1.

rule of thumb that approximately 2% of the total MgO

content in a cement clinker will remain in solid solution in
other clinker phases, and the remainder of the MgO is
expected to be present in the form of periclase crystals
2. The free MgO will decrease as Fe 2O3 increases in the mixture.
C4AF is an excellent stabilizer for MgO and is capable of a
transformation of considerable amounts of MgO into a nonexpanding compound, but it was conceded that the rapid
cooling of clinker also has a very beneficial effect on the
stabilization of MgO
3. Mix design guideline to avoid expansion
Alumina + MgO / Fe2O3 < 2.7
MgO:Fe2O3 > 1.53 plant in trouble; autoclave expansion
prevalent
MgO:Fe2O3 > 1.40 danger zone; high probability of
expansion;any appreciable free CaO gives excess expansion
MgO:Fe2O3 < 1.40 probability of expansion failure decreases
rapidly
MgO:Fe2O3 < 1.20 standard control target (maximum value)
failure due to MgO very unlikely
4. In a SO3 rich environment the silicates formed are C2S with a
high level of Sulphur substitution or a sulphosilicate phase.
Both are very difficult to convert to C3S and require hard
burning.
5. The presence of calcium langbeinite and propably spurrite (a
carbonated calcium silicate) indicates that the build up was
formed at about 800C in the presence of CO2 and therefore
while the limestone was undergoing calcination.
6. If reducing conditions prevail within the kiln burning zone, the
oxide blend of the raw mix design is upset.Specifically,
trivalent iron oxide (Fe2O3) is reduced to divalent FeO.FeO
replaces CaO in the C3S crystal lattice.There is thus more C3S
formed and less liquid phase.Free lime is unable to combine
with C2S becase the FeO is more mobile so free limes
increase.
7. As well as reduction of Fe2O3 to FeO, oxygen is stripped from
SO3 to produce SO2 gas. If SO2 is removed due to reducing
conditions, the alkali needs to combine elsewhere. In the
absence of available SO3, alkali becomes incorporated in the
aluminate phase, forming the so-called alkali-modified, or
prismatic,
C3A.This
phase
has
different
hydration
characteristics to the more usual cubic form and leads to
erratic setting behaviour and water demand.
8. Running a kiln in reducing conditions prevents sulphur from
escaping from the kiln system.The hotter the burning zone
temperature, the more alkalis are driven back.Either or both of
these conditions can seriously increase the incidence of
blockages.

9. Mid-kiln-Dense, low porosity and often elongated. Chemically

like clinker with low volatile content. Contains all clinker
compounds and CaO. Caused by long cold flame, fine dust
recirculation from front end. 7 to 13 kiln diameters
10.
Ash-Common with high ash coals. Very dense and
layered with glassy appearance. Similar to clinker but higher
belite which is often in layers. Very small alite crystals. 5 to 7
kiln diameters
11.
Sinter Rings-Grey/black, very hard, with small clinker
nodules embedded. Chemically similar to clinker. Often with
spurrite and belite in deeper parts. 2 to 7 kiln diameters
12.
Clinker Rings-Agglomerations of fine and coarse clinker very close to
the front end of the kiln. Sometimes encouraged by high ash coals especially if
flame is poor. 1 to 2 kiln diameters
13.
Much of the clinker sulfate is present as alkali sulfate, usually in the
form of aphthitalite (Na2SO4), arcanite (K2SO4) or calcium langbeinite
(2CaO.K2O.SO3) , or a mixture of some or all of these. Sodium and potassium
sulfates can affect strength development by increasing the alkalinity of the
pore fluid; when a sulfate ion reacts with aluminate phase to make ettringite
and is removed from solution, the loss of the sulfate ion is balanced by the
creation of two hydroxyl ions. This increased alkalinity accelerates alite
hydration, giving higher early strengths.
14.
Percentage of sulfatisation (SD) = %SO3/ 1.293 Na2O +
0.85 K20 x 100
15.
K2SO4 causes a decrease of the flow value of fresh mortar specimen
and lowers the bleeding and slump values of concrete specimens. Sodium
sulphate is found to be ineffective on the progress of hydration of C3A.
16.
If hydration of C3A in cement is not controlled, setting occurs very
rapidly and the resulting mix cannot be used for most construction
applications because of its high viscosity and low workability.
17.
Orthorhombic C3A lends itself to selective removal of Na from its
structure, creating two zones of attack; a surface layer or zone that is enriched
in Al, relative to the bulk composition and, at greater depth, a zone whereby
Ca and Al remain, but from which Na is actively removed by selective
hydrolysis. This selective removal explains the shorter reaction time of the
orthorhombic C3A
18.
Rheometric measurements showed that orthorhombic C3A mixes
presented higher increase in stiffness than cubic C3A at very early stages of
hydration. Thus, this crystalline form of Na-doped C3A (orthorhombic), when
present in high amounts in the clinker, may cause problems with setting time
and workability.
19.
In the presence of sulfur, alkalies preferentially form sulfates. If their
amount is more than the required stoichiometric balance, the excess will be
dissolved in the silicates, aluminates, and ferrites. The common alkali sulfate
phases formed are K2S04, also known as arcanite, sodium potassium sulfate,
also known as aphthitalite of a general solid solution composition (K,Na)2S04,
and Na2SO4, also known as thenardite .
20.
Burning conditions also significantly influence the formation of
sulphate so that oxidizing conditions produce calcium-potassium sulfate and a
reducing condition produces sodium-potassium sulfate.

