UNDERSTANDING CEMENT

WORKABILITY,HUDRATION, WATER DEMAND -&

SETTING TIME
Workability is the ease by which fresh concrete can be mixed, transported, placed,
compacted and used without segregation of its components.

Portland Cement when mixed with water for preparation of mortars and concrete,
should give a fluid mix, set in a reasonable time, develop good mechanical strength and
retain dimensional stability for long time.

When we talk about the workability of cement paste or mortar; than the common term
used is Consistency of Cement.

Consistency of Cement:

Consistency of cement refers to the relative mobility of freshly mixed cement paste or
mortar. The water demand of a cement is the amount of water required to form a paste
of standard consistence. The fluidity of a cement paste of given water/cement ratio may
be measured; the smaller the water demand, the greater the fluidity for a given
water/cement ratio. During cement testing, pastes are mixed to normal consistency as
defined by penetration of Vicat Needle. Mortars are mixed to obtain either a fixed water:
cement ratio (Vicat Apparatus) or yield a flow within a prescribed range (Flow
Table). Both the normal consistency method and flow table method are used to
regulate and check the optimum required water contents of pastes and mortars.Whereas
the test most commonly used for determining workability of concrete is known as
(Slump Cone Test) whereas (Compaction Factor Test) and (VEE - BEE
Consistometer Test) are also used to determine concrete workability.

Different factors affect the water demand or standard consistency of cement; in short
higher the reactivity of clinker / cement; more will be the water required to form a paste
of standard consistency.

In order to understand the workability a basic understanding of cement hydration is

required;

Cement Hydration:

Cement hydration is the reaction of cement constituents with water which finally results
in Hydrates which ultimately gives the properties of concrete like Strength, Setting
Time, Water Demand, Shrinkage / Expansion etc.
Macroscopic and Microscopic View of Cement Hydration:
Macroscopic View:

When cement / aggregates / water / (any admixture) are mixed together, a more or less
fluid mix is obtained. After casting in frameworks, it gradually increases in viscosity and
gains mechanical performances until framework can be removed. It carries on
hardening more or less quickly during first 28 days from mixing. During whole life
service, several reactions happen, depending both on interactions between internal
cement / concrete compounds and on interactions with external factors (eg.
Carbonation, degradation)

Microscopic View:

When cement, aggregates and water are mixed together; the chemical compounds
present in cement dissolve in water and release ions, that combine in different chemical
compounds (Hydration Products). The cement / aggregates / water mix is progressively
converted to a mix of solid substances that bind together aggregates.

Chemistry of Cement Hydration:

In hydration first step is Phase dissolution (Like C3S, C2S, C3A, Gypsum, C4AF) and
this dissolution results in ions. Once the ions are there in water; reaction starts and
precipitation of different hydrates like Aluminate Hydrates, Calcium Silicate Hydrates
(CSH) also known as Tobermorite Gel and Calcium Hydroxide (CH) / Ca(OH)2 starts
resulting in hardening and strength gain along with increase in viscosity. Hydrated
Portland cement contains 15---25 % Calcium Hydroxide (CH) / Ca(OH)2 & about 50 %
Calcium Silicate Hydrates (CSH) by Mass. The strength and other properties of hydrated
cement are primarily due to calcium silicate hydrates.

Because Portland cement is a relatively complex mixture, many studies having the aim
of elucidating its hydration chemistry have been made on its constituent phases. For a
given particle size distribution and w / s ratio, tricalcium silicate or alite sets and
hardens in a manner similar to that of a typical Portland cement. Using XRD and other
methods, it may be shown that about 70% of the C3S typically reacts in 28 days and
virtually all in I year, and that the products are calcium hydroxide (CH) and a nearly
amorphous calcium silicate hydrate having the properties of a rigid gel. βC2S behaves
similarly, but much less CH is formed and reaction is slower, about 30% typically
reacting in 28 days and 90 % in I year. In both cases, reaction rates depend on particle
size distribution and other factors. Development of compressive strength runs roughly
parallel to the course of the chemical reactions, and the strengths at 1 year are
comparable to those of Portland cements of the same w/s ratio and cured under the
same conditions.

This Precipitation and growth of hydrates follow the dissolution of phases; the two
process are strictly linked, from both thermodynamic (which type of phase dissolve and
which type are produced) and kinetic (how quickly this happens) point of view.
According to recent theories, driving force for dissolution and precipitation is always
related to ions in solution and super / under saturation conditions. When there is under
saturation than dissolution rate will be faster and precipitation rate will be low. When
there will be super saturation; than dissolution rate will be slow and precipitation rate
will be more / high.The most common hydrated phases are CSH (Calcium Silicate
Hydrates), CAH (Calcium Aluminate Hydrates), Ca(OH)2 & Ettrignite (Tri Calcium
Sulpho Aluminate Hydrate) etc.

The dissolution of phases to gives ions is the Plastic Mix stage whereas precipitation

of hydrates (CSH, CH, CAH, Ettrignite) is the Hardened Mix Stage.

