ASEC

Academy

Product Related To
Manufacture of
Portland Clinker

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1 Definition of Special Clinkers

These are clinkers that are used to produce cements having specific
(physical and chemical) properties, which exceed those of normal
Portland cement, namely:
 Improved strength development properties
 Increased resistance to chemical attack
 Improved compatibility with reactive aggregates
 Suitable for use at elevated temperatures and pressures
 May be used to produce cements having a specific colour

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1 Definition of Special Clinkers

From the manufacturing viewpoint the production of such clinkers

may require one or a combination of the following:
 
No change in either the clinker burning or Clinker cooling process
 A slight change in raw mix composition
 An appreciable change In mix composition
 A change in the clinker cooling process
 The use of a special kiln.

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1 Definition of Special Clinkers

A compilation of the most common special clinkers and their process

requirements are listed in Table 2. As can be seen, the clinkers have
been divided into three categories:
 
 Portland cement type clinkers
 Modified Portland cement type clinkers
 Non-Portland cement type clinkers
 
The basis for this classification is whether or not the clinkers are
composed of the normal Portland cement minerals, alite, belite,
aluminate and ferrite.

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(Clinker/cement) Cement Properties required Manufacturing Conditions
Rotary kiln Normal Special Product at
    possible Cooling coponents most plants
Poosible required
ASTM I/OPC normal OPC properties x x o x
Portland Cement Type          
ASTM II/SRC/IHC  improved sulfate resistance,        
  reduced heat of hydration x x o x
           
ASTM III/RHC higher early strength        
    x x o x
ASTM IV/LHC low heat development for        
  mass concrete x x o x
           
ASTM V/SRC sulfate resistant        
    x x o o
Low alkali cement no reaction with alkali        
  sensitive aggregates x x o o
           
Oil well cement suited for increased        
  temperatures and pressures x x o o
           
White cement white coloured cement, base        
  for pigmented x requires o o
      quenching +    
Tan cement tan coloured cement   reduction    
x   Tio2 source o
requires (1lemenited)  
quenching +
reduction

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(Clinker/cement) Cement Properties Manufacturing Conditions

Type required

Rotary kiln Normal Special Product

    Cooling coponents at most
possible Poosible required plants

Modified Portland Cement Types

Reqilated set extremely quick setting Flourspar +
x x o
cement (15-60min) Bauxite

Non- Portland cement Types

Expansive cement expansion shrinkage Bauxite +

x x o
additive compensating cement Gypsum

requires
Reverberatory
High alumina verey high early strength furnace special
(1 day), exterme sulfate system for Red Bauxite o
cements (complate
resistance crystallizatio
melting) n of melt

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2 Special Portland Cement

Type Clinkers

All the clinkers in this category

 Are produced in a rotary kiln
 Are composed of alite, belite, aluminate and ferrite
 With the exception of white and tan Portland cement clinkers,
require no special cooling of the clinker
 With the exception of tan cement clinker, require no special
additional components for their manufacture.

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A ASTM Type II - V Clinkers

 For the production of clinkers that can be used for the milling of
ASTM Type II-V cements, the following conditions (Table 3) in
excess of those demanded for ASTM Type I, must be met.
 While most plants are capable of producing Type II-IV clinkers,
only a restricted number have raw materials suitable for Type V.
 In comparison to Type I, the other types are produced in
approximately the following quantities:
 
• Type III ASTM 5 to 10%
• White cement 1,5%
• Rest of all kinds of cement not more than 2 to 3%

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 Table 3 : Requirements for ASTM Type II-V Portland Cements in
excess of those required for Type I ( ASTM C150-74
  Chemical Requirements
ASTM SiO2 Al2O3 Fe2O3 C2S C3S C3A C4AF+ 2C3A
type No Min. % Max. % Max. % Min. % Max. % Max. Max. %
               
I - - - - - - -
II 21.0 6.0 6.0 - - 8 -
III - - - - - 15 -
IV - - 6.5 40 35 7 -
V - - - - - 5 25

  Physical Requirements
ASTM Max. Heat Minimum Mortar Compressive
type No Development J/g Strength MPa
  7 days 28 days 1 day 3 days
I - - - -
II 290 330 - 10.3
III - - 12.4 24.1
IV 250 290 - -
V - - - 8.3
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B Low Alkali cement Clinkers

 Because certain aggregates contain amorphous forms of SiO2,

such as opaline and chert as well as dolomite, which react with the
alkalis in the cement to cause a deterioration of concrete, Portland
cements containing less than 0,6% Na2O-equivalent (i.e. Na2O +
0,658 K2O) are sometimes required.

