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Magazine of Concrete Research, 1995, 47, No. 172. Sept.

, 203-208

Specific heat and thermal diffusivity of J

hardening concrete
G. De Schutter* and L. Taerwe*

This paper focuses on the er’olution of the thermal 0 temperature

characteristics of ear!\-age concrete as a function of the 0” initial temperature of concrete (diffusivity test)
state of the hardening process. A literature review is X thermal conductivity of hardening concrete
presented, together bvith neM‘ test results obtained b) p density of concrete
means of impro\.ed test methods.. For the determination
oj.the specific heat of cement paste during hardening and
of the thermal di’sivio of hardening concrete, test
methods are de\,eloped based on existing methods. The At the University of Ghent, several research
speci$c heat is determined for hardening cement paste programmes have been executed concerning massive
samples made rcith blastfirnace slug cement. It is concrete armour units used for breakwaters. In particular,
concluded that the speci$c heat and thermal diffusivit) cracking due to thermal stresses caused by the heat of
decreases linearly rcith the degree of hydration. hydration, and impact resistance were studied. I-3 Due to
these thermal stresses external as well as internal crack
formation can occur during hardening. Wave loads can
Notation stimulate crack growth. Thus, service life can be reduced
a thermal diffusivity of hardening concrete markedly by thermal cracks. A thorough knowledge of
1‘ specific heat of hardening concrete the thermal stresses and crack formation is necessary in
(‘0 specific heat of hardened concrete order to evaluate their influence on durability. At the
(‘4 specific heat of aggregates University of Ghent a finite element program for the
1’.i specific heat of cement prediction of thermal stresses due to the heat of hydration
c,.~ fictitious specific heat of hydrated part of cement in massive concrete elements is being developed, taking
1 P specific heat of cement paste account of state-dependent properties of the hardening
(‘u specific heat of water concrete. This contribution focuses on the evolution of
E, energy supply in the absence of the cement paste the thermal characteristics of early-age concrete, as a
E2 energy supply in the presence of the cement paste function of the state of the hardening process. A literature
G, amount by weight of aggregate review is presented, together with new test results obtained
G, amount by weight of cement by means of improved test methods.
G, amount by weight of water
mp mass of the cement paste sample
r degree of hydration Specific heat of hardening concrete
18 initial temperature difference between concrete and Literature review
waterbath (diffusivity test) According to a 1982 state-of-the-art report,4 published
Ad, temperature increase due to E, data on the thermal characteristics of hardening concrete
.1& temperature increase due to E2 appear to be scarce. The available results dealing with
the evolution of specific heat during hardening are now
* Magnel Laboratory for Concrete Research, University of Ghent, summarized chronologically.
Belgium. In 1946, LGfquist4 found a minor decrease of the
Paper accepted 28 June 1994. specific heat of cement mortar during hardening - from
De Schutter and Taetwe

1~18kJ/kgperKatanageof3daysto1~16kJ/kgper converted, in an indicative way, towards values for a

