Materials and Structures/Mat6riaux et Constructions, Vol.
34, December2001, pp 619-628
Permeability and pore structure evolution of silico-
calcareous and hematite high-strength concretes
submitted to high temperatures
C. Gall6 andJ. Sercombe
Direction de I EneN~eNuclda~reD PC/S C CME CEA Saclay, 91191 Gif-sur-Yuette, France.
Paper received:January2, 2001; Paperaccepted:April 17, 2001
A B S T R A C T
Two high-strength concretes (HSC) only differing in
their aggregates - silico-calcareous and hematite - were
heated at temperatures up to 450~ (l~ The evo-
lution of their microstructural parameters - porosity, pore
structure, permeability - were analysed. Both concretes
showed equivalent initial microstructural characteristics.
From 60~ heating generated a large capillary porosity
characterized by pore accesses around 0.1 gm. The inten-
sity and especially the width of the porosity peaks
increased with temperature. For silico-calcareous HSC,
macropores - 50 to 0.3 g m - were detected by MIP stud-
ies at 250~ and especially at 450~ They were corre-
lated to microcracks visually observed at the surface of the
probes. Up to 250~ the intrinsic permeability increased
similarly for both concretes. Between 250 and 450~
permeability remained stable for hematite HSC while, for
silico-calcareous HSC, a major change was noticed. A
good correlation between permeability and total water
porosity was observed. At 450~ influence of the micro-
cracks on permeability was greater than the impact of the
increase of capillary pore size. As both concretes showed
similar initial microstructural features, conclusion was
reached that the differential behaviour can mainly be
attributed to internal thermal gradients discrepancies
related to the type of aggregates: hematite allows to limit
thermal gradient and thus, thermo-mechanical stresses. It
was globally observed that damage due to high tempera-
ture thermal treatments was lower for hematite HSC.
1. INTRODUCTION
For several decades now, high-strength concretes
(HSC) have been used more and more frequently in var-
ious industrial domains. As a result, its extended applica-
tion has been associated to new using conditions such as
severe thermal environment. Fire remains one of the
most serious potential risk for any building or structural
1359-5997/01 9 RILEM
R I~ S U M I~
Deux b~tons a hautes pe~rmances se distinguant uni-
quement par leurs granulats - silico-calcaires et h6matites -
ont subi des traitements thermiques allant jusqu'a 450~
(l~ L'&olution de leurs propri~t& microstructurales
-porosit6, structure des pores, perm&bilit~ - a ~tg exami-
n&. Initialement, les caract&istiques microstructurales des
deux b6tons sont identiques. D& 60~ le chauffage pro-
voque l'apparition d'une importante porosit~ capillaire dont les
acc& de pore se situent au voisinage de 0,1 btm. L'intensit~ et
surtout la largeur des pics de porosit~ augmentent avec la tem-
p&ature. Pour le b6ton silico-calcaire, des macropores -dans
la gamme 50 a 0.3 btm - ont ~galement ~t~ mis en &idence
par la porosim&ie mercure a partir de 250~ et surtout
450~ Ceux-ci ont ~t~ corral& a des microfissures d~tect&s
visuellement a la su~ce des ~prouvettes. Jusqu'a 250~ on
observe pour les deux b&ons une augmentation de la perm&-
bilit~ au gaz. Entre 250 et 450~ ce param~tre n'&olue
pas pour le b6ton d'h~matite alors qu'une &olution majeure
est de nouveau observe'epour le b&on silico-calcaire. Ces &o-
lutions sont bien corr~l&s a celles de la porositd totale a l' eau.
En tenant compte de la similitude microstructurale initiale de
la phase cimentaire des deux b6tons, cette difl&ence de com-
portement a 6t~ principalement attribu& a des diff&ences de
gradients thermiques internes li~es au type de granulats, l'h~-
matite permettant de limiter les gradients thermiques et par
cons6quent les contraintes d'origine thermo-m&aniques.
Globalement, l'endommagement lid aux traitements ther-
miques est moins cons6quent pour le b6ton d'hdmatite.
material [1, 2], but in other specific environments, such
as the storage of high level nuclear waste packages, con-
crete structures could be sujected to relatively high tem-
peratures - 200~ - in case of failure of cooling systems.
At high temperatures, high-strength concretes are sub-
ject to significant damages like microcracking, fractur-
ing, spalling [3-9]. Due to their limited porosity (com-
pactness) and low permeability, high-strength concretes
61 9
Materials and Structures/Mat6riaux et Constructions,Vol.34, December2001

