Clinker under the microscope.

Learning from microscopic analysis

Arthur Harrisson
 What might we learn?
• Microscopic examination might point to deficiencies in the burning
regime.

• It might highlight raw material preparation deficiencies.

• Examination might reveal factors relating to the fuel type and

preparation.

• Any of these can adversely affect production or quality or both.

• Regular examination can be used to monitor the effects of changes in

the process or raw materials.

• This can then be used to effect optimisation of burning conditions,

raw material selection and preparation and fuel use
 Clinker Microscopy
• Optical Microscopy

– identify crystal types and forms

– measure crystal sizes

– analyse crystal relationships one to another.

 What might we learn?
• Examination might point to deficiencies in the burning regime which
adversely affect either production or quality or (probably) both.
50 µ
50 µ
 What might we learn?
• Examination might point to deficiencies in the burning regime which
adversely affect either production or quality or (probably) both.

• Examination might highlight raw material preparation deficiencies

which will affect either production or quality or (probably) both.
100 µ
 What might we learn?
• Examination might point to deficiencies in the burning regime which
adversely affect either production or quality or (probably) both.

• Examination might highlight raw material preparation deficiencies

which will affect either production or quality or (probably) both.

• Examination might reveal factors relating to the fuel type and

preparation which will affect either production or quality or
(probably) both.
250 µ
 What might we learn?
• Examination might point to deficiencies in the burning regime which
adversely affect either production or quality or (probably) both.

• Examination might highlight raw material preparation deficiencies

which will affect either production or quality or (probably) both.

• Examination might reveal factors relating to the fuel type and

preparation which will affect either production or quality or
(probably) both.

• Regular examination can be used to monitor the effects of changes

in the process or raw materials.

• This can then be used to effect optimisation of burning conditions,

raw material selection and preparation and fuel use
 Clinker microscopy
• Optical microscopy

– Many cement plants use optical microscopy as a

routine method of control

– Ono developed procedures for kiln control using

optical microscopy.

– A summary of the Ono parameters follows:

 Ono
• Crystal size and colour have formed the basis of the Ono
method which has been used in various modifications
throughout the world.

• The next slide shows the basics of the method and the
rationale behind the measurements.

• They are concerned with the length of burning, the maximum

temperature experienced by the clinker and the degree of
cooling within the rotary kiln.
Summary of the Ono method characteristics

Burning condition Hydraulic activity

4 3 2 1
Excellent (+) Good (VV) Average (v) poor (-)
___
Heating rate Quick __ Slow
Size of alite (µ) 15-20 20-30 (25) 30-40 40-60 (120)
Maximum High __ __ Low
Temperature 0.010 – 0.008 0.007 – 0.006 0.006 – 0.005 0.002
Birefringence of
alite
Burning time Long __ __ Short
Size of belite (µ) (20) 25 – 40 (60) (15) 20-25) (10) 15-20 5-10
Cooling rate Quick __ __ Slow
colour of belite Clear (C) Faint yellow (FY) Yellow (Y) Amber (A)
Birefringence of 0.012 0.015 0.017 0.018
belite
Content of alpha Abundant (40%) Medium (20%) Few (10%) Nil (0%)
 Ono
• In summary the method advocates a slow start to the burning regime
while the C2S (belite) forms, then a short hot production of C3S (alite)
and rapid cooling.

• The slow start means that the highest temperatures are only
encountered for a short section close to the kiln outlet.

• In this method the cooling rate is measured by the colour of the belite
crystals which slowly exsolve impurities from the lattice as the crystals
cool, giving a cloudy apearance in slowly cooled clinker.

• An alternative approach is to examine the crystals which form out of

the liquid phase of the clinker. Rapid cooling of a liquid gives finely
divided crystals while slow cooling produces coarse tricalcium
aluminate and calcium aluminoferrite crystals.
 Regular examination
• The Ono method has been successfully used on plant throughout the
world as a means of (almost) on-line diagnosis of the status of clinker
production.

• Most microscopists who operate the Ono system use variations achieved
through experience.

• Instrumentation today, often linked to kiln control software, has made this
type of hands-on control less common.

• There is a considerable benefit to be gained from long term analysis of

clinkers with correlations to the wealth of data available on a modern
cement plant. Observations need to be related directly to the process
conditions prevailing at the time of sampling.
CALCINATION AND MINERALOGY
Formation of Calcium Silicates
800oC 1000oC 1350oC 1450oC

C3S

C2S
 Calcining Zone
• At the end of the drying stage in the cement kiln, already some liquid
formation is occurring.

