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UNDERSTANDING CEMENT

Clinker: compositional parameters


Parameters based on the oxide composition are very useful in describing clinker
characteristics. The following parameters are widely used (chemical formulae represent
weight percentages):
Lime Saturation Factor
The L! is a ratio of "a# to the other three main oxides. $pplied to clinker% it is
calculated as:
L!&"a#'((.)i#( * +.($l(#, * -../!e(#,)
#ften% this is referred to as a percentage and therefore multiplied by +--.
The L! controls the ratio of alite to belite in the clinker. $ clinker with a higher L! will
have a higher proportion of alite to belite than will a clinker with a low L!.
Typical L! values in modern clinkers are -.0(1-.0)% or 0(210)2.
3alues above +.- indicate that free lime is likely to be present in the clinker. This is
because% in principle% at L!&+.- all the free lime should have combined with belite to
form alite. 4f the L! is higher than +.-% the surplus free lime has nothing with which to
combine and will remain as free lime.
4n practice% the mixing of raw materials is never perfect and there are always regions
within the clinker where the L! is locally a little above% or a little below% the target for
the clinker as a whole. This means that there is almost always some residual free lime%
even where the L! is considerably below +.-. 4t also means that to convert virtually all
the belite to alite% an L! slightly above +.- is needed.
The L! calculation can also be applied to Portland cement containing clinker and
gypsum if (-.5 x #,) is subtracted from the "a# content. (67: This calculation (ie: -.5
x #,) does not account for sulfate present as clinker sulfate in the form of potassium
and sodium sulfates) and this will introduce a slight error. 8ore particularly% it does not
account for fine limestone or other material such as slag or fly ash in the cement. 4f
these materials are present% calculation of the original clinker L! becomes more
complex. Limestone can be 9uantified by measuring the "#( content and the formula
ad:usted accordingly% but if slag or fly ash are present% calculation of the original clinker
L! may not be conveniently practicable.)
Silica Ratio (SR
The silica ratio (also known as the ilica 8odulus) is defined as:
; & i#('($l(#, * !e(#,)
$ high silica ratio means that more calcium silicates are present in the clinker and less
aluminate and ferrite. ; is typically between (.- and ,.-.
The silica ratio is sometimes called the <silica modulus.=
Alumina Ratio (AR
The alumina ratio is defined as:
$;&($l(#,'(!e(#,)
This determines the potential relative proportions of aluminate and ferrite phase in the
clinker.
$n increase in clinker $; (also sometimes written as $'!) means there will be
proportionally more aluminate and less ferrite in the clinker. 4n ordinary Portland
cement clinker% the $; is usually between + and >.
Clinker: reactions in t!e kiln
This page reviews the reactions which take place as the feed passes through the kiln.
The blended% milled raw materials go to a silo and from there to the kiln.
The reactions which take place in the kiln can be considered under three broad
headings:
?ecomposition of raw materials 1 reactions at temperatures up to about +,-- ".
$lite formation and other reactions at +,-- "1+>/- " in the burning @one.
"ooling of the clinker.
Decomposition o" ra# materials $ reactions at temperatures up to a%out
&'(( C
This includes:
i. Aater evaporation in the raw feed% if any.
ii. Loss of carbon dioxide from the limestone (ie: calcining).
iii. ?ecomposition of the siliceous and aluminosilicate fractions of the feed.
iv. !ormation of a sulfate melt phase.
The decomposition products react with lime to form intermediate compounds which in
turn form other compounds as clinkering proceeds.
)ater e*aporation
4n wet1process kilns% and their derivatives% water must first be driven off. 4n a wet1
process kiln% calcining takes place after the water has been driven off% about a third of
the way down the kiln. 4n the more modern pre1calciner kilns% the feed is calcined prior
to entering the kiln.
Calcinin+
4n isolation% decarbonation of calcium carbonate at + atmosphere takes place at )0> ".
This temperature is reduced to /-- "1.-- " if the reaction takes place in contact with
9uart@ or the decomposition products of clay minerals% which react with the calcium
oxide as it forms.
