Burnability and Clinkerization of Cement Raw-Mixes

BURNABILITY AND
CLINKERIZATION OF
CEMENT RAW-MIXES
T.K. Chatterjee
Mysore Cements Limited
UC0 Bank Building, Parliament Street
New Delhi 110 001, India
1. INTRODUCTION
T
he chemical, physical and mineralogical behaviour of raw-mix
considerably influences its burnability and reactivity. This ultimately
explains clinker formation in the presence of solid liquid gaseous
environments through extremely complex physico-chemical transformations
at regular temperature intervals. The characterization and evaluation of raw-
mix is essential for achieving suitabfe design of the raw-mix, smooth operation
of the kiln and cooler and better quality of clinker.
The reaction sequence during raw-mix sintering covers both solid- and
liquid-phase mechanisms, with the formation and decomposition of regular
intermediate compounds which, in turn, get transformed into major clinker
phases, such as C3S, &C2S, C3A and C,AF.
This paper attempts to highlight the burnability and reactivity of raw-mix
and its effects on the behaviour of raw materials, as well as the reaction
sequence and kinetics of clinker formation, with a view to ascertaining their
importance in a clinker-making process. A study on these lines is obviously
difficult but will, however, provide positive guidelines for further development
in the existing technology, reduction in energy consumption, improvement
in clinker quality and optimization in system design.
2. BURNABILITY
Burnability of raw-mix has been a matter of great importance in cement

technology. Raw-mix behaviour during its sintering process is greatly
influenced by its chemical, mineralogical and granulometric compositions.
Variations in these affect kiln operation, refractory lining, fuel consumption
Burnability and Clinkerization I1
and clinker quality. Each cement raw-mix burns in its own way, resulting
in variation of clinker quality.
2.1 Definition
The burnability of a cement raw-mix conceptually denotes the amount of
mass transfer of its constituents with ease or difficulty to the clinker phases.
By convention, burnability is measured by determining the CaO, (free lime)
after burning the raw-mix for a certain time (19) at a certain temperature (T);
i.e.
CaO, = f (0, T)
when melt is formed, above 1300°C burnability decreases by increasing this
parameter.
2.2 Expression
Burnability is generally expressed by either of the following two quantities:
- Measure of CaO, of a pseudo-isochrone (0= const.) at a given
temperature. Increasing values of CaO, correspond to decreasing
burnability.
- Measure of time (0) of a pseudo-isotherm (T = const.) for CaO,<2%.
The increasing of 8 corresponds to decreasing burnability.
2.3 Factors Affecting Burnability

The following are the important parameters which considerably affect the
bumability of raw-mix:
2.3.1 Raw-mix-Mineralogical composition

- Lime components
- Clay components
- Corrective ingredients
- Modifiers
2.3.2 Raw-mix-Chemical composition

- Main component relations
- Minor non-volatile components
- Minor volatile components
2.3.3 Raw-mix-Granulometric composition

- Fineness
- Particle-size distributions
- Homogeneity and compaction
2.3.4 Raw-mix-Thermal Treatment

- Firing temperature
- Heating rate
- Burning period
- Burning activation
12 Progress in Cement and Concrete
2.3.5 Liquid phase formation

- Appearance temperature
- Amount
- Viscosity
- Surface tension
- Ionic mobility
2.3.6 Clinker quality

- Silicate phases
- Alumino-ferrite phases
2.3.7 Coal ash

- Amount absorbed
- Composition
- Fineness
2.3.8 Kiln atmosphere

- Oxidation
- Reduction
2.3. I Raw-mix-Mneralogical Composition

Cement raw-mix represents a polymineral and polydispersive mixture whose
composition can vary within a wide range due to the character of raw
materials used. In the clinker-making process, 90% of the raw-mix
constituents comprise the four major oxides, viz. C, A, S and F, and the
remaining 10% is made up of minor constituents. These oxides occur in the
form of minerals and compounds in the raw materials and dissociate into
oxides through high-temperature treatment in kiln. Constituents and
compositions of raw-mix are shown in Table 1.
Table 1. Raw Mix-Constituents and Compositions
Raw Mix
Corrective
Lime components Clay components ingredients Modifiers
Consisting mainly Consisting mainly Consisting mainly

of CaC03 and a of SiO2 with of any of the main Consisting of
very small quantuy considerable oxides (C,A,S,F) different
of the following in amounts of the inorganic
the order: following in the compounds which
S-M-R-F-S-N-K order: accelerate the
R-F-C-M-S-N-K clinkerization
reactions.
Burnability and Clinkerization 13
2.3. 1. 1 CaO-carriers
Calcite, aragnonite, dolomite, ankerite, etc. are the main carriers of CaO.
The dynamics of carbonates in the raw-mix depend on the type of carbonates,
their crystal structures, microstructural peculiarities, and the dispersability
of crystals and impurities present. The dissociation temperature of the
individual mineral and appearance of CaO in the most reactive state decreases
in the order:
Calcite (aragonite)-dolomite-ankeritecl)
2.3. 1.2 Acidic oxides IS, A and 17 carriers

It is well known that SiOZ and A1z03 are found in raw-mix in the form
of various clay minerals (kaolinite, montmorillonite, hydromicas, chlorite,
etc.) micas, amphiboles, epidote, pyrophyllite and feldspar; Fez03 and
Al203 are often found in diaspore, bohemite, hydrohaematite,
hydrogoethite, goethite, etc. The reactivity of clay minerals with CaCOJ
increases according to the following order:
muscovite-montmorillonite-chlorite-illite-kaolinite~~~~~
Amorphous Si02 or Si02 combined with A&O3 and/or CaO, and/or
Fez03 shows better reactivity than free SiOZ. The reaction of different forms
of silica with CaO increases in the following order:
quartz-chalcedony-opal-cr-crustobalite-o-tridymite-silica of
feldspar+silica of micas and amphiboles-silica of clay minerals-silica
of glassy slags(r)
Minor volatile and non-volatile components are always present in main
oxides. The concentration of minor constituents in the raw-mix is in the
following order(h):
M - K - S - N - Ti - Mn - P - Sr - F - a - Cr
The temperature and rate of volatilization of miner volatile compounds
are dependent on the mineral form of materials bearing these components.
As, for example, S from pyrites volatalizes at much lower temperature than
from gypsum. Similarly, alkali from silica vaporizes at lower temperature
than feldspars.
2.3. 7.3 Correc rive ingredients

Whenever necessary, the raw meal is corrected with small amounts of
ingredients to adjust the raw-mix design in the desired range. Usually siliceous
materials, laterites, bauxite, pyrite, flue dust or sand (5) are used, depending
on the lacking oxide and the material available at the lowest cost.
2.3.1.4 Modifiers
These are minor components called fluxes and mineralizers acting in the
liquid and/or liquid-solid phase. Whereas fluxes lower the temperature at
which the liquid phase appears, mineralizers accelerate the rate of
clinkerization@. CaFz, Na$SiF6, CaSO,. 2H20, Caj (PO,),, etc., are often
used in a very small quantity with the raw-mix as modifiers.
2.3.2 Raw-mix-Chemical Composition

Raw-mix constitutes four main oxides (C. A, S and F), together with the
minor volatiles (K, N, S, p, F, fi and H and the non-volatiles (Sr, M,
Ti, Mn, Sr and Cr). Each component of the raw-mix has individual and
combined (M,, MA, LSF and Ms) effects on its bumability, which has been
illustrated in Table 2. The approximate range of chemical composition of
raw-mix and the potential clinker minerals formed after burning the raw-
mix are shown in Table 3.
2.3.3 Raw-mix-Granulometric Composition
2.3.3. 1 Fineness and particle-size distributions

Fineness and particle-size distributions greatly affect raw-mix burnability.
The more fine grained the raw-mix with greater surface area, the easier it
is to sinter and lower the sintering termperature. In some raw-mixes, further
grinding has particularly no influence on burnability.
Increasing the coarseness of alumina and limestone is found to have an
effect on raw-mix burnability whereas the coarseness of quartz is found to
have a marked effect(43). One percent quartz grains over 100 pm can be
regarded as equivalent to 6% calcite grains of the same sizecU). Increasing
the size of Si particles from 0.09-0.15 mm to 0.3-0.46 mm increases CaOr
from 0.5 to 0.8% at 1550°C but increasing the coarse silica from 0.5 to 2.0
mm and burning at 1500°C for 30 min. increases CaOr from 0.7 to 3.7%f45).
So it could be pointed out that more than 0.5% Si particles about 0.2 mm
size of 1% between 0.09 and 0.2 mm should not be present in the raw-mix.
Calcite particles above 0.15 mm size can be tolerated without serious effect,
while with enriched siliceous limestone, the proportion of coarse particles
could be higher.
In fact, the maximum permissible particle size of quartz, feldspars and
calcite is recommended to be 44 pm, 63 pm and 125 pm, respectively@@.
The normal target of fineness of raw-mix is 12% residue on 170 BSS mesh
and 2.6% residue on 72 BSS mesh. This target differs from plant to plant.
Control of particle size is very important since the sintering rate is roughly
proportional to the inverse of the particle sizd4’). It has also been seen that
the reactivity of cement raw-mix decreases linearly with the reciprocal value
of the product of the squares of the average calcite and quartz grains(4@.
2.3.3.2 Homogeneity and compaction

Homogenization of kiln feed is a major operation in cement manufacturing,
as it affects the quality of clinker, burning process and fuel consumption.
Low reactive materials like quartz, due to their differential grinding,
concentrate primarily in the coarse fractions of raw-mix and thus disturb
their homogeneity. It is very difficult to get an absolutely homogenized mix
since there are always grain contacts between A-A, A-S, S-S, etc., resulting
in micro inhomogeneity. Mineral homogeneity is increased by using the least
number of raw materials in a mix.
?A
Parameter/ Empirical Limiting Preferable Effects Ref.
Characteristic formula range range 003
3
2
3. Lime- 0.66 - 1.02 0.92 - 0.96 A higher LSF 8, 12-15 se
saturation L S F , = - loo’ 1. makes it difficult to burn raw-mix
factor (LSF) 2.8S+ 1.65A+0.356 Q
2. tends to produce unsound cement 3
(MA >0.64)
(high CaO,) 3
1OOC 3. increases C$i content :
LSFz = 2.8S+l.lA+0.7F - 4. reduces C2S content 5
W,t Q0.W 5. reduces C,S content
6. causes slow setting with high early s
LSF = _ lOO(C +0.75M) strength R
3 a
2.8S+ 1.18A+0.6+ 3
(Mg2.0)
lOO(C+UM)
or =
2.8S+ 1.8A+0.65F-
(M > 2.0)
B. Minor Non-volatile Components A higher St 8

1. Free silica Sl O-3% as low as 1. increases power and fuel consumption
(SiO, in possible 2. causes difficulty in coating formation
different 3. deteriorates refractory lining
forms) 4. increases the radiation of heat from kiln
shell
5. increases kiln exit-gas temperature
(Table 2 Contd.)

