CEMENTand CONCRETERESEARCH. Vol.20, pp. 227-235, 1990. Printed in the USA.

0008-8846/90. $3.00+00. Copyright(c) 1990PergamonPress plc.

THE PORE STRUCTURE OF P A S T E IN C O N C R E T E

Douglas Winslow
Ding Liu

School of Civil Engineering

P u r d u e University
West LaFayette, Indiana

(Communicated by J.P. Skalny)

(Received May 1, 1989)

ABSTRACT

T h e pore size distribution of the cement paste t h a t develops in concrete and m o r t a r was
measured b y m e r c u r y intrusion. T h e intruded pore volumes were expressed on a per
unit mass of paste basis and c o m p a r e d with the pore structure of plain paste t h a t
h y d r a t e d without aggregate. The paste in concrete is more porous, and the difference
increases with increasing hydration. The additional porosity occurs mainly in pore sizes
t h a t are larger t h a n the plain paste's threshold pore diameter.

Introduction
The pore structure of p o r t l a n d cement paste has been studied extensively for the past
20 years. This research has been of considerable value in efforts to u n d e r s t a n d the
nature of this complex material. A tacit assumption behind these investigations has
been t h a t w h a t is learned a b o u t plain, i.e. without aggregate, pastes is applicable to
paste in m o r t a r and concrete. T h a t is, it has been assumed t h a t when paste forms in the
presence of aggregate, it has the same pore structure as it has in the absence of
aggregate. However, some research has indicated t h a t the paste t h a t forms near the
interface with an aggregate particle has a different microstructure.
T h e only paste pore structure of practical i m p o r t a n c e is the one t h a t is formed in
concrete. It is this pore structure t h a t greatly influences such crucial concrete properties
as strength, shrinkage, permeability, and durability. To date, there has been no
information available concerning whether this paste has the same pore structure as the
m u c h studied plain paste. It was the purpose of the research reported here to look into
this question.

227
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O. Winslow and Ding L i u

Experimental Work
The plan of this research was to measure the pore structure of the paste in a series of
concrete samples, each of which differed from the others in some controlled way such as
water:cement ratio or curing t e m p e r a t u r e . In each case, companion samples of m o r t a r
and plain paste were also prepared. After a p p r o p r i a t e hydration periods, the pore
structures of the samples were determined by m e r c u r y intrusion. All samples were
tested at two different degrees of hydration: a p p r o x i m a t e l y 9.5% and 14.5% non-
evaporable water content. After intrusion, the paste content of each sample was
determined b y chemical analysis so t h a t the pore volume of all samples could be
expressed on a unit mass of dry paste basis.

Materials
T h e portland cement was A S T M T y p e I. The aggregate was non-porous quartzite
from Baraboo, Wisconsin. It was used to eliminate the aggregate's pore volume f r o m the
pore structure measurement. The aggregate was crushed and sieved into b o t h fine and
coarse size fractions. T h e gradations of the aggregate are listed in Table 1.

T a b l e 1 -- Gradations of Aggregate

Sieve S i z e Concrete Mortar

(% passing) (% passing) Table 2 -- Mix Proportions

1" 100.0 Mix Type Water Cement Aggregate

3/4" 96.4 (ml) (g) (g)
1/2" 81.4
3/s" so.4 Concrete, w/c~0.45 164 364 1491
~4 39.7 100.0 Concrete, w/c~--~0.55 200 364 1491
#8 37.6 94.4 Mortar, w/c~0.45 52 116 212
#16 25.4 64.6 Mortar, w/c~-~0.55 64 116 212
#30 ~6.0 41.4
#50 7.5 19.0
#1oo o.o 0.0

T h e concrete mix was proportioned using t h e A C I procedure. T h e mix proportions

are listed in Table 2. T h e a m o u n t of the aggregate in the m o r t a r was chosen such t h a t
its total surface area, per unit mass of paste, was the same as it was for the concrete.
This was achieved b y using slightly more fine aggregate in the m o r t a r t h a n in the
concrete.

P r e p a r a t i o n of Samples
Four groups of samples were prepared. Each group consisted of paste, m o r t a r and
concrete specimens. T h e variables t h a t distinguished each group are given in T a b l e 3.