For complete hydration of Portland cement, only about 40% water by mass (a water-to-
cement ratio of 0.40) is needed. If a water-to-cement ratio greater than about 0.40 is
used, the excess water not needed for cement hydration remains in the capillary pores or
evaporates. If a water-to-cement ratio less than about 0.40 is used, some cement will
remain unhydrated. The amount of water added to the mixture controls the strength
and durability as well. The space initially taken by water in a cementitious mixture is
partially or completely replaced over the period of time as hydration reaction proceeds.
Cement pastes having low and high water to cement ratio after drying will have the
equal mass (Evaporable water was removed). The cement consumed the same amount
of water in both paste, results in more bulk volume in the higher water –cement ratio
paste.

As the water to cement ratio increases; the capillary porosity increases and the strength
decreases. Also transport properties such as permeability and diffusivity are increased;
allowing detrimental chemicals to more readily attack the concrete or reinforcing steel.

Although water in excess of that required for complete hydration of the cement may be
employed in the concrete mix, in order to make the fresh concrete sufficiently workable
for proper placing and compaction, too large an excess must be avoided since ultimate
strength is inversely related to the overall water/cement ratio. An external supply of
liquid water must remain available to the cement after setting, during the initial
hardening period, if the full potential of the cement is to be realized, since the hydration
reaction is virtually stopped if relative humidities fall below about 95 per cent.

Water is found in cementitious materials in several forms. Free water is mixing water
that has not reacted with the cement phases. Bound water is chemically combined in the
solid phases or physically bound to the solid surfaces. A reliable separation of the
chemically combined water from the physically adsorbed water is not possible.
Therefore, it is useful to distinguish between evaporable and non-evaporable water . The
non-evaporable water is the amount retained by a sample after it has been subjected to a
drying procedure intended to remove all the free water (traditionally, by heating to
105°C). Evaporable water was originally considered to be free water, but it is now
recognized that some bound water is also lost upon heating to this temperature. All non-
evaporable water is bound water, but the opposite is not true.
Cement hydration behavior can also be studied using heat of Hydration testing method;
Cements do not generate heat at a constant rate. The heat output during hydration of a
typical Type I Portland cement is illustrated in below figure. The first peak shown in the
heat profile is due to heat given off by the initial hydration reactions of cement phases
such as tricalcium aluminate. Sometimes called the heat of wetting, this first heat peak
is followed by a period of slow activity known as the induction period. After several
hours, a broad second heat peak attributed to tricalcium silicate hydration emerges,
signaling the onset of the paste hardening process. Finally,there is the third peak due to
the renewed activity of tricalcium aluminate; its intensity and location is normally
dependent on the amount of tricalcium aluminate and sulfate in the cement.

In calorimetry testing, the first heat measurements are obtained a few minutes after
mixing the paste; as a result, only the downward slope of the first peak is observed
(Stage 1, below figure). The second peak (C3S peak) often occurs between 6 and 12
hours. The third peak (renewed C3A peak on conversion of ettringite to monosulfate)
occurs between 12 and 90 hours. This information can be helpful when trying to control
temperature rise in mass concrete. When heat generation must be minimized in
concrete, designers should choose a lower heat cement, such as a TypeII Portland
cement with the optional moderate heat of hydration requirements.

It may be noted that Initial Setting Time is observed approximately together with the
end of induction period on the heat evolution curve and the final set takes place in the
middle of the acceleration period.

Figure Above --Heat evolution as a function of time for cement paste.

Stage 1 is heat of wetting or initial hydrolysis. Stage 2 is a dormant period
also known as an induction period. Stage 3 is an accelerated hydration
reaction. Stage 4 is a deceleration in hydration. Stage 5 is a slow, steady
hydration

Setting Time:

The object of setting time is to determine 1) The time that elapses from the moment
water is added until the paste ceases to be fluid and plastic (Called Initial
Setting) and 2) The time required for the paste to acquire a certain degree of
hardness (Called Final Setting)

Initial setting must not occur too early and final setting must not occur too late. The
background for this is that the Initial Setting Time should be sufficient to provide
appropriate time for preparation of concrete mix, mixing of concrete mix, transportation
of concrete mix and finally the placing of concrete mix. The reason that why Final
Setting Time should not be too late is that the concrete should harden and develop
appropriate strength within a reasonable time period which will allow to remove the
framework; hence to sustain and retain the load of the structure and to not loose the
structural integrity.

The setting time indicates that a paste is or not undergoing normal hydration reactions.
Sulphate (from gypsum or other sources) regulates setting time, but setting time is also
affected by other parameters primarily cement fineness, water cement ratio, clinker /
cement reactivity and any admixture that may be used.

Setting time of concrete not correlate directly with setting time of cement paste due to
water loss to air or substrate, presence of aggregates, and because of temperature
difference in the field (as compared to the controlled temp in the lab)

The setting time is measured using Vicat Apparatus or Gillmore needle method.

The vicat tests governs if no test method is specified by the customer.

