wong, Y. L., Poon, C. S. and Lam, L., Strength development of

normal and high strength PFA concrete under different curing

393

environments. In Concrete 97, Proceedings of 18th Biennial Conference. Concrete Institute of Australia, 1997, p. 145
18 Day, R. L. and Marsh, B. K., Measurement of porosity in
blended cement pastes. Cement and Concrete Research, 1988, 18,
63
19
20

Taylor,
1990
Robler,
between
cement

H. F. W., Cement Chemistry. Academic Press, London,

M. and Odler, I., Investigations on the relationship
porosity, structure and strength of hydrated Portland
pastes, 1. Effect of porosity. Cement and Concrete Re-

search, 1985, 1.5, 320