 From the viewpoint of clinker production, the all-important

requirement is that raw materials, sufficiently low in K2O and
especially Na2O, should be available. In very many plants this is,
however, not the case, so that material/ technological changes such
as
• Rejection of kiln dust
• The use of CaC12 to increase alkali evaporation

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 must be employed. These measures are, however, not to be

favoured as they are associated with:
• Reduced kiln output and increased energy consumption
• Additional dust disposal problems
• Increased corrosion within the kiln system
• More difficult kiln operations, etc.

 While an appreciable decrease in K2O can be achieved by the

proposed measures, a significant reduction in the level of Na2O
often only occurs after the removal of the bulk of K2O.

 Because of all these difficulties, the production of a low alkali

clinker should be strictly limited to the areas where it is
absolutely necessary, i.e. in areas having reactive aggregates
such as North America and Germany.
 In these countries, specifications for low alkali cement are
included in the defined standards.
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C Oil Well cement Clinkers

 Oil-well cement is a hydraulic cement suitable for use under high

pressure and temperature in sealing water and gas pockets and
setting casing during the drilling and repair of oil wells.

 It often contains retarders and with low surface area to meet the
requirements of use.

 The production of clinkers for oil well cements is essentially

associated with no more difficulties than those encountered with
the equivalent ASTM types.

 The clinker contains more -C2S as well C4AF than ordinary

Portland cement.

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The physical requirements demanded of the cements

are, on the other hand, considerably more difficult to
satisfy.
The quality control of the finished cements requires
special equipment for testing at elevated temperatures
and pressures, and moreover the cement particle size
distribution has to be controlled as well as the Blaine
fineness.

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D Tan Coloured cement Clinkers

 In order to achieve certain architectural effects. in which the grey

colour of Portland cement is replaced by a warm brown (tan) colour,
the use of a tan coloured cement has been proposed.

 Although this is a normal Portland type cement, i.e. contains alite,

belite, aluminate and ferrite, and can essentially be produced from
normal raw mixes, the following changes to the production process
are required:

• Chemical change: addition of TiO2-rich minerals (Rutile,

Ilmenite) so that the clinker contains approximately 0,8% TiO2
• Process change: quenching of the clinker in water from
temperatures above 1400C

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 In comparison to that of normal Portland cement clinker, the

production of the special clinker is associated with increased
costs and manufacturing difficulties due to:

• Increased material costs associated with the addition of

approx. 1% of ilmenite (FeTiO3)
• Heat losses due to quenching of the clinker
• Drying of wet clinker
• Requires a definite clinker granulometry (Particles < 2.0 cm in
diameter)

In addition, the production of the cement is made more

expensive by:
• The need for finer grinding to offset the effects due to
hydration on quenching
• The need to produce cement of a guaranteed colour.

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E White cement Clinkers

 The essential criterion for being able to produce this type of
Portland cement clinker is that raw meal components are available
which allow the values of the colouring oxides in clinker to be as
follows:
• Fe2O3 < 0,5%
• Cr2O3 < 0,03%
• Mn2O3 < 0,03%
 As most plants do not possess materials of such purity, it can be
easily appreciated why white Portland cement can only be produced
by a relatively limited number of cement plants.
 Although a few plants do have a limestone of sufficient purity, the
securing of an acceptable alumina-silicate component is far from
easy.
 The most usual source of the latter is kaolin, but due to its price and
its availability, it is often partially replaced by a pure quartz sand, or
less often wholly replaced by a quartz sand/bauxite mixture
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From the typical range of white cement clinker

compositions
21.4 – 250 SiO2  It can be seen that the range of alumina
3.0 – 4.6 Al2O3 and silica ratios lie appreciably above
0.2 – 0.5 Fe2O3
those of ASTM Type I-V clinkers.
 As a consequence white cement clinkers
65.9 – 68.9 CaO are always more difficult to burn,
4–8 SR requiring an elevated burning
6 -18 AR temperature.

 Coating is usually not formed in the kiln, so that refractory

consumption is high.
 In addition to the water quenching of the clinker, just as is the
case for tan cement, white cement clinkers are usually
"reduced" prior to cooling.
 This is achieved by spraying the glowing clinker with oil or using
propane gas , and results in a cement .of improved whiteness.

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3 Modified Portland
Type Cement Clinkers

A Regulated Set ( Regset )Clinkers

 The most common modified Portland cement type clinker

encountered is "regulated-set" cement clinker,

 used to produce cements having extremely short setting times

(15 - 60 mins.) due to the presence of a calcium aluminate
fluoride of composition C11A7CaF2.