Characteristic formula range range
2. hlagnesium M O-S% o-2% ’ A Higher M

oxide (h&O) 1. reduces viscosity and surface tension of
clinker liquid and increases ionic mobility
2. favours the dissolution of C,S and CaOl at
higher temperature and lets C,S form more
quickly.
3. tends to ball easily in the burning zone
which affects kiln operation
4. leads to unsoundness by forming periclase
crystals when M > 2%
5. increases CpS and melt but has no effect on
C2S (M <2Qo)
6. volume instability in the presence of
2 )M 26, neutralizes when Qo SO, = 0.67
3. Titanium O-4% 1S-2% A higher Ti
oxide (TiO,) 1. results in sharp reduction in C,S content
with equal gain in C# content and
appreciable variations in other phases.
2. reduces viscosity and surface tension of the
melt
3. reduces grain sizes of alite and belite
4. causes slower setting and lower early
strength
5. forms darker colour clinker
(Table 2 Contd.)
C. Minor Volatile
Components
1. Alkalies
(KsO + NazO) (K+N) o-l% 0.243% A higher (K+N) l&u),24
29-30
1. improves burnability at lower temperature
and deteriorates at higher temperature,
specially when (K + N) > 1%
2. increases liquid content and coating
formation
3. lowers the solubilty of CaO in the melt
4. breaks down alite and belite phases
5. creates operational problems due to external
and internal alkali-cycle formation (volatility
(K>N)+
6. when (N% + 0.659 Kilo) >0.6%-causes
alkali expansion
2. Sulphur s O-4% OS-2% A higher S
compounds
(SZ-, sop, 1. acts as an effective mineralizer and modifier
sot- of the alkali-recycle by forming less volatile
(N,K) SO4 compounds&en S > (K + N)+
2. lowers the appearance temperature of liquid
phase by oved lOO”C, decreases its
vtscostty and surface tension and increases
ionic mobility of oxides.
(Table 2 Contd.) 8
Parameter/ Empirical Limiting Preferable Effects Ref. 2

CllUWthtiC formula range range 8
ii
3. increases belite formation where there is no
effect on alite or melt
4. decomposes alite at 1250°C if high alkali
sulphates are present.
5. when SO, >2.5-4.0%, causes sulphate
expansion
6. improves burning of raw-mix at lower
temperatures and deteriorates the same at
higher temperatures
7. decreases hydraulic and mechanical strength
3. Phosphorous P O-l% 0.3-0.970 A higher P
pentoxide 1. accelerates the clinkcrixation reaction
(pm 2. reduces the intensity of internal recycle
3. reduces early strength
4. reduces C3S content
4. Fluoride (PI- F O-0.6% 0.03-0.08% A higher F
1. leads to hrgher values of Pco, = f(t) and
modifies the kinetics of all the burning
reactions
2. lowers the jemperature of C,S formation by
1 so-200°C
3. has no effect on the internal cycle in the
kiln
4. decreases mechanical strength of the
clinker
(Table 2 Contdl
Parameter/ Empirical Limiting Preferable Effects Ref

5. Chloride O-0.6% O-0.015% A higher Cl 8,20,35

(Cl’ -) 1. forms more volatime (K,N) Cl and
causes operational problem due to its
complete vaporization in the burning
zone
2. increases liquid formation and melting
point of the absorbed phase is
drastically changed
3. increases ring formation by readily
forming spurrite (2CrS.CaCOs)
4. a by-pass is required if ni>O.O15
6. Moisture lo-35% 15% (dry) A higher H
OH’-) 30-35% 1. increases bumability
Wet) 2. increases fuel consumption
loss on ignition
l When M,, = 1.23. liquid appears at 1338T in C-A-S-F system.

MA = 1.63, liquid appears at 1301°C under MgO saturation conditions.
t when g(N +K) < 1.25 -alkali bypass is not required(*)
# Sulphate modulus, M&42) is defined as S/O.85 (K + 1.52N) Whsn Ms < 0.5-S bounds to alkalies,
0.5 >MQ< 1.0 - an increasing portion of S bounds to calcium (CaSO,),
Mi = 1.0 - a constant fraction (70-90%) of the alkalies found as sulphate, (N,K)$$04.
Table 3. Composition of Raw-Mix and CUnker Minerals
Raw-mix-Composition Clinker minerals-Composition
Chemical Chemical Mineralogical

composition Range (o/o) composition* Range (Vo) composition+ Range (@IO)
LOI 35*2 LOI 0.3 f 0.2 c,s 55*10

C 42*2 C 62&S c2s 25+10
s 14*2 S 20*6 C3A 9*4
A 5i2 A 6i2 C,AF 11*4
F 2fl F 3&2 M 3.5* 1.5
M 3kl.5 M 3.5+ 1.5 CaOr l+l
W+N 0.7 f 0.3 W+N) 0.7sto.3
S l.Szt1.2 S 1.5k1.2
l Traces of other minor constituents. LOI = Loss on ignition

+ Liquid - 24 f4%
fluctuation of the kiln feed measured as 070 CaCOj should not be more
than k0.29’0 from the holding point. An increase of 1% CaC03 will
increase CgS by 13% and reduce C2S by about 11.5%.
The ultimate homogeneity depends on the physicochemical characteristics,
fineness and particle-size distribution, method of mixing and efficiency of
the blending system.
2.3.4 Raw-mix Thermal Treatmtnt
2.3.4.1 Firing temperature
In clinker burning, the temperature must be fairly enough for the formation
of the alite phase. Burning of raw-mix is generally carried out at 14%1500°C.
An excessivelv high burning temperature results in high stress on the kii
and the refractory lining, more fuel consumption, reduction in cement
strength(* and larger alite crystalso@. Increase in burning temperature from
1360 to 1420°C results in lowering the burning period by half. Maximum
firing temperature was determined by a multiple regression analysi@) of
raw meal containing only the four main oxides as given below:
“C = 1300 + 4.51 C3S - 3.74 C3A - 12.64 C&F (1)
2.3.4.2 Holding time
On increasing the holding time, the following changes may be
observed(“):
1. C3A content decreases and C&F content increases.
2. Q3 decreases and C3S increases.
3. Higher mechanical strength at later ages and lower at early ages.
4. Heat of hydration at early ages decreases.
5. Unburnt clinker produces highquality cement even in the presence of
high CaOr.
2.3.4.3 Burning rate

Rapid burning is favoured for the following reasons(52$53):
1 . More coarse-grained materials can be charged
2 . Materials differing in their degree of fineness can be charged.
3 . Fine grains of C# are formed which accelerate the interaction of CzS,
CaOr and liquid.
2.3.4.4 Burnmg activation
Thermal activation may be enhanced by either accompanying it with
mechanical (vibratory mill) or chemical (mineralizer) activation. Mechanical
activation gives better results than chemical activatio@J.
2.3.5 Liquid phase of formation
A, F, M-minor volatile and non-volatile components-generally govern the
amount of liquid formed, its appearance, temperature, viscosity, surface
tension and ionic mobility in the clinkerization process, which is explained
in Table 2. The range of clinker composition may be fairly wide if the amount
of liquid phase increases slowlyC~s).
A clinker with about 25% liquid phase from a raw-mix is generally
considered an ideal raw-mix for kiln lining, fuel saving, rapid C3S
formation through the dissolution of CIS and CaO, and economical clinker
grinding. The liquid phase at 1450°C is usually calculated by the Lea and
Parker formulacss) which is written as:
3.0 A-2.28F+K+N+M (2) when MA > 1.38 (2)
8.5 A-5.22F+K+N+M (3) when M, c 1.38 (3)
2.3.6 Clinker Qua&y
It has been see@) that the burnability becomes worse as the potential C3S
content increases at the expense of other clinker constituents, while an
increasing C3A and C&F potential content improves the burnability the
C&F being significantly more effective in this respect.
2.3.7 Coal Ash Ztt~ence
When coal is used as the fuel for clinker-making, its ash content, composition
and fineness affect bumability. Generally the composition of coal ash varies
within the limits: S-35-60%, A-15-35%, F-5-20%, C-O-IO% and M, ?l and
alkalies are often present in the ash in small amounts. In general, the ash
composition shows a very high S/C ratio and moderately high A/F ratio.
On the whole, the effects of ash absorption on burning are as follows:
1 . LSF decreases and Ms increases.
2 . The composition of silicate phases changes.
3. Liquid content increases with reduced viscosity and increased ionic
mobility.
4 . Molten ash penetrates rapidly from the outer surface into cracks and
openings in the clinker ininerals by permitting the ash to react in pockets,
resulting in C,S-rich areas(m.
5 . Introduction of a degree of microinhomogeneity due to ash-clinker
reaction, resulting in some reduction in the strength.
24 Progrcrs in Cbnent and Concrete
2.3.8 Kiln Atmosphere