4n a wet1process or preheater system without a pre1calciner% most of the calcination
takes place in the rotary kiln within a moving mass of feed. This situation is not ideal
for calcination because heat transfer has to take place through a large mass of material
and "#( has to escape outwards as heat moves inwards.
$ pre1calciner calcines the raw material much more efficiently than a wet1process kiln.
;aw meal is dispersed in the hot gas and calcination takes place in seconds% rather than
the half an hour or so inside a kiln at the same temperature.
Formation o" earl, an- interme-iate compoun-s
?uring calcination% the lime produced starts to react with other components of the raw
feed. The initial silicate product is belite. ome calcium aluminate and ferrite phases
also start to form.
$ number of phases are formed in the clinker feed before the burning @one proper is
reached. These intermediate phases dissociate in the burning @one and are not
therefore found in clinker but assist in forming the final clinker minerals.
Sul"ate melt p!ase
$t intermediate temperatures% sulfates combined with calcium and alkalis form a li9uid
phase. This is separate from the aluminate and aluminoferrite1based li9uid formed in
the burning @one 1 the two li9uids are immiscible.
$s with the main li9uid phase% the sulfate li9uid phase contributes to ion mobility and
promotes combination.
Alite "ormation an- ot!er reactions at
&'(( C$&./( C in t!e %urnin+ 0one
4n the burning @one% above about +,-- "% reactions take place 9uickly. The clinker is in
the burning @one for perhaps +-1(- minutes but in this time a lot happens:
i. The proportion of clinker li9uid increases and nodules form.
ii. 4ntermediate phases dissociate to form li9uid and belite.
iii. 7elite reacts with free lime to form alite.
iv. ome volatile phases evaporate.
Clinker li1ui- an- no-ule "ormation
$bove about +,-- " the proportion of li9uid starts to increase 1 by +>/- "% perhaps (-1
,-2 of the mix is li9uid. The li9uid forms from melting ferrite and aluminate phases
and some belite. The li9uid content is more than the sum of the aluminate and ferrite
phases in the cooled clinker because of the dissolved lime and silica.
The additional li9uid causes coalescence of clinker particles% leading to the formation of
nodules.
Dissociation o" interme-iate p!ases
The intermediate phases dissociate to form mainly aluminate phase% which then
becomes part of the li9uid% and belite.
Alite "ormation
$lite forms by the transition of some of the belite to alite and also directly from free
lime and silica to alite. These reactions occur rapidly once the clinker temperature is
above about +>-- ".
E*aporation o" *olatiles
3olatile phases in the cement kiln are principally alkali sulfates% with a much smaller
proportion of alkali chlorides. $s the part1burned feed approaches the burning @one%
these volatile phases are in li9uid form and a proportion volatili@es% the remainder
passing out of the kiln in the clinker as inclusions within the pores.
The volatili@ed material passes back down the kiln% where it condenses on the relatively
cool incoming feed. 4t again becomes part of the sulfate melt phase% promoting
reactions% and is once again carried within the clinker towards the burning @one.
This recirculating load of alkali and sulfate can occasionally become excessively high.
Large 9uantities of condensing volatiles can then cause blockages in the kiln or in the
preheater as the condensed li9uid sticks feed particles together% forming accretions.
Coolin+ o" t!e clinker
$s the clinker cools% the main li9uid phase crystalli@es to form aluminate phase% ferrite
and a little belite.
!ast cooling of clinker is advantageous 1 it makes for more hydraulically1reactive
silicates and lots of small% intergrown% aluminate and ferrite crystals.
low cooling gives less hydraulically1reactive silicates and produces coarse crystals of
aluminate and ferrite 1 over1large aluminate crystals can lead to erratic cement setting
characteristics. 3ery slow cooling allows alite to decompose to belite and free lime.
Cement kiln re"ractories
;efractories play a critical% if unseen% role in both the rotary kiln lining% and the lining of
the high volume static e9uipment areas that comprise a modern pre1calciner kiln
system.