• Potassium sulphate begins to melt and in the presence of large quantities

of sulphate, calcium langbeinite (calcium potassium sulphate)will form.

• Ideally these compounds remain within the feed material where they
initiate the formation of nodules by binding the other materials together.

• However, in a preheater kiln, the liquid can as easily bind to the

refractories or the sides of the kiln if the temperature for liquid formation
coincides with an environment where the sticky liquid can lodge or where
there is a locally cooler area, such as an inspection door, a kiln seal, a
sharp bend in the ductwork.
Buildup samples
 Buildup

FL-free lime; a-anhydrite; cl-calcium langbeinite; b-belite also some spurrite.

 Buildup
• The presence of calcium langbeinite and propably spurrite (a carbonated
calcium silicate) indicates that the build up was formed at about 800°C in
the presence of CO2 and therefore while the limestone was undergoing
calcination.

• Depending on the exact position of the blockage, a lengthening or

shortening of the flame or an adjustment of the fuel split in a precalciner
kiln can frequently move that temperature zone to a part of the kiln where
there are fewer irregularities on which the build up can form.
 Buildup

• Optimisation of the kiln in terms of avoiding buildup involves

trying to avoid the temperature profiles where condensation
of volatiles occurs at a location where sticky liquid will lodge.
 Typical Composition of Kiln
Back End Deposits
Condensing volatiles form sticky liquid and passing
material adheres to the liquid reacting to form compounds
such as:

Spurrite 4CaO:2SiO2:CaCO3

Kleins Compound 3CaO:3Al2O3:CaSO4

Calcium Sulphosilicate 4CaO:2SiO2:CaSO4

Calcium Langbeinite 2CaSO4:K2SO4

These compounds densify the deposit and produce a mass of

interlocking crystals.
 Build-up phases, formation
temperatures.

• Ca Langbeinite
– forms between 600°C and 900°C.
• Spurrite
– forms between 750°C and 900°C. Requires CO2
• Anhydrite
– forms between 550°C and 1150°C.
• Sulphosilicate
– can form from 850-1150 °C, easiest between 900 and
1100°C
 Relationships of compounds

1600

1400

1200

1000

800

600

400

200

0
Ca langbeinite Spurrite Anhydrite silicosulphate easy silicosulphate slow calcite free lime
 Low Temperature Melt Formation

• At temperatures as low as 700°C, low melting point alkali

salts start to bind the powdered meal into nodules and
facilitate the start of the clinker forming chemical
reactions.

• At 700°C in a precalciner kiln the meal is spinning through

the cyclones.

• Further down the kiln, as the material approaches the

burning zone, the aluminates and aluminoferrites melt
and greatly accelerate the reactions by dissolving other
components.
 Recycling of material in the preheater

• Once through the drying and calcining zones, in a preheater kiln the
feed passes down the feed pipe and into the rotary kiln. At this point
the finely divided material meets the kiln gases coming through the
kiln and into the riser duct.

• The gases are already carrying dust from the kiln and are capable of
picking up further material from the incoming feed. Most of the feed
is at least partly calcined limestone, in precalciner kilns some 90%+
calcined.
 Recycling of material in the preheater

• Some fine calcined grains are easily entrained into the gas stream
and are carried round the cyclone system to rejoin the feed and
pass again into the kiln, resulting in an increased proportion of
limestone in the hotmeal to the kiln compared to the feed and the
clinker.

• In a precalciner kiln the LSF of the hotmeal is typically 2 or 3 points

higher than the clinker due to his effect but in the less stable kilns
this can fluctuate widely and bring about a high variability in the
clinker quality.
Hotmeal >90µ

1000 microns
CLINKERING AND MINERALOGY
Formation of Calcium Silicates
800oC 1000oC 1350oC 1450oC

C3S

C2S
 Clinkering
• Within the burning zone the clinkering reactions take place.

• Free lime combines first with alumina and iron oxide to form the
liquid phase, then with silica to form C2S and finally with C2S to form
C3S.

• In terms of clinker quality and fuel conservation the aims in this area
are the same. The clinker should be burned only as hard as will
reduce the free lime to the target and should be cooled as soon as
possible once the combination has been achieved.

