CEMENT

MANUFACTURING
AND
CEMENT CHEMISTRY
Module CMT xxx
26 Jun 2000
1

Cement Material & Manufacture of

Cement
Raw Materials

CALCAREOUS-2 parts
Limestone (CaCO3)
Cement rocks
Chalk
Marl
Marine shells and coral
Alkali waste

ARGILLACEOUS- 1 part
Clays
Shales
Slate and Mudstones
Blast furnace slag
Ashes (fly ash)
Cement rock

Grind + Heat Treat in Kiln

Temperature + 1500oC

CEMENT CLINKER

Clinker

Gypsum

C3S : Tricalcium Silicate

C2S : Dicalcium Silicate
C3A : Tricalcium Aluminate
C4AF : Tetracalcium Aluminoferrite
Ca + Mg Oxides, Ca (OH)2, CaCO3, Na2SO4, etc
Controlled Cooling

ADD 3 - 5% Gypsum (Ca.SO4. 2H2O), or Blend of Gypsum + Plaster

Pulverise mixture

Portland Cement

To second grinding mill

And Blend

PORTLAND CEMENT
C2S + C3S + C3A + C4AF + CaSO4. 2H2O + CaO + MgO
+ (Na2SO4 + NaKSO4 + CaK2(SO4)2 , or K2SO4
(depending on the cement)

Sources of Cement Variability

MIXING AND PROPORTIONING RAW

MATERIALS

KILNING (BURNING)
COOLING

GRINDING AND ADDITION OF GYPSUM

5

Alternative Blending of Materials

Schematic flow diagram of the dry process - Inexpensive, inconsistent

Schematic flow diagram of the wet process - Expensive, Consistent

Heat treatment, grinding and

storage

Schematic flow diagram of the burning process

8 Schematic flow diagram of the grinding and storage

Burning and Cooling Operations

Blend Fed Into One End of an Inclined Rotary Kiln

160 to 800 ft Long, 10 to 25 ft Diameter
1 to 3 rpm
Temperature Zones Through Kiln (Max 1500oC)
Refactory Lined
I
Up to 200oC
Water Evaporation
11

Reaction zones in
a rotary cement kiln

200-800oC +

Preheating, release of Clay

water

111 800 - 1100oC

Dissociation of Carbonates
CaCO3

1V 1100 - 1300oC

Exothermic reactions

V 1300 - 1500 - 1300oC Sintering

VI 1300 - 1000oC

Crystallisation of Clinker
Compounds

Cement Compounds
TRICALCIUM SILICATE
Major Component

(CaO)3SiO2 , C3S
50%

or

Alite

DICALCIUM SILICATE

(CaO)2SiO2, C2S or Belite

Medium Component 25%
Exists in inert and reactive form

TRICALCIUM ALUMINATE

(CaO)3Al2O3 , C3A

CALCIUM ALUMINO FERRITE

(CaO)4Al2O3Fe2O3, C4AF

Alumnate
Minor Component 3%
Undesirable

Ferrite
Minor Component 12%
Slow reacting and regulates level of

10

C 3A

or

or

Cement Clinker Grain Structure

C3A: Tricalcium Aluminate
3CaO. Al2O3

C2S: Dicalcium Silicate

2CaO. SiO2

C4AF: Tetracalcium Aluminoferrite

4CaO. Al2O3.Fe2O3

11

C3S: Tricalcium Silicate

3CaO. SiO2

Effects of Major Clinker Components

C3S, Tricalcium silicate

Major component in cement (formed from CaO and SiO 2)

Hydrates more rapidly than C2S - Controls setting time
Contributes to all stages of strength development (esp. early)

C2S, Dicalcium Silicate

Formed from CaO and SiO2

Hydrates very slowly with lowest heat of hydration
Affects long-term strength

C3A, Tricalcium Aluminate

Formed from CaO and Al2O3

Hydrates rapidly and produces
highest heat of hydration
Plays important role in:

C4AF, Tetracalcium aluminoferrite

Formed from CaO, Al2O3 and Fe2O3
Gives colour to cement
Little effect on set cement propertie
Produces low heats of hydration

Early strength development

Rheology behaviour of slurry
Controlling setting and thickening times

Hydrated C3A is readily attacked by sulphate water

Concentration controlled in MSR & HSR cements

12

Effect of Cooling Rates on Cement

Properties & Phases
SLOW COOLING
Enhances Crystallisation, Poor Grindability,
more C3A and MgO formed, C3S & C2S more highly ordered,
more hydraulically active, More unsoundness, higher early
compressive and lower longer term strength.
FAST COOLING
Forms Glassy Material, Better Grindability
Less C3A and free MgO stays in glassy phase, C3S & C2S
less highly ordered, less unsoundness, lower early
compressive strength and higher longer term strength.
OPTIMUM COOLING
4 - 5 C/min 1500oCto 1200oC