in severe thermal environment often behave in a brittle Table 1 - Thermo-mechanical properties of aggregates
way [7]. It is generally admitted that HSC behaviour at Properties Silico-cal. Hematite
high temperature is governed by thermo-mechanical
processes related to temperature gradients which gener- Specific density (kg/m 3) 2500 5000
ate thermal expansion gradients [10, 11] and by thermo- Thermal conductivity (W/m/~ 2.5 11
hydric processes linked to water movements in the Thermal capacity (J/kg/~ 800 650
material porosity [9, 12, 13]. For the first aspect, con-
Thermal expansion coefficient (1/~ 11.10 -6 8.10 -6
crete thermal conductivity and expansion - widely
dependent on the characteristics of its components: Elastic modulus (GPa) 70 209
cement paste and aggegates - are major influential fac-
tors [1, 13, 14]. For the second aspect, permeability is
one of the key parameters controlling internal fluid Table 2 - Concretes mix design (kg/m 3)
transfer and thus the generation of potential over-pres-
Ordinary HSC
sure gradients during temperature heating. It still
remains difficult nowadays to know which process is Silico-calcareous aggregates 8/20 mm 800
predominant. It obviously depends not only on material Silico-calcareous aggregates 4/12 mm 400
properties but also on the geometry of the structure and Silico-calcareous sand 0/4 mm 750
the heating rates. Water 150
In this paper, a comparative study of the thermal Cement CEM I 350
behaviour of two HSCs which differ only by the type of Plasticizer (Gienium 27) 1.75
aggregates is presented. It is carried out in the frame- Hematite HSC
work of a research programme on long-term surface Hematite aggregates 6/25 mm 1700
storage c o n d u c t e d by the French Atomic Energy Hematite aggregates 0/8 mm 900
Commission (CEA). The mix-design properties of the Hematite sand O/1 mm 1000
two HSCs are chosen in order to dissociate the thermo- Water 150
hydric and thermo-mechanical processes occuring dur- Cement CEM I 350
ing heating: similar cement content and water/cement Plasticizer (Glenium 27) 5.25
ratios are used to obtain close transfer properties -
reflected by porosity, pore size distribution and gas per-
meability - (and thus thermo-hydric processes of similar
magnitude), hematite aggregates are used in one case to Ordinary and hematite HSC mean compressive strength
increase the global thermal conductivity of the material at 60 days were of 63 and 78 MPa, respectively.
and thus limit thermo-mechanical phenomena during
heating. To evaluate the consequences of the differential
thermo-mechanical behaviour of the two HSCs, the 2.2 Experimental heating conditions
experimental programme focuses on the evolution of the
materials pore structure identified by MIP in close rela- High-strength concrete probes were heated at 60,
tionship with their permeability. Results are presented 110, 250 and 450~ in a Carbolite oven during 75, 40,
and discussed in this paper for specimen heated to tem- 20 and 15 days on average, respectively. Durations of
peratures up to 450~ thermal treatments were adapted to obtain a stable mass
loss (< 0.01%/24h) in order to ensure that water was
totally removed for each temperature. During heatings,
2. EXPERIMENTAL PROGRAMME heating rates were kept at l~ At the end of the
heating tests, temperature was cut off and probes were
2.1 Materials cooled slowly in the ovens until reaching 60~ Then
materials were stored in sealed containers until the
The materials used for this study were two CEM I beginning of the experimental characterization.
(OPC) concretes. Specimens were French "11 x 22"
normalized cylindrical probes (Ol13 mm, H220 mm).
Ordinary HSC was prepared with silico-calcareous 2.3 Equipments and measurements
aggregates while hematite HSC was prepared with
hematite aggregates. At present, these concretes are stud- Mercury intrusion porosimetry (MIP) tests were per-
ied as structural materials in the context of long-term formed with a Micromeritics Autopore III 9420 appara-
surface storage [15]. Average thermal and mechanical tus. This technique, w h i c h is widely used for
properties of the two types of aggregates [16] are given in microstructural investigation of cement-based materials,
Table 1. Hematite aggregates were used for their high consists in injecting, isostatically, incrementally and
thermal conductivity and their reduced thermal expan- under very high pressure, a non wetting fluid (mercury)
sion coefficient. into the evacuated pores of the porous material. The test
The materials were cured in sealed bags for a period of is analyzed according to the Washburn equation in
two months. Concretes mix design are given in Table 2. which the size of penetrated pore accesses, assimilated to