The durability of the rotary kiln brick lining generally determines the duration of a kiln
operating campaign. Ahilst great efforts are made to ensure appropriate refractory
brick materials selection% installation% deployment (@oning) and the optimisation of the
kiln light1up% it is primarily the nature and stability of the subse9uent kiln operation that
influences rotary kiln lining life.
$ large number of kilns now use alternative fuels. 8any of them substitute these
alternative fuels through the main kiln burner as well as in the pre1heater ' pre1
calcinerB the chemical and heat1release changes caused by inevitable short1term
fluctuations in the fuel(s) mix has a ma:or influence on the thermal% coating and
atmosphere conditions existing through the rotary kiln into the pre1calciner.
Cxpert systems are available that help limit the influence of fuel mix fluctuations on the
flame shape% but not many cement kilns are e9uipped with such systems.
"onse9uently% the main influence of the use of alternative fuels is often on clinker
chemistry due to the different ash compositions of individual alternative fuels.
uch fuel variations may produce any or all of the following :
$lternative fuel fall through ( from the pre1heater' pre1calciner )
$dverse minor phase re1circulation effects ( gasriser )
Cxcessive build1up or clogging ( kiln inlet or gasriser )
Cxcessive coating in the rotary kiln ( ringformation )
;educing conditions or damaging atmosphere effects( rotary kiln )
Thermal wash1outs ( rotary kiln )
!luctuations in flame length ( rotary kiln )
?estabilisation and stripping of clinker coating (rotary kiln )
2ortlan- cement clinker $
o*er*ie#
$lite or tricalcium silicate or ",
7elite% or dicalcium silicate or "(
Tricalcium aluminate (or the Daluminate phaseD) or ",$
"alcium alumino1ferrite (or the <ferrite= phase) or tetracalcium aluminoferrite or
">$!
Portland cement clinker is a dark grey nodular material made by heating ground
limestone and clay at a temperature of about +>-- "1+/-- ". The nodules are
ground up to a fine powder to produce cement% with a small amount of gypsum
added to control the setting properties.
This page gives a thumbnail sketch. !or more information see the following
pages% or better still% the Enderstanding "ement e1book 1 links at the bottom of
this page.
Polished
section of
nodule
(scanning
electron
microscope image). 8ost of the nodule is alite (light grey) 1 some clusters of
belite are visible (arrowed). $luminate and ferrite are present but not visible at
this relatively low magnification.

6odules range in si@e from +mm to (/mm or more and are composed mainly of
calcium silicates% typically 5-21)-2. The strength of concrete is mainly due to
the reaction of these calcium silicates with water.
Portland cement clinker contains four main minerals:
Alite: approximately tricalcium silicate (typically about ./2 of the total)
3elite: approximately dicalcium silicate (typically about +/2 of the total)
Aluminate: very approximately tricalcium aluminate (typically about 52 of the
total)
Ferrite: very approximately tetracalcium aluminoferrite (typically about )2 of
the total)
The balance is made up of alkali sulfates and minor impurities. The typical
mineral contents shown are sub:ect to wide variation.
#ptical
microscope image (polished section) of nodule. 7rown crystals are alite% blue
crystals are belite% bright interstitial material is mainly ferrite% with small dark
inclusions of aluminate. Frey material is the epoxy resin used to make the
specimen. 67: $lite is not actually brown and belite is not actually blue 1 they
appear brown and blue here because the polished section has been etched to
show the crystals more clearly.
$ clinker chemical analysis is normally given in oxide form 1 a typical example
might be:

E4ample o" a t,pical clinker anal,sis (o4i-e #ei+!t56


Si78 Al87' Fe87' Ca7 M+7 987 Na87 S7' L7I IR Total
(+./ /.( (.) .... +.- -.. -.( +.- +./ -./ 0).0
!ree lime & +.-2 "a#
7alance is typically due to small amounts of oxides of titanium% manganese%
phosphorus and chromium.

!rom the chemical analysis% the 9uantity of each of the four main minerals can
be calculated using the D7ogueD calculation (click on the link below for more
information.)