13

18 - 20 C/min to Ambient

Changes in Gypsum Content

GYPSUM ADDED TO PREVENT FLASH SET
Flash Set is the Uncontrolled Reaction of C3A Gypsum
Renders C3A Inert in Early Stages of Hydration C3A

GYPSUM CAN DEHYDRATE TO FORM PLASTER (or Anhydrite)

CaSO4.2H2O

= CaSO4.0.5H2O + 1.5H2O

Subsequent Re-hydration of Plaster to Gypsum is A FALSE SET

15

Effect of Manufacturing Process Steps on Cement

Properties
Material

1. Proportioning
of Raw Materials

2. Cooling
Process

3. Grinding process
& Gypsum
Addition

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Conc (%)

CaO
SiO2
Al2O3

65
22
5

Fe2O3
MgO

4
1

TOO LOW

TOO HIGH

Low early strength

Rapid setting
Increased kiln
temperature
required for burning

SLOW COOLING
Allows clinker crystallisation
Ensures better Grindability
More C3A + MgO to crystallise out
Produces - C2S (almost inert)

Cracking +
Unsoundness
Slow setting
Rapid setting

Rapid setting
Unsoundness (>5%)
FAST COOLING
Glass formation
Clinker difficult to grind
Preserves -form of C2S
Causes less C3A + MgO to form

FINER GRIND:

Increased proportion of cement reacts

Rate of hydration increased
Higher early strength development

GYPSUM :

Controlled addition difficult

Calcium sulphate hemi-hydrate
formation leads to shorter hydration times
Too little gives gelation problems

API Cement Classification

CLASS A : Intended for use from surface to a depth of 6,000 ft (1,830 m), when special
properties are not required. Similar to ASTM Type I cement.
CLASS B : Intended for use from surface to a depth of 6,000 ft (1,830 m). Moderate to
high sulphate resistance. Similar to ASTM Type II, and has a lower C 3A content than Class
A.
CLASS C : Intended for use from surface to a depth of 6,000 ft (1,830 m) when
conditions require early strength. Available in all three degrees of sulphate resistance,
and is roughly equivalent to ASTM Type III. To achieve high early strength, the C3S
content and the surface area are relatively high.
CLASS D :
Intended for use from 6,000 ft (1,830 m) to 10,000 ft (3,050 m) under
conditions of moderately high temperatures and pressures. It is available in MSR and
HSR types.
CLASS E : Intended for use from 10,000 ft (3,050 m) to 14,000 ft (4,270 m) under
conditions of high temperatures and pressures. It is available in MSR and HSR types.
CLASS F : Intended for use from 10,000 ft (3,050 m) to 16,000 ft (4,880 m)depth
under conditions of extremely high temperatures and pressures. It is available in MSR
and HSR types.
CLASS G + CLASS H : Intended for use as a basic well cement from surface to 8,000
ft (2,440 m) as manufactured, or can be used with accelerators and retarders to cover a
wide range of well depths and temperatures. No additions other than calcium sulphate or
water, or both, shall be interground or blended with the clinker during manufacture of
Class G and H well cements. They are available in both MSR and HSR types.

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C3S and C2S Hydration

100

CnS Hydrated (%)

C
80

S
2

60

25C

40

20

0
0.01

ie.,

21

0.03

0.05

0.1

0.3

0.5

10

Time (days)

30

50

100

300

2C3S + 6H ---> C3S2H3

+ 3CH

(FAST)

2 C2S + 4H ---> C3S2H3

+ CH

(SLOW)

1000

C3S + C2S + WATER ---> C-S-H GEL + PORTLANDITE (Ca(OH)2)

Hydration of C3A and C43AF

Without Gypsum:

2 C3A + 27 H --> C2AH8 + C4 AH 19

C2 AH8 + C4AH19 --> 2 C3AH6 + 15H

50

Products are a range of CALCIUM

No Gypsum

OF REACTION

40

ALUMINATE HYDRATES which Interconnect

30

Rapidly: FLASH SET

With Gypsum

20

C3A + 3 CSH2 + 26H

RATE

With Gypsum:

-->C3A . 3CS. 32H

C3A + Gypsum + water -->ETTRINGITE

10

0
0

ETTRINGITE Produces a protective layer to

stop hydration of C3A and prevent flash set
All gypsum finished:

C3A. 3CS. 32H + 2C3A + 4H -->

22

3C3A.CS.12H

10

20

30

40

(time hrs)

50

60

Hydration of Cement
I

min

23

II

III

IV

hr

I.

PRE - INDUCTION PERIOD

II.

INDUCTION PERIOD

III.

ACCELERATION PERIOD

IV.

DECELERATION PERIOD

V.