Reducing conditions (inadequate oxygen in the kiln gas) during cement
clinker-burning substantiahy affect the colour of the clinker by producing
ferrous oxide, accelerate the setting by enhancing C,A content at the
expense of C,AF, and reduce the strength by breaking down C,S during
clinker coolir@~. Therefore, oxidizing conditions (O-l-2 vol. % in exit gas)
should be maintained in the kiln for better clinker quality.
3. RAW-MIX CHARACTERIZATION AND EVOLUTION

The characterization and evaluation of raw-mix is essentially done through
some tests for optimizing the burning of clinker raw meal. These tests are
accompanied with two divisions:
(A) Proposed raw-mix
(B) Laboratory-prepared clinker
(A) Proposed Raw-mix

A raw-mix is prepared similar to that proposed to be used to manufacure
cement. The raw-mix should then be evaluated by the following routine
analysis:
1. Fineness and particle-size distributions
2. Chemical analysis
3. X-ray diffraction
4. Volatility test
5. Differential thermal analya.
6. Thermogravimetric analysis
7. Burnability test
(B) Laboratory Prepared-clinker

Laboratory prepared-clinker is made by burning the proposed raw-mix for
a certain time (usually 60 min) at 1400°C. The laboratory prepared clinker
is characterized by:
1. X-ray diffraction
2. Scanning electron microscope
In this chapter only the techniques for the evaluation of raw-mix bumabiity
will be discussed.
The burnability of raw-mix can be characterized by:
(i) a purely theoretical approach,
(ii) a semi-experimental approach, or
(iii) a purely experimental approach.
3.1 Theoretical Approach

In this approach, empirical equations are used for calculating the bumability
index (BI) factor (BF) through physical or chemical character istics of raw-
mix. The empirical relations shown in Table 4 are derived by different authors.
Burnability and Clinker&ion 25
Tab&k 4. Empirical Equations Used for Burnabi&y In&x Ga&&tion
Burnability Empirical equation Equation Reference
index/factor No.
BI, C3S/C,AF + C,A (4) 58

BIZ C3S/C,AF+C,A+M+K+N (5) 59
BFI LSF+IOMs-3(M+K+N) (6) 60
BFz LSF+6(Ms-2)-(M+K+N) (7) 59
Btll 55.5+ 11.9R++ + 1.58 U-9 61
(LSF, - 9oy - 0.43 Lf
Where L, = amount of liquid phase at 1350°C after IMII@~

R +9o*m = mass % raw meal retaines on 9Ow sieve.
The BF seems to be more practical as it involves LSF and moduli. In the

case of BI, the potential composition of phases are calculated, using Bogue’s
equation(43). However, Bth, which takes into account the chemical
characteristics, granulometry, heterogeneity and liquid content, seems to be
more accurate.
3.2 Semi-experimental Approach

In this approach, a minimum number of experiments are used in empirical
equations to calculate the burnability indices.
3.2.1 Freei%ne Temperature Integration iUethodc61,

In this method, the burnability capacity is measured by a quantitative
expression related to the CaOr = (‘I,@ trend in the overall 10W’C to 1450°C
range, maintained for 20 min, at each temperature and is expressed by:
B C = y (9)
where C is the sum of total CaOr at different temperatures (lOOO-145O”C),
expressed as :
+4c MOOT + ~%o”c (10)

This method seems to be rational, as it evaluates bumability on the basis
of the course of reactions in the overall lOOO-145O’C range.
3.2.2 Statistical MO&W

In this method, ten parameters have been chosen to determine burnability
indices. These are MS, LSF. M& R+~o,,,,,, (N+ K), M, S, S+ZOO,, Ms.MA, F
and mica minerals (GI). The model expressed by:
0.022Y - 1 - J(O.022Y - 1)s + 0.01 l&W
CaOis’ 1400°C =
0.008Y
26 Progms in Cbnent and Concrete
Y = Y,f + g aiXi
i=l (12)
and CaOref - 5
Y&= .
- 0.oo4@0,f - 5>2 + O.O22(CaO,,r - 5) + 1.174
(13)
where CaOrd = CaOf of the reference raw-mix
xi = difference between value of each parameter and reference
mix,
a, = (constant), coefficients of xi defining the regression.
3.2.3 Chemico Granulometdc Approachc6J,
In this approach, both chemical and granulometric composition are taken
into account and CaOr is determined affter firing at 1400°C for 30 min.
Caq’,,., = 0.33 LSFs + 0.018Ms + 0.56CaCOs. izrm
+ 0.9353+,, - 0.349 (14)
This equation is justified for moderate variations from the reference sample,
representing the average values:
LSF, = 0.953 f 0.038; (Jaw + 12sw = 0.026 f 0.021
MS = 3.7*1.5; S +o)cm = 0.018*0.020
MA = 2.2 f 1.6 and CaOt = 0.057 f 0.043
However, for larger variation in LSFs and Ms, a non-linear expression will
be needed to fit data.
The above approach was further modified recently@@ by the following
expression:
Caq’ r,., = 0.33 (LSF-(LSF) (MS)) +0.93S+44cm
+ 0.56 CaCO, + lurm + 0.24 (15)
where LSF (Ma) is a function of Ms and determined experimentally by a
correlation analysis:
LSF (Ms) = -5.1 Ms+ 107 (16)
This equation is valid for 88<LSF<lOO and 2<Ms<6, and
Ap = total acid residue - quartz.
It has been seen that excellent burnability could be obtained if
0.56 C&O3 + ,=,,,,, < 1% and A, < 2%.
This expression, as claimed, can be used in any plant for evaluating the
effect of changes in raw-mix design on bumability.
3.3 Experimenti Approach
The best way to determine the bumability of a raw-mix is by an experiment
In the hboratory which takes care of all known and unknown factors
hfhmchg It. ‘i’be C&f content in the burnt clinker thus becomes the single
criterion to arrive at any conclusion. Several methods are derived for

measuring CaOf experimentally.
3.3.1 Bumability Scalef~~

BS = 070 CaOf (10% LOI)
(17)
% cao,
One gram of raw-mix is heated at 1100°C for 20 min. and then the CaOf
is determined. The LO1 and CaOf are determined from the original raw-mix.
A higher BS signifies a harder burning mix.
3.3.2 Practical Bumability@l)

In this method, Practical Burnability, I& is determined by the time
required for firing the raw-mix in a rotary furnace at a constant temperature
of 1350°C to attain a CaOf <. 2%. This results in the possibility of the
prediction of a theoretical burnability, Bc,...e.q. 8
(correlation coefficient, 7 = 0.94)
The temperature-dependent practical burnability may be derived@@ from
the CaOf - 8 slope and follows an exponential equation:
B*r = B1sa exp (0.0126 (1360-T)) WI
In another approach, CaOf -8 was further modified by accounting
simultaneously for the temperature effect, This new bumability factor@)) is
expressed by:
Ca0f.B. (T°K)4.
A higher value signifies a poor mix. It is claimed that this approach would
provide a rapid and reliable evaluation of cement-raw-mix.
However, for practical purposes, the characterization of the raw-mix may
be evaluated at three significant temperature intervals: SOO-lOOO”C,
lOOO”-1300°C and 1300-1450°C. Under standard conditions of temperature
and time gradient, these could supply a more useful resuM4).
4. REACTIVITY
4.1 Definition
The reactivity of raw-mix is defined by the overall rate of chemical reactions
among the represented constituents of the raw-mix, attained on burning it
at a certain temperature for a certain time, i.e. I& = f (T,@; this parameter,
however, has no effect on reactivity when melt is formed above 1300°C.
4.2 Factors Affecting Reactivity

The reactivity of raw-mix is influenced by:
1. Physiwchemico-miner~o~~~~~o~c composition as explained
in Section 2.3.
2 . Chemical process of clinker mineral formations as explained in Section
5.2 and 5.3.
4.3 Division and Characteristics

Reactivity may be divided into two groups:
(a) Low reactive raw-mix
(b) High reactive raw-mix
Low and high reactive raw-mixes show marked influences on process and
clinker character. This has been shown in Table 5. The above characteristics
chart reveals that a high reactive raw-mix is always preferred.
Table 5. Characteristics of Low and High Reactive Raw Mixes

Characteristic Low reactive High reactive
Feed consumption High Normal

Sintering temperature figh Comparatively low
Burning period Long Relatively short
Molecular dispersion rate Low High
Diffusion process rate Low High
Clinker mineral formation rate Low High
Mineral formation Unsatisfactory Desirable
Ring/coating formation Uncontrollable Adjustable
Kiln Capacity’ Larger Optimum
Fuel consumption High Economical
4.4 Determination
The reactivity of raw-mix may be determined@@ from the chemical
composition and sieve analysis of the raw material and sieve analysis of
insoluble residue. An empirical equation proposed to determine raw meal
reactivity may be written as:
J&c 1 (19)
R, =
r2 r2
= 9 C 3 S ma% “5
where
L = liquid-phase quantity in the clinker
C3L = equilibrium C3S content in the clinker
5 = average particle radius out of 25% of the coarsest ra&meal
particles
% = average particle radius (only retained on 40~ sieve) of the
insoluble residue of the meal in HCl
s = computed for reference raw meal
The proposed method neglects the errors accounted for minor constituents,
liquid-phase quantity, alite contents and insoluble residue. These simple
aperiments, therefore, are suitable to investigate the reactivity of raw meals
collected from the same localities.
6. REACTION SEQUENCE
The course of reaction inside a rotary kiln has been of great interest to the
cement technologists, since the kiln is computer-controlled and, obviously
a mathematical model to explain the reaction process is to be constructed
in order to find a logical relation between the process variables.
5.1 Kiln Temperature Profile
It might be worthwhile to have an idea of the specified zones which give
a clear picture of the reaction sequence in burning a cement raw-mix at critical
zones to finally obtain the clinker through a complex physico-chemical
transformation. The zones are conceptually defined by the temperature ranges
and reaction profiles shown in Table 6.
Table 6. Zones Defmed by Temperature Ranges and Reaction Profiles
Zone Temperature Reaction