620
Gall~,Sercombe

cylindrical capillaries, are inversely proportional to the

applied pressure:
p= 4ycos0 (1)
d
where P is the mercury injection pressure (Pa), y is the
surface tension of mercury (N/m), 0 is the contact angle
between solide and mercury (o) and d is the pore access
diameter (m).
For calculations, a contact angle of 130 ~ was
assumed. MIP tests were achieved with a minimum and
maximum pressures of 0.006 and 413 MPa, respectively.
For each temperature, MIP investigation was Carried out
with at least ten specimens. In addition, for non heated
specimens, the removal of water was achieved by using
the freeze-drying technique.
Gas permeability measurements were achieved with a
Hassler apparatus (Fig. 1). This device is a constant-head
permeameter type [17] originally developed for the oil
industry. It allows to apply gas injection pressures up to 5
MPa. Permeability tests were performed on "11 x 22"
cylindrical probes using dry nitrogen gas. Gas flow rates
were measured with bubble flowmeters.
Effective gas ~ermeability
r k g was calculated with
Darcy's law as modified by the Hagen-Poiseuille relation:
2QLP2~
kg -- S(P12 _ p22) (2)
Fig. 1 - S c h e m a t i c o f the Hassler gas permeameter.
where k_ is the effective gas permeability (m2), Q is the gas
flow rate measured at pressure P2 (m3 s-l), L is the speci-
men length (m), ~t is the dynamic gas viscosity (Pa s), S is
the specimen cross sectional area (m2), Pl is the absolute Table 3 - HSC's initial properties (20~
injection pressure (Pa) and P2 is the exit pressure (Pa). Ordinanj Hematite
Intrinsic permeability k was determined using the
Specific density (kg/m 3) 2378 _+8 4067 _+58
Klinkenberg approach [18, 19]. This widely-used
Total porosity (%) 10.4 + 0.4 10.0 + 0.5
method allows to estimate an intrinsic permeability from
Effective permeability (10 -19 m 2) 1.6 _+ 1.9 3.9 + 4.7
effective permeability measured at different pressures,
Intrinsic permeability (10 -20 m 2) 4.5 _+ 7.2 8.1+ 7.3
according to the following equation:
Thermal conductivity (W/m/~ 2.7_+0.1 7.3 + 0.4
Compressive strength (MPa) 63_+ 4 78_+ 5
kg=k(l+p) (3)
Elastic modulus (GPA) 49_+ 4 81+2
Poisson's ratio 0.23 + 0.05 0.26 _+0.04
where k_ is the effective gas permeability (m2), k is
the mtransac permeabilty (m2), P is the average pressure
(PI + P2)/2 and [3 is the constant of Klinkenberg.
The intrinsic permeability, as defined in the these conditions, the initial microstructural properties of
Klinkenberg approach, is regarded as independent from the concretes cementitious phases were expected to be
the average pressure and as a characteristic of the porous almost identical. This assumption was confirmed by the
medium alone. Gas permeability measurements were measurements of mass loss and, from the microstructural
achieved on five specimens for each temperature with at point of view, by porosity and permeability data.
least three gas injection pressures per specimen. The total amount of water - free water, adsorbed
water on pores and hydrates bound water - removed after
the different thermal treatments were close (Fig. 2) and
3. EXPERIMENTAL RESULTS showed that the dehydration stages were comparable for
both concretes. Moreover, average cumulative (Fig. 3) and
3.1 Initial characteristics differential (Fig. 4) pore volume distributions were simi-
lar for both HSCs. A bigger discrepancy is observed on
Initial microscopic and macroscopic properties for cumulative curves. But it is rather limited if we compare
both concretes are given in Table 3. The two HSCs were the standard deviation of total cumulative volumes for
prepared with different aggregates but with the same ordinary and hematite HSC, 0.050 + 0.011 ml/g and
CEM I (OPC) cement and water/cement ratio (0.43). In 0.031 + 0.015 ml/g,respectively. These results proved that

621
Materials and Structures/MaMriaux et Constructions, Vol. 34, December 2001

16 0.1
0 Ordinary HSC X Hematite HSC
-~ 0.09 __2o~ .... 6o~163--11O~ Ordinary HSC I
14 .'. ". "250...C. ~ 450....C .. /1111111 IIIILI4'
A

- 12
~ 0.08 IIIIIIlll
0.08
0.07
IIIIIIll
IIIIIII
IIIIlll
IIIIII iiJiiiill IIIIIII ~TIII
Illlll IIIIllll I IIIIIIb Ililll,r
O
~. .05
IIIIIIII IIIIIII IIIIII IIIIIIIII IIII1,ti -'Ill,U,I*
81o 0.04 11111111 IIIIIII 111111 IIIIIIIII IZli.l,' ~11~
.~ 0.03 IIIIIIII IIIIIII IIIIII IIIIIII1~ All
8 0.02 IIIIIII1: IIIIIII IIIIII lluv,.t'rl ,,.t1'llLI. "1111111
~0.01 11111111 IIIIIII ~ ~ 1 1 IIIIIII
o 0 !1111111.....Ultld~=~-.......i.. ZII ZII
0 50 100 150 200 250 300 350 400 450 500 1000 100 10 1 0.1 0.01 0.001
Temperature (~
Pore access diameter ( p m )

Fig. 2 - Total mass loss evolution versus temperature. "~ 0.1

g 0.09 ~j...... 20~163 ' -- -. (30;'C m l i0';C ~ Hematite HSC[
250~ 45~176 Jlrllll i iiill i '
0.08 i! ............
0.06 ,liliii
~=0.07 I,IIIII ,,ll ,,17m,llll m,ii i,,llll
,,,lll,l, lll,,I]ll II, II
,,11
.... Cumulative - Ordinary HSC]
E
>
0.05 0.08
-- Cumulative" Hematite HSCI IW'I ~. 0.05
0.04 => 0.04
11111111 IIIIII IIIIIIIII IIIiill i IIIIIIJ,I-" II11.1.1
,1t11 0.03 11111111 IIIIII Ililllllllllllll ! II~IL,.-:I~.I.H
== 0.03
E0.02
IIIII IIIIIIIII IIIIIII i ZILI,,J,'P''r I~
>= 0.02 0.01 11111111 IIIIII IIIIIIIII IIIIIII "~IIL.-.TIIIII
0 !1111111 lltiil !!!!!!!! !~ "lllllTII IIIIII
0.01 gglttt.... Igl 1000 100 10 1 0.1 0.01 0.001
o 0 Pore access diameter (IJm)
1000 100 10 1 0.1 0.01 0.001
Pore access diameter (pm)
Fig. 5 - Average cumulative pore volume versus temperature.

Fig. 3 - hfitial HSC pore structure: average cumulative pore volume.

