M. K.

SEN ( OFFICER ) NCP

Factors affecting on Optimum Gypsum Content (O.G.C)
1. C3A content: Increase C3A content need to increase O.G.C because higher
percentage will react in short time.
2. Cement fineness: Increase in cement fineness promote to increase O.G.C.
3. Alkali content: Increase in alkali content means increase reaction of gypsum that
leads to increase O.G.C.
4. Curing temperature: Increase in temperature of curing cause increase the reacrion
of C3A with gypsum that means increase O.G.C.
5. Curing time: Increase in curing time promote to increase O.G.C because of
(Autogenously Healing).
6. Free CaO and MgO: Increase of these oxides lead to decraese in O.G.C.
7. Chloride: Increase of chloride lead to decrease in O.G.C
Gypsum as set retarder in Cement
Harold F. W. Taylor

The gypsum in cement affects not only the setting time. but also the strength
development and the volume stability. During the early and middle periods of reaction
in a cement paste, gypsum or other forms of calcium sulphate dissolve and react at or
close to the surfaces of the clinker grains, or more specifically those of the aluminate
and ferrite phases. The factor most directly influencing the course of the early reactions
is not so much the relative amounts of calcium sulphate, aluminate and ferrite phases,
as the rates at which the relevant ionic species are made available at the surfaces of the
cement grains. The rates at which Ca²⁺ and SO4²ˉ ions are supplied by the calcium
sulphate thus depend both on the amount of the latter and on its physical and chemical
nature. Hemihydrate or soluble anhydrite supply ions more quickly than does gypsum.
which in turn supplies them more quickly than anhydrite. Other major factors affecting
the supply of these ions are the particle size distribution of the calcium sulphate and the
distribution in space of the particles; Tang and Gartner (T34) found that a given
proportion of gypsum added by intergrading was much more effective than the same
proportion added by blending, all other conditions being as nearly as possible equal.
Intergrinding presumably brings the gypsum particles into more intimate contact with
those of the clinker. Increase in any of the factors rendering the CaSO₄, more readily
available will tend to decrease the amount that is needed to produce a given effect in
the early stage of reaction. Increase in temperature has a similar effect (C39).

Factors affecting the rate at which Al₂O₃ is supplied include its content in the clinker, its
distribution among the clinker phases and especially the j amount present in the
aluminate, the specific surface area of the ground clinker, the reactivities of the
aluminate and ferrite, and the microstructure j of the clinker particles, or, more
specifically, the areas of surface composed of aluminate and ferrite phases and the
manner in which these phases are intergrown with each other and with the silicate
phases. Any factor increasing the availability of the A1₂0₃ will tend to increase the
amount of gypsum that is required to produce a given effect in the early reactions.

Sulphate ion is also supplied by the clinker, especially as alkali sulphates or calcium
langbeinite, and Ca²⁺ ions are supplied by the clinker phases. including free lime. The
alkali sulphates provide a highly available source of SO₄²ˉ but the alkali cautions, or
more probably the OHˉ ions that they produce, have additional effects (Section 7.6.3).

The minimum content of SO₃ required to control setting is typically around 2%. Increase
in SO₃ content beyond the minimum required has little effect on setting unless the
proportion of hemihydrate or soluble anhydrite is so high as to cause false set. It causes
a progressive decrease in the shrinkage that occurs in dry atmospheres (e.g. at 50% RH)
and a progressive increase in the expansion that occurs in water. Hobbs (H39) gave data
for cements containing more than the normal amounts of gypsum. Mechanisms of
expansion are discussed. If expansion is excessive. the concrete disintegrates; this limits
the permissible SO₃ content, which. In typical specifications, is set at 2.5-3.0%,
depending on the potential C₃A content of the clinker.

The effects on strength are complex and not well understood. In general, for any
particular clinker and source of SO₃ there is an optimum content of SO₃ at early ages. In
a careful study, in which strengths were corrected empirically for the effects of differing
particle size distributions and contents of entrapped air, Osbaeck and Jens (08) found
maximum I-day strengths at 3-5% SO₃ for a number of cements having different alkali
contents and clinker S0₃/alkali ratios. At later ages, somewhat variable results have been
reported; in general, the optimum seems to shift to higher values but to become less
pronounced. The results of Osbaeck and Jms, and of Jelenic rt 01. (J25), indicate that it is
more definitely upwards if the alkali content is high. In evaluating the effect of gypsum
content on strength or other properties, it is necessary to ensure that other relevant
factors are as far as possible kept constant. Thus, if cements with the same clinker but
different gypsum contents are ground to the same specific surface area, the clinker will
be less finely ground the more gypsum is present, and this will tend to decrease the rate
of strength development.