K at 10 days. In 1970, Brown and Javaid’ determined a conventional gravel concrete consisting of 300 kg cement,
more fundamental decrease. They stated that the specific 150 kg water, 670 kg sand and 1280 kg gravel, the
heat of hardening concrete decreases linearly with time decreases summarized in Table 1 are found.
by about 20%. Martchal, 6.7 in 1972 and 1973, found
only minor fluctuations of the specific heat during Determination of the speci$c heat of hardening
hardening. The linear decline with time found by Brown cement paste
and Javaid was refuted in 1982 by Reinhardt et aI. who, Test merhod As mentioned above, Hansen et a1.9
for hardening concrete, proposed a linear function of the proposed a test method for the determination of the
degree of hydration also with a reduction of 20% specific heat of hardening cement paste which is very
similar to the traditional methods. The specific heat is
c = ~(1.25 - 0.2%) (1) determined by measuring the temperature rise in a
where c is the specific heat of the hardening concrete, calorimeter caused by a certain energy supply. The first
c0 is the specific heat of the hardened concrete and r is measurement is taken in the absence of the cement paste
the degree of hydration. and serves as a calibration of the calorimeter. A known
However, Reinhardt et al. do not give the origin of this energy supply E, causes a temperature increase Af?,. A
relation. In 1982 a test method for the specific heat during second measurement takes place in the presence of the
hardening, taking account of the hydrational heat cement paste, leading to a temperature increase A02
production, was described by Hansen et a1.9 For cement caused by an energy supply Ez. It can be proved that the
paste they found a decline from 1.92 Id/kg per K at 1.5 specific heat of the cement paste cP is given by
to 1.65 kJ/kg per K at 120 h. The decline was found to
be linear with the logarithm of time, which for common (3)
cement types is very similar to a linear decline with degree
of hydration. In his 1988 research on thermal stresses in where cp is the specific heat of the cement paste. jnp is
hardening concrete, Hamfler,” like many others, the mass of the cement paste sample, E? and E, are the
neglected any fluctuations of the specific heat during energy supplies with and without the paste sample
hardening. In 1991, Van Breugel” postulated a linear respectively, and A& and A8, are the temperature rises
decrease with degree of hydration, based on the fictitious with and without the paste sample respectively.
specific heat of the hydrated cement At the Magnel Laboratory this principle was used in
order to study the evolution of specific heat as a function
c = 1 [G,qr + G,(l - r ) + G,c, + G,c,] ( 2 ) of the degree of hydration. Fig. 1 shows the test
P equipment. The calorimeter is placed in a thermostatic
where G,, G,, G, are the amounts by weight of cement, waterbath and is partly filled with heptane. Heptane is used
aggregate and water, cc, c,, c, are the specific heats of instead of water because of its lower specific heat ( f 2 100
cement, aggregate and water, and cCf is the fictitious J/kg per K). This enables a more accurate determination
specific heat of the hydrated part of cement. This implies of the specific heat of the paste sample. The energy E,
that or Ez is supplied by means of a known electrical
resistance. The effect of the heat of hydration is taken into
ccc = 0.008419 + 0.339 &J/kg per K) (3) account implicitly by determining the temperature rise
where 8 is the actual temperature of the sample. A& as shown in Fig. 2. The temperature history in the
Almost every author in the literature review reported calorimeter is recorded during a sufficiently long period
a decrease of the specific heat during hardening, while before and after the supply of energy. The slope of the
nobody found an increase. However, there seems to be linear parts of the curves before and after the supply of
no agreement concerning the magnitude of the decrease. energy is determined by two effects, namely the heat
It is significant that some researchers published data exchange with the surrounding waterbath and the heat
obtained on concrete specimens, while others tested production due to hydration. The temperature rise A& is
cement paste or mortar. When all the results are determined by the intersection points A and B of the

Tuble I. Evolution of thermal characteristics of concrete during hurdening

Ref. 4 Ref. 5 Refs 6, 7 Ref. 8 Ref. 9 Ref. I I The present


Specific heat c -1% -20% Constant -20% -5% -4% - 13%

Thermal Constant - 15% Maximum at +12% -9%
diffusivity a 50 h (paste)
Thermal -30% Maximum at -50% -21%
conductivity X 50 h

204 Magazine of Concrete Research. 1995. 47. No. 172

Thermal properties of hardening concrete


Fig. I Calorimeter



0 2 4 6 a 10 12 14 16
Time. mln

Fig. 2. Determination of the temperature rise AtI

extrapolation of the linear parts with the almost vertical with degree of hydration holds quite well. Linear
part of the recorded temperature history. The temperature regression yields
peak immediately after the supply of energy is due to the
fact that a certain time is needed to reach thermal c&r) = 1300(1 a5 - 0.5r) (J/kg per K) (5)
equilibrium between the cement paste and the heptane.
Test results The tests were carried out on a cement For the fresh cement paste (r = 0) this yields cP =
paste with water-cement ratio (w/c) of 0.5, using 1950 J/kg per K, which coincides very well with the value
blastfurnace slag cement CEM III/C 32.5. In order to CP
= 1954 J/kg per K obtained by applying a
obtain the evolution of the specific heat during hardening, superposition rule on a cement paste with w/c = 0.5 and
cement paste samples were tested at ages ranging from specific heats of the cement and water of 857 and
1 day to 7 days. The corresponding degree of hydration 4187 J/kg per K.
was calculated as the fraction of heat released, using a Equation (5), valid for cement paste, can be converted
newly developed hydration model.2 Until testing, the into an expression for the conventional gravel concrete
cement paste samples were stored at 20°C and 95% mentioned above:
relative humidity.
The test results are shown in Fig. 3. A linear decrease c(r) = 1000 (l-5 - 0.15r) (J/kg per K)
Maga:ine of Concrete Research, 1995, 47, NO. 172 205
De Schutter and Taerwe


” 0

0 0.1 02 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Degree of hydration r

