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Cement Additives PDF
Cement Additives PDF
Cement Additives
Additives
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Dowell
Well Conditions
ADDITIVE CATEGORY
Additives
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Dowell
Cement Additives
l Accelerators and Retarders
n Change thickening time
n Alter rate of compressive strength development
l Extenders
n Reduce slurry density
n Increase slurry yield
l Weighting Agents
n Increase density
l Dispersants
n Improve mixability
n Reduce friction pressure
Additives
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Dowell
Cement Additives
l Fluid Loss Control
l Lost Circulation Material
l Specialty:
n Antifoam/defoamer additives
n Bonding agents
n Expansive additives
n Gas migration control additives
n Gelling and suspending additives
n Foaming additives
Additives
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Dowell
Conductors
l Prevents washing out under
rig
l Short rig downtime
l Quick setting cement - rapid
development of compressive
strength
l Accelerated slurries, e.g..:
n Neat cement + NaCl (D44) 3-5%
n Neat Cement + CaCl2 (S1) 2-4%
n Neat cement + seawater
l Lightweight slurries
Additives
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Dowell
Surface Casings
l Unconsolidated zones
l BOP support
l Protect surface waters
l Prevent fluid flow
l Very large volumes of slurry
l Light weight slurries
l Strong slurry at shoe (accelerated)
l Extended lead with neat tail, e.g..:
n Prehydrated bentonite 2-3% 12.8 ppg
n Neat cement + 0.5-1% S1 15.8ppg
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Dowell
Thickening & Setting Time
l Control to
n Reduce WOC (reduce rig-time)
n Reduce chance for fluid/gas flow
n Allow time to complete job
l Affected by
n Temperature
n Pressure
n Cement type (class and grind)
n Mixing and placement methods
n Accelerators and Retarders
n Other additives (salt, dispersant, fluid loss additives)
Additives
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Dowell
Accelerators
l Applications
n Shallow casings (conductor, surface)
n Low temperature conditions
n Offset retarding effects of other additives
l Additives
n Calcium Chloride (CaCl2) - 1-4%
n Sodium Chloride (NaCl) - <15%
n Other salts (carbonates, silicates, nitrates, etc..)
n Organic chemicals (formates, oxalic acid, etc..)
l Reduced water
Additives
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Dowell
Calcium Chloride
l S1, S2, D77
n Most active accelerator
n Range 1-4%
n Effect on Thickening Time
Additives
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Dowell
Compressive Strength
Additives
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Secondary Effects of CaCl2
l Increased temperature
n Heat of solution of CaCl2
n Additional accelerating effect (on surface?)
n Casing expansion
Additives
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Dowell
Sodium Chloride
l Sodium Chloride (D44) as an accelerator
nNot very efficient
nActs as an accelerator < 15% BWOW
nPreferred range is 3 - 5 % BWOW
Effect of Salt concentration:
8
136°F (58°C)
Time to reach 100 Bc (hr)
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)
Additives
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Dowell
Retardation of Cement Systems
l Applications
n Intermediate and production strings
n Surface and conductor casings (long pumping times)
n Squeeze and cement plugs
n High temperature and depth
Additives
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Dowell
Lignosulfonates
l Low to mid temperature use
n D13 (D81) <185oF
n D800 (D801) 140o - 220oF
l Pulping by-product
n Variable performance
Additives
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Dowell
Hydroxycarboxylic Acid
l Powerful retarders
n D110 (D109) - 175o - 325oF
n D45 (salt dispersant)
Additives
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Dowell
Inorganic Retarders
l Retarder aid - D93
n Has no retarding capacity by itself
n Extends temperature range for other retarders
n Detrimental effect on fluid loss
Additives
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Dowell
Cellulose
l CMHEC (D8) - Diacel LWL
n Sometimes used for retardation
n Viscosifying
n Effective to 250oF
n Some fluid loss control
Additives
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Dowell
Blended Retarders
l Generally lignosulfonate with other material
n D28 (D150) - 220o - +300oF
n D121 - 250o - 350oF
l Dispersing action as well, especially at high
concentration
l D121 erratic below 300oF
l D121 may overdisperse
Additives
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Dowell
D161
l High Temperature Retarder (>250oF)
l Rapid Strength Development
n Lengthens Dormant Period; not Hydration Rate
l Reduced Sensitivity to
n Concentration Error
n Temperature Error
Additives
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Dowell
Applications
l Cementing Long Liners and Casing
n Single Stage vs. Two-Stage Jobs
n Single Slurry Replacing a Lead and Tail Slurry
l Squeeze Cementing
l Kick-off Plugs
l Coiled Tubing Applications
Additives
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Dowell
D161 Setting Characteristics
8
320@oF320oF
7
Conventional
6
oF350oF
psi50@psi
5
350@
4
TTR
@TT
3
of 50
to TTto
of TTR
2
RatioRatio
1 D161
0
0 2 4 6 8 10 12
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Dowell
CS to TT Ratio
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Dowell
Compressive Strength Development
22
20 3000 psi
Time to reach compressive
18
strength at 320°F (hr)
16
500 psi
14
12 50 psi
10
8
6
4
2
0
2 3 4 5 6 7 8 9 10
Additives
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Dowell
Slurry Density
CHANGING OF SLURRY DENSITY
LIGHTER
MORE
WATER*
LIGHT
ABSORBENT
MATERIAL
LOWER
DENSITY
15.6 Class A
Neat Cement 15.8 Class G
16.4 Class H
* D124 and Foamed Cement are exceptions