range “ C profile
I up to 200 Evaporation (slurry drying)
II 200-800 Preheating (dehydration,
dehydroxylation and fiit
appearance of new phases)
III No-1100 Decarbonization (calcination)
IV 1100-1300 Exothermic reactions
V 1300-1450-1300 sintcring
VI 1300-loo0 COOlhg
The material and gas temperatures as well as reaction zones are

differentiated and illustrated in Fig. 1.
5.2 Basic Reaction-Experimental Observations
There is a glaring lack of clarity in the understanding of the reaction sequence
of cement raw-mix in a kiln, owing to the wide variations in raw-mix physico-
chemical compositions, kiln operating conditions and, the practical difficulty
of taking out hot samples from different points of kiln for study in the hot
condition.
One of the very early studies(‘Q demonstrated that in the burning process,
dehydration, dissociation and decarbonation of the raw-mix components
proceeds simultaneously with the formation of new phases.
Subsequent experimental observations by different investigator@~ 619 7i-74)
have been summarized in Table 7(79. These studies also revealed the
following phenomena:
1. The first aluminate phase “CA” is fomed at lower temperatures
(5%-600”C) and this, in turn, combines with free CaO resulting in the
30 Progress in Cemeai.anU Concrete
Dry proccr kiln
0
1 and11 Zones 111 IV v
-2000~ I II 111 IV v
Wet proara kiln
tsoo-
% otthe kiln length from. feed end
Figure 1. Material and gas temperature as well as reaction zones in

wet and dry process rotary kiln.
formation of an intermediate phase &A7 and finally it converts into
Cpl above !WO’@).
2. The formation of C&S as an interm&ate phase is likely but dependent
on the nature of raw materials used@s* 72+ ‘3).
3. The ultimate formation of C&F at higher temperatures (1300-14WC)
is consecutively followed by the appearance of ferrite phases (CF and
C2F’) at lower temperatures (800-900”C)(72~.,
Parallel and/or subsequent plant studieso679) on the reaction sequence in
the clinkerization process led to the following observations, which also
confirmed the above findings:
1. The reaction sequence of raw-mix is almost identical in dry, semi-dry
and wet kiln.
Table 7. Clinkerization Reaction Sequence as Observed in Some Investigations
Reactions Temperature range (’ C)
Ref. 71 Ref. 72’ Ref. 55 Ref. 74 Ref. 61
Commencement of compound formation 550-600 800 up to 800 550 600

and reaction products CA C2F CA + CF C2S + different CA+ CL2A, + C$
(CF appears aluminates +
at 800-900) C2 (A.F)
Commencement of decarbonization 600 - 600
Coexistence of free lime with
other phases - - 900 17% at lCKtO+
Formation of C;S 700-750 9cKLllOO 800-900 550 600
Formatron of t&A, 950 1000-1100 !900-1000 550 600
Appearance of C,A 950 1100-1200 1100-1200 - 1000
Appearance of ajumino-ferrite 950 1300-1400 1100-1200 -
Appearance of liquid phase - 1200 1280 -
Formation of CsS - low-1100 1200-1450 1280 At higher
temperature
l Free CaO does uot occur in cxccss of 2% until the entire A1203, Fe303 amI SiO3 have combined with CaO.
+ CoUktbphases at different temperature8 as reported: GF (8W’C). C2F + CF (900°c), C2S + C2S + C2AS + CF + C2F(l@)00C),
C3S + C3AS + CsAdC12A7) + C3S + CF + C3F (1 loO’C), C3S + C3A + C3A3 (Cl3A7) + C3F + C3S (lZOO”C), C3A + C3S + C3S + C3F (13OO’C)
and C,A+CsS+C#+C&F (MOO*C)
3 2 Progress in Cement ond Concrete
2. The dissociation and decarbonation of raw-mix components start at
550600°C. The CaO formed during decarbonation reacts with other
components simultaneously in such a way that about 2% CaOr at 800°C
and about 17% at complete decarbonation temperature (1000°C) remain
unreacted(‘Q .
3 . The first detectable phases CA+C12A7+ C$S were noticed at 700°C.
The amount of these phases increases with temperatures up to
900-lOOO”C, when poorly detectable C&S and some C4AF/C2F are
traced(‘6).
4. In some other investigationsc 7rv7*), the first phases detected are
CF + CA + CS which are subsequently converted into clinker phases with
rise of temperature in accordance with the following scheme:
CA C12A7 C3A
CF C2F C4AF
CS c3s2 c2s
5 . a-Fe, Fe0 and Fe203, along with the formation of a-wollastonite

almost concurrently with P-C2S are detected from a series of charge
samples@@.
6. An extensive study was rnade(‘9) after comparing with five kiln
charges/coating and a reaction sequence was derived accordingly (as
shown in Fig. 2), which further confirmed the above observations.
Row mater ids Intermediate phase Clinker phases
Figure 2. Reaction sequence in cement rotary kiln.

Burnability and Ciinkerization 33
7. The solid-state reactions are almost complete at a temperature of about

1300°C and a melt phase appears.’ The melt phase contains a complete
melting of CsA + C&F, and partial melting of CzS and CaO with the
incorporation of constituents such as MgO. The formation of CsS is
activated through the diffusion of CzS and CaO in the presence of melt.
The final clinker phases appear with the formation CsA, C&F, C#,
CsS, MgO and glass after crystallization of the residual liquid.
5.3 Secondary Reactions-Presence of Minor Constituents and

Catalytic Additives
Apart from the controversial appearance of intermediate phases like CS,
C& CzAS, various investigators identified different intermediate
compounds or complexes stably co-existing in the presence of various catalytic
additives or minor constituents in raw-mixes, at temperatures ranging from
100 to 1300°C. Important findings of various investigators after the
compilation of the observations, are summarized in Table 8c”).
In addition to the above findings, the formation of spurrite 2C#. CaCOs
is detected from the coating samples when they were withdrawn at
temperatures ranging from 680-lOOO”C, particularly in the presence of halides
and alkalies in the raw-mix. The mechanism of its formation has been studied
by different investigators and explained on the following lines:
1. Low melting alkali/calcium carbonates might form and promote spurrite
formatiotW.
2. Spurrite formation is perhaps due to faulty control of burning
conditions(s2).
3. The most logical argument(79) probably was that spurrite formation was
initiated by CzS since spurrite + quartz or spurrite+&CzS were not
found.
4. Spurrite, after reaching the very hot atmosphere of the kiln where CO2
content is low enough, decomposes into CsS or CzS + CaO. Thus it
helps in CsS formation.
5. The formation of C12A7. CaCOs has also been reported along with
spurrite(
Gehlenite, C2AS (or melilite with very little magnesia), was detected in the
coating sampledsO) from a kiln and it has been suggested that CzAS is the
product of the reaction between kiln refractories and clinker-forming
materials. C2AS is particularly found where high alumina bricks would
normally be used, but akermanite and melilite would also be expected when
dolomite or magnesite bricks are used.
It is reported that magnesio-ferrite, MgO/Fe0.Fe20s, is formed when
raw-mix is burnt in a coal-fired kiln under reducing condition@).
From the above studies onthe reaction sequence, it is evident that the
clinkerization process involves the ultimate stabilization of CsS, &C&I, CsA
and C&F through various stages of decomposition, interactions and
crystallization. The stability ranges of the more commonly encountered phases
Tab& 8. Intermediate Compounds

Catalytic Intermediate Stability range Remarks
additives or compounds
minor
constituents
Phosphorous 7Ca0.P20,.2Si02 up to 1450°C At 1450-1500°C they

pentoxide 9 Ca0.P,05.3Si01 dissolve, recrystallizing
5Ca0.2P,05.Si02 C2S + C3S. Some com-
5 .3Ca0.2Pz05.Si02 pounds may remain in
7.3 CaO.P,Os.SiOs clinker without decom-
27CaO.P,0,.12SiOs position. The presence of
Ca3PW3F CsP and C,P is possible,
if P,Or >0.5
Chromium cao .cr203 1ooo-1400°c Cr in clinker is normally
oxide CaOCrO, present as Cr3+, Cr5+
and
ZCaO.Cr,Os Cfi+ and rarely as Cr2+
3Ca0.Cr205
9Ca0.4Cr0,.Cr203
3Ca0.Cr203.3Si02
18Ca0.10CrO~.Cr,03
7Ca0.Cr,0s.2Si02
4Ca0.3Al,0s.CrOs
Sulphur 3(CA).CaSO, 900-1400°C
compounds Z(C,S).CaSO,
3(CsS).CaSO,
CaSO,. 1.75SiOs
2CaSO,.K,SO,
3Na$3O,.CaSO,
Alkali Na2WC03)2 up to The resultant eutectic
compounds Na2C0s.2Na2S04 780-830°C melt helps the develop-
CaS0,.3Na2S0, ment of Na20.Si02,
2CaS0,.K2S04 Na20.Ca0.Si02,
K2CWW2 8Ca0.2Naz0.5Si02,
4 CaO. 2 Na,O, 3Si02,
Na,O. A1203, K20.A120s,
which decompose of melt
at 1 lOO-1200°C
The stable phases at
1300-1450°C are
KC23SL2, NGA,
KCBA3, Na#O.,, KsS04
and 3K2S0.,Na2S04
4(Qdr0.6)
Strontmm oxtde 0.3A120,.SOj
.
(Table 8 Contd.)
Catalytic Intermediate Stability range Remarks

