Fig. 1.8. Simplified model of paste structure.
1.22
Solid dots represent gel particles; interstitial
spaces are gel pores; spaces such as
those marked C are capillary pores. Size of
gel pores is exaggerated
Because most of the products of hydration are
colloidal (the ratio of calcium silicate hydrates to
Ca(OH)2 being 7 : 2 by mass
1.60
) during hydration
the surface area of the solid phase increases
enormously, and a large amount of free water
becomes adsorbed on this surface. If no water
movement to or from the cement paste is permitted,
the reactions of hydration use up the water
until too little is left to saturate the solid surfaces,
and the relative humidity within the paste
decreases. This is known as
self-desiccation
. Because
gel can form only in water-filled space,
self-desiccation leads to a lower hydration compared
with a moist-cured paste. However, in selfdesiccated
pastes with water/cement ratios in excess
of 0.5, the amount of mixing water is sufficient
for hydration to proceed at the same rate as
when moist-cured.
Volume of products of hydration
The gross space available for the products of hydration
consists of the absolute volume of the dry
cement together with the volume of water added
to the mix. The small loss of water due to bleeding
and the contraction of the paste while still
plastic will be ignored at this stage. The water
bound chemically by C3S and C2S was shown to
132
be very approximately 24 and 21 per cent of the
mass of the two silicates, respectively. The corresponding
figures for C3A and C4AF are 40 and
37 per cent, respectively. The latter value is calculated
on the assumption that the final reaction
of hydration of C4AF is, in approximate terms,
C4AF + 2Ca(OH)2 + 10H → C3AH6 +
C3FH6.
As mentioned earlier, these figures are not accurate
because our knowledge of stoichiometry
of the products of hydration of cement is inadequate
to state the amounts of water combined
chemically. It is preferable, therefore, to consider
non-evaporable water as determined by a given
method (see p.
36
). This water, determined under
specified conditions,
1.48
is taken as 23 per cent of
the mass of anhydrous cement (although in Type
II cement the value may be as low as 18 per cent).
The specific gravity of the products of hydration
of cement is such that they occupy a greater
volume than the absolute volume of unhydrated
cement but smaller than the sum of volumes
of the dry cement and the non-evaporable water
by approximately 0.254 of the volume of the latter.
An average value of specific gravity of the
products of hydration (including pores in the
densest structure possible) in a saturated state is
2.16.
As an example, let us consider the hydration
of 100 g of cement. Taking the specific gravity of
dry cement as 3.15, the absolute volume of unhydrated
cement is 100/3.15 = 31.8 ml. The nonevaporable
water is, as we have said, about 23 per
cent of the mass of cement, i.e. 23 ml. The solid
products of hydration occupy a volume equal
to the sum of volumes of anhydrous cement and
water less 0.254 of the volume of non-evaporable
water, i.e.
31.8 + 0.23 × 100(1 – 0.254) = 48.9 ml.
Because the paste in this condition has a characteristic
porosity of about 28 per cent, the volume
of gel water,
wg
, is given by
133
whence
wg
= 19.0 ml, and the volume of hydrated
cement is 48.9 + 19.0 = 67.9 ml.
Summarizing, we have:
It should be noted that the hydration was assumed
to take place in a sealed test tube with
no water movement to or from the system. The
volumetric changes are shown in
Fig. 1.9
. The
‘decrease in volume’ of 5.9 ml represents the
empty capillary space distributed throughout the
hydrated cement paste.
134
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