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1 Production of Regset Cement Clinker

 As can be seen in Table 1, this clinker can be produced in a normal

kiln from most raw meal compositions, and requires no special
cooling process.
 The only special requirement is that the clinker contains an increased
A12O3 content and approx. 0,5 - 1.0% fluoride, this being supplied
from either bauxite and fluorspar (CaF2) (fluxing agent) or from
industrial wastes rich in A12O3 and F.
 Because of its increased aluminate content, the clinker contains more
liquid phase, and requires a lower burning temperature of
approx.1350 C.
 The formation of large clinker balls is, however, possible and care
must be taken to avoid these during production.
 To ensure the maximum formation of C11A7CaF2 and the minimum of
C3A, it is advisable to have the burner so far into the kiln so as to
allow the clinker to cool to approx. 1300 C
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2 Mineralogy of "Regset" Clinker

 "Regset" clinker is a modified type of Portland cement clinker in

that it does not contain the normal aluminate phase (C3A)

 but a less lime-rich calcium aluminate of approximate composition

12CaO · 7A12O3 (actually C11A7CaF2) which itself is more lime-rich
than CaO . A12O3 (i.e. CA)

 the principal ingredient of high alumina cement (HAC).

 The other clinker minerals alite, belite and ferrite remain the same.

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3 General Evaluation

 Although the production of regset cement clinker is essentially as

cheap and easy as that of normal Portland cement, the problems
associated with controlling the setting behavior have never been
fully solved, and so it has not been possible to achieve the full
potential of this cement, offered by its very early setting
characteristics.

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4 Non Portland Cement Clinkers

A High Alumina Cement Clinker

 High alumina cement (HAC) is a special cement well-known for
its excellent properties including: 
• a normal setting time combined with ultra rapid hardening
(almost full strength development is reached after only 24
hours)
• excellent sulfate resistance properties
• winter concreting possible
• ability to produce refractory concretes.

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 Its general application is, however, severely limited because of:

• Its high production costs (materials and fuel)
• Its unsuitability for mass-concreting (due to its ultra-rapid heat
development)
• A tendency for HAC concrete to loose strength at temperatures
above 25 - 30C

 From the viewpoint of clinker formation, production is restricted

by:
• The need for a special type of furnace (reverberatory furnace) or
refractory crucibles
• The need to cool a fully molten or sintered clinker
• The necessity of using bauxite to achieve the level of
approximately 40% A12O3 normal for the clinker.

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1 Mineralogy of HAC Clinker

 As a typical analysis of a HAC clinker is as follows, 

4–5% SiO2
38 – 40 % Al2O3
 it is not surprising that the clinker
8 – 10 % Fe2O3 mineralogy is totally different
36 – 39 % CaO from that of Portland cement
5–7% Mg clinkers.
2% Tio2

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The usual mineral constituent are considered as being:

 The aluminous cement clinker is divided to three types according to
the alumina content.

 The low grade 38% Al2O3, medium grade more than 50% and the
high grade more than 70% Al2O3 .

 As the Al2O3, increase the refractoriness of the cement increases.

 Therefore the low grade cement composes mainly of ( C12 A7), the
medium grade is composed from (CA) whereas the high grade
aluminous cement is mainly composed of (CA2).

 The minor constituents are -C2S, C4AF, C2AS and C6A4MS.

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( CA ) Monocalcium aluminate Major Constituent

(C2S) Belite
(C2AS) Gehlenite
(C4AF) Ferrite Minor Constituents
(C12A7) Calcium aluminate
(C6A4MS) (M = MgO) "fibrous" phase

Of these minerals only CA contributes to the

ultra rapid hardening, and so the quantity of
this constituent should be kept at a maximum.

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2 Production of HAC Clinker

A simplified diagram,
showing the basic steps in
the production of HAC
clinker is shown in Fig. 2.

Fig. 2: Manufacture of high-alumina cement

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As can be seen,
 the two mix components bauxite and limestone are not milled but
are fed to the furnace in lump form so as not to hinder the free
passage of the exit gases up the vertical shaft part of the kiln.

 As the raw mix is in any case fully molten in the horizontal part of
the furnace (at approx. 1500 - 1550C) previous grinding is not
necessary.

 The then formed molten clinker issues continuously from a tap hole
in the side of the furnace, and is allowed to cool relatively slowly,
without heat recuperation, in a moving iron pan conveyor.

 Fuel consumption is very high being approx. 8'400 kJ/kg clinker

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B Expansive Cement Types

Expansive cements are cements, which when mixed with

water, form pastes that tend to increase in volume to a
significantly greater degree than Portland cement paste.

Expansive cements are thus used to compensate for

volume decrease due to shrinkage or to induce tensile
stress in reinforcement (post-tensioning)

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 In the USA three types of expansive cement are designated by the

American Concrete Institute, based on their mineralogical
composition and not on their physical properties.
These are:
1. Expansive cement, Type K.
 An expansive cement containing anhydrous alumine-sulfate
3CaO.3Al2O3.CaSO4 , (burned simultaneously with a Portland
cement composition, or burned separately when it is to be
interground with Portland cement clinker or blended with
Portland cement calcium sulfate (CaSO4), and free lime (CaO)

 One mole of 3CaO.3Al2O3. CaSO4 must be prepared with 8

moles CaSO4 and 6 moles CaO in the expansive clinker to give
ettringite.