Calcium sulphate additions probably affect both the quantities of products that are
formed, especially at early ages, and the microstructure at all ages. Addition of CaSO₄ is
reported to increase the rate of hydration, both of pure C₃S and of the alite in cement
(C39,B104,J25,J26,L36). This could explain an increase in strength at early ages due to
additions up to the optimum, but not a decrease with larger amounts. The fact that
calcium sulphate additions affect the drying shrinkage also suggests that the micro- 236
Cement Chemistry structure is modified. This could occur in various ways, e.g. by
changes in the micro morphology of the C-S-H or by incipient precipitation of ettringite
throughout the gel. The latter effect, if it happened at an early age or to a limited extent,
could augment strength through a decrease in porosity, but if it happened later or to too
large an extent could decrease strength through localized expansions.

Attempts to formulate equations relating optimum gypsum content to composition and

particle size distribution have proved of little practical value, and gypsum contents are
normally decided on the basis of empirical strength tests. In practice, the molar ratios of
total SO₃ to total AI₂O₃ in modern cements range from 0.5 to 0.9, with an average of
about 0.6 (K35). In order to adjust the supply of SO₄²- to that required at different stages
of the hydration process, it may be desirable to use mixtures of different forms of
calcium sulphate; for example, with cements high in aluminate phase, a mixture of
anhydrite and hemihydrate, the latter produced by dehydrating gypsum during milling,
has been recommended (L36).

M. K. SEN ( OFFCIER ) NCP

..............................................................................................................................................
.

Gypsum (CaSO4∙2H2O) loses its water in two steps, at around 100 to 140°C to
hemihydrate (CaSO4∙0.5H2O) and at 140–150°C to anhydrite (CaSO4).

Gypsum used in cement manufacturing process is generally of natural origin, but many a
times by-product gypsum from different origin is used. By-product gypsum contains
different type of impurities, which affects the setting and hardening property of resultant
cement. Hence suitability of gypsum based on its reactivity as a set retarder is one of the
key factor while selecting the gypsum. In order to establish reactivity and suitability of
gypsum, a comparative evaluation study has been carried out on four different varieties
i.e. mineral gypsum, chemical gypsum, marine gypsum & Phosphogypsum.

Tricalcium aluminate (C3A) present in cement reacts with water very rapidly forming
various phases and leads to very fast setting, known as flash setting in cement if it does
not contain gypsum or the cement is under dosed. The reaction of C3A / Ferrite + gypsum
leads to the formation of ettringite & mono-sulfate and setting is controlled by the
formation of ettringite which envelopes the reactive C3A grain . As a result temporarily,
it causes the retardation of rapid hydration of this reactive phase. Sulfate ions contributed
to the solution by dissolution of gypsum have a retarding effect on the aluminates but an
accelerating effect on the hydration of silicate phases

[AlO₄]- + 3 [SO₄]2- + 6 [Ca] ²⁺+ H₂O -----> C6AS3H32 (ettringite)

[AlO₄]- + [SO₄]2- + 4 [Ca]²⁺ + H2O --------> C₄ASH12 (mono-sulfate)

Mineral gypsum is available from natural reserve and its addition during grinding of
clinker depends on the purity. Many a times its availability is insufficient and it becomes
essential to use the gypsum from other source. Marine gypsum is recovered as a by-
product during the production of common salt, when sea water is subjected to solar
evaporation. The contamination of chlorine in marine gypsum is one of the
main constraint to consume in large quantity
Chemical gypsum here refereed to is a by-product from Chemical Industries
manufacturing the dye intermediates called H-acid, which generate large quantity of
gypsum sludge, and after drying, it is used as chemical gypsum. In the process, the
neutralization is done by soda ash and hence alkali impurities may be higher in it.
Phosphogypsum is a by-product generated during manufacture of phosphoric acid using
rock phosphate and sulfuric acid as raw materials through two processes viz. Di-hydrate
(single step) and hemihydrate dihydrate (two step) process. This variety usually is
contaminated with P2O5 and fluoride, and possesses detrimental effect as a set retarder.
Soluble fluorides and phosphates are primarily responsible for set retardation of
cement. Phosphatic impurities with at least one acidic hydrogen show more retardation in
setting time. The fluorine compounds which possess alkaline unstable linkage have been
reported to be most deleterious to setting
P₂O5 & fluoride impurities are known to react with Ca⁺² in solution when cement is
mixed with water and the reaction products (calcium phosphates, calcium fluorides, etc.)
precipitate on the anhydrous cement grain causes the slowdown of reaction between cement
particles & water. Presences of soluble part of these two impurities are the prime cause for
delayed setting time & poor early strength development. It has also been observed that
fluoride contribute more in delayed setting time than P2O5 . Phosphogypsum obtained from
hemihydrate-dihydrate process contains generally lower impurity level than from dihydrate
process