0.08
I o n ' ; nia~] L,a "- g'{~J
0.06 0.07
0.05 ~ .... Differential-Ordinary HSC ] A 0.06 IIIII I iMBiMIi
0.05 ;!llllglllllllll
== 0.04
I[ .-.'--.'.Differential
. - Hematite HSC [
0.04 I ,,,,i m,lllll,,Hi i l[l!!!llllllrlt
E
0.03 0.03 IIIIIIII IIIIIIIII IIIIIII ! ,.t;tilllMI
o
0.02 IIIIII IIIIIIII IIIIIIIII IIIIIII i: Illl!i~iiiid311
0.02
0.01 IIIIII IIIIIIU JIIllli~q~, IIl~l'-'t=i~iilltll
OOl Illllll lltl.tl".,!
LH;4 0 IIIIII =[tt~ ~..~-- iilllllllllllllll
0
.. 4#1" IIIIIII 1000 100 10 1 0.1 0.01 0.001
Pore access diameter (pm)
1000 100 10 1 0.1 0.01 0.001
Pore access diameter ( p m )
0.08 ....... 60~ -- 11o~ I Hematiie Hsc]
Fig. 4 - lnJdal HSC pore structure: average cumulative pore volume. 0.07
0.06
--450~ ,,,,,, IIliiiii iiiiiiii
g [lllilll iillllll llllllll
_g' 008 iii[iii iiiiiiii ~L!tt iiiiiiii
r"t

the cement paste porous space structuring of the two 004 lltlltl ZII I~.I !!!!!!#
HSCs was equivalent. This point is important for further lo
003 ~,',',~,~,', J!!!!!!V11111F~.~!~!
interpretation of the concretes differential behaviour. 002 """" iiiiiiJ/;/llllllr~.~.~
On the contrary, thermal conductivities of the two 0.01 ;~;;;;; ;
0 ~""" ~ r " ,-~ ~11T]
HSCs differ by a factor of 3. Elastic moduli are also
strongly dependent on the mechanical characteristics of 1000 100 10 1 0.1 0.01 0.001
aggregates and thus differ by nearly a factor 2. As Pore access diameter (pro)

expected, hematite aggregates provide a high thermal

Fig. 6 - Average differential pore volume versus temperature.
conductivity and rigidity to hematite HSC.

initial pore size distributions was already mentioned.

3.2 Pore structure
Pore structure evolution versus temperatures for both
HSCs are given in Figs. 5 and 6 (average data based on at
least ten specimens each). The similarity of the concretes
Without thermal treatment, both HSCs showed no sig-
nificant capillary porosity (Fig. 4) - macroporosity (pore
access around and up to 0.1 I.tm). Two main classes of
pore access corresponding to C-S-H intrinsic porosity,
are generally detected in regions between 0.01-0.02 ~tm

622
Gall~, Sercombe

and around a few nm. These pore access classes can be

associated with outer C-S-H (microporosity) and inner A 14
I-<~ Ordinary HSC'-U-'Hematite fiSC
C-S-H (nanoporosity), respectively [20]. Cumulative =~13
intrusion curves globally showed a constant increase of
the total intruded volume as temperature rises. Similar /F
/
results were observed by other authors for mortars and /
concretes heated at high temperatures [6, 7, 21, 22]. This
can be related to the alteration of the porous space and .... 41k.~176