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2. Expansive cement, Type M.

 A mixture of Portland cement high alumina cement, and calcium
sulfate.

3. Expansive cement, Type S.

 A Portland cement containing a large calculated C3A content and
modified by an excess of calcium sulfate above usual optimum
content.

 The expansion of all these cements is due to the formation during

setting of ettringite (a calcium sulfoaluminate hydrater
3 CaO. A12O3 . 3 CaSO4 .32 H2O).

 It is of little importance how this mineral is formed in the hydrating

paste.

 Consequently, the initial materials used to obtain expansion are

of secondary importance.
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Mineralogy and Production of Expansive Cement Additive (Type

K) (Denka CSA)

 Very little is known concerning these topics. It is known that the

additive contains the minerals:
% 25 ~ 4 CaO . 3 A12O3 . SO2
20% ~ CaO
~ 50% CaSO4

 The raw materials required for the production of this special clinker,
when produced in a rotary kiln, are bauxite, gypsum and limestone.

 A temperature sufficiently high to promote the formation of the

above minerals should be chosen, but not so high as to cause
difficulties due to evaporation of SO3 and due to ring formation.

 The latter results when partial melting of the charge takes place.
The firing temperature ranges between 1150-1200°C.
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 After preparation, the special clinker is ground to a Blaine fineness

of approx. 2800 - 3000 g/cm2, and sold in that form as an
expansive agent, suitable for intergrinding with Portland cement
clinker or intermixing with milled Portland cement during the
preparation of concrete.

 It is in principle also possible to produce a modified Portland

cement clinker containing alite, belite, ferrite and the calcium
sulphoaluminate 4 CaO .3A12O3 .SO3.

 This process is, however, not preferred, as to attain the final

hydrated mineral ettringite 3 CaO . A12O3 .3 CaSO4 . 32 H
responsible for the expansion, different ratios of CaO : A12O3 : SO3
are necessary.

 Kaolin from Sinai or kalabsha with high content of Al2O3 can be

used instead of bauxite for the preparation of expansive clinker.

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 To prepare an expansive cement clinker by using Kaolin instead of

bauxite the weights of Kaolin, limestone and gypsum needed to
make an expansive clinker of given phase composition ,
Referred to the ignited weights, were calculated by the following
equation:
Kaolin = 100
Limestone = 1.78 [( 0.55 + 0.183 n) P + 1.17 F + 1.875]
Gypsum = 1.13 [ 0.445( 1+m) P + 1.13S ]
Where
P = % Al2O3 - 0.426% Fe2O3 in Kaolin The amounts of kaolin and gypsum
F = Fe2O3 % must be calculated and mixed with
100 parts of Kaolin.
S = SiO2 %
M = desired molar ratio CaSO4 / C4A3 The prepared clinker contains the
n = desired molar ratio CaO/C4A3 in clinker ordinary Portland cement clinker
in addition to expansive clinker.

You can change the m and n as you

want for the degree of expansion .

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Conclusion

 When considering the long list of special cements, and

hence special clinkers, one might ask why ordinary
cement is still used.
 In reality, however, only a very small proportion of
special clinker is manufactured.
Type III ASTM
 Represents about 5 to 10% of total cement production,
 white cement about 1,5%
 the rest not more than 2 - 3% altogether.

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Considering That

 Modern marketing and publicity try to push new ideas and new
materials

 Cement salesmen on a competitive market try to expand their sales

with new products

 There must obviously be strong pressures at work which limit the

consumption of special cements.

 These forces can be summarized as follows:

 People are reluctant to experiment and prefer approved

methods and materials an outlook especially true in the building
industry.

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 Both cement manufacturer and user prefer a small number of
products. An excessive variety requires large stores and more
silos, and thus the risk of confusion increases.

 The application of special cements requires expensive skilled

labour. Instead of an improvement, very often a lowering of the
concrete quality results.

 The production of special clinkers often requires an interruption

in the manufacturing plant and necessitates supplementary
storage rooms and silos The manufacturer therefore prefers to
produce only one type of clinker and to vary only the fineness.

 The energy consumption in manufacturing special clinkers is

often higher than for ordinary Portland cement clinker.
Moreover, special mineral resources are often required.

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 The costs for all special cements are usually much higher than
those of an OPC.
 
 The application of a special cement in buildings requires an
official acceptance in most countries, if it is not covered by the
standard specifications.

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