Cement !,-ration
7y the process of hydration (reaction with water) Portland cement mixed with sand
gravel and water produces the synthetic rock we call concrete. "oncrete is as essential
a part of the modern world as are electricity or computers.
#ther pages on this web site describe how P" is made and what is in it. Gere% we will
discuss what happens when it is mixed with water.
This page is a short introduction. The Enderstanding "ement e1book contains a more
detailed description of the hydration process and the hydration products.
"linker is anhydrous (without water) having come from a hot kiln. "ement powder is
also anhydrous if we ignore the small amount of water in any gypsum added at the
clinker grinding stage.
The reaction with water is termed HhydrationH. This involves many different reactions%
often occurring at the same time. $s the reactions proceed% the products of the
hydration process gradually bond together the individual sand and gravel particles% and
other components of the concrete% to form a solid mass.
T!e !,-ration process: reactions
4n the anhydrous state% four main types of minerals are normally present: alite% belite%
aluminate (",$) and a ferrite phase (">$!). !or more information on the composition of
clinker% see the clinker pages. $lso present are small amounts of clinker sulfate (sulfates
of sodium% potassium and calcium) and also gypsum% which was added when the clinker
was ground up to produce the familiar grey powder.
Ahen water is added% the reactions which occur are mostly exothermic% that is% the
reactions generate heat. Ae can get an indication of the rate at which the minerals are
reacting by monitoring the rate at which heat is evolved using a techni9ue called
conduction calorimetry. $n illustrative example of the heat evolution curve produced is
shown below.

Three principal reactions occur:
$lmost immediately on adding water some of the clinker sulphates and gypsum dissolve
producing an alkaline% sulfate1rich% solution.
oon after mixing% the (",$) phase (the most reactive of the four main clinker minerals)
reacts with the water to form an aluminate1rich gel (tage 4 on the heat evolution curve
above). The gel reacts with sulfate in solution to form small rod1like crystals of
ettringite. (",$) reaction is with water is strongly exothermic but does not last long%
typically only a few minutes% and is followed by a period of a few hours of relatively low
heat evolution. This is called the dormant% or induction period (tage 44).
The first part of the dormant period% up to perhaps half1way through% corresponds to
when concrete can be placed. $s the dormant period progresses% the paste becomes
too stiff to be workable.
$t the end of the dormant period% the alite and belite in the cement start to react% with
the formation of calcium silicate hydrate and calcium hydroxide. This corresponds to the
main period of hydration (tage 444)% during which time concrete strengths increase.
The individual grains react from the surface inwards% and the anhydrous particles
become smaller. (",$) hydration also continues% as fresh crystals become accessible to
water.
The period of maximum heat evolution occurs typically between about +- and (- hours
after mixing and then gradually tails off. 4n a mix containing P" only% most of the
strength gain has occurred within about a month. Ahere P" has been partly1replaced
by other materials% such as fly ash% strength growth may occur more slowly and
continue for several months or even a year.
!errite reaction also starts 9uickly as water is added% but then slows down% probably
because a layer of iron hydroxide gel forms% coating the ferrite and acting as a barrier%
preventing further reaction.
:,-ration pro-ucts
The products of the reaction between cement and water are termed Hhydration
products.H 4n concrete (or mortar or other cementitious materials) there are typically
four main types:
Calcium silicate !,-rate: this is the main reaction product and is the main source of
concrete strength. 4t is often abbreviated% using cement chemistsD notation% to H"11G%H
the dashes indicating that no strict ratio of i#( to "a# is inferred. The i'"a ratio is
somewhat variable but typically approximately -.>/1-./- in hydrated Portland cement
but up to perhaps about -.. if slag or fly ash or microsilica is present% depending on the
proportions.
Calcium !,-ro4i-e 1 "a(#G)(: often abbreviated to D"G.D "G is formed mainly from
alite hydration. $lite has a "a:i ratio of ,:+ and "11G has a "a'i ratio of
approximately (:+% so excess lime is available to produce "G.
AFm an- AFt p!ases: these are two groups of minerals that occur in cement% and
elsewhere. #ne of the most common $!m phases in hydrated cement is monosulfate.