thus to the development of additional porosity. At

equivalent temperatures, ordinary HSC intrusion vol- 8
umes are significantly higher than those of hematite 0 50 100 150 200 250 300 350 400 450 500
HSC. This reveals a higher preferential damaging for Temperature (~
ordinary HSC. However, for heterogeneous materials Fig. 7 - Total water porosity evolution versus temperature.
like concrete, the total intruded volume does not reflect
the real porosity of the samples as the amount of non
porous aggregates and paste can vary from a sample to Table 4 - Relative increase (%) in porosity associated to
another. Additional comparative interpretations will be macropores (> 0.3 ~tm), capillary pores (0.3 - 0.02 ~tm)
provided with water porosity data analysis at the end of and hydrate pores (< 0.02 ~tm) versus temperature
this section. OrdinaryHSC Macropores Capillarypores Hydratespores
Differential curves provided more interesting results (> 0.3 p m) (0.3 - 0.02 p m) (< 0.02 p m)
concerning pore space thermal degradation. For the two 60~ -2.2 +55.4 -32.4
HSCs, the various thermal treatments generated an impor-
110~ -6.6 +55.5 -25.7
tant capillary porosity in which major pore access classes
are centered around 0.1 Hm. This phenomenon is detected 250~ -0.9 +59.0 -26.0
early for quite moderate temperatures such as 60~ On 450~ +22.6 +69.5 -27.8
the contrary, pore accesses associated to C-S-H porosity
Hematite HSC Macropores Capillarypores Hydratespores
seem to be influenced by temperature treatments in a (> 0.3 p m) (0.3 - 0.02 p m) (< 0.02 p m)
moderate way. For both HSCs but more especially for
60 ~ -6.0 +62.8 -32.1
hematite concrete, nanopores representativeness is smaller
after heating. This is probably linked to a reduction of pore 110~ -3.0 +62.3 -39.2
network connectMty. Similar observations were reported 250~ -4.8 +78.7 -26.7
for hardened cement pastes [23].
450~ +10.0 +116.8 -32.9
The evolution of the created capillary porosity is char-
acterized by an enlargement of the porosity peak as tem-
perature rises. This phenomenon was observed for both until stable mass loss. Then, the probes were water resat-
HSCs. At 60~ peak boundaries are located around 0.3 urated under vacuum and oven-dried again at 60~
and 0.02 tim while, at 250~ these boundaries vary Ordinary HSC total porosity increases as heating
between 0.9 and 0.009 btm. Consequently, the pore access temperature rises. This phenomenon is significant for
domain which is thermally affected, seems to extend from temperatures over 110~ The porosity increase is about
capillary porosity to outer C-S-H porosity as temperature 10% at 250~ and about 30% at 450~ This evolution
rises. It was also observed that the intensity of distribution was not observed for hematite HSC which porosity
peaks tends to increase with temperature. Comparable remained stable whatever the level of temperature
behaviours were observed by other authors with high- (around 10% with a small increase between 250 and
performance concretes and mortars heated up to 800~ 450~ With the pore size distributions obtained
[21, 22}. It was also observed that, after temperature expo- through MIP investigation, it seems that the develop-
sures, hematite HSC porosity peaks were significantly ment of this additional porosity is mainly related to the
smaller than that of ordinary HSC. formation of macropores, ranging from 50 to 0.3 l.tm,
Additional comments should be made concerning and that in such conditions, the increase in size of the
larger macropores. At 250~ and especially at 450~ capillary pores plays a minor role. To confirm these
pores accesses located approximately between 50 and results, the pore size distribution curves obtained by MIP
0.3 ~tm are detected for ordinary concrete (Fig. 6). This analysis were split in 3 classes : "macropores" (> 0.3 gm),
was not observed for hematite concrete. They are proba- capillary pores (0.3-0.02 gm) and micropores related to
bly associated with cracks that showed up at the surface the hydrates (< 0.02 lim). In Table 4, the increase (or
of heated probes of ordinary concrete. Cracking was not decrease) in porosity relative to the initial porosity at
observed for hematite concrete probes. 20~ (obtained by MIP) is given for each class of pores
Total water porosity measurements provided com- and temperature treatments.
plementary information about concrete porous space From Table 4, several points can be underlined:
thermal degradation (Fig. 7). Porosity was estimated by 9 The macroporosity remains almost stable for both
water mass difference on 40 m m in diameter and HSCs till 250~ and then increases at 450~ particu-
80 mm-high probes subjected to different temperatures larly for ordinary concrete (+ 23%). This is certainly due

623
Materials and Structures/Mat6riaux et Constructions, Vol. 34, December2001
to internal or external stresses related to the expansion of
the aggregates (more important for siliceous aggregates
than for hematite) or structural thermal gradients during
heating.
9 As reflected by Fig. 6, the capillary porosity
increases drastically for both HSCs (+ 55% for ordinary
concrete and + 62% for hematite concrete), for tempera-
tures as low as 60~ Surprisingly, this increase remains