• Heat should be at the front of the kiln so that these aims can be
achieved. Microscopy has been used for many years as the means
of diagnosing the quality of clinker and pointing the way to
improvements.
50µ
 For Optimum Clinker Quality

• The kiln feed chemistry must be of low variability

• The raw meal must be adequately ground
• The coal ash must be uniformly incorporated into the
clinker
• The clinker must be rapidly cooled from the burning
zone temperature
100µ
50µ
50µ
100µ
 For Optimum Clinker Quality

• The kiln feed chemistry must be of low variability

• The raw meal must be adequately ground
• The coal ash must be uniformly incorporated into the
clinker
• The clinker must be rapidly cooled from the burning
zone temperature
50µ
50µ
50µ
 Summary of the Ono method
characteristics
Burning condition Hydraulic activity

4 3 2 1
Excellent (+) Good (VV) Average (v) poor (-)
___
Heating rate Quick __ Slow
Size of alite (µ) 15-20 20-30 (25) 30-40 40-60 (120)
Maximum High __ __ Low
Temperature 0.010 – 0.008 0.007 – 0.006 0.006 – 0.005 0.002
Birefringence of
alite
Burning time Long __ __ Short
Size of belite (µ) (20) 25 – 40 (60) (15) 20-25) (10) 15-20 5-10
Cooling rate Quick __ __ Slow
colour of belite Clear (C) Faint yellow (FY) Yellow (Y) Amber (A)
Birefringence of 0.012 0.015 0.017 0.018
belite
Content of alpha Abundant (40%) Medium (20%) Few (10%) Nil (0%)
Reducing Conditions in the Burning
Zone
• If reducing conditions prevail within the kiln burning zone, the oxide
blend of the raw mix design is upset.

• Specifically, trivalent iron oxide (Fe2O3) is reduced to divalent FeO.

• FeO replaces CaO in the C3S crystal lattice.

• There is thus more C3S formed and less liquid phase.

• Free lime is unable to combine with C2S becase the FeO is more
mobile so free limes increase.
Reducing Conditions in the Burning
Zone
• The incorporation of FeO in the C3S phase leaves less iron oxide to
form liquid phase.

• Therefore combination is more difficult.

• As oxygen rich secondary air enters the kiln, with the clinker still at
temperatures in excess of 1300°C, FeO is reoxidised to Fe2O3 within
the C3S crystals.

• This cannot be retained within C3S and decomposition occurs at the

crystal fringes.
20µ
Reducing Conditions in the Burning
Zone

• The release of Fe2O3 into the matrix changes the liquid composition
causing a resurgence of liquid phase.

• Which, under oxidising conditions, encourages further dissoution of

C3S.
Liquid phase formation and liquid composition

Liquid % at 1338 C
Liquid % at 1400 C
Reducing Conditions in the Burning
Zone

• As well as reduction of Fe2O3 to FeO, oxygen is stripped

from SO3 to produce SO2 gas.

• Most cement clinker raw feeds have a balance of alkalis

(Na2O and K2O) with SO3 which permits the formation of alkali
sulphates in the clinker.

• If SO2 is removed due to reducing conditions, the alkali needs

to combine elsewhere.
Reducing Conditions in the Burning
Zone

• In the absence of available SO3, alkali becomes

incorporated in the aluminate phase, forming the so-
called alkali-modified, or prismatic, C3A.

• This phase has different hydration characteristics to the

more usual cubic form and leads to erratic setting
behaviour and water demand.
20µ
 Kiln Feed Variability
Effect upon Kiln Operation

• Timescale of variability.
• Influence on burning temperature.
• Influence on fuel consumption.
• Influence on output.
• Influence on stability of operation.
 Kiln Feed Variability
Influence on Kiln Stability

• Running a kiln in reducing conditions prevents

sulphur from escaping from the kiln system.

• The hotter the burning zone temperature, the more

alkalis are driven back.

• Either or both of these conditions can seriously

increase the incidence of blockages.
 Sulphur Cycle
SO3 INPUT
Potential to
Kiln Feed
• Sulphate convert to :
SO2 Gas
• Sulphide

What goes In = What comes out

SO3 INPUT
Fuel
• Organic

Reducing
SO3 OUTPUT SO3 OUTPUT
Conditions
Stack Emission Sulphate to SO2/SO3 Clinker
• SO2 Gas • Sulphate
 Kiln Feed Variability
Burning Zone Variation,°C

±1 LSF = ± 10-
13°C

±0.1 SR = ± 7-
14°C

±0.1 AR = ± 6°C

±1% ≥90 µ = ± 8°C

 Kiln Feed Variability
Fuel Consumption

Increased BZ temperature equates to additional

fuel from:
• Higher shell losses
• Higher gas exit temperatures
• Higher clinker cooler entry temperatures.

Estimated impact of 10°C = 7.5 kcal/kg clinker

 Fuel Consumption vs. Variability
900

875

850
kcal/kg

825

800

775

750

725
0 1 2 3 4 5 6 7
Kiln Feed LSF Std. Dev.
 Kiln Feed Variability
Kiln Output

Increased fuel consumption means higher specific

heat transfer per unit of clinker is required. This in
turn dictates a lower mass of material that can be
processed in the kiln when fuel and air are at the
system maximum.