T a b l e 3 -- Distinguishing Characteristics of Sample Groups

Group 1 w/c~0.45 Hydrated at lO°C

Group 2 w/c~0.45 Hydrated at 2o°c
Group 3 w/c~0.45 Hydrated at 3o0c
Group 4 w/c~0.55 Hydrated at 2o°c
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PORE STRUCTURE, PASTE, CONCRETE, MORTAR

All mixing was done in an evacuated c h a m b e r to minimize the a m o u n t of e n t r a p p e d

air. The mixing was done on a paint shaker for 2 minutes. The concrete samples were
cast in 7.5x15 cm cylindrical molds and consolidated with vibration. T h e m o r t a r and
paste samples were cast in 2.5x8 cm plastic test tubes. The samples were demolded after
a b o u t one d a y and p u t into lime-saturated w a t e r at the a p p r o p r i a t e t e m p e r a t u r e until
the test date.
At the desired age, the samples were t a k e n out of the lime water, and several small
pieces were cut f r o m t h e m with a small d i a m o n d saw. Breaking with a h a m m e r m i g h t
have caused cracking. After cutting, the samples were dried and stored in a v a c u u m
oven at 105°(7 to prevent carbonation.

Determination of Non-evaporable W a t e r
The non-evaporable water content was determined as the weight loss of the paste in
a sample after ignition at 1050°C. T h e sample size was a b o u t 1.5 g for paste, 3 g for
m o r t a r and 9 g for concrete. The losses on ignition of unreacted cement and aggregate
were also measured to m a k e the necessary corrections to the final results. Samples t h a t
had been intruded retained some m e r c u r y and, so, could not be ignited safely.
Therefore, the non-evaporable water content of an intruded sample was assumed to be
the same as t h a t determined by ignition of companion specimens t h a t had not been
intruded.

Mercury Intrusion
T h e pore size distributions of the samples were obtained by m e r c u r y intrusion. T h e
i n s t r u m e n t was capable of a m i n i m u m intruding pressure of 20 m m H g , and a m a x i m u m
of 414 M P a . T h e contact angle assumed in this s t u d y was 118 ° t h a t had been measured
on a v a c u u m oven dried paste (1). Thus, the corresponding range of pore diameters was
between a b o u t 320/~rn and 20 A. T h e intruded volume could be read to an accuracy of
4-0.001 crn 3. T h e size of the samples was: a b o u t 4 grams for concrete, 1.5 grams for
mortar, and 0.8 grams for paste.

Determination of Paste C o n t e n t of M o r t a r and Concrete

The paste content of each m o r t a r and concrete sample was determined f r o m the sum
of the weight of cement and the n o n - e v a p o r a b l e water in the sample. The a m o u n t of
cement in the sample was determined by E D T A titration of calcium. The sample, after
either ignition or m e r c u r y intrusion, was dissolved in HC1. The solution was separated
from the insoluble quartz aggregate by filtration. Then the solution was titrated with
E D T A to determine the a m o u n t of calcium. The cement content of the sample was
calculated f r o m the a m o u n t of C a O in the cement.

E n t r a p p e d Air in the M o r t a r and Concrete

The m o r t a r and concrete samples contained a small volume of e n t r a p p e d air voids in
spite of the v a c u u m mixing technique. This volume was determined by examining
polished sections with a light microscope. The m a j o r i t y of this e n t r a p p e d volume was
found to lie in voids with sizes between 10 ~m and 100 ~m. In the case of mixes with
w / c -~ 0.45, the volume was found to be a b o u t 0.02 cm:~/gof paste. In the w / c --~ 0.55
mixes, it was a b o u t 0.005 cm3/g of paste. These volumes were subtracted f r o m the total
measured pore volumes so t h a t the resulting pore structures would represent only pores
innate to the hydrating cement.
230 Vol. 20, No. 2
D. Winslow and Ding Liu

T a b l e 4 -- S u m m a r y of A v e r a g e D a t a for All S a m p l e s

Sample Group Age at Non-evaporable Total Intruded

Type Number Test Water Content Pore Volume
( m3/g po,t )
- - - Less H y d r a t e d S a m p l e s - - -

Paste 1 5.0 0.093 0.275

Paste 2 1.5 0.099 0.277
Paste 3 1.1 0.094 0.274
Paste 4 1.1 0.093 0.352

Mortar 1 5.0 0.098 0.270

Mortar 2 0.9 0.091 0.285
Mortar 3 0.6 0.098 0.269
Mortar 4 1.1 0.093 0.348

Concrete 1 2.5 0.095 0.286

Concrete 2 0.9 0.098 0.307
Concrete 3 0.6 0.098 0.309
Concrete 4 1.1 0.090 0.339

- - - More Hydrated Samples - - -

Paste 1 42.0 0.144 0.185

Paste 2 21.0 0.148 0.191
Paste 3 14.0 0.14{} 0.198
Paste 4 21.0 0.148 0.241

Mortar 1 25.0 0.139 0.219

Mortar 2 20.0 0.148 0.229
Mortar 3 10.0 0.147 0.197
Mortar 4 11.0 0.145 0.294

Concrete 1 25.0 0.145 0.249

Concrete 2 20.0 0.148 0.242
Concrete 3 8.0 0.142 0.205
Concrete 4 14.0 0.141 0.287

