International Centre for Mechanical Sciences (CISM)

Course on
Effect of Heat on Concrete
9-13 June 2003, Udine, Italy

Thermo-Hydral behaviour Khoury 5 - Moisture

Khoury, G. 1 and Majorana, C.2

1. Imperial College, London University, UK
2. Padua University, Italy

1. INTRODUCTION ......................................................................................................................... 1
2. ROLE OF WATER IN HEATED CONCRETE............................................................................ 1
3. TYPES OF FLUIDS IN CONCRETE ........................................................................................... 3
4. EFFECT OF HEATING ................................................................................................................ 6
4.1 Phase-change processes of heated water................................................................................. 6
5. TRANSPORT MECHANISMS................................................................................................... 14
5.2 Diffusion ............................................................................................................................... 14
Fick’s Law .................................................................................................................................... 14
5.3 Permeability .......................................................................................................................... 14
Darcy’s Law.................................................................................................................................. 14

1. INTRODUCTION

This chapter provides the basic principles of moisture in concrete and the experimental data of
moisture flow in heated concrete that lead to the theoretical treatments of later chapters.

2. ROLE OF WATER IN HEATED CONCRETE

There exists at least several reasons why the role of water (evaporable and chemically combined) is
important in heated concrete:

a) Properties: Water affects the properties of concrete (thermal and mechanical) at ambient
temperatures (e.g. Figure 1), and more so during heating in both the sealed and unsealed
conditions. In the sealed condition, water acts as a catalyst for increased hydration below 100oC
and for hydrothermal reactions at higher temperatures. In the unsealed condition, the main
influence of water is the loss first of evaporable water (e.g. influence on shrinkage, strength,
conductivity, thermal expansion etc.) and then the influence of the loss of chemically bound
water above 100oC on practically all the properties of concrete.
b) Spalling: The pore pressures that develop when water expands upon evaporating contributes to
explosive spalling. Even the chemically combined water could contribute to spalling when it is
released into a dense system. In this process the role of the permeability of concrete is crucial.
CISM - Effect of Heat on Concrete Moisture

c) Heat absorption: On the positive side, the latent heat absorbed by water upon evaporation in
this endothermic reaction helps retard the flow of heat into the concrete (similar benefits occur
when Ca(OH)2 dehydrates at about 400oC and also when CaCO3 dissociates at about 600-
700oC).
d) Radiation shielding: Also on the positive side, the presence of the light elements in water (e.g.
Hydrogen) contributes to the slowing down and capturing of nuclear radiation (e.g. thermal and
fast neutrons). This is important in its biological shielding role in nuclear reactors.
e) Role of water after cooling: Water also plays a role after cooling. On the positive side
hydration can take place of anhydrous cement compounds thus contributing to the “healing”
process, but on the negative side, the re-hydration of CaO is accompanied by a significant
increase in volume which is disruptive to the paste.

Essentially, these processes take place in the cement paste which is a fine colloidal structure of a high
specific surface area, and therefore very sensitive to the physically and chemically bound water at
both ambient and high temperatures. The C-S-H binds the cement paste together by means of primary
chemical bonds and secondary cohesive (van der Waals) forces. Although the cohesive forces of
attraction between surfaces are much weaker than the chemical bonds, the large surface area of C-S-H
(about 250 m2/g compared with 0.3 m2/g for the original dry cement) and the relative proximity of
those surfaces (few Angstroms apart) ensure that cohesive forces contribute significantly to the
strength of hcp (as much as 50% according to Wittmann). The cohesive forces are therefore dependent
on the dielectric properties of the medium (water, air etc.) between the interacting surfaces and are
diminished as water is adsorbed. Dehydration, whether by drying or heating, will therefore affect the
properties of hcp, partly through the influence on the cohesive forces. The formation of new chemical
bonds on drying is another important factor contributing, for example, to irreversible shrinkage.

Aggregates also contain pores in varying degrees, but these are usually larger, inert and
discontinuous. However, the water in the aggregates can contribute to the latent heat and spalling
effects in concrete, and also influences its thermal properties.