DIFFUSION PERIOD

days

NOTE:
(1) For C3S phase hydration
(2) Constant temperature

STAGES 1 and 2: Pre Induction and Induction

Periods
Ca

Al OH Ca Si
SO4

Seconds

ETTRINGITE

Hours
C - S - H Gel
PROTECTIVE LAYERS STOPS REACTIONS ???? - PUMPING TIME

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STAGE 3
Induction Period Almost Inactive - Ca Increases in Solution
End of Induction Period Indicated by Renewal of Product Growth
and Formation of Calcium Hydroxide as Additional Product
Mechanism for End of Stage 2 Unclear ???

ETTRINGITE

Ca(OH)2

C - S - H Gel

AS PARTICLES CONNECT RHEOLOGY INCREASES

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STAGES 4 and 5
THE PERIOD OF ACCELERATED REACTION TO GIVE A FULL SET
(HOURS - DAYS)
SLURRY DEVELOPS COMPRESSIVE STRENGTH IN STAGE 4
REACTION SLOWS DOWN IN STAGE 5 DUE TO DIFFUSION LIMITATION

ETTRINGITE

C - S - H Gel

26

Ca(OH)2

Laboratory Performance Variability

Variability In Thickening Times and Gelation

100 Bc
Bc

Time / hours

To Control Thickening Times or Gelation Means

Modifying Retarder or Dispersants
30

Magnesium and Sulphate

Resistance

Mg + Na Sulphates in formation fluids react with Ca(OH) 2

crystals in the cement to form:

Ca(OH)2 + MgSO4 + 2H2O ---> CaSO4 . 2H2O + Mg(OH)2

Ca(OH)2 + Na2SO4 + 2H2O ---> CaSO4 . 2H2O + NaOH

Crystals of Mg (OH)2 weaken cement

A solution of NaOH Increases Permeability because NaOH is
Soluble
If Source of Mg is the Cement the Slurry Rheology Increases
During Early Hydration
OH + Mg ---> Mg(OH) 2
Formation of Ettringite after cement has set

expansion and cracking of cement

swelling due to the replacement of the Ca(OH)2 by
Mg(OH)2
Sulphate reacts With Unreacted C3A to form more Ettringite

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Solutions
Minimise C3A in Cement

High Sulphate Resistant (HSR) Cement Has Less

Than 3%
Medium Sulphate Resistant Cement 3% to 8%
Construction Cements 8% +
Minimise Magnesium Content of Cement

Regular Class G HSR required to have < 6%

Typically > 1%
Use of Pozzolanic Material Under Review

Ca(OH)2 + SiO2 ---> Calcium Monosilicate

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(Durable, Resists Expansion)

Strength Retrogression at Elevated

Temperatures

Temperatures above 110oC

Geothermal Steam Wells
Deep Oil and Gas
Wells Using Steam Injection

Require Thermal Cement System

Loss of Compressive Strength Caused by Mineral
Transformation Above 110oC. High Temperature Phases are
weaker Than Low Temperature Phases.
Also Shrinkage and Permeability increase
35% BWOC Silica added to prevent this
Strength Retrogression 25% to 40% is required. 35% typical

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Compressive Strength / psi

Compressive Strength at 230oC /

15ppg
50
40

SiO 2 35 % BWOC

30
Neat Cement

20
10
0
0

10

15

20

25

Curing Time / Months

Notable Reduction in C/S After 1 Month Curing For Neat System

Addition of Silica Increases C/S and Prevents Retrogression

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P e rm e a bility / m D

Permeability Reduction at 230oC /

15ppg
100
Neat Cement

10
1
0.1

SiO2 35% BWOC

0.01
0

10

15

20

25

Curing Time / Months

Permeability Increase After 1 Month Curing For Neat System

Addition of Silica Decreases Permeability

35

Cement Durability
Cement Is Strong In Compression But Weak In Tension

Thermal and Pressure

Changes Cause Stresses
At Interfaces

Tensile Stresses Lead to

Cement Sheath Failure

Casing

Radial Cracking

Formation
37

Cement Sheath

Cement Durability With D600

Latex Particles Provide Tensile Strength = Elasticity

No D600
38

2 gal/sk D600

API Specification of Class G Cement

Quality Control: Composition and Performance
Specification

API Schedule 5 Thickening Time (52 oC) 90 - 120 min

Consistency after 15 min Stirring
Max 30 Bc
8 hours C/S at 100F Min 300 psi
8 hours C/S at 140F Min 1500 psi
Free water
Max 3.5 ml

MgO Max 6%
SO3
Max 3%
LOI
Max 3%
Insoluble Residue Max 0.7%
C3 S
48% to 65%
C3 A
Max 3%
C4AF + 2 C3A Max 24%
Total Alkalis Max 0.75

39