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5.

CEMENTING

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Habiburrohman, B.Eng, M.Eng.
Cement Manufacture
Dry Process
LIMESTONE CLAY

CRUSHER WASH MILL

SILOS PROPORTIONER STORAGE BIN


SILOS

COAL
GRINDER UNIT

PULVERIZER
DRYER ROTARY KILNS

OIL OR GAS CLINKER COOLERS PACKAGING PLANT

GYPSUM CLINKER HOPPERS CEMENT SILOS

GYPSUM HOPPERS GRINDINGMILLS


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Cement Manufacture
Wet Process
LIMESTONE WATER CLAY

CRUSHER WASH MILL

SILOS STORAGE BIN

WET GRINDING MILLS

CORRECTION BASINS CEMENT SILOS PACKAGING PLANT

COAL
STORAGE BASINS GRINDING MILLS GYPSUM HOPPERS

PULVERIZER
KILN FEEDERS CLINKER HOPPERS GYPSUM
DRYER

OIL OR GAS ROTARY KILNS CLINKER COOLERS


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Cement Hydration

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Clinker Grain Structure

C3CS C3A
C2S C4AF
Silicates are approximately 80% of total material

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Principle Components of
Portland Cement
• C3S Tricalcium silicate
• C2S Dicalcium silicate
• C3A Tricalcium aluminate
• C4A Tetracalcium alumino ferrite

• C3S often used as model for cement


hydration
• All phases have a role in sequence of
hydration events and impact setting process
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Hydration Mechanisms

• Four Main Hydration Phases:

– Wetting
SHARP EXOTHERMIC PEAK; LASTS < 5 MINS
– Induction
ACTIVITY SEEMS LOW; CEMENT REMAINS FLUID
– Setting
SUSTAINED EXOTHERMY; CEMENT THICKENS
– Hardening
LOW HEAT FLUX; STRENGTH STILL INCREASING

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Heat Flow During Hydration

% Hydrated Cement
Heat Flow Acceleration Deceleration
% Hydration of Cement
Heat Flow

Pre-induction Diffusion
40-50%
Period Hydrated Cement
(2%to 3% Hydration)

Induction Period
(Silicates Have Low Reactivity Setting and
During This Period) Hardening

min hours days

Time
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Hydration Mechanisms

• Two main theories of hydration process


– Protective Coating Theory
– Delayed Nucleation Theory

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Protective Coating Theory
• On contact with water, C3S AND C2S
react to form calcium silicate hydrate (C-
S-H) gel
• Initial surge or reactivity due to heat or
hydration of free lime occurs
• C-S-H external reactions inhibited by
semi-permeable gel coat, but internal
reactions continue
• This is called the “dormant” or “induction”
phases 10
Cement Hydration (C3S)

C3S

H2O

Ca2+
2 OH-
MIXWATER

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Cement Hydration (C3S)

C3S C-S-H - Gel


(Calcium Silicate Hydrate)

H2O

Ca 2+
2 OH -
MIXWATER

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Protective Coating Theory
• Osmotic pressure within C-S-H builds due to
internal reactions
• This causes C-S-H membrane to rupture
• Materials released include Ca(OH)2.
• Tubular growths of C-S-H (fibrils) form a
network of interlocking with other hydration
products

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Cement Hydration (C3S)

C3S C-S-H - Gel


(Calcium Silicate Hydrate)

H2O

Ca 2+

2 OH -
MIXWATER

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Delayed Nucleation Theory
• C3A enters into reaction with gypsum to form
ettringite (calcium-sulpho-aluminate-hydrate)
• Ettringite coats C3A surface, reducing reaction
until all gypsum present is consumed
• Ettringite then converts to calcium aluminate
hydrates

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Cement Hydration (C3A)
C3A

CaSO4

MIXWATER

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Cement Hydration (C3A)
C3A CASH
(Calcium Alumino
Sulphate Hydrate)

CaSO4
Ca 2+ + SO4 2-
MIXWATER

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Thickening Time

• The viscosification that is observed from a


consistometer test is the result of:
– Interlocking effect of the hydration products
– Consumption and immobilization of internal
water
• The rate of viscosity build-up to final set is
influenced by:
– Temperature
– Additive chemistry 18
Oilwell Cement

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Oil Well Cementing ?

• CEMENTING
• What is Oil Well Cementing ?
• Oil well cementing is a process of mixing a
slurry of cement and water and pumping it
through the casing pipe into the annulus
between the casing pipe and the drilled hole.
• Cement plugs are also set in the wellbore to
isolate zones e.g. loss zones, water bearing
zones
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Oil Well Cementing

• Two general classifications of oil well


cementing are :-
1. Primary Cementing
2. Secondary or remedial cementing

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OBJECTIVES OF CEMENTING
• Primary Cementing
• Main objectives of primary cementing are :-
 to support the casing pipe
 to restrict the movement of formation fluids
behind the casing
• Cement also provides the following advantages :-
 seal off zones of lost circulation (fractured
formation)
 protect the casing from shock loads during
drilling deeper section
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 protect casing from corrosion
OBJECTIVES OF
CEMENTING (continued)
• Secondary Cementing
• Most common secondary cementing jobs
are :-
 Circulation squeeze
 plug back cementing
 squeeze cementing