Figure 1. Effect of evaporable water on several properties of concrete [Browen & Blundell, 1972]

Khoury, G. & Majorana, C. 2

CISM - Effect of Heat on Concrete Moisture

3. TYPES OF FLUIDS IN CONCRETE

Concrete essentially contains two types of fluid: water in its various forms and “dry air”. The water in
hydrated cement paste is held in increasing degrees of firmness as follows:

a) Free water vapour in capillary and other large pores beyond the range of surface forces of the
solid phase.

b) Free liquid water in capillary (average size 1.3 µm) and other large pores beyond the range of
surface forces of the solid phase.

c) Water physically adsorbed onto the surface of gel particles in gel pores (18 Å).

d) Interlayer or zeolitic water held between the C-S-H surfaces.

e) Chemically bound water in the C-S-H and in the CH (which is part of the solid).

Table 1. Forms of fluids in concrete and their mathematical expression (Khoury and
Majorana, 2003).

Fluid in Solid Liquid Gas

gw Water vapour
ga Dry air
gwa Moist air ga+gw
w Free water
b Adsorbed water
cb-I Interlayer water
cb-C CSH water*
cb-CH CH water*
cb-CO2 CO2 in CaCO3*
tf Total fluid ga+gw+w+b+cb

* = Chemically bound fluids are released (shaded) at certain temperatures/pressures

Capillary water is described as free water whereas adsorbed and interlayer water are subject in various
degrees to surface forces of the solid phase. On heating cement paste water would be removed
approximately in the order listed above.

Cement paste is hygroscopic owing to the hydrophilic character of cement coupled with the presence
of sub-microscopic pores. The actual water content of the paste depends on the ambient humidity. In
particular, capillary pores, because of their comparatively large size, empty when the ambient relative
humidity falls below about 45 per cent but water is adsorbed in the gel pores even at very low ambient
humidities. Water was found to yield similar porosities to nitrogen if it is dried to 11% RH only. At
that level, Feldman and Sereda consider that most, if not all, of the interlayer water to be retained and
one monolayer of adsorbed water. Therefore, water in hydrated cement is held with varying degrees
of firmness as reflected by the shape of the desorption/adsorption isotherms.

Khoury, G. & Majorana, C. 3

CISM - Effect of Heat on Concrete Moisture

Figure 2. Probable structure of hydrated silicates [Feldman & Sereda, 1968]

It has become common to classify the pore structure on the basis of the physical state of the water in
the pores. Using IUPAC classification the pore system is divided into three categories:

(a) Micropores (<26Ådia.): in which water is under the influence of physical forces. Since according
to Powers, adsorbed water films are 5 molecules thick at saturation, it may be concluded that all water
in pores that are 26Å in diameter or less will be influenced by surface forces.

(b) Mesopores (26-500Å dia): in which at least part of the water will be free from surface forces and
in which water menisci can exist (Kelvin radius at 45% RH being 13Å). Capillary effects due to the
creation of menisci are primarily operative in the lower range of the mesopores since their magnitude
is inversely proportional to the pore radius. The physical adsorption methods employing water or
nitrogen have been traditionally used to determine the distribution of mesoporosity.

(c) Macropores (>500Å dia.): in which water is mostly free from surface forces and capillary effects
are negligible.

The micropores are also regarded as being part of the C-S-H structure into which nitrogen is unlikely
to penetrate. The meso- and macro-pores together can be described as the capillary pore component.
The pore structure can, therefore, also be divided into two regions using 26Å as the dividing line.
Recent studies, however, suggest that the pore structure of saturated paste is more open than
previously thought and that microporosity may only be created during drying.

There is no technique available for determining how water is distributed between these different
states, nor is it easy to predict these divisions from theoretical considerations as the energy of binding
of combined water in the hydrate is of the same order of magnitude as the energy of binding of the
adsorbed water. However, investigations using nuclear magnetic resonance suggest that gel water has
the same energy of binding as interlayer water in some swelling clays; thus the gel water may well be
in interlayer form.

A convenient, but rather arbitrary approach, is to divide water in hydrated cement into two categories:
evaporable and non-evaporable (Figure 3). The is the approach commonly adopted in high
temperature applications.

