Effect of Pore-Size Distribution

on Shrinkage of Concretes
T. Aly1 and J. G. Sanjayan2
Downloaded from ascelibrary.org by Vel Tech Dr.Rr & Dr.Sr Technical University on 08/05/19. Copyright ASCE. For personal use only; all rights reserved.

Abstract: The effects of pore structure of concrete made with slag-blended cement on shrinkage behavior of concrete when exposed to
drying were presented in this paper. The investigated parameters were the length of curing 共1-day and 7-day curing兲, slag and gypsum
contents in mixtures. Pore structure analysis was studied by conducting mercury intrusion porosimetry and nitrogen gas adsorption
technique tests. The results show that 65% slag concrete with 7-day curing exhibited the lowest shrinkage evolution compared to 0, 35,
50% slag mixes. This is attributed to the highest pore radius where meniscus forms when drying in these concretes. It was found that
addition of gypsum in slag mixes tend to reduce the nanopores 共within the range from 4 to 20 nm pore size兲 and decrease the proportion
of mesopores. The higher proportion of mesopores and the lower value of meniscus pore radius could explain the increase in drying
shrinkage of concrete made with 65% slag cement containing 0% added gypsum.
DOI: 10.1061/共ASCE兲0899-1561共2010兲22:5共525兲
CE Database subject headings: Dewatering; Shrinkage; Pore size distribution; Concrete.
Author keywords: Drying; Shrinkage; Pore-size distribution; Concrete.

Introduction PSD of OPC/slag concrete becomes finer with increasing slag

Drying has a significant influence on the degree of shrinkage and
the stress state of concretes 共Jennings and Xi 1993; Grasley and
Lange 2004; Gawin et al. 2007兲. The rate of drying is primarily
dependent on the microstructure, which in turn, is influenced by
the type of cementitious material, especially if they contain a
supplementary cementitious material such as slag 共Kanna et al.
1998兲. The mechanical properties of hydrated slag-blended ce-
ment products tend to develop slower than ordinary portland ce-
ment 共OPC兲 products due to the relatively slower early-age
reaction rate 共Zhou et al. 2006b兲. Hence, the pore system in slag
concrete changes with the degree of hydration at a different rate
to OPC concrete 共Anwar 2004兲. Slag greatly improves the dura-
bility of concrete through the pore refinements, and has the capa-
bility for continued long-term pozzolanic reactions or hydration
共Swamy 1997; Hooton 2000兲. It is due to the hydration of slag
共Manmohan and Mehta 1981兲, which is a reaction between slag
and calcium hydroxide 共originated during the hydration of port-
land cement兲 forming calcium silicate hydrate 共CSH兲 gel filling
up the pores. Many researchers reported that slag concrete has a
finer pore-size distribution 共PSD兲 than OPC concrete 共Manmohan
and Mehta 1981; Roy and Idorn 1985; Zhou et al. 2006a兲. The
1
WorelyParsons Services, Level 7 QV1 Building, 250 St. Georges
Terrace, Perth WA 6000, Australia. E-mail: Tarek.aly@worleyparsons.
com
2
Professor of Concrete Structures, Faculty of Engineering and Indus-
trial Sciences, Swinburne Univ. of Technology, P.O. Box 218, Hawthorn,
Victoria 3122, Australia 共corresponding author兲. E-mail: sanjayan50@
gmail.com
Note. This manuscript was submitted on May 6, 2008; approved on
October 19, 2009; published online on April 15, 2010. Discussion period
open until October 1, 2010; separate discussions must be submitted for
individual papers. This paper is part of the Journal of Materials in Civil
Engineering, Vol. 22, No. 5, May 1, 2010. ©ASCE, ISSN 0899-1561/
2010/5-525–532/$25.00.
replacement 共Gjorv and Vennesland 1979; Aldea et al. 2000兲.
Geiseler et al. 共1995兲 reported that increasing content of slag in
concrete resulted in lower permeability of concrete to chloride ion
penetration due to a decrease in volume of capillary pores and
pore continuity, and an increase in the paste density.
There are three different microstructure models presented in
the literature to explain the shrinkage behavior of concrete,
namely: the Powers model 共Powers 1968兲; Feldman-Sereda
model 共Feldman and Sereda 1968兲; and Munich model 共Wittmann
1973兲. The precise nature of the mechanism is subject to debate
between these models. However, all of them have recognized the
importance of the role that pore structure plays in deformation
associated with drying. It was found that the magnitude of drying
shrinkage is highly influenced by the characteristics of CSH gel
and PSD 共Wittmann 1973; Garci Juenger and Jennings 2002兲. The
studies of Parrott 共1981兲 suggested that the porous gel in hydrated
cement shrinks, even with quite moderate drying. The shrinkage
of the gel seems to occur from a reduction in volume of the small
pores, without any change in total porosity. Pentala and Rautanen
共1990兲 concluded that the initial creep and shrinkage rate of high
and normal strength concretes is governed by the evaporable
water amount lost to the external environment. It is clear from
these studies that the pore structure of concrete affects the shrink-
age behavior 共Garci Juenger and Jennings 2002; Zhou et al.
2006a兲. However, the available data on the effect of slag and
gypsum content on micropore structure and shrinkage behavior is
insufficient to draw any general conclusion.
In the current study, an experimental investigation was carried
out to find the influence of length of curing 共1-day and 7-day
curing兲, slag replacement level 共35, 50, and 65%兲 and gypsum
content 共0 and 3%兲 in slag cement on the pore structure and its
effect on shrinkage of concrete when dried at 50% ⫾ 5% and tem-
perature at 23⫾ 1 ° C. The pore structure analysis was studied by
conducting mercury intrusion porosimetry 共MIP兲 and nitrogen gas
adsorption technique tests.

JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / MAY 2010 / 525

J. Mater. Civ. Eng., 2010, 22(5): 525-532

 Table 1. Property of Cementitious Materials
Constituent/property percentage
SiO2 Al2O3 Fe2O3T MgO CaO Na2O TiO2 K 2O MnO P 2O 5 SO3 LOI F S.G
OPC 19.90 4.70 3.38 1.30 63.93 0.17 0.245 0.446 0.079 0.063 2.54 2.97 360 3.15
Slag 32.5 13 0.22 5.47 42.1 0.21 1.08 0.25 5.47 bd 4.1 0.35 435 2.92

Table 2. Concrete Mix Proportions

Ground granulated blast-furnace slag
Downloaded from ascelibrary.org by Vel Tech Dr.Rr & Dr.Sr Technical University on 08/05/19. Copyright ASCE. For personal use only; all rights reserved.

Water OPC cement 0% gypsum 3% gypsum Coarse aggregate Fine aggregate

Mix name 共kg/ m3兲 共kg/ m3兲 共kg/ m3兲 共kg/ m3兲 共kg/ m3兲 共kg/ m3兲 Curing type
OPC 183 360 0 0 1,100 849 1-day 7-day
OPC/S35 183 195 — 105 1,100 849 1-day 7-day
OPC/S50 183 150 — 150 1,100 849 1-day 7-day
OPC/S65 183 105 — 195 1,100 849 1-day 7-day
OPC/S65-gy 183 105 195 — 1,100 849 1-day —

Experimental Investigation d = − 4␥共cos ␪兲/P

Materials, Concrete Mixture Proportions

The binders used for this study are various proportions of ground
granulated blast-furnace slag 共referred in this paper as slag兲 and
OPC that conforms to the international standard. Their chemical
compositions are shown in Table 1. The results of X-ray diffrac-
tion analysis showed that the phase chemical composition of slag
cement has 97% amorphous and 3% gypsum 共CaSO4.2H2O兲. The
mixtures OPC/S35, OPC/S50, and OPC/S65 are formulated by
the slag cement that contains 3% gypsum and the mixture OPC/
S65-gy is made with the same slag but contains 0% gypsum con-
tent. The concrete mixture proportions used in this study are
summarized in Table 3. The total cementitious content in all con-
crete mixtures 共Table 2兲 was kept constant at 300 kg/ m3. All
concrete mixtures were maintained at a constant slump of
80⫾ 10 mm by adjusting the water reducer amount for each mix
with the maximum dose of 1 , 200 mL/ m3. The coarse aggregate
was 14-mm maximum size basalt with a specific gravity of 2.95
and 24 h water absorption of 1.2%. The fine aggregate was
washed fine sand with a specific gravity of 2.65, 24 h water ab-
sorption of 0.5%, and a fineness modulus of 2.19.
MIP Tests
Test Procedure
MIP is based on the premise that a nonwetting liquid 共one having
a contact angle greater than 90°兲 will only intrude capillaries
under pressure. The relationship between the pressure and capil-
lary diameter is described by the Washburn equation 共Cook and
Hover 1993兲
Table 3. Classification of Pores according to Their Width
Width
Pore type 共nm兲
Micropores ⬍2.5
Mesopores 2.5–50
Macropores 50–10,000
Entrained air voids, entrapped air voids, pre-existing 10,000–100,000
microcracks
where d = apparent pore diameter being intruded; ␥ = surface ten-
sion of the mercury; ␪ = contact angle between the mercury and
the pore wall; and P = absolute pressure causing the intrusion.
The PSD was determined using a Micromeritics Autopore III
9429 porosimeter, which was capable of pressures from 0 to 414
MPa 共60,000 psi兲. A hydraulic pump generates the pressure and a
contact sensor measures the volume of the intruded mercury. All
operations are automated by microprocessor and are conducted
within a fully enclosed pressure chamber. The data are automati-
cally recorded by microprocessor. The assumed surface tension of
the triple-distilled mercury was 0.485 N/m at 25° C. The density
of the mercury was 13.53 g/mL and the assumed contact angle
was 117°.
Six numbers of samples were tested for each given concrete
mix shown in Table 1 to ensure repeatability of the MIP results.
The results presented in this paper are average of the six tests.
Test Outline
The effect of curing was studied by subjecting the samples for 1
and 7 days of moist curing. For 1-day curing mixes, six concrete
cylinders 共100 mm diameter⫻ 200 mm length兲 for each mix
type were made from the same batch prepared for the shrinkage
tests. The concrete cylinders were stored for the first day in the
mold and covered with plastic sheet at 23° C. At the age of 24 h,
the cylinders were demolded and transferred to a constant drying
room maintained at humidity 50% ⫾ 5% and temperature at
23⫾ 1 ° C. The samples were tested by MIP at 3, 7, 28, and 56
days of age. At these ages of testing, three small cubic 共25 mm
size兲 samples were carefully taken from the center 共interior兲 of
each cylinder using a concrete saw to avoid introducing any
cracks to the concrete samples and transferred to a vacuum oven
at 100° C for 24 h, before being subjected to the MIP tests.
For 7-day curing mixes, the concrete cylinders were stored for
the first day in the mold and covered with plastic sheet at 23° C.
At the age of 24 h, the cylinders were demolded and maintained
in lime saturated water. At the age of 7 days, the cylinders were
transferred to a constant drying room 共humidity 50% ⫾ 5% and
temperature at 23⫾ 1 ° C兲. After 24 h in drying room, the MIP
samples prepared as described above and were tested by MIP.

