Fig. 1.21. Relation between 7-day strength of
cement paste and the C3S content in cement.
1.37
Each mark represents cement from
one plant
An extensive review by Odler
1.79
has shown,
moreover, that a generally applicable strength
prediction equation for commercial cements is
not possible for several reasons. These are: the interaction
between the compounds; the influence
of the alkalis and of gypsum; and the influence of
the particle size distribution of the cement. The
presence of glass, which does not contain all the
compounds in the same proportions as the rest of
the clinker, but which affects reactivity, as well as
the amount of free lime, are also factors varying
between cements with nominally the same composition
of the four main compounds.
Attempts
1.93
have been made to generate
strength prediction equations for mortar on the
basis of parameters which include, in addition to
the main compound composition, terms for SO3,
CaO, MgO and the water/cement ratio, but the reliability
of prediction is marginal.
From the foregoing, we can conclude that the
relations between strength and compound composition
of Portland cements in general which
have been observed are stochastic in nature. Deviations
from these relations arise from the fact
that they ignore some of the variables involved.
1.14
It can be argued, in any case, that all
constituents of hydrated Portland cement contribute
in some measure to strength in so far as all
products of hydration fill space and thus reduce
porosity.
Furthermore, there are some indications that
the additive behaviour cannot be fully realized.
In particular, Powers
1.22
suggested that the same
products are formed at all stages of hydration of
the cement paste; this follows from the fact that,
for a given cement, the surface area of hydrated
cement is proportional to the amount of water of
hydration, whatever the water/cement ratio and
age. Thus the fractional rates of hydration of all
compounds in a given cement would be the same.
162
This is probably the case only after the rate of
diffusion through the gel coating has become the
rate-determining factor, but not at early ages,
1.65
say up to 7 days.
1.49
Confirmation of equal fractional
rate of hydration was obtained by Khalil
and Ward,
1.70
but we now accept that early hydration
of the different compounds proceeds at different
rates; later on, the rates become equal.
There is another factor influencing the rate of
hydration: the fact that the composition is not the
same at different points in space. This arises from
the fact that, for diffusion to take place from the
face of the still unhydrated part of the cement
grain to the space outside (see p.
13
), there must
be a difference in ion concentration: the space
outside is saturated but that inside is supersaturated.
This diffusion varies the rate of hydration.
It is likely, therefore, that neither the suggestion
of equal fractional rates of hydration, nor
the assumption that each compound hydrates at
a rate independent of other compounds, is valid.
Indeed, we have to admit that our understanding
of the hydration rates is still unsatisfactory.
For instance, the amount of heat of hydration
per unit mass of hydrated material has been found
to be constant at all ages
1.34
(see
Fig. 1.22
), thus
suggesting that the nature of the products of hydration
does not vary with time. It is therefore
reasonable to use the assumption of equal fractional
rates of hydration within the limited range
of composition of ordinary and rapid-hardening
Portland cements. However, other cements which
have a higher C2S content than ordinary cement
or rapid-hardening cement do not conform to this
behaviour. Measurements of heat of hydration indicate
that C3S hydrates earlier, and some C2S is
left to hydrate later.
163
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