Gypsum on heating gives the following transformation

The first two changes are reversible, where as the last one is irreversible. It is
established that up to 200 0C raise in temperature and subsequent sufficient cooling in
air , the re-conversion of hemihydrate to gypsum was found to be around 30-40 % for the
three types of gypsum, viz. marine, mineral and chemical 

The chemical analyses of four different variety of gypsum is  given below  

Solubility of different gypsum in saturated aqueous solution

PSD of ground gypsum samples

Effect of gypsum on cement by preparing four different batches

of Ordinary Portland Cement (OPC) using same quality clinker, maintain
SO₃ level of cement 2 +/- 0.05 % and maintaining Blaine value ~ 3100-
3150 cm2/gm. The cement samples were tested for normal consistency
(NC), setting time (IST & FST) & strength at different ages up to 28 days. 
The rate of reaction between C₃A and gypsum depends on the availability of
dissolved in water. More the solubility more will be the reactivity of the
gypsum. It is revealed from study that the solubility of chemical gypsum is
higher than all other variety, which enhances its property as set retarder. It is
revealed from literature that the presence of alkali in gypsum increases the
solubility of gypsum. During H-acid production neutralization of excess sulfuric
acid is done with limestone & soda ash and hence chemical gypsum is mildly
contaminated with alkali. It leads to higher solubility of it as compared to other
variety. Further, the solubility data indicate that the solubility of hemihydrate is
more than the di-hydrate irrespective of the type of gypsum

Since the solubility of hemihydrate is more as compared to dihydrate

irrespective of type of gypsum, the reactivity of gypsum is dependent on the
peak temperature. Though the peak temperature for first conversion is lowest in
case of phosphogypsum, the reactivity of chemical gypsum is highest among the
all variety. This is because of the fact that phosphogypsum contains some
impurity of P2O5 & fluoride which inhibits the reactivity. This is also
corroborated with the result of strength gain at early ages & setting time value.
The highest strength gain at 28 days in case of phosphogypsum may be due to
filling of extra pores by calcium silicate hydrate (CSH gel) phase developed at
later stage by reaction of protected reactive phases with water.

Among the four varieties, chemical gypsum is easier to grind. The average

particle size of ground chemical gypsum is as low as 17.29 m, where as in case
of marine gypsum it is as high as 39.06 m. The residue on 45 um is 15.51 % for
Chemical gypsum , but 42.04% for marine gypsum. The increasing trend of
finer particle of different ground variety is in the order of Marine< Mineral <
Phospho < Chemical. Hence the dispersion of gypsum particle in OPC is highest
in case of chemical gypsum, which contribute significantly to enhance the
reactivity of chemical gypsum.

Chemical gypsum exhibits highest reactivity among the four varieties. OPC

prepared using Chemical gypsum shows highest early strength gain also setting
time value within limit, establishes it as most suitable. Because of the presence
of soluble P2O5 & fluoride content in Phosphogypsum the early strength gain
lowest & setting time maximum. The conversion of di-hydrate to
hemihydrate occurs at lower temperature in case of phosphogypsum. The
particle size of gypsum in OPC with chemical gypsum is very fine. 

Common forms of calcium sulfate and their shorthand notation are:

Anhydrous calcium sulfate....................................... CS¯

Calcium sulfate dihydrate (gypsum)......................... CSˉH2

Calcium sulfate hemihydrates.................................... CSˉH1/2

Gypsum (calcium sulfate dihydrate) is the predominant source of sulfate used in

cement. However, during milling, some of the gypsum is partially dehydrated by the
heat generated and the other calcium sulfate forms are obtained; they are all readily
soluble and contribute to setting control.

Calcium sulfate. Anhydrite (anhydrous calcium sulfate), gypsum (calcium

sulfate dihydrate), or hemihydrate (also known as plaster of paris, or bassanite,
or, formally, calcium sulfate hemihydrate) is added to cement during final
grinding to provide sulfate to react with C₃A to form ettringite (calcium
trisulfoaluminate hydrate). This controls the hydration of C₃A. Without sulfate,
cements and concretes would set rapidly. In addition to controlling setting and early
strength gain, the sulfate also helps control drying shrinkage and can influence
strength through 28 days.

The various forms of calcium sulfate are analyzed as SO₃. This analysis also includes
sulfate contributed from the clinker, generally in the form of alkali sulfates which are
readily soluble and contribute to set control and other properties. A small amount may
also be incorporated in the interior of cement grains, and thus may only become
released as the cement hydrates. As shown in Table 9.1.2, U.S. cements contain
between about 2% and 4.5% SO₃.