526 / JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / MAY 2010

J. Mater. Civ. Eng., 2010, 22(5): 525-532

 16.0 1-day 16.0 1-day
3-days 3-days
7-days 7-days
12.0 28-days 12.0 28-days

Porosity (%)
Porosity (%)
56-days 56-days
8.0 8.0

4.0 4.0

0.0 0.0
1 10 100 1000 10000 100000 1000000 1 10 100 1000 10000 100000 1000000
Downloaded from ascelibrary.org by Vel Tech Dr.Rr & Dr.Sr Technical University on 08/05/19. Copyright ASCE. For personal use only; all rights reserved.

Pore width (nm) Pore width (nm)

Fig. 1. Cumulative PSD for OPC mix exposed to drying from day Fig. 3. Cumulative PSD for OPC/S50 mix exposed to drying from
one day one

MIP and Mass Loss Test Results

Nitrogen Gas Intrusion „ASAP Micrometrics… Tests
The nitrogen gas intrusion 共ASAP Micrometrics兲 test analysis
were carried out at liquid nitrogen temperature 共77 K兲 using
ASAP 2020 apparatus. The tests were performed on small pieces,
3–3.5 mm in size, which were obtained by splitting the cubic
samples taken from the concrete cylinders without any coarse
aggregates. The sample tube and its contents were loaded into the
degassing port of the apparatus and initially degassed at room
temperature until the required vacuum reached. A heating mantle
was then applied to the sample tube and the contents are heated
under vacuum to 100° C for 4–6 h. All pore volume is filled by
liquid nitrogen at relative pressures better than 0.99. The tests
were performed at the specimen age of 56 days. These tests were
done for mixes OPC, OPC/S50, OPC/S65, OPC/S65-gy after 24 h
curing and exposure to drying for the remaining time 共56 days兲.
The mix OPC/S35 was not tested due to the fact that there were
no significant changes in test results between OPC/S50 and OPC/
S65 mixes.
Effect of Slag-Blended Cement on Porosity PSD
The MIP results of cumulative PSDs, which are presented as per-
centage of total porosity versus pore diameter for OPC/slag con-
cretes, are shown in Figs. 1–4. The pore system in cement-based
materials consists of four types of pores according to the conven-
tional classification of the International Union of Pure and Ap-
plied Chemistry 共IUPAC兲 共1972兲 system, which is summarized in
Table 3.
Table 4 shows the breakdown of the pore sizes according to
the IUPAC classification. The analysis of the incremental PSD
data shows that OPC/slag mixes have higher proportion of pore
sizes within the mesopores range than OPC concrete at 56 days of
age. The results suggest that the highest shrinkage exhibited by
OPC/S50 mix, as shown in Fig. 5, is likely to be due to the
highest proportion of mesopores found in these concretes com-
pared to all other mixes, and confirms the previous findings of
Collins and Sanjayan 共2000兲 for alkali activated slag concrete.

16.0
3-days 16.0
3-days
7-days 7-days
12.0 28-days 12.0 28-days
Porosity (%)

Porosity (%)

56-days 56-days
8.0 8.0

4.0 4.0

0.0 0.0
1 10 100 1000 10000 100000 1000000 1 10 100 1000 10000 100000 1000000
Pore width (nm) Pore width (nm)

Fig. 2. Cumulative PSD for OPC/S35 mix exposed to drying from Fig. 4. Cumulative PSD for OPC/S65 mix exposed f to drying from
day one day one

Table 4. Pore-Size Breakdowns according to IUPAC Classifications

Mesopores percentage Macropores percentage Voids/microcracks percentage
Age
共days兲 OPC S35 S50 S65 OPC S35 S50 S65 OPC S35 S50 S65
3 33.4 37.5 40.6 34.3 62.4 58.0 55.7 63.7 4.3 4.5 3.7 2.0
7 37.7 39.5 45.9 37.9 59.0 57.1 50.7 59.3 3.2 3.4 3.4 2.8
28 37.5 45.3 43.1 39.9 59.6 50.5 54.7 55.5 2.9 4.1 2.2 3.1
56 38.4 42.3 45.1 40.3 59.1 53.2 51.6 57.8 2.5 4.5 3.3 1.9

JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / MAY 2010 / 527

J. Mater. Civ. Eng., 2010, 22(5): 525-532

 0 total mass loss兲 in the first 24 h of exposure to drying. This is
OPC
attributed to the relatively big size of pores at this time 共24 h of

Shrinkage strain (x10-6)

-150 OPC/S35
OPC/S50
age兲 because of the slow hydration of high percentage 共65%兲
-300
OPC/S65 slag-blended cement 共Zhou et al. 2006b兲. The water contained
-450 within these open big pores behaves like bulk water. Hence, a
-600 paste containing a high proportion of big pores are expected to
lose large amount of moisture when exposed to drying condition.
-750 It seems that the loss of water 共free water兲 from such big pores
-900 did not affect the shrinkage of concrete when subjected to drying
0 28 56 84 112 140 168 196 at 1 day of age; and this may explain the low shrinkage of OPC/
Downloaded from ascelibrary.org by Vel Tech Dr.Rr & Dr.Sr Technical University on 08/05/19. Copyright ASCE. For personal use only; all rights reserved.

Age (days) S65 mix at very early-age.

For OPC and OPC/S35 mixes, the corresponding mass losses
Fig. 5. Shrinkage versus age for OPC/slag concretes exposed to dry- were 61 and 52% of the total mass loss at 182 days of age,
ing from day one respectively. The results presented in Fig. 5 show that the mea-
sured shrinkages after 24 h of drying for concretes containing 0,
0.0%
.

35, 50, and 65% slag content were 100, 71, 57, and 24 micros-
-1.0%
OPC trains, respectively. It can be seen that the shrinkage 共drying
OPC/S35
OPC/S50
+ autogenous兲 measured after 24 h of drying 共at 2 days of age兲 for
-2.0%
OPC mix was higher than that of all the other mixes 共Aly and
Mass Loss

OPC/S65
-3.0% Sanjayan 2008c兲. The explanation for that is the measured shrink-
-4.0% ages at this time are not likely to be caused by the loss of water
from pores 共drying shrinkage兲. These shrinkages are most likely
-5.0%
to be due to the hydration of cement 共autogenous shrinkage兲 since
-6.0% the degree of cement hydration in OPC concrete was higher than
0 28 56 84 112 140 168 196 that of OPC/slag mixes during the first two days of age. During
Age (days) the period from 2 to 189 days of age, the loss in mass for OPC
was 17, 32.5, and 28.4% higher than that of OPC/S35, OPC/S50,
Fig. 6. Mass change for OPC/slag concrete mixes exposed to drying and OPC/S65, respectively.
from day one

Effect of Capillary Tensile Forces on Drying Shrinkage

Mass Loss Results
Mass loss results of the prisms are presented in Fig. 6. Mass loss
results obtained in constant drying conditions provide a good
basis for comparing the permeability and diffusivity of different
type of concrete. The permeability and diffusivity are controlled
by the volume, size distribution, shape, tortuosity, and connectiv-
ity of pores 共Neville 1998兲. The mass loss data 共Fig. 6兲 shows that
OPC/S65 mix rapidly lost significant moisture 共about 73% of the
A micromechanical model developed by Shimomura and
Maekawa 共1997兲 to analyze the drying shrinkage behavior of con-
crete is based on the PSD of concrete. The proposed model in-
volved the computation of the parameter rs that is defined as the
radius of the pores where the meniscus forms. The pores whose
radii are smaller than rs are assumed to be filled with water while
pores larger than this are assumed to be dry. As the drying
progresses, percentage of water filled pores 共the volume of water

Table 5. Computation of rs and Measured Drying Shrinkages for OPC/slag Concretes

Measured Total mass Volume of water Total porosity rs 共from cumulative PSD
Age drying shrinkage loss of prisms dried from prisms 共from porosimetry兲 using volume water dried兲
Mix name days 共⫻10−6兲 共%兲 Vd共%兲 共%兲 共nm兲
OPC 3 ⫺142 ⫺2.269 5.248 14.4 64.5
7 ⫺204 ⫺2.741 6.453 13.0 38.9
28 ⫺462 ⫺3.396 7.994 12.8 24.7
56 ⫺586 ⫺3.649 8.707 12.3 15.5
OPC/S35 3 ⫺102 ⫺2.141 4.969 14.8 52.3
7 ⫺223 ⫺2.798 6.816 12.8 38.7
28 ⫺436 ⫺3.362 8.196 12.4 18.3
56 ⫺526 ⫺3.513 8.628 12.3 10.3
OPC/S50 3 ⫺102 ⫺3.270 7.828 14.9 45.1
7 ⫺281 ⫺3.609 8.215 14.8 27.9
28 ⫺479 ⫺3.970 9.305 13.5 17.3
56 ⫺610 ⫺4.072 9.402 12.8 8.1
OPC/S65 3 ⫺101 ⫺3.771 8.732 15.0 45.6
7 ⫺249 ⫺4.085 9.734 14.2 21.5
28 ⫺390 ⫺4.460 10.526 13.7 8.0
56 ⫺438 ⫺4.600 10.939 12.5 2.0

