Cementing Additives

Module CF204
15 Sep 99
 Well Conditions
ADDITIVE CATEGORY
PROBLEM SLURRY PARAMETER SOLUTIONS
Well control Density Extenders
over pressure and Weighting agents
weak formations
Temperature Thickening time Accelerators
Retarders
Permeable formations Fluid Stability FLAC
Fluid loss control
Mud removal Rheology Dispersants
Friction pressure Gelling Agents
Mixability/Pumpability
Lost circulation Plugging/Bridging properties LCM
Density Extenders
Abnormal and specialized conditions:
Heat retrogression Silica
Hydration product Foaming agent &
Foamers
Foam
Stabilized foam capability
Foaming tendency
{ stabilizers
Etc. Anti foamers

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 Cementing additives
 Accelerators and retarders
– Change thickening time
– Alter rate of compressive strength development
 Extenders
– Reduce slurry density
– Increase slurry yield
 Weighting agents
– Increase slurry density
 Dispersants
– Improve mud removal
– Improve mixability / reduced water slurries
– Reduce friction pressure (Lower ty and Pv)
 Fluid Loss Control
 Lost Circulation Material (LCM)

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 Cement Additives
 Accelerators and Retarders
 Change thickening time
 Alter rate of compressive strength development
 Extenders
 Reduce slurry density
 Increase slurry yield
 Weighting Agents
 Increase density  Specialty:
 Dispersants  Antifoam/defoamer agents
 Improve mud removal  Bonding agents
 Improve mixability  Expansive additives
 Reduce friction pressure  Gas migration control additives, et
 Fluid Loss Control  Thixotropic systems
 Lost Circulation Material

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 Antifoam Agents
 Why use antifoam agents ?
– Prevent slurry gelation
– Prevent pump cavitation
– Allow true slurry density to be mixed and pumped
 To be effective they must:
– Be insoluble in the foaming fluid
– Be more surface active than the foaming fluid
 Mechanism of action:
– Spread on foam surface with lower surface tension
– Enter foam reducing film and causing rupture
 Types of antifoam agents
– Polyglycol ethers Solid : D46 (0.2 lb/sk)
Liquid : D47 (0.05 - 0.07 gal/sk)
– Silicones Liquid : D144 (0.01 - 0.02gal/sk)
Liquid : M45 (0.05 gal/sk)

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 Conductor pipe
 Prevents washing out under rig
 Customer wants short rig downtime
 Quick setting cement - rapid
development of compressive strength
 Accelerated slurries, e.g.:
– Neat cement + NaCl (D44) 3-5%
– Neat Cement + CaCl2 (S1) 2-4%
– Neat cement + seawater
 Cemented with stab-in or just driven

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 Accelerators
 Used to shorten stages I and II and to accelerate stages III and IV -
hydration of main cement phases is increased plus a change in the C-
S-H gel structure
 Can be used to offset retarding effects of other additives
 S1 - CaCl2 - 1 to 4%BWOC
– Check type of CaCl2 - S1 is 77% pure
– Disolution in water is exothermic (see field data handbook page 700.004)
 D44 - NaCl - <10%BWOW
 Seawater
– Check consistency - near river mouths
 D77 - CaCl2 in liquid form - 0.2 to 0.4 gps
 ARCTIC SET For Low Temperature

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 Sodium Chloride
 Sodium Chloride (D44) as an accelerator
Not very efficient
Acts as an accelerator < 10% BWOW
Preferred range is 3 - 5 % BWOW
Effect of temperature:
8

136°F (58°C)
Slurry consistency (hr)
Time to reach 100 Bc

154°F(68°C)
4

179°F (81°C)
210°F (99°C)
2

0
0 5 10 15 20 25 30
NaCl IN MIX WATER (% BWOW)

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 Surface Casings
 Unconsolidated zones
 Low Temperatures (New challenge in
deep O/S - temperature very low)
 Large volumes of slurry
 Light weight slurries
 Strong slurry at shoe
 Extended lead slurries with neat tail,
e.g.:
– Prehydrated bentonite 2-3% 12.8 ppg
– Neat cement + 0.5-1% S1 15.8ppg
– 2/3 lead - 1/3 tail annulus height