Hydration Reactions of Major Portland Cement Phases (Oxide

Notation)
Note: This table illustrates only primary reactions and not several minor reactions. In
particular, many products of the hydration of C₃A and C₄AF are known. The
composition of calcium silicate hydrate (C-S-H) is not stoichiometric.

Figure 9.1.17. Relative volumes of the

major compounds in the microstructure of
hydrating Portland cement pastes (top) as
a function of time (adapted from Locher,
Richartz, and Sprung, 1976) and (bottom)
as a function of the degree of hydration as
estimated by a computer model for a
water to cement ratio of 0.50 (adapted
from Tennis and Jennings 2000). Values
are given for an average Type I cement
composition (Gebhardt, 1995): C₃S=55%,
C₂S=18%, C₃A=10% and C₄AF=8%.
“AFt and AFm” includes ettringite (AFt)
and calcium monosulfoaluminate (AFm)
and other hydrated calcium aluminate
compounds. See Table 9.1.7 for
compound transformations.

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M. K. SEN ( OFFCIER ) NCP

Gypsum in cements
-:John Bensted:-
Introduction

When Portland clinker is ground on its own and then mixed with water, the aluminate
phase C₃A tends to react rapidly, the alite C₃S progressively, with the other phases
ferrite C₄AF and belite C₂S contributing too [3]. It is commonly said that when this
happens there is a marked increase in temperature and irreversible stiffening, which is
quickly followed by setting, which corresponds to what is commonly referred to as
‘quick set’ or ‘flash set’.

The calcium sulphate-water system

Gypsum partially dehydrates upon heating above circa 97°C (sometimes at lower
temperatures when the relative humidity is much less) to give at first the hemihydrate:

This form of the hemihydrate, when produced under dry calcined conditions is often
referred to as β - hemihydrate. α-hemihydrate is made in a more moist atmosphere
under saturated steam conditions.

Hemihydrate can only be obtained pseudomorphically within the calcium sulphate-

water system by dehydration of gypsum. It does not form as an intermediate when
insoluble anhydrite (see below) reacts with water to produce gypsum.

Heating calcium sulphate hemihydrate gives the ubiquitous phase known as ‘soluble
anhydrite’ dehydrated hemihydrate or ᵞCaSO4.

The role of gypsum in set regulation of Portland cement-based

systems
Gypsum reacts with the aluminate phase C3A primarily and also with the ferrite phase
C₄AF (C₂A0.5F0.5) to form the calcium trisulphoaluminate hydrate known as
ettringite

These reactions can be represented simply as:

From aluminate phase:

From ferrite phase:

Aluminates react faster with gypsum than ferrites in ordinary Portland cements.
Details of their hydration chemistry have been given in greater detail elsewhere.
Owing to the effects of solid solution and the presence of impurity ions in the clinker
phases, and as a consequence of the hydrated phases as well, ettringite formed from
the aluminate phase and ettringite formed from the ferrite phase are in reality
indistinguishable. They form a continuous hydrated phase.

Such clinkers are more difficult to grind than clinker gypsum combinations (gypsum
is a grinding aid for Portland clinker), give inferior workability and lower compressive
strength development (due to lower sulphate content) than Portland cements
containing ground-in gypsum. At higher surface areas, Portland clinkers will show
flash set at lower C₃A levels, but then set regulation with gypsum requires greater
additions to avoid flash set, as with ultra rapid hardening Portland cement, where
surface areas are often in excess of 700 m2 /kg.

Flash set
When Portland clinker is ground alone and mixed with water, the aluminate (C₃A)
phase initially reacts rapidly, the alite phase progressively and the other main phases
(ferrite and belite) contribute as well. If the C₃A level is appreciable (circa 9 per cent
or more at clinker surface areas around 325 m2 /kg), or the surface area is high, then a
so-called flash set or quick set is likely to ensue. The C₃A reacts quickly with water to
form C₄AH13, a hexagonal plate phase, which is stable in the high-lime environment.
This reaction is accompanied by hydration of the other phases as well. There is a
considerable increase in temperature, which is followed by irreversible stiffening,
which is referred to as a flash set or quick set. Since plasticity of the mix is not
restored after flash setting, it is clearly deleterious to concrete production. In order to
prevent flash set from taking place, and to ensure smooth set regulation prior to
normal setting, gypsum is ground into cement.

The reaction that normally triggers flash set is the hydration of the aluminate phase in
the high lime environment to Hydrocalumite:

C₃A + CH + 12H  C₄AH13

Hydrocalumite is a hexagonal plate type phase, which is stabilized by the presence of

the high-lime environment.