528 / JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / MAY 2010

J. Mater. Civ. Eng., 2010, 22(5): 525-532

 -700 25
OPC OPC
20 OPC/S35
Shrinkage (x10 )
OPC/S35
-6 -500

Porosity (%)
OPC/S50 OPC/S50
15
OPC/S65 OPC/S65
-300 10

c 5
-100
0
0 20 40 60 1 10 100 1000 10000 100000 1000000
Downloaded from ascelibrary.org by Vel Tech Dr.Rr & Dr.Sr Technical University on 08/05/19. Copyright ASCE. For personal use only; all rights reserved.

rs (nm) Pore width (nm)

Fig. 7. Measured drying shrinkage versus rs for OPC/slag concretes Fig. 8. Cumulative PSD for OPC/slag concretes cured for 7 days
exposed to drying from day one

100
per unit concrete volume兲 will decrease, and hence the parameter 90

Cumulative volume (%)

80 OPC
rs will decrease. The smaller the value of the parameter rs, the OPC/S35
70
larger the capillary tensile forces set up at the meniscus 共the in- 60 OPC/S50
terface between water and air兲, hence higher the resulting shrink- 50 OPC/S65
age. 40
The volume of water dried from the concrete prisms was cal- 30
culated using mass loss data for OPC, OPC/S35, OPC/S50, and 20
10
OPC/S65 mixes that were presented in Fig. 6 multiplied by the
0
concrete bulk densities measured by MIP tests at 3, 7, 28, and 56 1 10 100 1000 10000 100000 1000000
days of age. The rs values were calculated for each mix using the Pore width (nm)
cumulative PSD curves shown in Figs. 1–4.
Table 5 shows the calculated values of rs for slag concretes are Fig. 9. Normalized intruded pore volume for OPC/slag concretes
within the 52.3–2.0 nm range, whereas for OPC, the values of rs cured for 7 days
are from 64.5 to 15.5 nm, which are larger than the mesopores. At
the age of 3 days, the rs values for OPC/slag mixes are lower than
that of OPC mix; however, the shrinkages measured for OPC/slag pore diameter. Ye et al. 共2006兲 developed a model for water per-
mixes were lower than that of OPC mix at this time. This could be meability in cementitious materials and reported that the pre-
attributed to the effect of inducing high pressure 共414 MPa兲 dur- dicted permeability is highly sensitive to the cement particle
ing the MIP test that would have affected the pore structure of distribution, especially to the minimum size of the cement par-
weak paste such as of slag cement 共Ye 2003兲. Also, the higher ticles. It was evident that, by decreasing the minimum particle
sensitivity of the samples at 24 h to damage during sample prepa- size, the permeability also becomes lower. This suggests that the
ration 共sawing—oven drying兲 may cause more microcracking due permeability of 65% slag concrete is likely to be reduced more
to the weakness of the slag samples at 1 day of age 共Ye 2003兲. than that of OPC concrete at later ages due to the fact that the slag
Fig. 7 shows that the magnitude of shrinkage measured for has a higher fineness than OPC. This is probably the main cause
each mix is inversely related to the calculated value of pore radius for the reduced mass loss and shrinkage measured for OPC/S65
rs. The results presented in Fig. 7 show that the shrinkage has a mix though it has similar PSD and lower value of rs compared to
stronger relationship with rs values than the relationship with OPC mix at 56 days of age.
mass loss data. This explains why some concretes, regardless of
high mass losses, still have low shrinkages 共e.g., OPC/S65%
Effect of Initial 7-Day Moist Curing on PSD
mix兲.
and Shrinkage
The higher fineness of slag cement than OPC cement increased
the total fineness of the binder when greater amount of slag ce- Table 6 shows the results of pore structure using the MIP tests
ment was used 共OPC/S65% mix兲. This would have decreased the that were conducted on all mixes after 24 h of drying. The mois-
minimum particle size and consequently, decreased the critical ture loss data for the mixes, which was discussed in the “Mass

Table 6. Computation of rs and Measured Drying Shrinkage for OPC/slag Concretes Moist Cured for 7 Days
Mix name OPC OPC/S35 OPC/S50 OPC/S65
Measured drying shrinkage after 24 h exposure 共⫻10 兲 −6
160 180 80 65
Percent of moisture loss from prisms 1.57 1.88 2.08 0.93
Volume of water dried from prisms, Vd 共%兲 3.5 4.2 4.4 2.0
Total porosity percentage 共from porosimetry on concrete兲 17.4 19.9 23.8 21.1
rs 共from PSD using volume water dried兲 共nm兲 46 48 106 153
Percent of mesopores 63.4 60.8 55.7 80.6
Percent of macropores 33.3 35.0 40.1 16.3
Percent of voids and microcracks 3.3 4.2 4.2 3.1

JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / MAY 2010 / 529

J. Mater. Civ. Eng., 2010, 22(5): 525-532

 -240 100

Cumulative volume (%)

OPC/S65% 90 OPC
-200
80
OPC/S50
Shrinkage strain (x10 )
-6 -160 70
OPC OPC/S65
60
-120
50
OPC/S35
-80 40
30
-40
OPC/S50 20
0 10
0
40
1 10 100 1000
Downloaded from ascelibrary.org by Vel Tech Dr.Rr & Dr.Sr Technical University on 08/05/19. Copyright ASCE. For personal use only; all rights reserved.