21.
There exists a speed of rotation (the "critical speed") at which the
contents of the mill would simply ride over the roof of the mill due to
centrifugal action. The critical speed (rpm) is given by: nC = 42.29/d, where
d is the internal diameter in metres. Ball mills are normally operated at around
75% of critical speed, so a mill with diameter 5 metres will turn at around 14
rpm. The larger the diameter, the slower the rotation. If the peripheral speed of
the mill is too great, it begins to act like a centrifuge and the balls do not fall
back, but stay on the perimeter of the mill. The point where the mill becomes a
centrifuge is called the "Critical Speed", and ball mills usually operate at 65%
to 75% of the critical speed.
22.
C3S is much more reactive than C2S and under standard temperature
conditions of 20C approximately half of the C3S present in a typical cement
will be hydrated by 3 days and 80% by 28 days. The CSH produced by both
C3S and C2S has a typical Ca to Si ratio of approximately 1.7. This is
considerably lower than the 3:1 ratio in C3S and the excess Ca is precipitated
as calcium hydroxide (CH) crystals. Carbon dioxide is slowly absorbed to
convert the portlandite (Ca(OH)2) into insoluble calcium carbonate
C3S + 4.3H C1.7SH3 + 1.3CH
C2S + 3.3H C1.7SH3 + 0.3CH
23.
In the absence of soluble calcium sulfate C3A reacts rapidly to form
the phases C2AH8 and C4AH19, which subsequently convert to C2AH6. This
is a rapid and highly exothermic reaction. If finely ground gypsum
(CaSO42H2O) or hemihydrate (CaSO40.5H2O) is blended with the C3A
prior to mixing with water then the initial reactions are controlled by the
formation of a protective layer of ettringite on the surface of the C3A crystals.
C3A + 3C + 3SO4 + 32H C3A.3CSO4. 32H
C3A + dissolved calcium (Ca2+) + dissolved sulfate (SO42)+ water ettringite
When the available sulfate has been consumed the ettringite reacts with C3A
to form a phase with a lower SO3 content known as monosulfate.
C3A.3CSO4.32H + 2C3A + 4H 3(C3A.CSO4.12H)
Many studies have shown that the hydration of C4AF (or more correctly the
C2A C2F solid solution) is analogous to that of C3A but proceeds more
slowly. The iron enters into solid solution in the crystal structures of ettringite
and monosulfate substituting for aluminium. In order to reflect the variable
composition of ettringite and monosulfate formed by mixtures of C3A and
C4AF they are referred to respectively as AFt (alumino-ferrite trisulfate
hydrate)and AFm (alumino-ferrite monosulfate hydrate) phases.
24.
When cement is first mixed with water some of the added calcium
sulfate (particularly if dehydrated forms are present, and most of the alkali
sulfates present), dissolve rapidly. If calcium langbeinite is present then it will
provide both calcium and sulfate ions in solution, which are available for
ettringite formation. Sulphur combined in the clinker phases was reported to
have an accelerating effect on the cement setting while the sulphate combined
as alkali sulphate has a retarding effect.