Flash set can also arise at very high surface areas, as with ultra rapid-hardening
Portland cements [35], unless there is adequate set regulation by gypsum and
sometimes adequate retardation by a suitable retarding admixture as well.

False set
False set is sometimes also known as early stiffening, premature stiffening or gum set.
It refers to cement which when gauged with water and mixed for a short while,
stiffens up and appears to set. Remixing breaks up this stiffening and the cement
proceeds to a normal set. Unlike flash set, where considerable heat is evolved,
comparatively little heat is released in false set.

False set is primarily caused by the rehydration of hemihydrate/soluble anhydrite

(formed by dehydration of gypsum during clinker-gypsum grinding at circa 115°C or
above) back to gypsum. Since the former have solubilities circa 2–3 times that of
gypsum, they are supersaturated with respect to gypsum in solution. As a result, when
they rehydrate back to gypsum:
the gypsum being formed is precipitated to some extent from solution, giving the
observed stiffening effect. Remixing allows the remaining hemihydrate/soluble
anhydrite to rehydrate rapidly back to gypsum. Once this is achieved, the cementitious
hydration proceeds in the normally expected smooth manner. Stiffening effects from
soluble anhydrite, because of its lower water content than hemihydrate, tend to be
more severe than those experienced with hemihydrate.

M. K. SEN ( OFFCIER ) NCP

---------------------------------------------------------------------------
Joseph Aspdin of Leeds patented Portland cement
Delayed ettringite formation (DEF) has recently achieved some notoriety
Ettringite, 3CaO.Al2O3.3CaSO4.31 H2O, forms early in the hydration of cement leading
to setting and hardening of cement. It appears that under certain circumstances,
principally curing temperatures above about 70°C, ettringite decomposes and
subsequently reforms in the presence of water to cause expansion and cracking of
concrete. The search for causes has become somewhat emotional but, to date, there is no
evidence that this is the result of anything but incorrect concrete practices.

False set is the result of gypsum dehydration due to overheating of cement

(CaSO4.2H2O----» CaSO4.1/2H2O). Upon mixing with water, crystallisation of
reformed gypsum causes stiffening of the mix within a few minutes. Usually false set is
only a problem with very rapid mixing systems as false set can be broken up after a few
minutes and no subsequent problems result. Rapid precipitation of ettringite
(3CaO.Al2O3.3CaSO4.31H2O) and/or syngenite are also possible causes of false set. The
desirable form of ettringite is that which forms on the surface of C3A thereby retarding its
hydration. Aerated or carbonated cement has a strong tendency to false set and strength
loss and, while false set is not usually accompanied by significant release of heat, setting
time (C191) is often lengthened.

Flash set or quick set is the result of uncontrolled hydration of C3A before the
formation of surface ettringite. It is accompanied by rapid release of heat and loss of
workability and is caused either by insufficient gypsum or of insufficient sulphate
solubility, If the latter, partial dehydration of gypsum to hemihydrate in the cement mill
may solve the problem. Flash set which is not accompanied by heat release can be caused
by excessive precipitation of gypsum, syngenite or ettringite.

It should be noted that false set or flash set may be caused by certain concrete admixtures,
particularly water reducers.
 M. K. SEN (OFFCIER) NCP
Cement Production Technology
A. K. Chatterjee

Chemical properties of gypsum

The CaSO₄ – H₂O system is represented by three solid phases that coexist at room
temperature in air containing water vapour, namely calcium sulfate dihydrate
(CaSO4.2H2O), calcium sulfate hemihydrate (CaSO₄.1/2H₂O), and insoluble anhydrite
(CaSO₄ – insol.). In addition to these phases, another phase is identified as soluble
anhydrite (CaSO₄ – sol.), which has the same crystal structure as hemihydrate. Two
transformations are very important for these substances. They are (1) dehydration from
the dehydrated state and (2) rehydration to the dehydrated state. Dehydration refers to the
stepwise loss of water of hydration that is accomplished by increasing the temperature of
dehydration for the purpose of obtaining one of its dehydration products, i.e.,
hemihydrate, soluble anhydrite, and insoluble anhydrite. The temperature ranges
applicable for the individual dehydration steps depend on whether the process is static or
kinetic. In general, the static conditions appear to proceed at a lower temperature but they
require more time. For example, the dihydrate phase begins to dehydrate at about 46°C
but conversion takes months or even years to complete. Rehydration is the exposure of
these dehydrated materials (hemihydrate, soluble anhydrite, and insoluble anhydrite) to
liquid water for the purpose of obtaining the dihydrate state again at standard conditions.
This process proceeds by the crystallization of the dihydrate phase in water. If the starting
material is a hemihydrate, a supersaturated solution is formed prior to crystallization. In
the case of an insoluble anhydrite as the starting material, the rate of conversion to
gypsum is affected by the degree of its solubility and the temperature. The solubility of
the dihydrate, hemihydrate, and insoluble anhydrite phases are an important consideration
for a variety of reasons but primarily because they allow a distinct separation between the
three phases on a theoretical basis. Their approximate solubility curves are shown in
Figure 1.18 (17).