Khoury, G. & Majorana, C. 4

CISM - Effect of Heat on Concrete Moisture

Figure 3. Solid and fluid Constituents of concrete

Evaporable water is that which is driven out from the cement paste by drying to equilibrium (i.e. to a
constant mass) at 105 °C and atmospheric pressure. At ambient temperature and pressure, about 50%
by volume of saturated cement paste and between 2 to 10% by volume of saturated structural concrete
is occupied by evaporable water. However, it should be noted that some water of hydration is lost at
105oC from calcium sulphoaluminate and hexagonal tetracalcium aluminate hydrates. In fact,
4CaO.A12O3.19H2O is known to lose 6 moles of water just by drying at ambient temperatures below
85% RH. The classic model by Powers was criticized on account that drying of hcp at 105oC removes
bound and interlayer water, both considered part of the solid, and because the pore size distribution
was found to be continuous. Therefore, the distinction between ‘chemical’ and ‘non-chemical’ water
is approximate and somewhat arbitrary, and a clear separation of the water and solid phases is not
possible in practice.

Non-evaporable water is the water driven from cement paste when heated to temperatures above
105oC and generally contains nearly all chemically combined water in the C-S-H, all the water in the
Ca(OH)2,and also some water not held by chemical bonds. It takes 1,670 J/g to establish a bond of
non-evaporable water in the C-S-H while the energy of the water of crystallization of Ca(OH)2 is
3,560 J/g. Non-evaporable water has a vapour pressure lower than that of the ambient atmosphere and
the quantity of such water is, in fact, a continuous function of the ambient vapour pressure. The
amount of non-evaporable water increases as hydration proceeds but, in a saturated paste, non-
evaporable water can never become more than one-half of the total water present. In well-hydrated
cement, the non-evaporable water is about 18% by mass of the anhydrous material; this proportion
rises to about 23% in fully hydrated cement. It follows from the proportionality between the amount
of non-evaporable water and the solid volume of the cement paste that the former volume can be used
as a measure of the quantity of the cement gel present, i.e. of the degree of hydration.

Khoury, G. & Majorana, C. 5

CISM - Effect of Heat on Concrete Moisture

4. EFFECT OF HEATING

4.1 Phase-change processes of heated water

Water exists in different phases under different conditions. This paragraph describes the relation
between temperature and specific volume at a constant 1 atmospheric pressure throughout. At 20 °C
and 1 atm pressure water exists in the liquid phase (compressed liquid, or super-cooled liquid),
meaning that it is not about to vaporise. As the temperature rises, the liquid water expands slightly,
and so its specific volume increases. As more heat is transferred, the temperature will keep rising until
it reaches 100°C but water is still a liquid. Any additional heat will cause some of the liquid to
vaporise, meaning a phase-change process from liquid to vapour is about to take place. A liquid that is
about to vaporise is called saturated liquid water. Once boiling starts, the temperature will stop rising
until the liquid is completely vaporized accompanied by a large increase in the volume and a steady
decline in the liquid level as a result of more liquid turning to vapour. In this phase change state, the
mixture is called the saturated liquid water - water vapour mixture since the liquid and vapour phases
coexist in equilibrium at this state. As heat transfer is continued, the vaporisation process will
continue until the last drop of liquid is vaporised. Any heat loss from this vapour will cause some of
the vapour to condense (phase change from vapour to liquid). A vapour that is about to condense is
called dry saturated water vapour. Once the phase-change process is completed, water is back to a
single-phase region again (this time vapour), and further transfer of heat will result in an increase in
both the temperature and the specific volume. In this state, when for example the temperature of the
vapour is 300 °C, if some heat is lost from the vapour, the temperature may drop somewhat but no
condensation will take place as long as the temperature remains above 100 °C (atp = 1 atm). A vapour
that is not about to condense (i.e. not saturated vapour) is called superheated steam, or superheated
water vapour.

The temperature at which water starts boiling depends on pressure. Therefore, if the pressure is fixed,
so is the boiling temperature. Under atmospheric pressure, water boils at 100°C. However, if the
pressure is held at 1 MPa, water would start boiling at 179.9 °C. At a given pressure, the temperature
at which water changes phase is called the saturation temperature Tst Likewise, at a given
temperature, the pressure at which water changes phase is called saturation vapour pressure Psvp.
Saturation tables for water that list the saturation vapour pressure against the temperature are available
as steam tables (Table 2). During a phase-change process, pressure and temperature are obviously
dependent properties, and there is a definite relation between them, that is, Psvp = (Tst) as shown in
Figure 4.