almost stable with higher temperatures. This increase in
porosity could be associated with the removal of free and
adsorbed water from the material, which may induce
damaging of the C-S-H, owing to their structure [8]
(the removal of the inter-layer water could induce a col-
lapse of the C-S-H sheets). It should be added that min-
eralogical transformations of C-S-H hydration products
owing to hydrothermal conditions during heating at
temperatures exceeding 80-100~ may contribute to
microstructural changes of cement paste [14]. However,
no XRD-analyses were performed on heated materials
in this study.
9 The microporosity decreases for both HSCs (- 32%
for ordinary and hematite concrete), also for temperatures
as low as 60~ As for capillary pores, this increase does
not evolve with higher temperatures and could be related
to the collapse of the C-S-H sheets, leading to a reduced
amount of voids of this size.
These results are in good agreement with those
obtained through water porosity measurements showing
the major role of macropores in the generation of extra
porosity for the ordinary HSC. In fact, all the samples used
for water porosity measurements were oven-dried at 60~
before resaturation. The small evolutions of capillary
porosity and microporosity between 60 and 250~ for the
two HSCs (+ 5 - 10% for the capillary porosity and - 5%
for the microporosity) in comparison to their evolutions
between 20 and 60~ (+ 55 - 60% for the capillary poros-
ity and - 30% for the microporosity) explains the fact that
no increase (or nearly no increase) in water porosity was
detected between reference samples (heated at 60~ and
samples heated up to 250~ The increase in water poros-
ity between 250 and 450~ observed particularly for ordi-
nary HSC seems therefore rather related to the increase in
macroporosity (+ 23% for ordinary concrete and + 10% for
hematite concrete). Part of it could also be related to an
additional increase in capillary porosity due to the begin-
ning of the Portlandite decomposition. It is generally con-
sidered that the stability of calcium hydroxide decreases
from 400~ [5] and that its decomposition mainly occurs
in the 450-550~ temperature range [23].
In conclusion, MIP microstructural investigations
showed that the high temperatures thermal treatments of
both HSCs are responsible for the increase in capillary
pore sizes. This p h e n o m e n o n can be related to the
release of adsorbed water physically bound to the solid
surface of capillary pores and to C-S-H microporosity
[24] and to water intrinsically bound in C-S-H and to
the other cement hydrates (portlandite). Dehydration
processes thus lead to the formation of an additional void
space in the porous medium. The size of enlarged pores
depends on the level of applied temperature and thus on
624
the type of hydrates. Sinfilar conclusions were reached
through previous studies [21, 23, 25]. In addition, total
water porosity measurements showed a significant
increase in total porosity for ordinary HSC. This phe-
n o m e n o n can be mainly associated to generation of
microcraks which were not observed for hematite HSC.
3.3 Gas permeability
The evolution of intrinsic permeabilities versus tem-
perature are provided in Fig. 8 (a similar trend was
observed for the evolution of the effective permeability
with temperature). The intrinsic gas permeabilities of
ordinary and hematite concretes - measured at 60~
after complete drying - proved to be similar, around 2
and 1.5 10-17 m 2, respectively. Up to 250~ ordinary
and hematite HSC permeability evolutions follow a sim-
ilar trend and are thus characterized by a comparable
behaviour. After drying at 110 and 250~ permeability
increases are, respectively, of about an average factor
three (= 5 10-17 m 2) and a little more than one order of
magnitude (= 4 10 -16 m2). Ordinary HSC is always
slightly more permeable than hematite HSC.
The most important changes in permeability were
observed at 450 ~ C. At that temperature, intrinsic per-
meability discrepancy between the two concretes
reached two orders of magnitude. From 250 to 450~
the permeability increase for hematite HSC is very lim-
ited (from 3 to 4 10-16 m 2) while, for ordinary HSC, the
permeability change is much more significant (from
5 10 -16 to 8 10 -14 m2). From a general point of view, the
permeability change observed up to 250~ for both
HSCs can be linked to the removal of free water from
the capillary porosity (mainly below 110~ to adsorbed
water release, to cement hydrates (C-S-H) dessiccation
(dehydration) and probably to the generation of fine
cracks. All these processes lead to the increase in the
porous network connectivity and in the porous space
volume available for gas transport (especially the capillary
porosity). Permeability data also showed that microc-
racks observed at the surface of ordinary HSC probes -
obviously correlated to macropores (50 - 0.3 ~tm)
detected by MIP analysis - have a greater influence on
1.E-12
O ()rdirlaryI~tSC' --'Average values
I v a . ~ e s~~
E 1.E-13 9 HematiteHSC --Average
2 1.E-14
~ 1.E-15
~ 1.E-16
9~ 1.E-17 , I '
1.E-18
50 100 150 200 250 300 350 400 450 500
Temperature(~
Fig. 8 - Intrinsic permeability evolution versus temperature.
GalIGSercombe