The intersection between two curves gives the equilibrium temperature, below which the
less-soluble phase is stable. For example, the curves show that above 40°C (point A)
insoluble anhydrite is the most stable phase. However, above this point, the dihydrate
phase, if in contact with water, should not convert to insoluble anhydrite, but in practice It
may do so but at a very slow rate. Below 100°C (point B) the dihydrate phase is more
stable than the hemihydrate. When the saturated solutions of hemihydrate are
supersaturated with respect to dihydrate, the dihydrate phase precipitates from the
solution. This dehydration-rehydration process appears to be relatively simple but a
number of critical conditions are to be met that finally ensure the transformation process.
For example, water vapour plays a significant role in the dehydration and rehydration of
soluble anhydrite. Also, the hemihydrate phase occurs in the α-form and ß-form
depending on the method of dehydration. When the hemihydrate phase is formed under
normal atmospheric conditions it is referred to as β-hemihydrate, while the α-form is
obtained from the dihydrate phase by autoclaving. Although the normal solubility of the
dihydrate phase is reckoned as 2.1 g/L at 20°C, the solubility of the β-hemihydrate is
much higher at about 8.8 g/L at 20°C but it reduces to 6.5 g/L for the α-phase. For all
practical purposes, the conversion temperature of dihydrate to hemihydrate lies in the
range of 100–180°C, hemihydrate to soluble anhydrite in the range of 180–350°C under
favourable water vapour pressure conditions and to insoluble anhydrite above 1180°C.
Insoluble anhydrite also occurs in natural deposits.

FIGURE 1.18 Solubility curves of calcium sulfate phases .

Air set:
Air set is a type of setting, usually caused by exposure to moist air and sometimes also
when stored at moderate humidity in silos etc. It is traditionally noticed by the
appearance of lumpiness. Such aeration, caused by abstraction of moisture and carbon
dioxide from the atmosphere causing partial hydration, leads to a reduction in
compressive strength, which at limited levels of increasing moisture may not produce
lumps to any significant degree. A typical situation quoted is where an increase in the
loss on ignition of a Portland cement of 0.5 per cent lowers the 28-day strength by
3N/mm2 (3 MPa) [38]. Upon further aeration, lumps develop and the cement becomes
difficult to disperse in the cement, mortar or grout. These lumps normally contain
significant levels of the mineral syngenite, a potassium calcium sulphate hydrate

(K₂SO₄.CaSO₄.2H₂O) No sodium analogue of syngenite is known. Syngenite is

formed by reaction of small amounts of potassium sulphate and/or calcium langbeinite
from the Portland clinker (K₂SO₄.CaSO₄.2H₂O) with gypsum (and/or other forms of
calcium sulphate present like hemihydrate/soluble anhydrite or insoluble anhydrite)
and water. The syngenite forming reactions can be represented thus:
Formation of syngenite provides a strong initial bonding between the particles of
Portland cement and assists, along with the partial hydration of the clinker phases,
with increased setting and lumpiness. Subsequent carbonation of some of the
hydrating phases may also militate against lumpiness.

Bagged cement is more prone to aeration than bulk cement, presumably on account of
the higher surface to volume ratio of the former, and to the effects of compaction
when the cement bags are piled on top of each other. Traditionally, air set has been
associated with syngenite formation. However, there is no correlation between the
extent of air setting and the quantities of syngenite formed [39]. Syngenite is merely
an intermediary and reacts on, with the alkali and sulphate largely entering the other
hydrate phases like C-S-H and ettringite, as they are being formed upon further
hydration. Also, the partial hydration of the main clinker phases, as mentioned above,
must be taken into account.