Table 2. Relation between temperature, pressure and specific volume of water phases
from the steam tables.
Specific volume (10-3 m3 kg-1)
Temperature Psvp
(oC) (MPa) Saturated liquid water Dry saturated water vapour
vl vg
20 0.0023 1.002 57791
100 0.1013 1.043 1674
180 1.0019 1.127 194
200 1.5537 1.156 127
300 8.5831 1.404 22
374 22.0640 3.106 3.106

Khoury, G. & Majorana, C. 6

CISM - Effect of Heat on Concrete Moisture

The constant-pressure phase-change process described above is illustrated on a T-v diagram in Figure
5. The entire process is reversed by cooling (at the same pressure). At increasing constant pressures,
the process will follow a path similar to the process path at 1 atm pressure, but the water will start
boiling at a much higher temperature (179.9 °C at 1 MPa) and the specific volume of saturated liquid
water is larger and the specific volume of dry saturated water vapour is smaller than the corresponding
values at 1 atm pressure. That is, the horizontal line that connects the saturated liquid water and dry
saturated water vapour states is much shorter.

Figure 4. Relation between the saturation vapour pressure of water and temperature.

As the pressure is increased further, this saturation line will continue to get shorter and it will come to
a point when the pressure reaches 22.064 Mpa at 373.99oC - the critical point - when saturated liquid
water and dry saturated water vapour states are identical. The pressure, temperature and specific
volume at the critical point are called, respectively, the critical pressure, critical temperature and
critical specific volume. At pressures above the critical pressure, there will not be a distinct phase-
change process. Instead, the specific volume of water will continually increase, and at all times there
will be only one phase present. Above the critical state, there is no line that separates the compressed
liquid water region and the superheated steam region. However, it is customary to refer to the water as
superheated steam at temperatures above the critical temperature and as compressed liquid water at
temperatures below the critical temperature. The saturated liquid water states in Figure 5 can be
connected by a line called the saturated liquid water line, and dry saturated vapour states in the same
figure can be connected by another line, called the dry saturated water vapour line. These two lines
meet at the critical point, forming a dome as shown in Figure 6. All the compressed liquid water states
are located in the region to the left of the saturated liquid water line, called the compressed liquid
water region. All the superheated steam states are located to the right of the dry saturated vapour line,
called the superheated steam region. In these two regions, the water exists in a single phase, either a
liquid or a vapour. All the states that involve both phases in equilibrium are located under the dome,
called the saturated liquid water - water vapour mixture region.

Khoury, G. & Majorana, C. 7

CISM - Effect of Heat on Concrete Moisture

Figure 5. T-v diagram of constant-pressure phase-change processes of

water at various pressures (Cengel and Boles, 1998).

Figure 6. T-v diagram of water (Cengel and Boles, 1998).

Khoury, G. & Majorana, C. 8

CISM - Effect of Heat on Concrete Moisture

Figure 7. Degree and rate of desorption of evaporable moisture in an idealised approach

[Harmarthy, 1970].

Figure 8. Degree and rate of conversion of tobermorite Gel (CSH) in an idealized

cement paste [Harmarthy, 1970].

Khoury, G. & Majorana, C. 9

CISM - Effect of Heat on Concrete Moisture

Figure 9. Degree and rate of conversion of Ca(OH)2 in an idealized cement paste

[Harmarthy, 1970].

Figure 10. DTA of three cement pastes during heating in nitrogen at 10oC/min [Khoury, 1986]

Khoury, G. & Majorana, C. 10

CISM - Effect of Heat on Concrete Moisture

Figure 11. Weight loss against time of 4 HPC and 2 UHPC cylindrical specimens (100 dia x
50 mm) at 105oC [After, Alonso and Andrade, CSIC, 1999].

