PLAIN & REINFORCED

CEMENT -1
PBL ACTIVITY-1
 Describe stages takes place during heat of hydration
of cement w.r.t time

Heat of Hydration
The heat of hydration is the heat generated when water and portland cement react. Heat of hydration is
most influenced by the proportion of C3S and C3A in the cement, but is also influenced by water-cement
ratio, fineness and curing temperature. As each one of these factors is increased, heat of hydration
increases.

Effects of Heat of hydration.

If the heat of hydration is not properly controlled, especially if it is in a large slab or structure, the heat
cannot escape easily. The heat of hydration can create very high internal temperatures in the structure.
This is particularly true during construction in hot weather, if a large amount of concrete is poured quickly,
or if there is a very high cement to water ratio.
If the heat of hydration is not managed during construction, it can cause expansion while the cement is
hardening and curing. A significant amount of heat, especially when combined with artificial or weather-
related cooling during the curing process, can create significant cracks. The expansion and contraction of
the concrete, along with the resulting cracks, can result in serious issues with the structural integrity of the
concrete.
In large mass concrete structures such as gravity dams, hydration heat is produced significantly faster than
it can be dissipated (especially in the center of large concrete masses), which can create high temperatures
in the center of these large concrete masses that, in turn, may cause undesirable stresses as the concrete
cools to ambient temperature. Conversely, the heat of hydration can help maintain
favorable curing temperatures during winter.
Cement Hydration
The reactions involved when cement is mixed with water are complex. It is important to understand these
reactions or the cementing operation may not be successful.
Stages of Cement Hydration process
Each phase hydrates by a different reaction mechanism and at
different rates (Fig. 1). The reactions, however, are not independent
of each other because of the composite nature of the cement
particle and proximity of the phases.In all, five distinct stages have
been identified:

 Stage 1: Pre-induction
 Stage 2: “Dormant” (induction) period
 Stage 3: Acceleration
 Stage 4: Deceleration
 Stage 5: Steady state Fig. 1—Schematic of cement-hydration reactions
In cementing operations, the most important of these are Stages 1 through 3. Stage 1 dictates the
initial mixability of the cement, and is attributed primarily to the aluminate and ferrite phase reactions.
Stage 2 relates to the pumpability time, while Stage 3 gives an indication on setting properties and
gel-strength development
Hydration of cement phase: Although the basic reaction mechanisms and theories on the
hydration of the pure phases pertain to the phases in
cement, there are some significant differences. A
schematic of the initial hydration reactions up to the
time of set is illustrated in Fig. 2.

Alkalis
The alkalis, primarily sodium and potassium, are
impurities that arise from shales, clays, or the fuel used
in the manufacture of the cement. Although present in
small amounts, < 1%, they have a significant effect on
the hydration. Typically, they are present as sulfates, in
the form of K2SO4 , Na2SO4, Na2SO4•3K2O
(aphthitalite), and/or 2CaSO4•K2SO4 (calcium
langbeinite), and they are usually deposited on the
surface of the cement particles. The alkali sulfates
dissolve almost immediately on contact with water, and
alkalis can also be present as impurities in the cement
phases, with sodium preferentially in the aluminate
(C3A) phase and potassium more widely distributed in
both calcium and aluminate phases. API Spec. 10A for
Class G and H cements limits the alkali to 0.75% as
Na2O4 to allow adequate thickening times to be
achieved downhole.
Fig. 2—Cement hydration from mixing to setting
In cements high in K2SO4, reaction between K2SO4 and gypsum in the presence of water can produce
syngenite, . This can cause lumpiness on storage of the dry cement powder under high-
humidity conditions (> 90% relative humidity) because the acts as an effective binder to the
dry cement particles. Precipitation of during cement hydration can cause false or even flash
setting.
Calcium sulfates
Gypsum is added to the cement primarily to retard the hydration of the
aluminate and ferrite phases. The effectiveness of the gypsum depends on the rate at which the
relevant ionic species dissolve and come in contact with each other. Thus, interground gypsum is far
more effective than interblending the same proportion because intergrinding brings the gypsum
particles into closer contact with the cement particles and produces a shorter diffusion distance
between the two. Temperature and humidity in the grinding mill can cause the gypsum to dehydrate,
resulting in the formation of hemihydrate and/or soluble anhydrite . Hemihydrate or
soluble anhydrite can rehydrate to give “secondary” gypsum, causing a rapid set, known as “false
set.” Pumpability can be regained on further mixing or addition of water, assuming the quantity of
secondary gypsum is not too great.
The reactivity and performance of cement is a culmination of the effect of the different impurities on
the number of defects and morphology of the crystal structure of the different phases. This is why
cement can vary not only from one source to another, but also between batches from the same
source.