80 Pore width (nm)

24 72 120 168 216 264

Age (hours)
Fig. 12. Cumulative PSD for OPC/slag concretes at 56 days of age

Fig. 10. Free expansion and shrinkage for OPC/slag concretes ex-
posed to drying at 7 days of age 共Aly and Sanjayan 2008b兲
Loss Results” section, was used to determine the volume of water
that was dried from 7-day cured concrete after 24 h of drying. The
cumulative PSD curves shown in Fig. 8 were then used to calcu-
late the parameter rs 共the radius of the pores where the meniscus
forms兲. The results show that both OPC and OPC/S35 mixes ex-
hibited higher rate of shrinkage due to the lower values of rs
compared to that of OPC/S50 and OPC/S65 mixes.
The results presented in Fig. 9 show that OPC/S65 mix has the
lowest proportions of macropores 共16.3%兲 than that of OPC,
OPC/S35, and OPC/S50 mixes. This is likely to be the main cause
that OPC/S65 mix exhibited 40% less mass loss than that of OPC
mix after 24 h of exposure to drying. The lowest shrinkage evo-
lution of OPC/S65 mix is attributed to the lowest mass loss and
the highest pore radius rs compared to all other mixes. While for
OPC/S50 mix, the higher proportion of macropores 共40.1%兲 and
the smaller pore radius 共rs兲 could explain the difference in shrink-
age behavior compared to OPC/S65 mix. The MIP test results are
consistent with the results obtained by Aly and Sanjayan 共2008b兲
for free drying shrinkage and water loss that are summarized in
Figs. 10 and 11, respectively.
Nitrogen Gas Intrusion Results
Effect of Slag Content on Porosity and PSD
It is known that mercury molecules cannot enter pore having
dimension smaller than the mercury molecules. It was reported
that pores with dimension smaller than 30 Å are not accessible for
mercury molecules, and therefore, the pore diameter is deter-
mined from nitrogen gas intrusion test analysis 共Webb and Orr
1997兲. The influence of gel pores 共micropores⬍ 2.5 nm兲 and the
capillary pores range from 2.5 to 250 nm on the shrinkage of
OPC, OPC/S50, and OPC/S65 mixes were studied by the nitrogen
adsorption tests at 56 days of age. The test results presented in
Fig. 12 show that both OPC/S50 and OPC/S65 mixes have less
porosity within the mentioned range of pores. Further, the results
show that the average pore width of OPC was 16 nm which was
higher than 14 nm for OPC/S50 and OPC/S65 mixes. The results
suggest that concretes made with 50 and 65% slag replacement
level have finer pore structure and probably less connected capil-
lary pores than OPC concrete within the mentioned pore-size
range.
By normalizing the total pore volume by 100% for each mix,
Fig. 13 shows that OPC/S50 mix has the highest proportion of
mesopores than that of OPC and OPC/S65 mixes. This is likely
the cause of the increased shrinkage measured for OPC/S50 mix
during the exposure to drying at later ages, as seen in Fig. 5.
These results are consistent with the MIP results discussed previ-
ously.
Effect of Gypsum Content in Ground Granulated
Blast-Furnace Slag Cement on Porosity and PSD
The results presented in Fig. 14 show the cumulative envelope for
OPC/S65 共made with slag containing 3% gypsum兲 and OPC/
S65-gy 共made with slag containing no gypsum兲 mixes at the age
of 56 days. It is clear that the OPC/S65-gy has higher porosity
within the mesopores 共pore size 4–20 nm兲 while it has less po-
rosity within the range from 20 to 136 nm. This is can also be
seen in Fig. 15 where the incremental pore volume for OPC/

-2.5%
Cumulative pore volume (cm /g)

OPC/S50
3

0.012
-2.0% OPC/S35 OPC
OPC
0.01 OPC/S50
Mass loss

-1.5% 0.008 OPC/S65

OPC/S65
-1.0% 0.006
0.004
-0.5%
0.002
0.0% 0
168 174 180 186 192 198 1 10 100 1000
Age (hours) Pore width (nm)

Fig. 11. Mass loss change for OPC/slag concretes exposed to drying Fig. 13. Normalized Intruded pore volume for OPC/slag concretes at
after 7 days of moist curing 56 days of age

530 / JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / MAY 2010

J. Mater. Civ. Eng., 2010, 22(5): 525-532

 Cumulative pore volume (cm /g)
0
0.01

3
w/b = 0.61
OPC/S65 -100

Shrinkage (x10 )
0.008

-6
OPC/S65-gy -200
0.006 OPC/S65-gy
-300
0.004 OPC/S65
-400
0.002
-500
0 -600
1 10 100 1000 0 28 56 84 112 140 168 196
Downloaded from ascelibrary.org by Vel Tech Dr.Rr & Dr.Sr Technical University on 08/05/19. Copyright ASCE. For personal use only; all rights reserved.