25.
Rapid setting by potassium sulphate is due to the syngenite
(K2(CaSO4)2H2O) formation with a reduction of the sulphate from the
solution which prevents satisfactory retardation of C3A hydration. K2SO4
causes a decrease of the flow value of fresh mortar specimen and lowers the
bleeding and slump values of concrete specimens
26.
Setting time is a function of clinker mineralogy (particularly free lime
level), clinker chemistry and fineness. The finer the cement and the higher the
free lime level, the shorter the setting time in general. Cement paste setting
time is arbitrarily defined as the time when a pat of cement paste offers a
certain resistance to penetration by a probe of standard cross-section and
weight.
27.
The dehydrated forms of gypsum dissolve more rapidly than gypsum
and this is beneficial in ensuring that sufficient Ca2+ and SO4 2 ions are
available in solution to control the initial reactivity of C3A by forming a
protective layer of ettringite. An inadequate supply of soluble calcium sulfate
can result in a rapid loss of workability known as flash set. This is
accompanied by the release of heat and is irreversible. However, if too high a
level of dehydrated gypsum is present, then crystals of gypsum crystallize
from solution and cause a plaster or false set. This is known as false set
because if mixing continues, or is resumed, the initial level of workability is
restored.
28.
In the cement system, the presence of ettringite depends on the ratio of
calcium sulfate to tri-calcium aluminate (C3A); when this ratio is low,
ettringite forms during early hydration and then converts to the calcium
aluminate monosulfate (AFm phase or (Al2O3-Fe2O3-mono)). When the ratio is
intermediate, only a portion of the ettringite converts to AFm and both can
coexist, while ettringite is unlikely to convert to AFm at high ratios.
29.
Heating gypsum to between 100 C and 150 C (302 F) partially
dehydrates the mineral by driving off approximately 75% of the water
contained in its chemical structure. The temperature and time needed depend
on ambient partial pressure of H2O. Temperatures as high as 170 C are used
in industrial calcination, but at these temperatures -anhydrite begins to form.
The reaction for the partial dehydration is:
CaSO42H2O + heat CaSO4H2O + 1H2O (steam)
The partially dehydrated mineral is called calcium sulfate hemihydrate or
calcined gypsum (commonly known as plaster of Paris) (CaSO4nH2O), where
n is in the range 0.5 to 0.8.The dehydration (specifically known as calcination)
begins at approximately 80 C (176 F), although in dry air, some dehydration
will take place already at 50 C. The heat energy delivered to the gypsum at
this time (the heat of hydration) tends to go into driving off water (as water
vapor) rather than increasing the temperature of the mineral, which rises
slowly until the water is gone, then increases more rapidly.
30.
In contrast to most minerals, which when rehydrated simply form
liquid or semi-liquid pastes, or remain powdery, calcined gypsum has an
unusual property: when mixed with water at normal (ambient) temperatures, it
quickly reverts chemically to the preferred dihydrate form, while physically
"setting" to form a rigid and relatively strong gypsum crystal lattice:

CaSO4H2O + 1 H2O CaSO42H2O

This reaction is exothermic and is responsible for the ease with which gypsum
can be cast into various shapes including sheets (for drywall), sticks (for
blackboard chalk), and molds (to immobilize broken bones, or for metal
casting). Mixed with polymers, it has been used as a bone repair cement.
Small amounts of calcined gypsum are added to earth to create strong
structures directly from cast earth, an alternative to adobe (which loses its
strength when wet). The conditions of dehydration can be changed to adjust
the porosity of the hemihydrate, resulting in the so-called alpha and beta
hemihydrates (which are more or less chemically identical).
31.
On heating to 180 C, the nearly water-free form, called -anhydrite
(CaSO4nH2O where n = 0 to 0.05) is produced. -Anhydrite reacts slowly with
water to return to the dihydrate state, a property exploited in some commercial
desiccants. On heating above 250 C, the completely anhydrous form called anhydrite or "natural" anhydrite is formed. Natural anhydrite does not react
with water, even over geological timescales, unless very finely ground.
32.
Once the cement is mixed with water, the potassium sulfate undergoes
an exchange reaction with calcium and hydroxide ions to produce a dilute
potassium hydroxide solution and calcium sulfate:
K2SO4 + Ca2+ + 2OH- 2K+ + 2OH - + CaSO4

33.

Initially the porewater in concrete is a closed system, and the pH can reach 13
due to the Ca2+ and K+ concentrations. However, over time the solution
reacts with atmosphere CO2 to produce potassium carbonate:
2K+ + CO3 = K2 CO3
Optimum (SO3) = 0.556(Na2Oeq %) + 0.017659 (blaine m2/kg) 0.1072
Fe2O3% - 3.6004