7y far the most common $!t phase in hydrated cement is ettringite. The general
definitions of these phases are somewhat technical% but for example% ettringite is an $!t
phase because it contains three (t1tri) molecules of anhydrite when written as
",$.,"a#>.,(G(# and monosulfate is an $!m phase because it contains one (m1mono)
molecule of anhydrite when written as ",$."a#>.+(G(#.
The most common $!t and $!m phases in hydrated cement are:
Ettrin+ite: ettringite is present as rod1like crystals in the early stages of reaction or
sometimes as massive growths filling pores or cracks in mature concrete or mortar. The
chemical formula for ettringite is I"a,$l(#G)..+(G(#J(.(G(#J or% mixing notations%
",$.,"a#>.,(G(#.
Monosul"ate: monosulfate tends to occur in the later stages of hydration% a day or two
after mixing. The chemical formula for monosulfate is ",$."a#>.+(G(#. 6ote that both
ettringite and monosulfate are compounds of ",$% "a#>(anhydrite) and water% in
different proportions.
Monocar%onate: the presence of fine limestone% whether interground with the cement
or present as fine limestone aggregate% is likely to produce monocarbonate
(",$."a"#,.++G(#) as some of the limestone reacts with the cement pore fluid.
#ther $!m phases that may be present are hemicarbonate% hydroxy1$!m and !riedelDs
salt.
ome important points to note about $!m and $!t phases are that:
They contain a lot of water% especially $!t 1 principally ettringite in the context of
cement.
$!m contains a higher ratio of aluminium'calcium compared with $!t.
The aluminium can be partly1replaced by iron in both $!m and $!t phases.
The sulfate ion in monosulfate $!m phase can be replaced by other anionsB a
one1for1one substitution if the anion is doubly1charged (eg: carbonate% "#(
(1
) or
one1for1two if the substituent anion is singly1charged (eg: hydroxyl% #G
1
or
chloride% "l
1
).
The sulfate in ettringite can be replaced by carbonate or% probably% partly
replaced by two hydroxyl ions% although in practice neither of these is often
observed.
4n a concrete made from cement containing :ust clinker and gypsum% ettringite forms
early on in the hydration process% but gradually replaced by monosulfate. This is
because the ratio of available alumina to sulfate increases with continued cement
hydrationB on first contact with water% most of the sulfate is readily available to dissolve%
but much of the ",$ is contained inside cement grains with no initial access to water.
"ontinued hydration gradually releases alumina and the proportion of ettringite
decreases as that of monosulfate increases.
4f there is eventually more alumina than sulfate available% all the sulfate will be as
monosulfate% with the additional alumina present as hydroxyl1substituted $!m phase
(hydroxy1$!m). 4f there is a small excess of sulfate% the cement paste will contain a
mixture of monosulfate and ettringite. Aith increasing available sulfate% there will be
more ettringite and less monosulfate% and at even higher levels of sulfate there will be
ettringite and gypsum.
4f fine limestone is present% carbonate ions become available as some of the limestone
reacts. The carbonate displaces sulfate or hydroxyl in $!mB the proportion of
monosulfate or hydroxy1$!m therefore decreases as the proportion of monocarbonate
increases. The displaced sulfate typically combines with remaining monosulfate to form
ettringite% but if any hydroxy1$!m is present% the sulfate will displace the hydroxyl ions
to form more monosulfate. The key here is the balance between available alumina on
the one hand% and carbonate and sulfate on the other.
:,-ro+arnet: hydrogarnet forms mainly as the result of ferrite or ",$ hydration.
Gydrogarnets have a range of compositions% of which ",$G. is the most common phase
forming from normal cement hydration and then only in small amounts. $ wider range
of hydrogarnet compositions can be found in autoclaved cement products.