additives or compounds
minor
constituents
Magnesium Ca0.Mg0.Si02 1200- 1350°C

oxide 2CaO.MgO.Si0, On raising the temperature
3CaO.Mg0.2SiOz beyond 1400°C the
2Ca0.Mg0.2Si02 magnesium compounds
7Ca0.Mg0.2Al,0j decompose and MgO
3Ca0.Mg0.2Al,0J crystallizes from the melt
MgO.Alz@ as periclase MgO can in-
MgO.Fe,O, clude as isomorphous im-
Formation of purity FeO, MnO, and
(CZ%.6.Gwh.4 ZnO upto 10% each and
between CzS about 0.1 Vo (atomic Ti,
and CjMSI Ni, SC, Hf.
Sodium 2CaO.SiOz.NaF 1000°C

fluoride
Calcium 2(C2S).CaF2 950- 1 170°C
fluoride 2Ca0.Si02.CaFz
3 (CS).Caf,
1 ICa0.7Al,O,.CaF,
4Ca0.4SiO,CaF, IllO- 1185°C Decomposes at I 185°C in-
to C,S + C2S + Liquid. This
phase in clinker may have
solid solubility of 4-5%
Al,O, and 364.5%
NazO. It has also been
considered as a solid solu-
tion of CaF, and C$ with
a formula 3(CrS)CaF2
3Ca0.3A120,.CaF, 1505°C
Calcium 2Ca0.Si0,.CaC12 1084-I 100°C C$.CaC& - Q -C2S + Ca-
chloride Cl,.
Cl- may enter into the
structure of aluminates
and aluminoferrites. The
formation of
chlorosilicates of different
basicity is reported in the
system CaO - SiOz - CaClz
are given in Fig. 3t61) and approximate reaction sequence in clinkerization

is given in Fig. 4.
CaCO3
Cristobati te
Qurrtx
C AS2
C2AS
Ct(AFl
CA
C12 At
C3A
c s
C2S
C3S
Co0
Boo 900 loo0 mo 1200 1300 1400 (500
.C
Figure 3. Stability ranges of different phases during clinkering.
279 600%
Clchydmtion and
dehydroxy lation
- 50% 1ooo”c
Dccarbonation
660°C 950°C
Break d o w n o f aluminosilicates A1203~Si02fF~03

1
sso”c 1280°C
Solid-state reactions 1, 1
f c2S+CA+C12q+hrritetCaOt
12eot 14w”c
Liquid phase sintering I ss +t+S melt
1000’C l3OO’C
Cooling I
S+C2S+C3A +C#
Figure 4. Approximate reaction sequence in clinkerization.

BumczbiMy and Clinkerization 37
5.4 Clinker Phases-Effect of Cooling Rate

It has been seen that the clinker phases, as well as the melt formed during
sintering, get affected by the rate of cooling. It is reported that the best clinker
is obtained by cooling slowly to 1250°C followed by rapid cooling. The effects
of the cooling rate on the clinker phase and their properties are summarized
in Fig. Vu) and the demand for rapid cooling (18-20”Umin) has been
suggested.
Figure 5. Effect of cooling rate on cement properties and phases
6. THERMODYNAMIC CONSIDERATIONS
The application of thermodynamics to a clinker-forming system is a highly
complicated one, since the system covers an extremely complex physico-
chemical transformation in the presence of solid-liquid-gaseous environments.
The presence of raw-mix-gaseous products, clinker phases, and clinker liquid
in the kiln atmosphere at regular temperature intervals, makes the system
so complicated that a clear understanding of thermodynamics is really
impossible. However, a systematic investigation(s) with simple oxide and
carbonate systems excluding minor constituents such as RzO, MgO, PzOj,
SO3 has so far been made from temperatures below 700°C to at least
1200°C.
The most probable basic reactions of clinker formation at temperatures
around 700°C area:
CaCOs + Alz0~.2Si0zL2Hz0 = CaO + AlzOs.2SiOz + CO2 + Hz0 (20)

SC&O3 + A120s.2Si02 = 2@ - 2CaO.SiOz) + CaO.AlzOs + SC02 (21)
5CaO + A120s.2Si02 = 2(/3 - 2CaO.SiOz) + CaO.Alz03 (22)
40 CaCOJ + 7(AlzO+2Si@) = 12Ca0;7AlzOs + 14 (13 - 2CaO.SiOz) + 40
(23)
F-%aO.SiO + CaO = 3CaOSiOz WI
7CaCOj + A1203.2Si02 = 2(3CaO.SiO2) + CaO.AlzOs + 7CO2 (25)
The following conclusions can be drawn from the study of the above
reactions:
1. The transformation of kaolinite to metakaolinite [(es. 20)] is
thermodynamically favourable during the early stages of the reaction.
2. The formation of CsS is thermodynamicahy possible when the reaction
between &CzS and lime [(eq.(24)] or calcite and metakaolinite [eq.(25)]
is subjected, while the interaction between C2S and calcite does not
thermodynamically yield C$S.
3. The reaction between calcite and metakaolinite is more favourable to
yield CtzA7 and CzS [eq.(23)] than CsS and CA (eq. [25)].
4. The formation of /3-CzS is thermodynamically possible when calcite or
lime reacts with metakaolinite [eqs.(21), (22), (23)], while the interaction
between calcite and kaolinite does not thermodynamically favour /3-C2S
formation.
5. The formation of CsA from CA+ CaO or CA + CaCOs is
thermodynamically impossible, while CA is formed by the interaction
between calcite or lime with metakaolinite [eqs. (22) and (25)]. It is
suggested that the formation of CsA requires a melt phase.
6. The formation of C&F from ferric oxide and calcite or lime is possible
over the entire temperature range but the conversion of C2F into C&F
in the presence of CA and calcite or lime is impossible, which apparently
suggests the presence of the melt phase.
It should be pointed out here that these reactions have little practical
significance, since their existence in a kiln feed below 700°C is limited. Hence,
the study of mechanisms and kinetics of clinker phase-forming reactions is
the great significance in order to establish a relation which could predict an
improvement in the burnability of raw-mixes and a reduction in the energy
requirement of the clinkerization process.
7. REACTION MECHANISM AND KINETICS
7.1 Simply Binary System

The simply binary systems were studied by different investigator+92). The
system consists of calcite/lime with silica/quartz or alumina under isothermal
conditions. The kinetics of simple system is controlled by solid-state
diffusion. The following common observations can be made from the study
of the simple system mechanism:
1. The solid-state reactions between lime and silica or lime and alumina
are diffusioncontrolled. These reactions are distinguished from reactions
of other categories in which the rate is controlled by the movement of
reaction interface, by nucleation and crystal growth or by an empirical
order of reactions(B). In the diffusion process, Ca2+ ions are the
diffusing species. Counter-diffusion of other ions like Si4+ or AP+ has
not been firmly established(ms92).
2. Originally, it was regarded that the diffusioncontrolled reaction in solid
phase followed Jander’s equation(s5)
(l-S&& = (k/rl)t (261
where 01 is the fraction reacted in time “t”,
k the rate constant, and
r the radius of the particles.
Recent studies(~~~) on the formation kinetics of clinker phases from
the constituent oxides indicate that these reactions are better explained
by the diffusion-controlled equation established by Ginstling and
Brounschetein:
F(a) = (1 - 2/3a) - (1 - (r)1/3 = (k/rs)t (27)
where a, t, k and r are the same as in eq. (26).
3. In another study, the reaction mechanism was explained by a suitable
model. The model is composed of intermediate phases, the outermost
bearing Ca-rich (silicates or aluminates) and the innermost bearing Si/Al-
rich. However, C# is formed directly without intermediates in the
system of CaO - Si02. Even CsS in the same system is formed by a
reaction between C2S and Cao(9**!Q and CsA in the system CaO - Al203
is formed through intermediate phases CA2 and t&A7 with other
reaction products like C& and CA.
4. The rate of C$ formation is significantly affected by the chemical
nature of the starting ingredients, the firing temperature, the rate of
heating, etc.t91).
7.2 Complex Systems
The complex systems consisting of limestone and clay minerals (kaolinite
and illite)(73~~~95), lime and alumino-silicate like siliceous clay, aluminous
clay or granulated slag@@ or lime-alumina-iron(~), are more or less
comparable with the cement raw-meal composition. Thus, the kinetics study
of complex systems is more significant in explaining the exact condition.
These studies confirmed all the findings reached with the simple oxide
system but in addition, the following observations were made:
1. The first appearance temperature of CrS is dependent on the nature of
the raw materials used. The effect of raw materials on the appearance
temperature is indicated in Table 9. It is clear from the table that the
variation in raw materials used appreciably changes the reaction
mechanism and appearance temperature of CJS formation.
Table 9. Effmt of Raw Mater& on the Appearance Temperature of C$
System Appearance temperature Reference

of C$(“C)
Lime - clay 1300 73

Lime - silica 1100 85
Marble - Kaolinite 1100 9s
Marble - Illite 1000 95
2. During the experimental work(%) on complex systems, Jander’s equation

was modified as:
(1 - 3&)N = (k/rz)t (28)
where N = tan 9 and $ is the angle between the straight line and ordinate,
varies widely with the raw materials, temperature and time of burning.
The following conclusions were drawn from the values of N and K:
(a) Contact reactions, followed by diffusion process, are predominant at
successive periods of heat treatment.
(b) Jander’s type equation is not effectively applicable to the burning of
portland cement clinker as “k” takes minimum values at medium
temperatures and the values of “N” become very high at high
temperatures.
(c) A more realistic kinetics picture would be obtained if the reaction ratios
and the formations of CzS (2C + S+C$j) and CsS (C + C+C3S) are
separately examined below and above 125O”C, respectively.
3 . In one of the recent additions@*) to the study of solid-state kinetics of
clinkering reactions, it was observed that three stages should be conceived
in the solid-state range of reactions:
(a) Dissociation of limestone and clays;
(b) Formation of calcium silicates and alumino-silicates of lower basicity
(pseudo-wollastonite, gehlenite, anorthite, etc.) which follow the
mechanism of volume diffusion of Ca2+ through reaction zones; and
(d) Formation of &C2S and aluminates including CsA following the
mechanism of surface diffusion.
The above reactions in the range 1000-l 100°C followed the pseudotopo-
kinetic equation, given as:
K‘= LIn l-cr (29)

al-m l+oL
where m is the heterogeneity factor equal to 0.98, signifying that solid-state

reactions occur in the kinetic field.
Further, in case of limestone slag mixes@), two steps, i.e. dissociation and
clinker mineral formation, were followed, since the intermediate phases
(calcium silicates and alumino-silicates) are already present in the slags.
7.3 Activation Energy in Solid-State Reactions