The progress of hydration of cement can be determined by different means:

 The measurement of the amount of Ca(OH)2 in the paste resulted from the
 hydration of the silicates.
 The heat evolved by hydration.
 The specific gravity of the paste.
 The amount of chemically combined water.
 The amount of unhydrated cement present (using X-ray quantitative analysis).
 Also indirectly from the strength of the hydrated paste.
Tests for Heat of Hydration Two methods of determining the heat of hydration are
commonly used. ASTM C 186, Standard Test Method for Heat of Hydration of Hydraulic
Cement, uses a heat of solution procedure. In this test, a sample is dissolved in an acid solution
inside a well-insulated container and the temperature rise is recorded. After correction for the dry
cement heat of solution and the heat capacity of the container, the heat of hydration for the
desired hydrating period can be calculated. Samples can be hydrated any length of time with this
technique. The other common method is conduction calorimetry. In this nonstandard procedure,
a sample of cement is placed in a conductive container and kept at a specific temperature (for
example, by a thermoelectric device). Water is added and the energy required to maintain the
sample temperature is continuously recorded. By integration, the heat of hydration at any time
can be obtained; however, the length of the test is usually limited to 3 days as the rate of heat
evolution becomes too low to measure beyond that time period.
Heat of Hydration of cement with time:
 The rate of hydration decreases continuously.
 The size of unhydrated cement particles decrease. For instance, after 28 days in contact with water,
grains of cement have been found to have hydrated to a depth of only 4 μm, and 8 μm after a year.
 This is due to:
1. Accumulation of hydration products around the unhydrated cement grains
2. which lead to prevent water from channeling to them.
3. Reduction of the amount of water either due to chemical reaction or
4. evaporation.
5. Reduction of the amount of cement due to reaction.
During normal concrete construction, the heat is dissipated into the soil or the air and resulting
temperature changes within the structure are not significant. However, in some situations,
particularly in massive structures, such as dams, mat foundations, or any element more than
about a meter or yard thick, the heat can not be readily released. The mass concrete may then
attain high internal temperatures, especially during hot weather construction, or if high cement
contents are used. Fig.1 demonstrates the effect of element size on concrete temperature with
time due to the heat of hydration. Temperature rises of 55°C (100°F) have been observed with
high cement content mixes.(2) These temperature rises cause expansion while the concrete is
 hardening. If the temperature rise is significantly high and the concrete undergoes non uniform
or rapid cooling, stresses due to thermal contraction in conjunction with structural restraint can
result in cracking before or after the concrete eventually cools to the surrounding temperature.
Contractors often insulate massive elements to control temperature changes. As a rule of thumb,
the maximum temperature differential between the interior and exterior concrete should not
exceed. 20°C (36°F) to avoid crack development.(3) The potential for thermal cracking is
dependent on the concrete’s tensile strength, coefficient of thermal expansion, temperature
difference within the concrete, and restraint on the member. Concrete placed in cold conditions
benefits from
the heat

generated by cement hydration, helping protect it from freezing and providing a more favorable
curing temperature. Adding insulation to the formwork helps trap the heat in the concrete,
allowing it to achieve the required strength.
Heat of Hydration of Portland Cements
Heat of Hydration of Portland Cements The heat of hydration of cement is usually determined in
accordance with ASTM C 186, Standard Test Method for Heat of Hydration of Hydraulic Cement (see
box). Table 1 has heat of hydration values for a variety of portland cements from 1992 to 1996. Although
this data is very limited, it confirms the general trends expected:
Type III cement has higher heat of hydration than other cement types (average = 88.5 cal/g at 7 days)
and Type IV has the lowest (average = 55.7 cal/g at 7 days). Portland cement evolves heat for a long
time.(4) Reference 4 and Fig. 2 present heat of hydration data out to 13 years. Fig. 2 shows that the rate
of heat generation is greatest at early ages. Usually, the greatest rate of heat liberation occurs within
the first 24 hours and a large amount of heat evolves within the first 3 days. For most concrete
elements, such as pavements, long-term heat generation is not a concern as this heat is dissipated into
the environment.