T!e a%o*e t!ree parameters are t!ose most commonl, use-6 A "ourt!;
t!e <Lime Com%ination Factor< (LCF is t!e same as t!e LSF parameter;
%ut #it! t!e clinker "ree lime content su%tracte- "rom t!e total Ca7
content6 )it! an LCF=&6(; t!ere"ore; t!e ma4imum amount o" silica is
present as C
'
S6
Some %asic -e"initions use- in
cement an- concrete
$ few useful basic definitions follow% since the meanings of the words DcementD and
DconcreteD are rather blurred in general use.
2ortlan- Cement: 8aterial made by heating a mixture of limestone and clay in a kiln
at about +>/- "% then grinding to a fine powder with a small addition of gypsum.
Portland "ement% the main sub:ect of this site% is the most common type of cement 1
Dbasic cementD% if you like. 4n particular% ordinary Portland cement is the normal% grey%
cement with which most people are familiar. #ther types of Portland cement include
Ahite Portland "ement and ulfate ;esisting Portland "ement (;P").
Clinker: Portland cement is made by grinding clinker and a little added gypsum. "linker
is a nodular material before it is ground up. The nodules can be anything from +mm to
(/mm in diameter.
Cement: Esually taken to mean Portland "ement% but could mean any other type of
cement% depending on the context.
?ifference
between Cement (left)
and clinker (right). The
coin is a EK
one1pound coin about
(,mm across.
A++re+ate: "obbles%
pebbles% gravel% sand and silt 1 the DrockD component of all particle si@es in concrete.
Concrete: ynthetic rock made using cement (usually% but not necessarily% Portland
cement) mixed with aggregate and water.
Mortar: 8ixture of cement and fine aggregate% mainly sand. Esed typically to bond
bricks and building stone.
Grout: 8ixture of cement (possibly of various types) and other fine material such as
fine sand. Esed in a wide range of applications from filling the gaps between bathroom
tiles to oil wells.
Composite cements: ome types of cement are mixtures of Portland cement with
other material% such as blastfurnace slag from iron production and pulverised fuel ash
from coal1fired electricity power stations. These widely1used mixtures are called
DcompositeD cements.
Non$2ortlan- cements
#f course% there are other types of cement apart from Portland cement. 4mportant
examples include:
"alcium aluminate cements
Lime concrete'mortar
Cxpansive cements
Calcium aluminate cements (CACs
These may also be termed D"iment !onduD and used to be called Dhigh alumina
cements.D They are made from lime or limestone mixed with bauxite (aluminium ore) or
other high1alumina material.
"oncretes made with "$"s develop strength 9uickly and are resistant to chemical
attack. "$"s have a wide range of compositions% mainly with different ratios of lime to
aluminaB strictly% <"iment !ondu= is only one part of this compositional range. "$"s are
generally brown or grey1black% but can be white if made from pure alumina.
$s well as being used in concrete% "$"s are also used in grouts and other specialised
applications% often mixed with Portland cement and other materials such as gypsum.
Lime concrete an- mortar
Lime mortar and concrete have been used for thousands of years (see history of
cement) so% historically% lime is probably the most basic cementitious material of all.
Today% lime mortar and concrete are used mainly in the rebuilding or repair of historic
or ancient buildings% although in the EK there has been some recent use of lime mortar
in the construction of new buildings. There are several advantages in using lime mortar:
"racks that develop in lime mortar tend to heal themselves% unlike conventional
mortar made with Portland "ement.
Lime mortar is usually weaker than mortars made with Portland "ement and so
can be removed from the brick or stone at the end of the useful life of the
building. Particularly in the case of bricks% this means that they can be recycled%
saving a lot of energy otherwise needed to make newbricks. 7ricks used with
mortar made with Portland "ement generally can=t be re1used as it is difficult to
detach the mortar from the brick without damaging it.
Lime is produced at a lower temperature than Portland "ement% so other things
being e9ual% it takes less energy to produce a lime mortar compared with a
mortar containing Portland "ement.
E4pansi*e cements
These are special cements designed to exert an expansive force on their surroundings
after the cement has set. (Aith most cements% manufacturers go to a lot of trouble to
make sure the cement is not expansive). Cxpansive cements are used mainly in
demolition and also in mining.
6ext ' Gome
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