The activation energy in solid-state reactions can be calculted from
Arrhenius’ equation:
.K = A.exp (- Ea/RT) (30)
where Ea (kcal/mole) represents the activation energy,

T(“K) is the temperature at which the process occurs,
A is a (quasi) constant< called frequency factor, equal to rate
constant, K when T = 00.
7.3.1 Activation Energy of Limestone Dissociation

It is well established that the activation energy of limestone has a strong effect
on the activation energy of clinker mineral formation. So it may be worthwhile
to have an idea of the variations in the activation energy of limestone
dissociation in the process of clinker mineral formation.
The commonly accepted value for the activation energy of CaCOs
dissociation is 45 kcal/mole(*), while 44.34 and 42.32 kcal/mole were
reported for the decomposition of calcite(tsQ and analytical grade CaCOs@@,
respectively.
It has been observed(ts@ from the study of plant raw-mixes that the
decomposition of limestone occurs in two stages and ultimate activation
energy in all the cases is higher than that of pure calcite (Table lo(rOr)).
The activation energy of limestone dissociation varies from 30 to 60
k&/mole. The variation is due to the associated impurities and proportion
of calcite in raw-mixes (Table 10); for example, the presence of impurities
like aragonite leads to an increase in the energy barrier for decomposition,
while clay minerals reduce the activation energy.
Table 10. Activation Energy of Calcium Carbonate Decomposition
system Ea (kcal/mole) Ref.
Plant raw-mixes Lower stage Upper stage

A - 53.72 100
B 29.82 47.41
C 25.61 45.79
D 34.97 49.19
Calcite + Kaolinite
3.5:1 34.36
6:l 35.78 98
9:l 41.61 98
Calcite+C,AS (1.5:1) 30.35
Increasing the proportion of calcite in raw-mix increases the activation

energy, resulting in decreasing the rate of &qS formation and lowering the
lime combination at 1300-14OO”c<9e,.
Using different proportions of CaC03 in the calcite-kaolinite mixes, for

example, mix ratios of 3.5:1, 6:l and 9:1, it was revealed(*) that
1. The rate of dissociation of carbonate and clay was two orders higher
than that of the new mineral formation, which confirmed that the rate
of dissociation does not limit the mineral formation process.
2. J3y increasing kaolinite in mixes, the activation energy for the dissociation
of carbonates decreases due to the presence of water vapour from clay
decomposition.
3. By increasing the carbonate content in mixes, there is an increase in the
energy requirement for dissociation, as a result of which the possibility
of volume diffusion of Ca2+ decreases. Consequently, the reaction
products in the three mixes are different:
3.51 mix - CaOr, metakaolinite, pseudo-wollastonite and gehlenite,
6:l mix -@-C$ and CsA in addition to the above phases.
9:l mix-CaOr, /3-CsS and CsA.
7.3.2 Activation Energy of Cllnku Mineral Formation
The reported values of activation energy for the formation of the major
clinker phases are presented in Table 1 l(lol). The following conclusions may
be drawn from there:
Table II. Activation Energy of Major Clinker Phases
Phases Ea (kcal/mole) Reaction system References
c3s -200 CaC4-alumino silicate like clay

and slags 96
8-W 127.76 CaO - SiOl (3: 1) 92
14.63 CaCO:, - Kaolinite 95
61.57 CaC03 - Kaolinite (6: 1)
42.85 CaCO, - Kaolinite (9:l) 98
25.10 CaC03-CzAS(1.5:1)
36.66 CaCO, - QAS(4: 1)
39.40 CaO -XiOl (2: 1) 92
C3A 48.41 CaO-A1203 (3:l) 90
119.34 CaC03 - Kaolinite (6: 1)
86.60 CaCO, - Kaolinite (9: 1)
35.50 CaC03-C2AS (1.5:1) 98
99.62 CaCO, - CIAS (4: 1)
C.,AF 104.68 CaO - A&O3 - Fez03 97
70.98 C3A - CF 97
1. Activation energy of each of the major phases varies significantly,

depending on the ingredients in the raw-mix as well as on the proportion
of the ingredients of the same raw-mix.
2. Activation energy of C3S formation in solid-state reactions is much

higher than the activation energies reported for serf-diffusion of Ca in
CaO (33.946405 kcal/mole)(i0zJcs), whereas the activation energy of
CzS formation, by and large, agrees with the self-diffusion of Ca and
CaO.
3 . Activation energy of C3A formation comes close to the activation
energy of self-diffusion of Ca in CaO only in certain cases (like CaO-
Al203 and 1.5:1 mix of CaCOs-CzAS). Thus, the reaction appears to
occur via Ca diffusion into AlzO3.
4 . Activation energy of C&F formation is similar to that of the diffusion
of Fe into Fe203(g), while in the reaction between CsA and CF, the rate-
controlling step may be the diffusion of Ca into CF to form Ca-rich
ferrites or the diffusion of Ca or Fe (or both) into the aluminate phase.
5 . A comparison of activation energies of carbonate dissociation and /3-
C2S and C3A formation in calcite-kaolinite mixes (6: 1 and 9: 1 in Tables
10 and 11) clearly shows the inverse relationship between the energy
barriers of dissociation and mineral formation in the same systems.
7.4 Diffusivity in Solid-State Reactions

It has been conceived that the solid-state diffusion process is controlled by
the diffusion of Caz+ ions in the acidic/acceptor oxides. The diffusion
phenomenon proceeds in three wayW%
(a) Surface diffusion (0,): It is followed by the mass transfer on the
external surface of the grains of acceptor oxides.
(b) Joint diffusion (DJ: It is governed by the mass transfer along the
surface joining the grains of the acceptor oxides.
(c) Lattice or volume diffusion( D, ): It is controlled by the mass transfer
inside the grains of the acceptor oxides.
Since a higher level of free energy is present inside the lattice than at the
surface or joints, activation energies of the process at the surface (Es), at
the joints (Ej) and inside the lattice (Ea), increase accordingly under
isothermal conditions(ies). Therefore,
Ea > Ej > Es (31)
It is then evident that the lattice or volume diffusion being the slowest one
controls the overall stationary process under isothermal conditions.
The diffusion coefficient (DJ can be expressed by a similar equationQO),
where the rate constant K is equal to D, and the frequency factor A is
denoted by D,:
D, = D, exp ( - Ea/RT) (32)
Some data on the diffusion coefficients of the clinker phase formation
reported earlier@QQ are presented in Table 12(iOi) in a selected summarized
form.
PP
3
3
Table 12. Diffusivity in Clinker Phase Formation Reactions s.
R
Diffusivity (m2 h-’ x 109) 9
P
1000 1100 1200 1250 1300 1350 1400 1450 ;;
System Layers “C “C “C “C “C “C “C Ref. &
45CaCOI + kaolinite - - - 5 10 17 20 90 200 94 9

2
CaO + kaolinite CZS - 0.71 1.02 - 2.18 - - - 95 2
- 0.68 0.94 - - - ip”
c3sz 0.79 -
cs - 0.77 1.02 - - - - -
- - 0.28 - 1.60 - - -
C3A
45CaC03 + illite - - 20 58 110 180 340 2000 94

CaO + illite a11 - - - - - - 95
c3s
c3s, 0.10 - - - - - - -
CAS; 0.03 - - - - - - -
The following conclusions can be drawn from the data on diffusion

coefficients (Table 12).
1. Values of diffusion coefficients are substantially different even in
identical systems under isothermal conditions.
2 . Diffusivety increases considerably with a rise in temperature.
3 . Diffusivety is strongly dependent on the nature of diffusion and hot
species.
7.5 Liquid Phase Sintering in Clinkerization

In all the investigations reported earlier, the presence of melt phase was neither
mentioned nor taken into account in explaining the reaction mechanisms,
whereas experimental studies and phase equilibria considerations of even the
simplified clinkering systems indicate the presence of a liquid phase at
clinkering temperatures. However, the possibility of a liquid phase modifying
the reaction mechanism of the formation of C3S was critically viewed(%) and
the observation of an anamalous activation energy of ($5 (see Table 11) was
also supported by this presumption. As a result, later studies on the kinetics
of clinker-phase formation reaction were more concerned with the ultimate
formation kinetics of C3S in the presence of a melt by a reaction (eq. 33)
than the preceding stages of reaction which were, by and large, in the solid
state.
c+c$3 ~
melt cjs (33)
The investigations carried out on C$S formation were based on experiments

with briquettes of varying clinker-phase compositions juxtaposed and fired
with or without a glass-layer inserted in between or adjacent to the briquettes.
Whatever, the composition of the glass, it corresponded to the 1338°C eutectic
of the CaO - A1203-Fe20J-Si02 systems!or a molten coal ash or a slag of
appropriate composition. Studies conducted so far on CsS formation in the
presence of a melt phase can be broadly classified and fired with our without
a glass-layer inserted in between or adjacent to the briquettes. Whatever the
composition of the glass, corresponded to the 1338°C eutectic ofthe CaO-
A1203-Fe203-Si02 systems, or a molten coal ash or a slag of appropriate
composition. Studies conducted so far on CsS formation in the presence of
a melt phase can be broadly classified under three group:
(i) Russian
(ii) Japanese
(iii) Danish
7.5.1 Russian Group Investigations

The important findings by the Russian group of investigators are summarized
belotite@:
1 . The clinkerization reaction in the presence of a melt phase has been
conceived to include three independent physico-chemical processes(t@%
(a) Dissolution of the minerals of raw materials and the product of solid-
state reaction in the liquid phase.
(b) Diffusion of Caz+ and SiOc4 ions into the melt.