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 Slurry Density
CHANGING OF SLURRY DENSITY

LIGHTER

MORE
WATER*

LIGHT
ABSORBANT
MATERIAL

LOWER
DENSITY

15.6 Class A
Neat Cement 15.8 Class G
16.4 Class H
* D124 IS AN EXCEPTION AS AN EXTENDER AS IS FOAM CEMENT

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 Classification of Extenders
 Water based extenders
– Water
– Clays (Bentonite) - D20, D128 - check viscosity - do not let it
built up
– Chemical extenders (Sodium Silicates) - D75, D79 (need Ca ++
to work)
 Low density solids
– Pozzolans (Fly ashes) - D35, D56, D61, D602
– Kolite and gilsonite - D42, D24
– Expanded perlite - D72
– Microsilica - D154 (solid) , D155 (liquid version) (Experience in
MBZ for LW slurries / High compressive strength with D155 in
horizontal wells) with D155.
 Very low density materials
– Nitrogen - FOAM CEMENT - need stabilizer
– Ceramic microspheres - D124 (LITEFIL) - Max 5000 psi / no VIP

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 Cement Extenders
Extender or Slurry Density (lb/gal)
Lightweight System 6 7 8 9 10 11 12 13 14 15
Bentonite 11.2 15
LITEPOZ 3 D35 12 14.7
LITEPOZ 7 D61 10.8 13.6
TXI Cement D911 12 14.
Trinity Lite-Wate Cement D49 11.9 13. 2
Diacel D D56 7
11 14.
Expanded Perlite D72 5
10.6 13.
Gilsonite D24 12 8 15
KOLITE D42 12 15
Sodium Metasilicate D79 11 14.5
Sodium Silicate D75 11.5 14.5
LITEFIL D124 9 12
Foamed Cement 6 15
Microsilica D154 / D155 11 15

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 Chemical Extenders
 Sodium silicates and metasilicates
– React with cations in the cement (Ca 2+, Mg2+)
– Form viscous, gelatinous silicate gel
- Capable of binding extra water
- Low free water separation
– Low rheologies for turbulent flow
– Better properties and mixing than bentonite slurries
– Better compressive strength than bentonite slurries
– No inherent fluid-loss control (use D112 FLAC)
– Relatively low concentrations required
– Ca - Silicate formed acts as accelerator
– Use D110 (or D109) retarders - beware of POD
 D79, SODIUM METASILICATE - dry
 D75, SODIUM SILICATE - liquid

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 Lightweight Aggregates
 POZZOLANS: Diatomaceous Earth (D61, D602) & Fly Ash( D35)
– React with calcium hydroxide in cement
– Corrosion brine resistance
– Low permeability
– Thermal resistance
 KOLITE (D42) and GILSONITE (D24):
– Coal (D42) and Asphalt (D24) based materials
– Effective lost circulation materials (Granular)
– Kolite (D42) is inert
 EXPANDED PERLITE (D72)
– Inert material - does not affect thickening times
– Normally add 2 - 6% BWOC bentonite to prevent floatation
– Gives reduced cement permeability
– Bridging action at higher concentrations
 MICROSILICA (Silica Fume, D154, D155):
– Pozzolanic material
– Good slurry properties (Increase Rc)

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 Ultra Lightweight Extenders

 Ceramic microspheres, LITEFIL D124 (Limit

5000 psi)
– Ceramic or glass microspheres
– Inert
– Density range: 8.5 lb/gal to 14.5 lb/gal
 Foamed cement systems
– Nitrogen injected into slurry with foamer
– Very low densities achieved > 6.0 lb/gal
– Good mechanical properties

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 Intermediate Casings
 Workable sections
 13 3/8” over 3000 feet deep
 Often 2 stage cementing
 Low cost
 Extended lead and neat tail, e.g.:

– Prehydrated bentonite 2-3%

– D75 0.28 gps + 1% S1
– 15.8 ppg tail slurries
 All slurries to be retarded
 Can have some fluid loss control

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 Hydration of Cement

I II III IV V

min hr days

I. PRE - INDUCTION PERIOD

II. INDUCTION PERIOD
III. ACCELERATION PERIOD
IV. DECELERATION PERIOD
V. DIFFUSION PERIOD

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STAGES 1 and 2: Pre Induction and Induction
Periods
Al OH Ca Si
Ca SO4