Figure 12. Schematic presentation of hydrothermal reaction between reactive silica (SiO2)
and calcium hydroxide crystals (Ca(OH)2) [Kotas, et. al. 1979]

Khoury, G. & Majorana, C. 11

CISM - Effect of Heat on Concrete Moisture

Figure 13. Effect of C/S ratio and temperature level on development of CSH hydration
products [Verbeck & Copeland, 1972].

Figure 14. Residual intrinsic permeability to water as influenced by temperature history and
moisture state [England & Khoury, 1992]. Note. These tests were performed at room
temperature after cooling and under “static thermal” conditions as opposed to “dynamic thermal”
testing during the heating up stage.

Khoury, G. & Majorana, C. 12

CISM - Effect of Heat on Concrete Moisture

Figure 15. Effect of temperature, water/cement ratio, and relative humidity on the diffusion
coefficient [Yuan et. al., 1972].

Figure 16. Schematic representation of the distributions of temperature, pore pressure and moisture
in normal and high performance concrete [Anderberg & Khoury, 2003].

Khoury, G. & Majorana, C. 13

CISM - Effect of Heat on Concrete Moisture

5. TRANSPORT MECHANISMS

5.2 Diffusion

Fick’s Law

When the transport of water, gas or vapour through concrete is the result of a concentration gradient,
and not of a pressure differential, diffusion takes place.

The diffusion equation applicable to water, vapour and dry air (and mixtures) follows Fick's first law
which can be expressed unidirectionally by:

dC
J = Dm (2)
dx

where C = concentration (kg/m3 or moles/m3) = m/V

m = mass (kg or moles)
V = volume (m3)
dC/dx = concentration gradient (kg/m4 or moles/m4)
Dm = mass diffusion coefficient (m2/s)
J = mass transport rate (kg/m2 s - or moles/m2 s)
x = distance (m)

Even though diffusion takes place only through the pores, the values of J and Dm refer to the cross-
section of the concrete sample; thus, Dm is, in reality, the effective mass diffusion coefficient.

The diffusion coefficient of a gas can be determined experimentally under a steady-state system, with
two sides of a concrete specimen being exposed, each to a different pure gas: the mass of the gases on
the side opposite to that where they were originally present is then determined. The pressure on each
side of the specimen should be the same because the driving force in diffusion is the difference in
molar concentration and not a pressure differential.

5.3 Permeability

Darcy’s Law

Fluid flow (water, vapour, dry air & mixtures) in capillary pores in concrete at room and at elevated
temperatures subjected to a pressure differential follows Darcy's law for fluid flow through a porous
medium, expressed unidirectionally by:

dm K Ad p
= (3)
dt g dx

where K = relative permeability coefficient (m/s)

m = mass (kg)
dm/dt = mass flow (kg/s)
dp/dx = pressure gradient (N/m3)
A = cross-sectional area (m2)

Khoury, G. & Majorana, C. 14

CISM - Effect of Heat on Concrete Moisture

g = acceleration due to gravity (m/s2)

K in this case is called the relative permeability coefficient in units of m/s which is dependent upon
the properties of the transported fluid.

In contrast, the coefficient K' represents the intrinsic (or absolute) permeability of the material, which
is supposed to be independent of the fluid involved and is expressed in units of m2:

µ
K′ = K
ρg

where K’ = Intrinsic permeability coefficient (m2)

µ = dynamic viscosity of the fluid (Nms/m3)
ρ = density of the fluid (kg/m3)
g = acceleration due to gravity (m/s2).

It should be noted that both µ and ρ are temperature and pressure dependent.

Because gases are compressible, the pressure, p0, at which the volume flow rate, q (in m3/s), is
measured, has to be taken into account, in addition to the inlet pressure, p, and outlet pressure, pa; all
pressures are absolute values in N/m2. The intrinsic permeability coefficient for a gas, K’, expressed
in m2, is:

2 q p0 L µ
K′ = (4)
(
A p 2 − p a2 )

where q = Volume flow rate (m3/s)

p0 = Pressure at which the volume flow rate q is measured (N/m2)
p = Inlet pressure (N/m2)
pa = Outlet pressure (N/m2)
A = cross-sectional area of the specimen in m2
L = its thickness (m)
µ = dynamic viscosity (Ns/m2).