(c) Crystallization of new phases.
2. Out of the above three steps, the first two relate to the burning process
and the third to cooling. The rate-controlling phenomena in burning and
cooling are different.
3. The rate-controlling phenomenon in burning is the dissolution of clinker
minerals in the liquid phase, which does not proceed through the
migration of the elementary particles (atoms, ions, molecules) into melt,
but proceeds by means of separation of indivdual blocks of up to 1 pm
size from dissolving crystals and polycrystaWOs) and is represented by
the equation
v,=vK’l’
’ ND exp [ - (E + AE)/RT]
a (34)
where
Vp = rate of dissolution of CaO or C$S in the liquid phase of clinker.
Vx = rate of clinker formation
= dissolution time
s’ = diameter of the elementary particles
YO = frequency of elastic vibrations of the elementary particles in the
solid state,
N = multiplication factor considering that lo9 - 1010 particles
separated as a whole block fit for one molecularly separated
particle,
E = activation energy of dissolution
R = gas constant
D = certain effective size of the grain
AE = activation energy of the block seperated from the grain
T = temperature
4. Crystallization of clinker liquid phase in the range 820-1450°C proceeds
very quickly during clinker cooling. The rate of crystal growth is the rate-
determining phenomenon, when only one phase crystallizes, and the rate
of crystal nuclei formation becomes the determining phenomenon when
more than one phase crystallizes out.
5 . The activation energy for the dissolution of CaO and CzS in the liquid
phase was reported to be 150 kcal/mole which is close to the activation
energy (200 kcal/mole) of the C$S formation from the solid-state
diffusion(%).
7.5.2 Japanese Group Investigations

Unlike the Russian investigations, the Japanese stud$t@) was basically
concerned with C,S formation only. In order to investigate the mechanism
of reactions on the boundaries of CaO-melt and CzS-melt, a powdered
glassy phase was sandwiched between two compacted discs of CaO and /3-
C$S. After subsequent heating and air quenching the specimens, the
following conclusions were reached:
1. The rate of CJS formation was dependent on the quantity and viscosity
of the melt phase, fineness of the particles of reactants and temperature,
the last parameter, in turn, helping in increasing the amount of melt,
decreasing its viscosity and increasing the diffusion coefficient.
2 . The broad mechanism of the reaction includes the dissolution of CaO
and ClS in the melt phase, supersaturation of the liquid with counter-
diffusion and crystallization of the CJS phase.
3. The apparent activation energy of dissolution of the solid phases
depended on the quantity of the melt phase, as indicated in Table 13.
The Ea-values obtained with a larger amount of the melt phase were closer
to the values reported by the Russian group, while the values with a lower
amount of melt were closer to those expected from the viscosity data.
These results led to the conClusion that counter-diffusion in the melt is
directly related to activation energy and unexpected greater values are
due to a change of tortuosity of the path for diffusion.
Table 13. Apparent Activation Energy
Melt phase Particle size Activation energy

(in wt% of CaO and C2S) r Olm) E, (kcal/mole)
30 5 123
30 7.5 121
15 5 42
15 7.5 42
4. The rate of reaction could be represented by an equation of Jander’s

type with a clear physical meaning where dissolution was considered in
spite of inward diffusion being assumed by Jander.
(l-36)2 = y K.t = K.t = F (ar)
where
a = reaction ratio
D = diffusion coefficient
AC = concentration gradient across the diffusion layer
T = time
r0 = radius of the dissolving spherical particles
K = reaction rate constant
7.5.3 Danish Group Investigations

Danish investigations were more or less an extension of the studies of the
3apanese group with a parallel attempt to correlate the kinetic data with phase
equilibria considerations of simplified ternary (C-A-S) and quaternary (C-
A-S-F) clinkering systems. The first reported investigations in this serie#*O)
experimentally confirmed the mechanism of diffusion in the melt as the rate-
controlling step in the interaction between portland cement clinker and molten
and molten coal ash. While in this study there was an extension of the liquid
phase in the clinker by a liquid of different composition (ash), the subsequent
studyoll) was restricted purely to the ternary system (CA-S). The above
studies revealed that:
1 . In this clinker and ash reaction, the diffusion coefficient of CaO in the
melt at 1500°C was about 5 x 1O-6 cm2/s and the activation energy
obtained from the diffusivety measurements of different clinker-ash
combinations was of the order of 42 f 17 k&/mole, which was close
to the value reported by the Japanese group.
2 . In the pure ternary system, however, D was observed to be 4.5 x lo-’
cm%, when the tortuosity of the diffusion path was taken into account
and the diffusion coefficient was obtained as 7.5 x 1W7cm2/s, although
the latter value was considered to be less accurate. Irrespective of the
difference between the values, the estimated D in the ternary system was
found to be significantly lower than in the quatemary system mentioned
above.
3 . Diffusivity increases with an increase in temperature and changes with
composition. When the free CaO is more, diffusivity is higher and free
CaO is essential for the ultimate formation of CsS.
As a further development of these studies, a simple model was established
for diffusioncontrolled reaction between spherical CaO particles and portland
cement clinker at 15OO”C(*tz), experimental results from which agreed well
with those predicted from data obtained in the independent diffusion
experiments. According to this model, if the fraction of CaO reacted is
represented by x, the time dependence of x is given by:
(1 + flx)z” - 2/3/3x = 1 - [@or B D A C)/di)] (t/ri) (36)
where
/3 = a function of composition and porosity
a! = volume fraction of liquid
D = effective binary diffusion Coefficient of CaO
At = concentration gradient of CaO across the reaction layer
4 = density of CaO
t = time
r. = radius of CaO particles
Applying the above model, it was observed that at 15OO”C, for a burning
time of 20 min, the maximum size of CaO particles that can completely react
is !+m corresponding to calcite grains of 120 pm size.
Recently, a sandwich technique was developed(ii31 i14) for determining the
rate of clinkerization in systems like C-A-S-F, C-A-S-F-M and C-A-S-F-M-
CaF2 with an advantage over powder technique by eliminating particle size
effects. Moreover, kinetics are simpler and often easier to interpret. The rate
constants were determined from the equations:
X2 = Kt (37)
K -- 2DmCx- An . H (38)
z
H = l/(C,C,)+l/(C,-c,) (3%
where
X =thickness of layer of CsS + C + melt and CsS + C# + melt)
K = rate constant
t = time
Dm = effective binary diffusion coefficient for CaO with
counter-diffusion
of SiOz + AlzOs, etc., in the melt
cx = weight fraction of the melt in the CsS layer
An = difference in the CaO concentration (weight fraction) for melt
in equilibrium with CsS +C, and melt in equilibrium
CJS + c2s
Cl, c2 = weight fractions of CaO in the two briquettes
cm Cb = weight fractions of CaO in the CsS layer at the briquette-I-
CsS interface and at the CsS-briquette-II interface
7 = factor < 1, for the tortuosity of the melt
The rate of constants obtained in the different systems are given in Table
14(10’) which reveals the influence of temperature and composition on K.
Table 14. Rate Constants in Different Systems

Composition (wtolo) Rate constant K x 108 cm%
at temperature (“C)
System II I - 1350 1375 1450 1500
1. C-A-F-S CaO 73 67
SiO, 21 27 - 12.2 22.4 31.5
A1203 4 4
Fe203 2 2
2. C-A-F-S-M CaO 73 67
SiO, 21 27
Al203 3.3 3.3 7.4 9.1 18.0 26.6
Fe203 1.7 1.7
MN 1.0 1.0
3. C-A-F-S- System 2+0.5% 17.4 - 38.6
M-CaF, CaF,
System-2 2+ 1.0% 21.3 42.4
CaF2
It is clear from eq.(38) that the rate constant ‘K’ is composed of four
factors. The factor ‘H’ is related to the microscopical distribution of the main
components whereas the remaining three factors-a, Dm, and An-are rather
insensitive to the distribution of main components but may be influenced
by change in the content of other components or temperature, as discussed
below:
7.5.3. 7 Melt Content la)

The melt, depending upon composition, cannot exist in stable equilibrium
with alite below a minimum temperature, Ta. The effect of composition on
TE and o can be seen from Table 15.
Table 15. Effect of Composition on ‘TE’ and ‘a’
Composition T,“C ‘CY’ at 1400°C (T)

(w/w~o)
C-S-A > 1450 0

C-S-A-M <1400 10-15
C-S-A-F < 1350 15-20
C-S-A-F-M = 1300 20-24
C-S-A-F-M
-Ti-Mn-N-K 1260-1280 24-28
Thus o, for a given composition, increases from zero to a finite value

as T passes Ta. With the addition of M,F or impurities (Ti, Mn, K, N, etc.)
in the main component, TE decreases and o increases at a certain
temperature(T).
7.5.3.2 Diffusivety (D,,,!