There are primarily three types of cement setting behaviors

A)    Flash Setting

B)    False Setting

C)    Normal Setting

Flash Setting:

If pure clinker is grinded and mixed with water it will immediately set and not allow for
casting, processing and use. This reaction is due to the fast reaction of Tricalcium
Aluminate (C3A) with water to form Calcium Aluminate Hydrates (CAH) which
immediately precipitate out and harden the mix (Flash Set). Flash set / quick set is
evidenced by a rapid and early loss of workability; it is usually accompanied by the
evolution of considerable heat resulting primarily by the rapid reaction of aluminates. If
the proper amount or form of gypsum (Calcium sulphate) is not available to control the
calcium aluminate hydration, stiffening becomes apparent. Flash set cannot be
dispelled, not the plasticity be regained by further mixing without the addition of water.
The (CAH) also covers the C3S slowing down the water diffusion and the subsequent
hydration of C3S / Strength development

In short we can summarize Flash Setting as under;

Reactive Cement / Slow Dissolving Gypsum----------------Flash Setting / Poor

Strength

False setting:

The most usual cause of false set is the presence of too much calcium sulphate in the
form of hemihydrate, which is rehydrated to give gypsum (called 'secondary' gypsum).
The setting is attributable to the interlocking of the gypsum crystals, which are tabular
and can be 5-10 µm in longest dimension. Additional mixing without added water
breaks up these crystals to restore workability. Dehydration of gypsum to hemihydrate
can occur during milling; hemihydrate may also be added deliberately, if a more reactive
form of calcium sulphate is required. With cements high in K2O, syngenite can be
precipitated; this also can cause false set. Ettrignite precipitation can also contribute to
false set.

From a placing and handling standpoint; false set tendencies in cement will cause no
difficulty if the concrete is mixed for a long time than usual or if it is remixed without
additional water before being transported or placed. False Set; final penetration should
be Minimum 50 % for ASTM C 150 Type –I (General Purpose Cement) as measured
using ASTM C 451.

In short we can summarize False Setting as;

Less Reactive Cement / Fast Dissolving Gypsum-----------False Setting / Not much

heat evolution and indicated by a significant loss of plasticity

Normal stiffening / Normal Setting

Normal setting occurs with the proper balance of sulphate ions (Gypsum) and clinker /
cement reactivity (which impact the hydration reaction as well as dissolution rates)

When Gypsum is added in addition with Calcium Aluminate Hydrates (CAH); some C3A
is consumed to form ettrignite (Tri Calcium Sulpho Aluminate Hydrate); this Ettrignite
due to different morphology; does not reduce the water diffusion and the subsequent
hydration of C3S, promoting a normal strength development.
At the optimum calcium sulfate level, the early hydration products of the C3A form
ettringite which deposits as a fine-grained material on the clinker surface. This
hydration product does not bridge the water-filled gaps between particles of clinker, and
the paste becomes only slightly stiffer due to initial hydration during the early period.
The equilibrium between CAH / Ettrignite is strictly related to the availability and
dissolution kinetics of Sulphate ions; hence to Calcium Sulphate % and the forms in
which it exists.

As per ASTM C 150 Initial Setting Time should not be less than 45 Minutes and Final
Setting Time not more than 375 Minutes for Type-I Cement (i.e. General Purpose
Cement) as per Vicat Method; whereas as per Gillmore test Initial Setting Time should
not be less than 60 Minutes and Final Setting Time not more than 600 Minutes for
Type-I Cement (i.e. General Purpose Cement)

Whereas as per EN 197 ; for 32.5 Strength Grade Initial Setting Time should be greater
than 75 Minutes , for 42.5 Strength Grade Initial Setting Time should be greater than 60
Minutes and for 52.5 Strength Grade Initial Setting Time Should be greater than 45
Minutes ; there is no Limit for Final Setting Time as per EN 197.

There can be two scenarios as far as normal setting is concerned:

Reactive Cement / Fast dissolving sulphate ---------------Normal Setting behavior

Less Reactive Cement / Slow Dissolving Gypsum---------Normal Setting behavior

Reactive Cement / Clinker can be summarized as having following properties:

High Blaine, Less Residues (90 /45 Microns etc)

High C3A

Orthorhombic C3A----Due to incorporation of alkalis

High C3S

Different forms of Gypsum with regard to setting behavior are as under:

Natural Di-Hydrate Gypsum------------------------------------Normal Release of Sulphate

Ions

Hemihydrate (Plaster of Paris) and Soluble Anhydrite------Quick release of Sulphate

ions

Natural Anhydrite Gypsum-------------------------------------Very slow release of Sulphate

Ions
Conclusion:

Normal hydration reactions are required to ensure that cement / concrete properties
remain within the acceptable limits as far as Workability, Setting Time, Water demand
& strength development /hardening are concerned. A thorough understanding of clinker
/ cement properties is required to avoid excessive water demand , False Setting , Flash
Setting and to have normal setting , strength development & workability characteristics