Syngenite formation is thus more likely to arise where there is a higher alkali
(potassium) content in the cement, and can play a part in accentuating the onset of air
setting. Once the syngenite-forming reaction starts with a little water, it can utilize
hydrate water from the calcium sulphate and become self-perpetuating. However, free
lime can offset or sometimes inhibit this reaction by preferentially reacting with the
water present to form calcium hydroxide [3], In addition, the mere presence of
syngenite is not per se an indication that air setting is underway. The vast majority of
Portland cements, even if to a very small extent, contain syngenite, which does not
ordinarily cause air setting. Only when the conditions for aeration mentioned above
prevail (including storage in moderate or high humidity conditions), will syngenite
become a potential problem in the onset of air setting. It has sometimes been said that
if a cement consignment is found to contain syngenite, then it should be discarded,
because the cement has already air set. From the foregoing comments, this is
undoubtedly nonsensical as a generalization. If any doubts arise, then the cement
should be checked for air setting. If no air setting is found, then the cement
consignment is safe to employ in construction.

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M. K. SEN ( OFFCIER ) NCP

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M. K. SEN ( OFFCIER ) NCP
 CHEMICAL GYPSUMS
Calcium sulphate dihydrate, CaS0₄.2H₂O, is a basic component of chemical gypsums.
Apart from the CaS0₄.2H₂O, the hemihydrate gypsum, CaS0₄.0.5H₂O, or anhydrite,
CaSO₄ can also be observed. The names of chemical gypsums are derived from the
primary manufacturing products created during chemical processing [1]. The chemical
reactions resulting in the different gypsum by-products are given below :

a) Phosphoric acid: Reaction between sulphuric acid and phosphorites. By-product:

Phosphogypsum.

b) Fluoric acid. By-product: Fluorogypsum:

c) Titanium white from ilmenite. By-product: Titangypsum:

d) Boric acid. By-product: Borogypsum-

e) Organic acids (e.g. citric acid). By-product: Citrogypsum :

f) Phenol. By-product: Phenologypsum:

g) Neutralization of sulphuric acid containing liquid wastes and galvanic sludges by use
of lime milk or limestone:
h) Production of soda using the Solvay method. Neutralization of calcium chloride. By-
product: Soda gypsum:

I) Recovery of NaCI from sea water. By-product: Salt gypsum:

Phosphogypsums-
Phosphogypsum is the most common of the by-product chemigypsums. It is produced in
the fertilizers plants as a result of the reaction between sulphuric acid and natural
phosphorites. The chemical compositions of different phosphogypsum materials produced
using a variety of methods are given in Table 1. Calcium sulphate dihydrate forms as a
main component of the by-product material and the impurity content is relatively small.
Phosphogypsums originating from phosphorites can be contaminated with radioactive
elements and organic substances (about 0.3%) [2]. Phosphogypsums from apatite
concentrates (deposits at Kola Peninsula in Russia) show a significant amount of
strontium and rare earth elements [3]. In practice, every 1 ton P20 S combined in the form of
phosphoric acid corresponds to 4 - 6 tons phosphogypsum [4]. Therefore, with an annual
production of P20 S of approximately 20 million tons, about 100 million tons
phosphogypsum are produced [5]. The chemically bound water content in calcium
sulphate from the phosphogypsum depends on the method of phosphoric acid production,
temperature and the sulphate and phosphate ion concentration in the solution at later
stages of the process. The storage of phosphogypsum in open stockpile leads to
combination with water and subsequent transformation ofCaS04,O.5H20 and anhydrite to
CaS04·2H20.

Table 2. Impurities Occurring in Phosphogypsum.

*PGl - Phosphogypsumfrom
India; dihydrate process [7]

PG2 - Phosphogypsumfrom
India; dihydrate-hemihydrate
process [7]
PG3 - Phosphogypsumfrom Turkey; dihydrate process [4]

The following requirements for the phosphogypsum used in the processing for gypsum
binder must be fulfilled in Poland [14]:

CaS0₄.2H₂0 content ≥ 92%

Fraction > 0, 1 mm < 1%

Blaine specific surface 3000-6000 [cm²/g]

Total P205 content: < 0.20 %

Soluble < 0.10 %

F ˉ content ˂ 0.05%

Alkalis as Na₂0 content ˂ 0.03%

Al₂0₃ + Fe₂0₃ content ˂0.15%

Use of Phosphogypsum in Cement Technology.

The role of gypsum in cement hydration has been widely reported and discussed. Briefly,
setting of cement, as well as the other properties, including mechanical strength is
strongly influenced by the presence of sulphate ions in the cement-water system.
Obviously, the natural gypsum replacement by the phosphogypsum by-product brings
about significant changes so pronounced as both materials differ one from another. The
potentially detrimental effects are connected with the high humidity, the presence of
impurities affecting the cement hydration and, finally, the grain size composition
differing from those for natural gypsum. The impurities become active on cement
hydration and subsequently influence the setting and strength development [23,24]. The
excess water content in phosphogypsum may cause some difficulties in transportation,
storage and dosage. The lower grindability of phosphogypsum should be taken into
account in cement production. Both the features - high humidity and fineness create some
technological problems but are of limited significance as it relates to cement properties.