The value for D, is = lO-‘j cmz/s at 1500°C. Dm increases
approximately twofold for a lOO“C temperature increase. This corresponds
to an activation energy about 45 kcal/mole. It has been seen that D,,, and alite
formation rates increase by lowering the viscosity of the melt when a suitable
modifier is added to the system. But this is not always true. Therefore, the
effect of composition on Dm remains open to justification.
7.5.3.3 Driving force (An)

An is an index for the driving force for inter-diffusion of CaO and SiOl
through the intertitial melt in the alite regions and for their growth. A positive
definite value for An signifies that alite is relatively stable to lime and belite
under the specified temperature and composition.
The temperature dependence is connected with the fact that alite has lower
stability temperature, To, typically at 12QO-125O”C, depending upon
composition. At T c To, lime and belite are comparatively stable to alite and
there can be no driving force or alite formation. Therefore,
An = 0 for T 6 To
The compositional influence upon An at a constant temperature T ( > To)
can be deduced from the many relevant ternary and pseudoternary phase
diagrams available. However, the value of An is so small that extremely
accurate analysis would be required.
If two or more of the An influencing components are added simultaneously,

their combined effect is expected to be simple superimposition of their
individual effects.
7.6 Effect of Minor Catalytic Constituents on the Formation

Rate of C&S
The study(l14) on the rate constant in system C-A-F-S-M with CaFs (Table
14) can be reckoned to be the beginning in the clinkerization process. The
addition of CaFz will, of course, change CL It may change the physical
properties of the liquid and thereby D,,, and possibly An and H [eq. (38)J.
It has been seen that an increase in CaF2 results in a corresponding increase
in K (Table 14). It should be mentioned here that the effect of CaF2 on K,
whether due to a non-linear relationship between An and CaFs or due to the
influence of CaFz on Dm or due to a variation in 7, is not clear.
7.7 Phase Equilibria Considerations

It has already been mentioned that in all Danish studies there was an attempt
to correlate the kinetic findings with phase equilibria considerations of the
simple ternary system C-A-S, the isothermal section of which at 1500°C is
reproduced in Fig. 6 and the phases in equilibrium in different parts of the
diagram indicated in Table 16(icr).
Figure 6. Isothermal section at 1500°C from CaO corner of system

Cao-Al,O,,-SiO,
Tab& 16. Zones with Equilibrium in the 15tW°C Isothermal Section of

C-A-S System
Region No. of Phases Phases in equilibrium
01 2 CaO (solid) + A - B (liquid)

02 3 CaO (S) + C$ (S) + B (L)
03 2 c2s (S) + c$3 (S) + c (L)
04 3 C$3(S) + C&s) + C(L)
03 2 C2S (S) + C-D (L)
From Fig. 6 and Table 16, the following conclusions have been drawn:
1. With the inherent microinhomogeneity present in raw-mixes, the
composition of microvolumes is likely to fall in different regions
(0, -OS), equilibrium in which will be attained quickly, giving rise to
phases determined by the equilibrium conditions of the local composition
and a given temperature. All further reactions are restricted to the
diffusion of the species between different regions for which reaction layers
with recognizable boundaries will develop.
2. When a clinker passes through the burning zone of a cement kiln, the
phases CaO, CzS are dispersed in a melt with concentration gradients
in many geometrical directions. The reaction would thus result from
diffusion between pockets of A (C + CsS) and B(C$ + CzS). The phase
diagram shows a very narrow finger for the primary field of CsS, so
that A and B compositions are similar (60.4% and 59.3% CaO,
respectively, at 15OO“C). The size of the concentration gradients is very
limited, which may be the reasons for sluggishness in the formation
reaction of CsS or complete assimilation of CaO under practical
conditions(tt2).
3 . As long as the melt composition in the belite cluster differs from C, CaO
will diffuse into the cluster and correspondingly SiOz+ A1203 will
counter-diffuse. In this manner, CJS will be dissolved at the boundary
and CzS will precipitate. As a result, a cluster of CzS with increasing
size is developed during the process(l15).
4 . The two-phase regions Or (CsS + melt) is developed when the three-
phase regions 4 (C+ C2S +melt) reacts with another three-phase
regions 0, (CsS + CzS + melt). If the surroundings still contain free
CaO, growth of Or regions will continue by reducing the extent of 0,
regions. If adequate free CaO is available, 0, region will degenerate into
a boundary interface and the belite cluster will be converted into C$.
Further, it has been seen that CsS-C2S regions are always separated
from CaO regions by a region consisting entirely of C$l + melt in a
normal clinker composition(tts).
7.8 Non-isothermal Reaction Kinetics

Almost all the studies reported earlier on the kinetics of clinkerization
reactions were based on isothermal investigations, although it is estimated
that only 20% of the reactions in actual practice can be so measured. In
studying the rate of clinker formation isothermally, some of the reactions
such as the decomposition of calcite with concomitant formation of CzS,
are ignored and the actual ones under kiln conditions were not taken into
account. The evaluation of non-isothermal data was reportedly
attempted(i10Ji6). A more comprehensive study was rnade(te@ with plant
raw-mixes. Based on the experimental studies, the course of burning cement
raw meals has been summarized by assuming a four-stage model in Table 17.
Table 17. Four-stage Model for Non-isothermal reaction Kinetics
Stage Reaction Mechanism Temperature Equation

range (“C)
1 Calcite Phase-boundary 570-890 g (a) = 1-(l-a)“2

decomposition controlled
2 Solid state Phase-boundary 600-800 Not established
reaction I controlled
3 Solid state Diffusion g(a) =2
reaction II controlled 1000-1250 1 - :a - ( 1 -a)2’3
4 Solid liquid Diffusion 1325-1450 g(a) = 2
reaction controlled I - :a - (1 -@*I3
8. CONCLUSIONS
Bumability and reactivity are fundamental concepts of cement making which
reflect the variation: in process parameters through mass and energy transfers.
It is necesary to distinguish the concept of burnability from reactivity since
this distinction is useful for comparing raw-mixes even with identical
composition. As a result, the thermal, chemical and physical behaviours of
raw-mixes and clinkers vary unexpectedly from plant to plant.
Evaluation of burnability by different methods covers chemical,
mineralogical and granulometric behaviour of raw-mix and establishes
complicated empirical relations at a certain temperature and time based on
free-lime determination. However, cement technologists prefer simple
relations based on simple and rapid experiments. To this end, the most rapid
and suitable model in laboratory-scale experiments is yet to be selected for
general acceptance, a model which could be equally applicable for plant
raw-mixes.
The reaction sequence in a cement rotary kiln is a complicated

phenomenon. The appearance and disappearance of a large number of
intermediate phases at early stages make the system unpredictable and
unreliable due to the lack of kiln data at operating conditions. Moreover,
the presence of minor constituents, solid-liquid-gaseous diffusion
environment, and the fluctuation and distribution of temperatures in the kiln
make the system more typical and ambiguous. These disputed phases are yet
to be fully explored. Mathematical modelling of the kiln processes may be
right solution to confirm the interstitial phases formed in the defined zones.
The kinetics of clinker formation appears impossible to be expressed by
common parameters. However, using the most recent models, the rate of
clinker formation could be established by means of apparent diffusion and
activation energy data which are believed to be still in the experimental stage.
Further investigation is necessary with actual. plant raw-mixes, taking
into account all possible factors and projecting the individual character to
arrive at more general kinetic characteristics and the equation of clinker
formation.
*Reproduced with permission from Pergarnon Press.
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Burnability and Clinkerization of Cement Raw-Mixes

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Burnability and Clinkerization of Cement Raw-Mixes

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BURNABILITY AND

Burnability of raw-mix has been a matter of great importance in cement

2.3 Factors Affecting Burnability

2.3.1 Raw-mix-Mineralogical composition

2.3.2 Raw-mix-Chemical composition

2.3.3 Raw-mix-Granulometric composition

2.3.4 Raw-mix-Thermal Treatment

2.3.5 Liquid phase formation

2.3.6 Clinker quality

2.3.7 Coal ash

2.3.8 Kiln atmosphere

2.3. I Raw-mix-Mneralogical Composition

Table 1. Raw Mix-Constituents and Compositions

Consisting mainly Consisting mainly Consisting mainly

2.3. 1.2 Acidic oxides IS, A and 17 carriers

2.3. 7.3 Correc rive ingredients

2.3.2 Raw-mix-Chemical Composition

2.3.3 Raw-mix-Granulometric Composition

2.3.3. 1 Fineness and particle-size distributions

2.3.3.2 Homogeneity and compaction

B. Minor Non-volatile Components A higher St 8

Parameter/ Empirical Limiting Preferable Effects Ref.

2. hlagnesium M O-S% o-2% ’ A Higher M

Parameter/ Empirical Limiting Preferable Effects Ref. 2

Parameter/ Empirical Limiting Preferable Effects Ref

5. Chloride O-0.6% O-0.015% A higher Cl 8,20,35

l When M,, = 1.23. liquid appears at 1338T in C-A-S-F system.

Chemical Chemical Mineralogical

LOI 35*2 LOI 0.3 f 0.2 c,s 55*10

l Traces of other minor constituents. LOI = Loss on ignition

2.3.4.3 Burning rate

2.3.8 Kiln Atmosphere

3. RAW-MIX CHARACTERIZATION AND EVOLUTION

(A) Proposed Raw-mix

(B) Laboratory Prepared-clinker

3.1 Theoretical Approach

BI, C3S/C,AF + C,A (4) 58

Where L, = amount of liquid phase at 1350°C after IMII@~

The BF seems to be more practical as it involves LSF and moduli. In the

3.2 Semi-experimental Approach

3.2.1 Freei%ne Temperature Integration iUethodc61,

+4c MOOT + ~%o”c (10)

3.2.2 Statistical MO&W

criterion to arrive at any conclusion. Several methods are derived for

3.3.1 Bumability Scalef~~

3.3.2 Practical Bumability@l)

4.2 Factors Affecting Reactivity

4.3 Division and Characteristics

Table 5. Characteristics of Low and High Reactive Raw Mixes

Feed consumption High Normal

Table 6. Zones Defmed by Temperature Ranges and Reaction Profiles

Zone Temperature Reaction

The material and gas temperatures as well as reaction zones are

Dry proccr kiln

Wet proara kiln

% otthe kiln length from. feed end

Figure 1. Material and gas temperature as well as reaction zones in

LOI 352 LOI 0.3 f 0.2 c,s 5510