Fig. 3. Specific heat of hardening cement paste CEM III/C 32.5: test results

This result shows a decrease of the specific heat of diffusivity during hardening according to the various
concrete during hardening of about 13 % . researchers is summarized in Table 1. The values are for
tests on concrete, unless otherwise stated.
Considering the conversion of free water into Determination of the thermal di@siviQ of hardening
chemically bound water, a decrease of the specific heat concrete
during hardening of concrete was to be expected. The Test method For thermal diffusivity measurements.
decrease obtained of about 13% is more or less an experimental non-stationary method was devised b>
intermediate in terms of the literature results (Table 1). MarCcha16*’ and by Hansen et a1.9 In this method a
The differences in Table 1 might be explained by different cylindrical specimen at temperature 19~ is sudden11
test circumstances, e.g. paste, cement or concrete; w/c; immersed in a waterbath at temperature B0 + A8. The
cement type; aggregate type; humidity. temperature O(t) at the cylinder axis is measured as a
function of time. The thermal diffusivity a can then be
calculated by fitting the experimental results to a
Thermal diffusivity of hardening concrete theoretical expression based on a Bessel function of the
Literature review first kind of order zero.’ This fitting is done by computer
While for specific heat there is some fundamental calculations. To avoid these difficult calculations another
agreement between the various researchers, literature data fitting approach can be applied. When log[(& + A8 -
on the thermal diffusivity of hardening concrete do not 0(t))lA0] is plotted as a function of time. the curve
seem to be coherent. Constant values during hardening becomes linear after some time, as shown in Fig. 4. The
are reported as well as increasing and decreasing slope of the experimental line thus obtained is directly
tendencies. In 1946, Liifquist4 reported a constant related to the thermal diffusivity.
diffusivity for concretes with different compositions. For Hansen proposed a At? of 2 K. It can be shown’ bq
example, a concrete with 350 kg cement and w/c = 0.5 numerical simulation that for concrete specimens the heat
had a constant thermal diffusivity a = 0.0037 m2/h for of hydration then influences the results adversely. In the
ages ranging from 1 to 7 days. case of cement paste, as for example in Hansen’s test.
Brown and Javaid’ also published test results for the the influence of the heat of hydration is expected to be
period ranging from 1 to 7 days. For hardening concrete, even worse. Less influence is noticed when A8 = 5 K
they found a decrease from 0.0034 m2/h at 1 day to or even 10 K.
0.0029 m2/h at 7 days. MarCcha16x7 postulated that the Test results The thermal diffusivity of hardening
thermal,diffusivity reaches a maximum at an age of about concrete was determined on sealed cylindrical concrete
50 h. His test results are based on concrete with rapid specimens of diameter 100 mm, made with concrete
hardening Portland cement, using a very simple test having the following composition per m3: 300 kg
procedure (see below). By means of the same test method, blastfumace slag cement CEM III/C 32 .5, 150 kg water,
Hansen et a1.9 found an increase of the thermal 670 kg sand, 1280 kg gravel. The cylinders are
diffusivity of hardening cement pate from about 0 *85 to permanently stored at 20°C. During the test A0 = 10 K
about 1.05 m2/1000 h. The evolution of the thermal is applied. Tests were carried out at ages ranging from
206 Magazine of Concrete Research, 1995. 47. No. 172
Thermal properties of hardening concrete

0 15 0.2 0.25 0.3 0.35 0.4
Time h

Fi~y. 4. Temprruture histo? nr qlinder crris during LI diffusirlity test


c 0.2 0.4 0.6 08 1
Degree ot hydration r

Fi,q. 5. Thermal\iry of hardening conc’refe CEM III/C 32.5: test results

day to 14 days. Fig. 4 shows the recorded temperature Physically a decrease is expected because of a decrease
history at the cylinder axis during a diffusivity test at an in free water and an increase in porosity due to hydration.
age of 3 days. As mentioned above, the heat production of the cement
The values obtained for the thermal difhsivity of paste might have influenced Hansen’s test results. The
hardening concrete are shown in Fig. 5 as a function of initial increase found by MarCchal, however, is not likely
the degree of hydration r. It can be concluded that a linear to have been caused by the heat of hydration effect.
relation agrees very well with the test results. Linear Mar&ha1 used very small cylinders (diameter 72 mm) and
regression leads to low test temperatures (0°C) combined with a A0 of 10 K.
However, he tested concrete with 350 or 500 kg rapid
a(r) = 4 x 10p3(1. 10 - O.lOr) (m’/h) (6)
hardening Portland cement.
For the thermal diffusivity, there is no mixing rule for Indications for the evolution of the thermal diffusivity
the conversion of concrete data into paste data or vice during hardening can also be obtained via a combination
versa. of specific heat and thermal conductivity:

Discussion a = h- (7)
Based on the diffusivity tests on hardening concrete,
a decrease during hardening of about 9% is found. In where h is thermal conductivity and p is the density of
Table 1 this value is compared with literature results. Why the concrete (= constant).
Hansen reports an increase (on cement paste) is not clear. Table 1 gives values for the evolution of the thermal
Magazine of Concrere Research. 1995. 41. No. 172 207
De Schutter and Taenve

conductivity of concrete according to several researchers. Differentiation of equation (9) and the introduction of
Brown and Javaid’ determined the conductivity equation (12) yield
experimentally, and found a decrease of about 30%.
dQ(t) = q[r(f), W)ldt (13)
Reinhardt et al.’ postulated a decrease of 50%, but dr(t) = ~
without showing how this figure is derived. As the Qm Q max
conductivity seems to decrease more than the specific heat, Hence, the value of r can be updated by substituting
a decrease in the diffusivity is expected. equation (13) in
r(t + df) = r ( t ) + dr(t) (14)
In this way the age of a specimen continuously stored at
1. For the determination of the specific heat of cement 20°C can be transformed into the corresponding degree
paste during hardening, a test method was developed of hydration. For more details on the hydration model
based on the method of Hansen et al.9 q[r(t), B(r)], which is to be determined experimentally.
2. The specific heat was determined on hardening see Ref. 2.
cement paste samples made with blastfurnace slag cement
CEM III/C 32 -5. It was concluded that the specific heat Acknowledgements
decreases linearly with the degree of hydration.
3. For the determination of the thermal diffusivity of This research project is partly financed by the Flemish
concrete during hardening, a test method was developed Ministry of Public Works. The first author is research
based on the method of MarCcha16,’ and Hansen et a1.9 assistant of the Belgian National Fund for Scientific
4. By means of tests on hardening concrete cylinders Research (NFWO), which also finances this research
it was concluded that the thermal diffusivity decreases project. These financial supports are greatly appreciated.
linearly with increasing degree of hydration.
Appendix. Calculation of the degree of 1. VAN DAMME L. er al. Quality and durabihty of concrete armour
hydration units. Proc. 2/sr Coastal Engirwriyg Conf. 3. chapter 156.
American Society of Civil Engineers. New York. 1988. pp.
The degree of hydration r(r) of a hardening 2102-211s
cementitious material is defined as the fraction of cement 2. DE SCHUTER G. rr crl. Experiment based predictIon of thermal
that has already hydrated: characteristics of hardening concrete I+?\.\. Z. Hochvch .W-hrr.
Baw~es. Weirnar. 1992. 3-5. 117-125.
amount of cement that has reacted at time t 3. DECHAENE R. er (I/. Thermal cracking m hardemng concrete
r(r) = armour units. Perm. Inr. Assoc. Na\.ig. Congr. Bull.. 1991. 82.
total amount of cement at time t = 0
(8) 4. RILEM COMMISSION 42.CEA. Propertws of set concrete at sari!
A practical method to estimate the degree of hydration ages. Marer. Consrrucr.. 1982. 14. 399-450.
5. BROWN T. D. and JAVAID M. Y. The thermal conductI\ It! of
is based on the exothermic character of the hydration fresh concrete Murrr. Construer., 1970. 3. 11 l-116.
process: 6. MAR!?CHAL J. -C. D&ermmation Gmultanee de la dlffusl\ ItP et

r(t) = ecr, (9)

de la conductiritC thermique du b&on pendant \on h!dratatmn.
Essurs Mes.. 1973. 306. 95-96
Q”MX 7. MAR&HAL J -C. DPretminarion simu/ranPe de ICI d[fusiuri et de
la conducrivirc’ rhermique du b&on pendanr .son h~drarariotl
where Q(r) is the total heat developed at time t (in Jig) R&m~on CIB W40. Holzkirchen. 1972.
and Qmax is the total heat development corresponding to 8. REINHARD~ H. -W. ef al. Temperature development in concrete
complete hydration (in J/g). structures takmg account of state dependent propsrues. Prw.
The total heat Q(f) can be calculated as RILEM Inr. Conf O,I Concrere a: Earl! Age\. Parts. 1982. pp
9. HANSEN P. F. er al. Thermal properties of hardening cement
paste. Proc. RlLEM Int. Conf: on Concrere ar Early Ages, Parts.
(10) 1982. pp. 23-36.
10. HAMFLER H. Berechnung wn Temperaruur-. Feuchre-. told
where q(r) is the heat production (in J/g per h). Verschiebungsfeldern i n erhdrrenden Beronbaureiletr nach der
In Ref. 2 a new hydration model is developed, yielding Merhode derjniren Nernenre. Deutscher Ausschus hir Stahlbeton.
a heat production q depending on the actual degree of Beuth Verlag. Berlin, 1988.
hydration r(t) and the actual temperature f?(r) 11. VAN BREUCEL K. Simulation hxdrarion and fif~rmarron oj
structure in hardening cement-based marerrals. PhD thesis. TU

q(r) = qP01, W>l (11) Delft, 1991.

From equations (10) and (11) it follows that at time t

___ = q(t) = q[r(t), O(t)] (12) Discussion contributions on this paper should reach the editor b!
df 29 March 1996

208 Magazine of Concrete Research. 1995. 47. No. 172