ordinary HSC transport characteristics than the increase

1.E-12
in the capillary pore size (0.1 btm). This is reflected by O Ordinary' HSC 9 Hematite HSC ]
the results obtained for ordinary HSC at 450~ 1.E-13
The cross-plot of intrinsic permeability and of the
measured total porosity (Fig. 9) showed a good correlation ~ 1.E-14
between these two parameters. These results confirm that ~1.E-15
extra porosity detected for ordinary HSC at 250~ and o II 9 0
above all at 450~ can be mainly associated to the genera- 1.E-16
tion of large cracks which apparently, at this scale, is absent _= immo
for hematite HSC. In that configuration, the generation 1.E-17
of cracks is the main factor controlling permeability evo- 9 10 11 12 13
Total porosity (%)
lution. These results meet those obtained by Tsimbroska
on HSC heated up to 400~ [7]. Fig. 9 - Relationship b e t w e e n intrinsic permeability and total
water porosity.

4. D I S C U S S I O N 5O
- - Ordinary HSC
This study was the opportunity to experimentally 40 Hematite HSC d
compare the microstructural behaviour at high tempera- d 9
#, i
tures of two high-strength concretes only differing in 30 i

their aggregates. Under similar thermal sollicitations, the

two concretes showed quite different responses, espe-
cially for thermal treatments exceeding 200~ Through A ,I
experimental investigations, the initial intrinsic perme- I f \ !
Q}" 9 9 ,..
ability and the pore structure of the two HSCs cement 0
paste proved to be identical. Since thermo-hydric 0 1 2 3 4 5
processes (internal vapor overpressure gradients) are Time (hours)
mainly related to transfer properties, this tends to indi-
cate that the observed behaviour discrepancy of the two ~. 0.8 -- Ordinary HSC I
HSCs is rather linked to thermo-mechanical processes. m Hematite HSC I
Thermo-mechanical damage during heating of concrete 0.6 - - 7 - - / ~
is known to originate from either structural thermal gra-
dients or thermal incompatibility between the aggregates i /
and the cement paste. The former depend mainly on the
macroscopic thermal conductivity of concrete, but are E 0.2 1/ :
also related to vaporization and dehydration (due to their
endothermal nature). The large difference in thermal 0.0
conductivities between ordinary HSC (2.7 W/m/~ 0 1 2 3 4
and hematite HSC (7.3 W/m/~ supports this interpre- Time (hours)
tation. The latter depends mainly on the thermal expan-
sion coefficient of the aggregates (11 10-6/~ for silico- Fig. 10 - Maximum thermal gradients and pore pressures.
calcareous aggregates and 8 10-6/~ for hematite
aggregates), the elastic moduli of the aggregates (70 GPa design properties and that of the aggregates (respectively
for silico-calcareous aggregates and 210 GPa for 2 and 8 W/m/~ for the thermal conductivity, 790 and
hematite) and the mechanical properties of the cement 660 J/kg/~ for the thermal capacities of silico-calcare-
paste (elastic modulus, thermal shrinkage). Since the ous and hematite aggregates).
cement type and water/cement ratios were identical for Maximum pore pressures and thermal gradients were
both HSCs, one may assume that the observed behav- found at the centre of the probe and are given in Fig. 10.
iour discrepancy comes rather from the aggregates. The maximum pore pressures were obviously not influ-
To check the validity of this assumption, the coupled enced significantly by the type of HSC (0.54 MPa for
thermo-hydric behaviour of the probes during heating ordinary HSC and 0.64 MPa for hematite HSC). It was
was modeled using the mathematical description pro- observed earlier in hematite HSC since temperature rises
posed by Ba~ant et al. [12, 13]. Thermal treatments at faster at the centre of the probe, owing to its high ther-
250~ and 450~ for both HSCs were simulated mal conductivity. The small difference in the maximum
(1~ with the finite element code CASTEM2000 pressure between the two HSCs is induced by the faster
[26]. The same intrinsic permeability and total porosity rise of temperature in hematite HSC which, in turn,
were considered in the calculations for the two HSCs leads to an increased quantity of dehydrated water. This
(respectively 10-19 m 2 and 10%). Only the thermal con- additional water contributes to increase the pore pres-
ductivities and the heat capacity of the dried materials (at sure. Calculations confirmed that thermo-hydric phe-
110~ were taken different, according to their mix- nomena should be of similar magnitude in both HSCs.