Pore width (nm) Age (days)

Fig. 14. Cumulative PSD for OPC/S65 and OPC/S65-gy mixes at 56 Fig. 17. Effect of 0 and 3% gypsum content in slag cement on
days of age shrinkage of concretes exposed to drying from day one

S65-gy is higher within the mesopores 共pore size 4–20 mm兲 and
lower within the pore-size range from 20 to 136 compared to that This is contrary to the general trend that the higher the mass
of OPC/S65 mix. loss, the greater the drying shrinkage. However, the calcula-
The results presented in Fig. 16 show that OPC/S65-gy mix tion of radius of pore, where meniscus forms, is high in 65%
has the highest proportion of mesopores than OPC/S65 mix. The slag mix specimens, regardless of the high mass loss due to
proportions of mesopores are 65.9 and 76.3% for OPC/S65 and large pores in these specimens in early ages. This particular
OPC/S65-gy mixes, respectively. This could explain the higher behavior of 65% slag mix demonstrates that the radius where
relative shrinkage of OPC/S65-gy mix than that of OPC/S65 mix the meniscus forms is more important than the mass loss data
at later ages, as shown from the results in Fig. 17. Garci Juenger in determining the shrinkage;
and Jennings 共2002兲 found that high surface area and pore vol- 2. When concrete dried from day one, 50% slag concrete mix
umes 共pore size 1–40 nm兲 corresponded with high values of total tend to have the highest proportion of mesopores size range
drying shrinkage. compared to 0, 35, and 65% slag concretes mixes at 56 days
of age. This explains the increase in drying shrinkage mea-
sured for this concrete at later ages;
Conclusions 3. Increasing the amount of gypsum into slag concrete mixes is
likely to cause increases in the rate of chemical reactions
1. Concrete made with 65% slag replacement was found to 共hydration兲 in slag mixes due to the fact that the hydration
have the highest mass loss but the lowest shrinkage values. products 共aluminate hydrates兲 are most affected by gypsum
content 共Frigione and Sersale 1983兲. This study has proved
that addition of gypsum in slag mixes tend to reduce the
Cumulative pore volume (cm /g)

0.0004
nanoporosity 共within the range of 4–20 nm pore size兲 and
3

OPC/S65
OPC/S65-gy
decrease the proportion of mesopores. This explains the rea-
0.0003
son why increasing the gypsum content in slag mix 共within
the allowable limit兲 reduces the shrinkage and the associated
0.0002
cracking of concrete under restrained condition 共Aly and
Sanjayan 2008a兲.
0.0001

0
1 10 100 1000 Acknowledgments
Pore width (nm)
The writers gratefully acknowledge the financial support provided
Fig. 15. Incremental pore volume for OPC/S65 and OPC/S65-gy by the Independent Cement and Lime Pty Ltd 共ICL兲 共Industry
mixes at 56 days of age Partner兲 and the Australian Research Council 共Linkage Project
Grant No. LP0349121兲 for this research project.
100
Cumulative volume (%)

90
80 OPC/S65
70 OPC/S65-gy References
60
50 Aldea, C.-M., Young, F., Wang, K., and Shah, S. P. 共2000兲. “Effects of
40 curing conditions on properties using slag replacement.” Cem. Concr.
30 Res., 30, 465–472.
20
10
Aly, T., and Sanjayan, J. G. 共2008a兲. “Effect of gypsum on free and
0 restrained shrinkage behaviour of slag-concretes subjected to various
1 10 100 1000 curing conditions.” Mater. Struct., 41共8兲, 1393–1403.
Aly, T., and Sanjayan, J. G. 共2008b兲. “Factors contributing to early age
Pore width (nm)
shrinkage cracking of slag concretes subjected to 7-days moist cur-
ing.” Mater. Struct., 41共4兲, 633–642.
Fig. 16. Normalized intruded pore volumes for OPC/S65 and OPC/
Aly, T., and Sanjayan, J. G. 共2008c兲. “Shrinkage cracking properties of
S65-gy mixes at 56 days of age slag-concretes with 1-day curing.” Mag. Concr. Res., 60共1兲, 41–48.

JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / MAY 2010 / 531

J. Mater. Civ. Eng., 2010, 22(5): 525-532

 Anwar, M. 共2004兲. The effects of type of cement and curing methods on
the pore structure of concrete, Civil Engineering Dept., Kyoto Univ.,
Japan, 287–296.
Collins, F., and Sanjayan, J. G. 共2000兲. “Effect of pore size distribution on
drying shrinkage of alkali activated slag concrete.” Cem. Concr. Res.,
30共9兲, 1401–1406.
Cook, R. A., and Hover, K. C. 共1993兲. “Mercury porosimetry of cement-
based materials and associated correction factors.” ACI Mater. J., 90,
152–161.
Feldman, R. F., and Sereda, P. J. 共1968兲. “The model for hydrated Port-
land cement paste as deduced from sorption-length change and me-
Downloaded from ascelibrary.org by Vel Tech Dr.Rr & Dr.Sr Technical University on 08/05/19. Copyright ASCE. For personal use only; all rights reserved.
chanical properties.” Mater. Constr., 1, 509–520.
Frigione, G., and Sersale, R. 共1983兲. “Gypsum in blast-furnace slag ce-
ments.” Am. Ceram. Soc. Bull., 62共11兲, 1275–1279.
Garci Juenger, M. C., and Jennings, H. M. 共2002兲. “Examining the rela-
tionship between the microstructure of calcium silicate hydrate and
drying shrinkage of cement pastes.” Cem. Concr. Res., 32, 289–296.
Gawin, D., Pesavento, F., and Schrefler, B. A. 共2007兲. “Modelling creep
and shrinkage of concrete by means of effective stresses.” Mater.
Struct., 40, 579–591.
Geiseler, J., Kollo, H., and Lang, E. 共1995兲. “Influence of blast furnace
cements on durability of concrete structures.” ACI Mater. J., 92共3兲,
252–257.
Gjorv, O. E., and Vennesland, O. 共1979兲. “Diffusion of chloride ions from
seawater into concrete.” Cem. Concr. Res., 9共2兲, 229–238.
Grasley, Z. C., and Lange, D. A. 共2004兲. “Modelling drying shrinkage
stress gradients in concrete.” Cem., Concr., Aggregates, 26共2兲, 115–
122.
Hooton, R. 共2000兲. “Canadian use of ground granulated blast-furnace slag
as a supplementary cementing material for enhanced performance of
concrete.” Can. J. Civ. Eng., 27共4兲, 754–760.
International Union of Pure and Applied Chemistry 共IUPAC兲. 共1972兲.
“Manual of symbols and terminology, Appendix 2, Part 1, colloid and
surface chemistry.” Pure Appl. Chem., 31, 578–638.
Jennings, H. M., and Xi, Y. 共1993兲. Creep and shrinkage of concrete, Z.
P. Bazant and I. Carol, eds., E & F Spon, London, 85.
Kanna, V., Olson, R. A., and Jennings, H. M. 共1998兲. “Effect of shrinkage
and moisture content on the physical characteristics of blended ce-
ment mortars.” Cem. Concr. Res., 28共10兲, 1467–1477.
Manmohan, D., and Mehta, P. K. 共1981兲. “Influence of pozzolanic, slag,
and chemical admixtures on pore size distribution and permeability of
hardened cement pastes.” Cem., Concr., Aggregates, 3共1兲, 63–67.
532 / JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / MAY 2010
J. Mater. Civ. Eng., 2010, 22(5): 525-532
Neville, A. M. 共1998兲. Properties of concrete, 4th Ed., Wiley, New York.
Parrott, L. J. 共1981兲. “Effect of drying history upon the exchange at pore
water method and upon subsequent methanol sorption behaviour in
hydrated alite paste.” Cem. Concr. Res., 11共5–6兲, 651–658.
Pentala, V., and Rautanen, T. 共1990兲. “Microporosity, creep, and shrink-
age of high-strength concretes.” Proc., 2nd Int. Symp. on High-
Strength Concrete, Vol. 121, Univ. of California, Berkeley, Calif.,
409–432.
Powers, T. C. 共1968兲. “The thermodynamics of volume change and
creep.” Mater. Struct, 1共6兲, 487–507.
Roy, D. M., and Idorn, G. M. 共1985兲. “Relation between strength, pore
structure and associated properties of slag-containing cementitious
materials.” Proc., Materials Research Symp. L, J. F. Young, ed., Vol.
42, Materials Research Society, Pittsburgh, 133–142.
Shimomura, T., and Maekawa, K. 共1997兲. “Analysis of the drying shrink-
age behaviour of concrete based on the micropore structure of con-
crete using a micromechanical model.” Mag. Concr. Res., 49共181兲,
303–322.
Swamy, R. N. 共1997兲. “Design for durability and strength through the use
of fly as and slag in concrete.” Advances in concrete technology, V.
M. Malhotra, ed. American Concrete Institute, Detroit, 1–72.
Webb, P. A., and Orr, C. 共1997兲. Analytical Methods in Fine Particle
Technology, Micromeritrics Instrument Corp.
Wittmann, F. H. 共1973兲. “Interaction of hardened cement paste and
water.” J. Am. Ceram. Soc., 56共8兲, 409–415.
Ye, G. 共2003兲. “Experimental study and numerical simulation of the de-
velopment of the microstructural and permeability of cementitious
materials.” Ph.D. thesis, Delft Univ. of Technology, Delft, The Neth-
erlands.
Ye, G., Lura, P., and van Breugel, K. 共2006兲. “Modelling of water per-
meability in cementitious materials.” Mater. Struct., 39, 877–885.
Zhou, J., Ye, G., and van Breugel, K. 共2006a兲. “Autogenous deformation
of portland cement paste blended with blast furnace slag measured by
mini-TSTM.” Proc., Int. RILEM Conf. on Volume Changes of Hard-
ening Concrete: Testing and Mitigation, Technical Univ. of Denmark,
Lyngby, Denmark, 20–23.
Zhou, J., Ye, G., and van Breugel, K. 共2006b兲. “Hydration of portland
cement blended with blast furnace slag at early stage.” Advances in
concrete through science and engineering, RILEM, Quebec City,
Canada.