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OBJECTIVES OF
CEMENTING (continued)
• Secondary Cementing
• Circulation squeeze
• Cement slurry is circulated into the annulus
through perforation, which are at the top and
the other at the bottom of desired interval
• Reason for circulation squeeze are :-
 supplementing a faulty primary job
 extending the casing protection above the
cement top
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OBJECTIVES OF
CEMENTING (continued)
• Secondary Cementing
• Plug back cementing
• Hole is plugged by cement in order to initiate a new
drilling operation
• Plug back is carried out for a number of reasons:
 Abandonment of the hole
 Sidetracking the hole
 Seal off lost circulation
 Shutting off of water or gas encroachment 25
OBJECTIVE OF CEMENTING
(continued)
• Secondary Cementing
• Squeeze Cementing
• Squeeze cementing involves forcing the
cement slurry under pressure into open holes
or channels behind the casing or into
perforation tunnels.
• The operation is performed during drilling,
completion and workover operations

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OBJECTIVE OF CEMENTING
(continued)
• Secondary Cementing
• Main purposes of squeeze cementing :-
• Supplementing a faulty primary cementing job
• Repairing casing defects
• Stopping lost circulation in open hole during
drilling
• Shutting off old perforation for recompletion
• Reducing water cut in a producing well
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API Classification of Cements

• A wide range of the properties of the


slurry (viscosity, density, and fluid loss)
and the set cement (strength, permeability
& porosity) are required to meet the down
hole temperature & pressure and other
conditions
• API provides specs covering eight classes
of oil well cement designated as class A,
B, C, D, E, F, G and H
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API Classification of Cements

• API Class A and B cements


 Intended for use in wells from the surface to
the depth of 6000 ft and 16 - 70 deg C
 The recommended water to cement ratio
according to API is 0.46 by weight (5.2
gal/sack or 19.71 ltr/sack)
• API Class C
 Is a high strength cement and used for oil
wells from surface to a depth of 6000 ft (16 -
77 deg C temperature)
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API Classification of Cements

• API Class D, E and F

 As a basic and regarded as retarded


cement
 Intended for use from surface up to
16,000 ft depth
 Premium cement because of high cost
 Resistant to surface water 30
API Classification of Cements

• API Class G and H


 Regarded as basic cement; chemically similar to class B
 Intended for use from surface up to 8000 ft depth
 Can be modified by adding accelerator or retarder to suit
wide range of depth and temperature
 The recommended water to cement ratio according to
API for class G cement is 44% (5 gal/sack or 18.9
ltr/sack) and class H cement is 38 % (4.3 gal/sack or 16.3
ltr/sack)
• The most common cement used in Malaysia is class G
produced by Pan Malaysian Cement (PMC) in Pasir Gudang
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Cement Additives

• The of API cement above are used for wells with moderate
bottom hole conditions
• It is necessary to modify cement properties to meet specific well
conditions such as deep wells, HPHT, lost circulation zones, etc
by adding chemicals
• The chemicals can be classified as follows :-
 Accelerators – reduce thickening time
 Retarders – increase thickening time
 Fluid Loss reducers – control amount of fluid loss to
formation
 Weighting materials – increase/decrease density
 Lost circulation materials – seal off lost circulation zone.
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Cement Additives
– Accelerator
• The accelerator is used to reduce the
thickening time and set the cement faster by
accelerating the hydration of chemical
compound of cement.
• Liquid cement (known as cement slurry) will
harden faster by adding accelerator
• Common Accelerators used are Sodium
Chloride, Calcium Cholride and Calcium
Sulphate (gypsum) 33
Mechanism of Accelerators

C3S C-S-H - Gel


INCREASED
PERMEABILITY

2 Cl -
H2O INCREASE RATE

Ca 2+ OF OH- EFFLUX BY
2 OH -
COUNTER-DIFFUSION OF CL-
MIXWATER

Hydrate morphology and ion flux


Mechanism of Accelerators
CASH
C3A
PRECIPITATION
INCREASED

SECONDARY
CaS04

CaS04 Ca 2+ + SO4 2-
MIXWATER
pH LOWERED
Accelerated nucleation
Cement Additives
– Retarder
• The retarder will increase the thickening time
or prolong the time of cement to set.
• It is necessary since more time is needed to
place cement in deeper wells or to combat the
thickening time reduction in high temperature
environment
• Common retarder are saturated NaCl,
lignosulfonate and its derivatives, cellulose
derivative and sugar derivatives 36
Mechanisms of Retarders
d+
LARGE ORGANIC MOLECULE
WITH NET NEGATIVE CHARGE
NET POSITIVE
HINDERS MOVEMENT OF
CHARGE ON SO3-
IONS ETC. ACROSS
CEMENT PARTICLE
GEL MEMBRANE
SO3-