Theoretically, the intrinsic permeability coefficient for a given concrete should be the same regardless
of whether a gas or a liquid is used in the tests. However, gases yield a higher value of the coefficient
because of the phenomenon of gas slippage; this means that, at the flow boundary, the gas has a finite
velocity. The difference between gas permeability and liquid permeability is larger at lower values of
the intrinsic permeability coefficient, the ratio of the former to the latter ranging from about 6 to
nearly 100.

Khoury, G. & Majorana, C. 15

CISM - Effect of Heat on Concrete Moisture

Figure 17. Phase diagram for waster in concrete at 887 days after heating for specimens of various
length heated on one unsealed faced at 125oC with water loss only from the cold face
[England & Khoury, 1992].

Figure 17. Variation of pore pressure with moisture loss from sealed basalt concrete specimen with
controlled release of moisture [England & Khoury, 1992].

Khoury, G. & Majorana, C. 16

CISM - Effect of Heat on Concrete Moisture

Figure 18. Effect of heating rate on the weight loss of a small initially moist basalt cylindrical
concrete specimen during the initial heating-up period compared with ultimate
weight loss as a function of temperature [Khoury, 2003].

Figure 19. Output of hydro-thermal-mechanical fully coupled model of concrete at high

temperatures [Schrefler, Khoury, Gawin, Majorana, 2002]

Khoury, G. & Majorana, C. 17

CISM - Effect of Heat on Concrete Moisture

Relative Humidity [Unsealed]

30 sec
100
60 sec
90 sec
90
120 sec

80 150 sec
180 sec
70 210 sec
240 sec
60
300 sec
RH [%]

50 360 sec
420 sec
40 480 sec
540 sec
30
600 sec

20

10

0
0 0.5 1 1.5 2 2.5 3
Distance [cm]

Figure 20. Calculated relative humidity versus distance at different times from the start of an ISO
fire at distance 0 of a C30 unsealed concrete wall (initial conditions 60% saturation,
80% RH) (Majorana, Pesavento and Khoury, 2003)

Relative Humidity [Sealed]

100
30 sec
90
60 sec

80 90 sec

120 sec
70
150 sec

60 180 sec
RH [%]

210 sec
50
240 sec
40
300 sec

30 360 sec

420 sec
20
480 sec
10 540 sec

600 sec
0
0 0.5 1 1.5 2 2.5 3
Distance [cm]

Figure 21. Calculated relative humidity versus distance at different times from the start of an
ISO fire at distance 0 of a C30 sealed concrete wall (initial conditions 60%
saturation, 80% RH) (Majorana, Pesavento and Khoury, 2003).

Khoury, G. & Majorana, C. 18

CISM - Effect of Heat on Concrete Moisture

Vapour Pressure [Unsealed]

0.9

30 sec
0.8
60 sec
90 sec
0.7
120 sec
Vapour Pressure [MPa]

0.6 150 sec

180 sec

0.5 210 sec

240 sec
0.4 300 sec
360 sec
0.3 420 sec
480 sec
0.2 540 sec
600 sec
0.1

0
0 0.5 1 1.5 2 2.5 3
Distance [cm]

Figure 22. Calculated vapour pressure versus distance at different times from the start of an ISO
fire at distance 0 of a C30 unsealed concrete wall (initial conditions 60% saturation, 80%
RH) (Majorana, Pesavento and Khoury, 2003).

Vapour Pressure [Sealed]

5.00E+00

4.50E+00

30 sec
4.00E+00
60 sec
90 sec
3.50E+00
120 sec
Vapour Pressure [MPa]

3.00E+00 150 sec

180 sec

2.50E+00 210 sec

240 sec
2.00E+00 300 sec
360 sec
1.50E+00 420 sec
480 sec
1.00E+00 540 sec
600 sec
5.00E-01

0.00E+00
0 0.5 1 1.5 2 2.5 3
Distance [cm]

Figure 23. Calculated vapour pressure versus distance at different times from the start of an ISO
fire at distance 0 of a C30 sealed concrete wall (initial conditions 60% saturation, 80%
RH) (Majorana, Pesavento and Khoury, 2003).

Khoury, G. & Majorana, C. 19