The use of phosphogypsum in cement industry is determined first of all by the chemical
composition. The hydration process is strongly influenced by the presence of phosphate,
fluorosilicate and fluoride particularly those present in soluble form and adsorbed on the
surfaces ofCaS0₄.2H₂0 crystals. The impurities incorporated in the structure are of less
importance. As it is commonly accepted the presence of [H₂P0₄] ˉ, [HP0₄]²ˉ, [P0₄]³ˉ.
[SiF6]²ˉ and F ions in the highly alkaline solution (pH=12-13) and supersaturated with
calcium ions leads to the formation of insoluble calcium phosphates, fluorides and
fluorosilicates covering the hydrating cement grains. The cement hydration process is
therefore retarded by a protective coating mechanism [1,25]. Some authors are of the
opinion that the precipitation products form the bridges reinforcing the hydrating cement
structure [24]. The influence of monocalcium phosphate, dicalcium phosphate and
sodium fluorosilicate which can be considered as model, soluble impurities [26,27] cause
the prolonged setting and compressive strength decrease with increasing admixture
content. It should be mentioned that the strength development decrease is less pronounced
than the setting time increase and occurs in different way for particular cements [1,28-
30]. However, the effect of phosphogypsum set controlling agent on the compressive
strength is found only within the first 7 days (Table 3).

Table 3. Properties of Cement Pastes Prepared With Different Set Controlling Agents
[29].

Since the delayed hydration of the phosphogypsum containing cements results from the
formation of impermeable layers composed of products forming between the calcium
hydroxide and impurities from phosphogypsum, one should expect that all the operations
reducing the durability of these layers would result in the hydration acceleration.
However, it has not been confirmed. Similarly, the retarding effect at low temperature on
the phosphogypsum containing cement has also not been confirmed. One should
underline that the substitution of natural gypsum by the phosphogypsum in Portland and
metallurgical cements subsequently used in concrete technology brings about only a small
changes in consistency, almost independent of the type and percentage of several
impurities.

Table 5. Chemical Composition of Chemical Gypsum.

Understanding of Cement
Cement milling and gypsum dehydration

Because the cement gets hot due to the heat generated by grinding,
gypsum can be partly dehydrated, forming hemihydrate, or plaster of
Paris - 2CaSO4.H2O. On further heating, hemihydrate dehydrates
further to a form of calcium sulfate known as soluble anhydrite
(~CaSO4). This is calcium sulfate with a trace of bound water in the
crystal structure and it has a very approximately similar solubility in
water at room temperature to hemihydrate, which in turn has a higher
solubility than either gypsum or natural anhydrite.

The different forms of calcium sulfate that may be present in cement

are:

Mineral name Composition

Gypsum Calcium sulfate dihydrate (CaSO4.2H2O)

Hemihydrate Calcium sulfate hemihydrate (2CaSO4.H2O),

(also known as Plaster of Paris)

Soluble anhydrite Gamma anhydrite (CaSO4·nH2O where n = 0 to 0.0

Natural anhydrite Beta anhydrite (CaSO4)

The relative proportions and different solubilities of these various types of calcium
sulfate, and of the different forms of clinker sulfate, are of importance in controlling
the rate of C3A hydration and consequently of cement set retardation. Problems
associated with setting and strength characteristics of concrete can often be traced to
changes in the proportions of the different forms of calcium sulfate due to differences
in temperatures during grinding. Variations in cooling rate of the clinker in the kiln
and subsequent changes in the proportions or size of the C3A crystals may also have
an effect on setting characteristics.

If the rate at which sulfate is supplied by the different sulfate salts exceeds the rate at
which the clinker minerals, principally the aluminate phase, can react, the pore
solution may become supersaturated with respect to gypsum. Crystals of gypsum form
which cause the mix to stiffen in what is known as a false set.
Conversely, if the rate at which sulfate is supplied is insufficient to control aluminate
reaction, the mix will stiffen due to the formation of monosulfate crystals, or possibly
of calcium aluminate hydrate; this is known as flash set.

In clinkers high in potassium, syngenite (CaSO4.K2SO4.H2O - calcium potassium

sulfate hydrate) crystal formation can also cause a false set.

For set regulation, the most important feature of aluminate is not necessarily the
absolute amount present, but the amount of surface which is available to water for
reaction. This will be governed by many factors, such as the surface area of the
cement, the grinding characteristics of the different phases and also the size of the
aluminate crystals. Over-large crystals can lead to erratic setting characteristics.

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M. K. SEN ( OFFCIER ) NCP

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