R e s u l t s a n d Discussion
T h e s a m p l e s in this s t u d y h y d r a t e d a t w i d e l y different rates. T h i s m e a n t t h a t t h e
o n l y r a t i o n a l w a y to c o m p a r e t h e i r p o r e s t r u c t u r e s was a t equal degrees of h y d r a t i o n ,
a n d n o t a t e q u a l h y d r a t i o n t i m e s . B y d o i n g this, t h e c o n f u s i n g f a c t o r of differing
a m o u n t s of h y d r a t i o n w a s e l i m i n a t e d . A n y differences t h a t were f o u n d a r e d u e solely to
the conditions under which the paste hydrated.
D u p l i c a t e d e t e r m i n a t i o n s of t h e p o r e size d i s t r i b u t i o n o f e a c h t y p e of s a m p l e were
m a d e . T h e r e s u l t s r e p o r t e d h e r e a r e t h e a v e r a g e of t h e s e d u p l i c a t e s . In t h e w o r s t cases,
Vol. 20, No. 2 231
PORE STRUCTURE, PASTE, CONCRETE, MORTAR

the replicate intruded pore volumes differed by no more than about 0.010 cm3/g. A
summary of the average total intruded pore volumes, non-evaporable water contents,
and hydration times is given in Table 4.
The data in Table 4 show several i m p o r t a n t points. The first one is that, at similar
degrees of hydration, the paste in concrete is more porous than similar paste hydrating
in the absence of aggregate. The difference is more pronounced as the hydration
increases. (This difference would be even greater if the pastes were compared at equal
ages since the paste in the concrete h y d r a t e d more rapidly than the plain paste.)
Secondly, within a sample type, accelerating or retarding the hydration by changing
the t e m p e r a t u r e did not significantly change the intruded pore volume of the paste when
all pastes were allowed to h y d r a t e equally. T h a t is, for a given sample type, the Groups
1, 2 and 3 samples have generally similar pore volumes. The only variable that altered
the pore volume, within a type of sample, was the water:cement ratio.
Not only are the total intruded pore volumes essentially the same for different
hydration situations, b u t the distributions of the pore volumes are also similar. The
range of temperatures t h a t were used changed the rate of hydration by factors ranging
from 2 to 8. However, when the reactions of the various pastes were allowed to proceed
equally, the pore structures of the pastes were essentially the same.
This study produced too m a n y pore size distributions to be reproduced here.
However, with the exception of the samples prepared at w / c ~ 0.55, all samples of a
type had essentially the same pore size distribution at the same degree of hydration.
Thus, a few typical examples can serve to demonstrate all of the i m p o r t a n t findings.
Figures 1 and 2 show the pore size distributions of the samples with w / c ~- 0.45 that

0.35
o Concrete
0,3 m
Mortar
Paste
0.25

0.2
Curn
Int
(cm3/g)
0.15

0.1

0.05

0.001 0.003 0.01 0.03 0.1 0.3 1 3 10 30 100 300 1000

Pore Diameter (~um)
Figure 1 - Pore Structure of Less Hydrated Samples, w / c ~ 0.45
232 Vol. 20, No. 2
D. Winslow and Ding Liu

hydrated at 20°C (Group 2). Figure 1 has the distributions for the lesser degree of
hydration, and Figure 2 has those that hydrated more. Figures 3 and 4 have the
corresponding distributions for the w / c = 0.55 samples (Group 4).

0.25

o Concrete
0.2 n
A Mortar

[] Paste
Cure 0.15
Int
( cm 3 / g) 0.1

0.05

0.001 0.003 0.01 0.03 0.1 0.3 1 3 10 30 100 300 1000

Pore Diameter (pm)

Figure 2 - Pore Structure of More Hydrated Samples, w / c = 0.45

0.4
o Concrete
0.35
Mortar

DPaste
0.3

0.25

Cum
Int 0.2
. (cm3/g)
0.15

0.1

0.05

0.001 0.003 0.01 0.03 0.1 0.3 1 3 10 30 100 300 1000

Pore Diameter (pm)

Figure 3 - Pore Structure of Less Hydrated Samples, w / c = 0.55
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PORE STRUCTURE, PASTE, CONCRETE, MORTAR

0.3

o Concrete
0.25 -
Mortar

o Paste
0.2

Cum
Int 0.15
(cm3/g)
0.1

0.05

0.001 0.003 0.01 0.03 0.1 0.3 1 3 10 30 100 300 1000

Pore Diameter (#m)