SO3- H2O
2 OH - Ca 2+ MIXWATER

ADSORPTION AND STERIC HINDERANCE


Mechanisms of Retarders

CEMENT C-S-H - Gel


GRAIN d+ INSOLUBLE PRECIPITATE
HINDERS MOVEMENT OF
IONS ETC. ACROSS
GEL MEMBRANE
H2O

Ca 2+
2 OH -
MIXWATER

PRECIPITATION THEORY
Mechanisms of Retarders

CEMENT C-S-H - Gel


GRAIN d+ CRYSTAL GROWTH
POISONERS ATTACH TO
CRYSTAL GROWTH NUCLEI
AND PREVENT CRYSTAL
H2O GROWTH

Ca 2+
2 OH -
MIXWATER

NUCLEATION THEORY
Mechanisms of Retarders
CEMENT C-S-H - Gel
GRAIN d+ CHELATING AGENTS
SEQUESTER IMPORTANT
IONS FROM INTERSTITIAL
WATER AND CHANGE ION
H2O BALANCE ACROSS GEL
MEMBRANE
Ca 2+
2 OH -
Ca 2+
Ca 2+ MIXWATER

COMPLEXION THEORY
Cement Additives
– Fluid Loss
• Fluid loss additives are used to control amount of liquid loss from
cement slurries to the surrounding environment.
• These additives control the fluid loss by one of the following
mechanisms :-
 Increasing the particle size distribution of the slurry so that it
holds or traps the liquid in it
 Making the interstitial slurry water viscous which increased
resistance to flow through porous formation
 Forming an impermeable film or miscells within filter cake
 Common fluid loss additives are organic polymers,
dispersants and synthetic polymers
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Mechanisms of Fluid Loss Additives
WALL BUILDING AND VISCOSIFICATION
PORE PLUGGING OF MIXWATER

ADSORPTION AND
RESTRICTION OF WATER
MOBILITY

SOLIDS PLUG
PORES AND BUILD MAT
MIXWATER

ADSORPTION, PORE FILLING, WALL BUILDING


Mechanisms of Fluid Loss Additives
WALL BUILDING AND VISCOSIFICATION
PORE PLUGGING OF MIXWATER

THE PRESENCE OF FOAMED


GASES CREATES MULTIPHASE
FLOW AND RESTRICTS FILTRATION
OF FLUIDS THROUGH THE
FILTER CAKE

MIXWATER

MULTIPHASE FLOW PHENOMENA


Cement Additives
• Weighting Materials
• Most stable cement slurries have densities in range of
15.5 - 17.5 lb/gal.Weighting materials are used to
increase the density of cement slurry depending on the
requirement

• Weighting Reducing Materials


The weight of cement slurry can be reduced by :-
• Adding material that increases the water content such
as clay and silicate materials
• Using light weight materials such as pozzolan,
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gilsonite or nitrogen
Cement Additives
– Weighting Materials (continue)
• Light weight cement is used on weak
formation or loss circulation zones
• The weight of cement slurries can be
increased by adding barite, illmenite or
hematite

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Cement Additives
– Lost Circulation Materials
• The lost circulation materials are used to combat
cement lost into very permeable, cavernous or
fractured formations
• The lost circulation materials prevent the loss of
cement by one or more of the following mechanisms
 Preventing fracture inducement by reducing
hydrostatic pressure as in lightweight cement
 Cure the lost circulation by forming a low
permeability bridge across the permeable opening
• Common LCM can be classified as fibrous, granular
and flakes 46
Special Problems

• Strength Retrogression
– Silica flour / sand prevents detrimental reactions at > 230 °F
– Up to 210 °F : hydration products differ only in morphology
and microstructure
– Above 210 °F: amorphous silicate hydrates form. Size
range from x-ray amorphous to highly crystaline
– Above 230 °F: onset of retrogression, large crystals, low
strength, high permeability
– Up to 300 °F : 35% silica sand or flour prevent formation of
di-calcium silicate hydrate (orthorhombic phase).
– Above 300 °F: 35% silica flour as increased surface area
required for inhibition.
Special Problems

• Gas Migration Control


– Agents that minimize slurry depressurization or
that decrease gas mobility in the cement paste
(eg. by permeability reduction) during liquid to
solid transition
• (BA-10, BA-29, BA-56, BA-58L, BA-86L, FL-45LS,
FLAG-56, BA-100L, BJ BLUE)
Special Problems

• Lost Circulation
– Agents which induce thixotropy can help prevent
or cure losses by reducing wellbore hydrostatic or
by building high flow resistance in the fractures
• Microannuli/Poor Bonding
– Agents which induce expansion after initial set, or
materials that impart adhesion or improve elastic
modulus may help provide better isolation
Free Water Control Additives
• Under downhole conditions, it is important to control:
– Free water
– Slurry stability
• Problems
– Zonal isolation
– Collapsed casing (steam) in geothermal wells
• Applications
– Horizontal, deviated and slimhole environments
– Geothermal wells.
• Products
– Impart strength to gel structure of cement
FWC-2, FWC-10, FWC-47, FWC-47L, BJ BLUE
Free Water Channels

Free water Measured

Channel Free Water

Cement
Slurry

45°
END

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