Seconds

ETTRINGITE

Hours
C - S - H Gel

PROTECTIVE LAYERS STOPS REACTIONS ???? - PUMPING TIME

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 Retardation of cement slurries
 Applications
– Intermediate and production strings
– Squeeze and cement plugs
– High temperature and depth

 Chemical Classes of retarders

– Lignosulphonates (D13, D81, D800, D801)
– Hydroxycarboxylic acids (D109, D110)
– Inorganic compounds (D93, D74)
– Cellulose derivatives (D008)
– Blended retarders (D28, D150, D121)
– (Blend of above components)
– Sugar is also a cement retarder

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 Mechanisms of Retardation
 Factors affecting mechanism of action
– Chemical nature of retarder
– Chemical composition of cement
 Retarders : Theories of mechanism of action
– Adsorption theory
– Precipitation theory
– Nucleation theory
– Complexation theory
 Possible negative effects on slurries
– Gelation
– Dispersion
– Increased fluid loss
– Incompatibility
– Slows the development of the compressive strength (D028)

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 Mechanisms of Retardation
 Adsorption theory
– Adsorbtion of Retarder on to Cement Surfaces to Inhibit
Contact with Water and Make the Surfaces Hydrophobic
– Modify CSH Gel to Make it Less Permeable
 Precipitation theory
– Ca and OH react with Retarder to Precipitate an
Impermeable Layer
 Nucleation theory
– Retarder Adsorbs to Poison Nucleation and Growth Sites
 Complexation theory
– Retarder Complexes with Ca to Minimise the Driving Force
for Reaction and Prevent Formation of Nucleation Sites

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 Cement Retarders
BHCT oF Fresh Sea 37%
Retarder 100 200 300 400 NaCl
D13/D81 100 140 X X
D13/D81 with Dispersant 100 185 X X
D800/D801 125 250 X X X
D800/D801 with D93/L10 250 310 X X X
D110 175 X X
300
D110 with D93/L10 300 375 X X
D28/D150 220 X X X
300
D28/D150 with D121 300 X X X
350
D28/D150 with D93 300 400 X X X
D74 100 140 X
D161 X
250 450

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 Fluid Loss in Cement Slurries
 Definition:
– Filtrate (aqueous solution) lost to the formation
– Filter cake deposited at formation face
– Cement particles left in annulus
 Why cement loses water:
– Differential pressure
– Permeable medium (formation)
– Water/cement ratio > hydration needs
 Fluid loss stages:
– Dynamic fluid loss
– Static fluid loss

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 Effect of Fluid Loss on Slurry
Properties
 Thickening time and yield point versus water
concentration
 Damage to some formations by filtrate
 Gas migration through thick filter cake and through
poor quality cement
 Other properties:

REDUCED INCREASED
 Slurry yield  Hydrostatic
(psi/ft)
 Free water Slurry
 density
 Thickening time  Plastic viscosity
 Settling  Yield point
 Bulk Shrinkage  Compressive strength
 Mud removal efficiency  Bonding

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Thickening Time versus Density
160
Thickening Time (min)

TH
ICK
EN
ING

Yield Value
TI M
E

E
YIELD VALU
40

15.6 Slurry Density (ppg) 16.4

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 Additives for Fluid Loss Control
 Particulate FLACs
D20, D600, D134
 Latex FLAC
D600 (MT,AD,L), D134

Water Soluble Polymers

 Cellulose Derivative
D60, D59(MT,ND,S), D112 (MT,LD,S)
 Non-Ionic Synthetic Polymer
D159(LT-MT,AD,L), D160 (LT-MT,AD,S)
 Anionic Synthetic Polymer
D603 (MT,ND,L), D143, D158 (MT-HT,HD,L), D156
(LT,AD,S)

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 Dispersants with FLACs
Mechanism of action
•• Disperse cement grains and improve packing --> reduced permeability
•• Flocculate w/salt ---> plugging action