Figure 4 - Pore Structure of More Hydrated Samples, w / c = 0.55

F r o m Figures 1 to 4 it can be seen t h a t the pore size distributions of the paste in

m o r t a r and concrete have the same general shape as those of plain pastes. However, the
paste in m o r t a r and concrete is more porous t h a n the corresponding plain paste. This
difference is m u c h more pronounced in the case of the more h y d r a t e d samples. Much of
the additional pore volume occurs in pores with diameters greater than the threshold
d i a m e t e r of the plain paste. This finding shows t h a t the presence of the aggregate does,
indeed, influence the microstructure of the paste t h a t forms around it.
This is the essential finding of this study. There are two i m p o r t a n t aspects to this
finding. One is t h a t the bulk of the additional pore volume in concrete paste lies in the
largest pore size range. These are the pores t h a t are most likely to affect properties such
as permeability and durability in an adverse way.
T h e other i m p o r t a n t aspect is t h a t the pore structure of plain paste is not a good
model for the porosity of the paste as it exists in concrete. In the past, it has been
assumed t h a t plain pastes and concrete pastes had the same pore structure. Correlations
based on this assumption are inevitably biased, and perhaps fatally flawed.
T h e results of this s t u d y show t h a t the paste t h a t develops in a m o r t a r has a pore
structure t h a t is m u c h closer to t h a t which develops in concrete t h a n t h a t of plain paste.
The similarity is more pronounced in the more m a t u r e samples. This finding is not
unexpected, because the fine aggregate, possessing the m a j o r i t y of the surface area of the
total aggregate, would be expected to be the m a j o r factor in any alteration of the paste.
A practical consequence of this is t h a t the pore structure of the paste in a m o r t a r m a y
be an adequate model for t h a t in concrete, and is m u c h easier to study.
One can examine the details of the differences caused by the aggregate by plotting
the cumulative difference in the intruded pore volumes between the plain pastes and the
concrete pastes vs. pore diameter. A typical result, for both levels of hydration of the
w / c ~--- 0.45 samples, is given in Figure 5. Plots for the other paste-concrete pairs in this
s t u d y have a similar appearance.
234 Vol. 20, No. 2
D. Winslow and Ding Liu

0.07

o More Hydrated Pastes

0.06
o Less Hydrated Pastes

0.05

Cum 0.04
Extra
Int
(cm31g) 0.03

0.02

0.01

0.001 0.003 0.01 0.03 0.1 0.3 1 3 10 30 100 300 1000

Pore Diameter (gm)
Figure 5 -- Differences Between Plain Paste and Concrete Paste, W / C ~ 0.45

One can see that, in the pore size range larger t h a n the threshold diameter of the
plain paste, the concrete paste has a larger intrusion volume, and the difference increases
to a m a x i m u m at the threshold diameter. In the pore size range just smaller t h a n the
threshold diameter, the plain paste a p p a r e n t l y has more pore volume t h a n the paste in
the concrete. (The curves in Figure 5 drop.) However, the plain pastes never catch up
to the concrete pastes t h a t always have a greater total pore volume.
W h e n the threshold diameter decreases with additional hydration, the m a x i m u m
difference in Figure 5 moves with it along the diameter axis. This result shows t h a t the
additional pore volume is intimately associated with the hydration process, and is not
merely shrinkage cracks. W h a t e v e r the threshold diameter of a plain paste m a y be, the
corresponding paste in a concrete always has a significant pore volume lying in pores
with diameters ranging up to a b o u t two orders of m a g n i t u d e larger t h a n the threshold
diameter.
At a later stage of hydration, a bigger difference is seen between the total intruded
volumes of the plain paste and the paste in concrete. Of course, the total pore volumes
of b o t h are reduced as h y d r a t i o n proceeds. However, the difference between the two
widens. This indicates t h a t paste of altered pore structure continues to be produced as
more hydration occurs. The difference would p r o b a b l y be even more pronounced in fully
h y d r a t e d concrete.

Conclusions
Some of the characteristics of the pore size distribution of the paste in concrete and
m o r t a r can be s u m m a r i z e d in the following points.
1. The cement paste t h a t forms in concrete has a pore structure t h a t is different from
t h a t in plain paste.
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PORE STRUCTURE, PASTE, CONCRETE, MORTAR

2. T h e paste in concrete is more porous, and the majority of the extra porosity has
larger diameters than are found in plain paste.
3. T h e paste t h a t forms in m o r t a r has a pore structure that is more like that in
concrete than plain paste.
4. Pastes with the same water:cement r a t i o t h a t h y d r a t e under different
circumstances, b u t to the same degree of hydration, have similar pore size
distributions.

References
1. Winslow, D. and Diamond, S., A S T M J Mtls, Vol 5, No 3, p 564, (1970)