It is estimated that 10°C = 0.6% output.

 Kiln Output vs. Variability
100

90
% of Output

80

70

60

50
0 1 2 3 4 5 6 7
Kiln feed LSF Std Dev.
 Kiln Feed Variability

Influence on Kiln Stability

Higher Burning Zone temperatures result in

higher volatile recirculating loads - particularly
sulphur. This in turn leads to potentially
increased ring formation in the kiln.
 Liquid Phase and Clinker Nodulisation

POOR NODULISATION OPTIMUM NODULISATION LARGE NODULES AND

DUSTY CLINKER SUITABLE CLINKER GRADING TENDENCY FOR
HEAVY COATINGS TO
FORM ON
REFRACTORIES

16 18 20 22 24 26 28

% LIQUID AT 1400ºC

3.0 2.8 2.6 2.2 2.0 1.7

CLINKER S/(A+F)
 01/12/2006
FLS Coating tendency = C3A + C4AF + 0.2(C2S) + 2(Fe2O3)

30/11/2006
29/11/2006
28/11/2006
27/11/2006
26/11/2006
25/11/2006
Coating tendency

24/11/2006
23/11/2006
22/11/2006
21/11/2006
>30 indicates heavy, unstable coating, rings

20/11/2006
19/11/2006
<28 indicates light coating. (too weak).

18/11/2006
Coating Tendency of the kilns.

17/11/2006
and snowmen. (too strong).
KILN 2 Nov 2006.

16/11/2006

Date.
15/11/2006
14/11/2006
13/11/2006
12/11/2006
11/11/2006
10/11/2006
09/11/2006
08/11/2006
07/11/2006
06/11/2006
05/11/2006
04/11/2006
03/11/2006
02/11/2006
01/11/2006
31/10/2006

33

32

31

30

29

28

27

26

25
Coating tendency factor.
Rings, Build-ups and Blockages

Flux (Liquid level)

• Al & Fe
• Minor Components
• MgO, SO3/Alkalis
 Plant A % Liquid in Clinker at 1450°C
29%
Formula – Fe & Al + MgO + Alkalis + SO3

24%

29%
Plant B – for comparison (same formula)

24%
 Rings, Build-ups and Blockages

Flux
• Amount
• Temp of formation
Minor Components • Viscosity
Volatile- SO3/Alks/Cl • Surface Tension

Clinker
Absorbed into clinker minerals – Alter
reactivity
Build Ups

Heat Transfer
Emissions
 Rings, Build-ups and Blockages
Non-Volatile - Main Oxides
+ Minor Components
• MgO etc

Flux
• Amount
• Temp of formation
• Viscosity
• Surface Tension

Clinker
Absorbed into clinker minerals
• Alter reactivity – Sub for CaO – Stabilise C 2S – Mineralise (ease formation of C 3S)
Typical Volatile Recirculating
Loads in a PC/SP System

Component % of Total Input

Chloride 3,000 – 7,000
K2 O 200 – 650
Na2O 150 – 200
SO3 200 - 800
Typical Maximum Allowable
Volatile Contents in a PC/SP
System

Level
Component Total Input
Recirculating
Chloride 1.6 0.03
Na2Oe 2.5 -3.5 1.0 - 1.5
SO3 2.5 - 4.5 1.5 - 2.5
 Kiln Rings

• Volatile rings near back end of kiln

• Mid-kiln rings: 7 to 13 kiln diameters
• Ash rings: 5 to 7 kiln diameters
• Sinter rings: 2 to 7 kiln diameters
• Clinker rings: 1 to 2 kiln diameters
 Kiln Rings
• Mid-kiln
Dense, low porosity and often elongated. Chemically like
clinker with low volatile content. Contains all clinker
compounds and CaO. Caused by long cold flame, fine dust
recirculation from front end.

• Ash
Common with high ash coals. Very dense and layered with
glassy appearance. Similar to clinker but higher belite which
is often in layers. Very small alite crystals.
 Kiln Rings

• Sinter Rings
Grey/black, very hard, with small clinker nodules embedded.
Chemically similar to clinker. Often with spurrite and belite in
deeper parts

• Clinker Rings
Agglomerations of fine and coarse clinker very close to the
front end of the kiln. Sometimes encouraged by high ash
coals especially if flame is ‘poor’
 Summary

• Microscopy is a valuable tool

• It gives data which provides

– information able to predict and control clinker quality

– information which can assist in modifying the operating

conditions to operational advantage.