WITHOUT DISPERSANT WITH DISPERSANT

FILTER CAKE

RANDOM PACKING ORDERED PACKING

HIGH PERMEABILITY LOW PERMEABILITY

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 Acceptable Fluid Loss Limits
Typical Values: (API, 1000 psi)
 Prevention of gas channeling 30 - 50 ml/30 min
 Liner cementing < 50 ml/30 min
 Casing cementing 200 - >300 ml/30
min
 Horizontal well cementing < 50 ml/30 min
 For squeeze cementing
– Formation with K < 1 md 200 ml/30 min
– Formation with K > 1 md <100 md 100 - 200
ml/30 min
– Formation with K > 100 md 35 - 100 ml/30
min
 High density slurries: < 50 ml/30 min
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 Production Casings
 Isolate production zones
 Small diameter casings
 Cost less important
 Good bonding
 Usually has fluid loss
control
 Low friction pressures
 Mud removal is important
 15.8 ppg or more slurries
 All slurries to be retarded

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 Dispersants
 Cement slurry rheology
– Volume of particles / total volume
– Inter-particle interactions
– Aqueous phase rheology

Change with dispersants

 Why dispersants ?
– Reduce viscosity and yield point
– Turbulent flow easier to achieve (Companies like
cement in turbulent flow for liners)
– Reduce friction pressures
– Improve cement slurry mixability (Lower Ty)
– Reduced water slurries (density up to 18.0 lb/gal)
– Improve efficiency of fluid loss additives

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 Dispersants
 Types:
 Superplasticizers
D65
D80 - D80A
D604M - D604 AM
D145A (the only one for D300 to work)
 Plasticizers
Lignosulphonates
Cement retarders (D13 , D 81 , D800, D801)
Mud Thinners
 Organic salts and acids
D45, D121

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 Dispersant Action
SO33
C2SH- + Ca + - 03S

CEMENT POLY

C2SH - + Ca + - 03S
DISPERSANT SO33
MOLECULE
 Amount of dispersant adsorbed depends on concentration
 Cement grain surfaces become uniformly negatively
 Alike signs repel one another ---> dispersion

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 Slurry Density
CHANGING OF SLURRY DENSITY

LIGHTER HEAVIER
MORE MORE LESS
WATER* WATER WATER

LIGHT HEAVY
ABSORBANT DISPERSANT
MATERIAL MATERIAL

LOWER HIGHER
DENSITY DENSITY

15.6 Class A
Neat Cement 15.8 Class G
16.4 Class H
* D124 IS AN EXCEPTION AS AN EXTENDER AS IS FOAM CEMENT

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 Weighting Agents
 Requirements
–
High specific gravity
– Compatible particle size and distribution
(settling)
– Low water adsorption (efficiency)
– Availability and acceptable cost
– Purity and consistency of product
– Inert
 Commonly used weighting agents
Code Agent SG Additional water
D31 BARITE 4.22 0.024 gal/lb
D76 HEMATITE 4.95 0.0023 gal/lb
(D907 CEMENT 3.20 0.0529 gal/lb)
D157 Manganese O (Mn3 O4) Mg
tetraoxide

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 Strength Retrogression
 Above 230 oF BHST unstabilized cement will
undergo:
– A reduction in strength
– An increase in permeability
 Due to structural change in C-S-H gel
 Prevented by the addition of 30 - 40% BWOC
silica reduces C/S ratio of C-S-H gel)

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 D30 Silica Sand & D66 Silica
Flour
D30 D66
NAME SILICA SAND SILICA FLOUR
Particle size 70 - 200 > 200
-US Mesh
±10% + 12%
Add. Water 1.34 gal/sk
1.12 gal/sk
Specific gravity 2.63 2.63
Applications:

High density Preferred Alternative

Low density Alternative Preferred

Settling Problems Alternative Preferred
Mixing Problems Alternative
(Rheology) Preferred

Use above 300°F Alternative Preferred

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 Antisettling Agent D153
 Controls free water and/or sedimentation
 Compatible with all Dowell products and
cements
 No significant effects on slurry properties,
except rheology
 Dry-blend or prehydrated (preferred), fresh or
sea water
 Temperature range: up to 302 F (150 C)
 Concentration range: 0.1 to 1.5%BWOC
(depending on density)

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