625
Materials and Structures/Mat&iaux et Constructions,Vol. 34, Decem ber 2001
Thermal gradients between the centre and the exter-
nal surface of the probes were found three times more
important for ordinary HSC (40~ than for hematite
HSC (12~ Independently of the HSC considered, the
endothermal nature of vaporization and dehydration
leads to peak values exceeding by nearly a factor of three
the thermal gradients obtained without hygral couplings
(respectively 15 and 5~ for ordinary and hematite
HSC). These peaks (which could induce significant
damage) occur however for the same local temperature
of 160~ (at the centre of the probes) but for different
external temperatures (195~ for ordinary HSC and
175~ for hematite HSC). These results were confirmed
experimentally on ordinary HSC probes heated at
l~ till 220~ (a maximum thermal gradient of
37~ was obtained for a local temperature of 170~ and
are correlated to tests performed by other authors [9, 11].
Consequently, this means that the maximum "structural
thermal stresses" will not differ for the tests performed
till 250 and 450~ This cannot therefore explain the
pronounced cracking observed at 450~ and not at
250~ for ordinary HSC.
Thermal incompatibility between the aggregates and
the cement could be at the origin of additional damage
during heating. The differential behaviour of the two
components induces tensile stresses within the cement
paste which are maximum at the interface between
aggregates and cement paste. According to several
authors [7, 8, 23], crack initiation in silico-calcareous
HSC starts for temperatures over 300~ This could
explain the important evolution of the intrinsic perme-
ability of ordinary HSC between 250 and 450~ This
increase in permeability (related to internal cracking) was
not observed for hematite HSC. Instead of being related
to structural thermal gradients during heating, the
observed different behaviour of the two HSCs could be
induced by internal stresses of higher magnitude in ordi-
nary HSC than in hematite HSC. To check this assump-
tion, a two-phase model consisting of spherical particles
was used to obtain comparative values of internal tensile
stresses at different temperature levels. In this approach,
the material consist of aggregate spherical particles
recovered by spherical layers of cement paste, such that
the ratio between the radii of the aggregate particle (a)
and that of the aggregate + cement paste particle (b)
remains constant, whatever the size of the aggregate par-
ticles [27]. The matter is assumed to be completely filled
up with these composite spherical particles, such that the
analysis can be carried out only on an elementary parti-
cle, represented in Fig. 11.
The stresses (radial stress % and tangential stress %)
within the aggregates and the cement paste must verify
the spherical conditions of equilibrium (4):
a{~r -~-2 ( ~ r
-- ~ t ) = 0 (4)
dr r decreases by 50 and 75% at 250 and 450~ respectively. A
The stress-strain relations are obtained assuming that
the materials behave elastically and include the following
phenomena: the aggregates expand with temperature
leading to thermal strains e th = aAT, the cement paste
626
~ Cementpaste
Fig.n -
Elementary
Aggregate spherical par-
ticle model.
Table 5 - Characteristics of aggregates and cement paste
Siliceous aggregates
Thermal expansion coefficient at 250~ (1/~ 15.10 -6
Thermal expansion coefficient at 450~ (1/~ 21.10 -6
Elastic modulus at 250 and 450~ (GPa) 80
Hematite aggregates
Thermal expansion coefficient at 250 ~ (1/~ 8.10 -6
Thermal expansion coefficient at 450 ~ (1/~ 11.10 -6
Elastic modulus at 250 and 450 ~ (GPa) 210
Cement paste
Shrinkage strain at 250~ -0.002
Shrinkage strain at 450~ -0.005
Elastic modulus at 250~ (GPa) 7.0
Elastic modulus at 450~ (GPa) 3.5
shrinks leading to shrinkage strains es h. To simplify the
system, the Poisson's ratios (v) are assumed identical for
the cement paste and the aggregates. The following sys-
tem is thus obtained:
E
r~r - (1 + v)(1 - 2v)[(1 - v)e r + 2ve, - (1 + v)~aisl
E (5)
[vgr + e, - (1 + v)edil]
%- (1+v)(1- 2v)
with E as the modulus ofelastidty of the aggregates or the
cement paste, er = du / dr and et = u / r, the radial and tan-
gential strains (with u(r) the radial displacement) and ca,y
the strains associated with thermal expansion of the aggre-
gates (eth = ~tkT) or shrinkage of the cement paste (esh).
Equations (4) and (5) are solved analytically to obtain an
estimation of the tangential stresses within the cement
paste at the interface with the aggregates (for r - a). The
characteristics of aggregates and cement paste considered
are summarized in Table 5.
Average values concerning the thermal expansion
coefficient of siliceous and hematite aggregates as well as
the shrinkage strain of Portland cement paste were taken
from [13, 16]. Siliceous aggregates are primarily consid-
ered for ordinary HSC since they are known to be more
sensitive to temperature than calcareous aggregates [13].
Elastic moduli for the cement paste were estimated from its
value at ambient temperature (14 GPa) assuming that it
mean value of 0.8 for both HSCs was considered for the
maximum aggregate packing density (g* = a3 / b3).
The maximum orthoradial thermal stresses within the
cement paste obtained for both HSCs are given in Fig. 12.
Gall~,Sercombe
4O
~ OrdinaryHSC
35 "" "HematiteHSC
30
25
~, 20 .......
18
e-
0
0 1O0 200 300 400
Temperature(~
Fig. 12 - Maximum orthoradial thermal stresses within the
cement paste.
Values are of course not realistic but can be used to com-
pare the behaviour of both concretes. Fig. 12 shows that
tensile stresses resulting from the thermal expansion of
aggregates are more important in ordinary HSC than in
hematite HSC. The difference is proportional to the ratios
between the thermal conductivities of the aggregates
(almost identical and equal to 1.9 at 250 and 450~ The
elastic moduli of aggregates were found to interfere little
on the maximum orthoradial stresses.
The maximum orthoradial shrinkage stresses within
the cement paste obtained for both HSCs are given in
Fig. 13. Tensile stresses associated with shrinkage were
found almost identical for ordinary and hematite HSCs.
The small difference (less than 5%) can be associated
with the differences in the elastic moduli of the aggre-
gates. Combining thermal expansion of the aggregates
and shrinkage of the cement paste, the maximum ortho-
radial stresses in the cement paste are the sum of the
independent components resulting from each phenome-
non. Obviously, the magnitude of these interfacial
stresses are mainly related to the thermal expansion coef-
ficient of the aggregates and are therefore more impor-
tant for ordinary HSC than for hematite HSC. They
depend little on the magnitude of cement paste shrink-
age and on the elastic moduli of the aggregates. This
could therefore explain the higher damage of ordinary
HSCs probes with respect to hematite HSC, especially at
temperatures exceeding 250~
5. CONCLUSION
The main purpose of this study was to evaluate the
microstructural property changes of two high-strength
concretes only differing in their aggregates - silico-cal-
careous and hematite - submitted to high temperatures.
The study of pore structure through MIP investigation
showed that between 60 and 450~ the thermal treat-
ments were responsible for the generation of a large capil-
lary porosity for both HSCs. The intensity and especially
the width of the porosity peaks increased with tempera-
ture. The increase in capillary pore size was related to the
release of adsorbed water of capillary pores and of cement
paste hydrates bound water. Over 250~ and above all at
"-"co25 __Ordinary
HSC
il5~:
5~u)
~ 200c.
~10 . . . 50
500
Fig. 13 - Maximum orthoradial shrinkage stresses within the
cement paste.
450~ macropores - ranged globally from 50 to 0.3 gm
- were detected for ordinary HSC and correlated to
microcracks observed at the surface of heated probes.
Such damage was not observed for hematite HSC. On
the contrary, at high temperature, finer C-S-H porosity
seems to be reduced for both materials. Total water
porosity measurements and MIP investigations con-
firmed that, at 250~ and especially at 450~ ordinary
HSC porous space is much more degraded than that of
hematite HSC. Similar trends were observed with per-
meability data. Up to 250~ the intrinsic permeability
evolution is similar for both HSCs. Permeability increase
is related to water removal from the porous network, to
adsorbed water release and to cement hydrates dehydra-
tion. These phenomena contribute to the increase in cap-
illary pore size and to the generation of fine cracks. On
the contrary, data provided by heating tests at 450~
clearly showed that microcracks formation is the main
factor controlling the permeability evolution and that the
increase of capillary pore size is less influent. The differ-
ential behaviour of ordinary and hematite HSC was
attributed to the thermo-mechanical discrepancy related
mainly to structural thermal gradients and differential
expansion of the cement paste and the aggregates. Owing
to its reduced thermal expansion coefficient and
increased thermal conductivity, hematite is obviously
responsible for the limitation of thermal stresses during
heating. Thermo-mechanical phenomena in heated
HSCs are therefore of great importance for the prediction
of damage at high temperatures.
ACKNOWLEDGEMENT
The study was carried out in the framework of the
1LEPO research programme at the CEA Saclay. The
authors acknowledge G. Arcier and M. Pin for achieving
experimental tests.
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