Additives
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Dowell
Cement Extenders
Extender or Slurry Density (lb/gal)
Lightweight System 6 7 8 9 10 11 12 13 14 15
Bentonite 11.5 15
LITEPOZ* 3 D35 12 14.7
LITEPOZ 7 D61 10.8 13.6
TXI Lightweight Cement 12 14.2
Diacel D D56 11 14.5
Expanded Perlite D72 10.6 13.8
Gilsonite D24 12 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 11 15
LiteCRETE* Cement 10.5 12.5
* Mark of Schlumberger
Additives
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Dowell
Classification of Extenders
l Water “absorbing” extenders
n Clays (Bentonite) - D20, D128
n Chemical extenders (Silicates) - D75, D79
• General properties:
n
n Water based extender nn Economical and widely available
n
n SG = 2.65 nn Decreases compressive strength,
n
n Dry blended or pre-hydrated increases permeability
n
n Concentration range, 0-20% BWOC nn Viscosifies slurries
n
n Density range, 11.5 - 15 ppg nn Provides fluid loss control
Additives
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Dowell
Bentonite (D20)
l Allow addition of extra water, yet control free water
n Optimum water content must be determined
n Starting point - 5.3% additional water per 1% bentonite
l Additional water means
n Reduced cost (increased yield)
n Reduced strength
n Increased permeability
n Reduced resistance to chemical attack by brines
l Viscosifies slurries (requires dispersant >6% D20)
l Slurry stabilizer (free water and sedimentation)
l High concentrations (>12%) provide fluid loss control (<400
mL/30 min
l May be prehydrated (1% prehydrated = 4% dry)
l Inhibited by salt
Additives
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Dowell
Chemical Extenders
l Silicates
n React with cations in cement system (Ca2+, Mg2+)
n Form viscous, gelatinous silicate gel
- Capable of binding extra water
- Low free water separation
n Low rheologies for turbulent flow
n Better properties and mixing than bentonite slurries
n No inherent fluid-loss control
n Relatively low concentrations required
n Ca - Silicate formed acts as accelerator
n Use D110 (or D109) retarders
60
40
470* 468*
20
0
0 20 40 60 80 100 120 140 160 180 200
Time (min)
Additives
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Dowell
Silicate Slurry Design
l Point of departure is the thickening time
n Optimize D75/D110
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Dowell
Lightweight Aggregates
l POZZOLANS: Fly Ash( D35), Volcanic Ash and
Diatomaceous Earth (D61, D602)
n React with calcium hydroxide in cement
n Corrosion brine resistance
n Low permeability
n Thermal resistance
l EXPANDED PERLITE (D72)
n Inert material and does not affect thickening times
n Normally add 2 - 6% BWOC bentonite to prevent floatation
n Gives reduced cement permeability
n Bridging action at higher concentrations
l MICROSILICA (Silica Fume, D154, D155):
n Pozzolanic material
n Good slurry properties
Additives
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Dowell
Pozzolans
l Naturally occurring
n Volcanic ashes
n Diatomaceous earth (D61)
l Artificial
n Fly ash
u Type F (D35, D48) - most common
u Type C (D132) - more reactive (cementitious)
l Key Properties
n React with Ca(OH)2
u Contribute strength
u Reduce permeability
n Increased brine resistance
Additives
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Dowell
Microsilica (silica fume)
l Amorphous sub-micron spheres
l Pozzolanic properties (reactive)
l Low bulk density (<15 lb/ft3)
l Provides some slurry stability
l Frequently blended with other lightweight additives (HiLITE -
blend with D124)
l Bulk blending is difficult with dry material
l Liquid can be stored with minimal agitation
l Concentration up to 20%
l Dispersant is required to effectively disperse in water and
prevent gelation
l Additives
n D154 - dry
n D155 - liquid
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Dowell
Ultra-Lightweight Extenders
l Ceramic microspheres, LITEFIL* D124
n Ceramic or glass microspheres
n Inert
n Specific gravity 0.7 - 0.8
n Fragile - pressure limitation of 5,000 psi
n Density range: 8.5 lb/gal to 14.5 lb/gal
n Enhanced strength and permeability
Additives
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Dowell
Lost Circulation Control
lReduce density
lReduce friction pressure
lAdd LCM
n Granular
n Flake
Additives
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Dowell
Granular Lost Circulation Materials
l D42 - KOLITE* additive
n Ground coal
n SG - 1.3
n Concentration - 5 - 25 lb/sk
n Slurry stability is key
l D24 - Gilsonite
n Ground asphaltinic material
n SG - 1.07
n Similar to D42
n Temperature limitation of 300oF due to softening
l Mechanism
n Bridging
n Mixing difficulties at high concentrations
Additives
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Dowell
Flake Lost Circulation Materials
l D29 (Cellophane flake)
n Concentration - 1/8 to 1/2 lb/sk
l Mechanisms
n Form “mat” on fractures, vugs, etc..
l Handling
n Mixing difficulties at high concentrations
Additives
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Dowell
Intermediate Casings
l Protect weak or sensitive
formations (production)
l May be 2 stage
l Low cost
l Extended lead and neat tail
l Most slurries are retarded
l May require fluid loss control
l May require special properties
(e.g.. gas migration control)
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Dowell
Production Casings
l Isolate production zones
l Smaller diameter casings
l Cost less important
l Good bonding
l Fluid loss control is usually
required
l Low friction pressures
l Mud removal is important
l 15.8 ppg or more slurries
l All slurries to be retarded
Additives
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Dowell
Dispersants
l Cement slurry rheology
n Volume of particles / total volume
n Particle interactions
n Aqueous phase rheology
l Why dispersants ?
n Reduce viscosity and yield point
n Reduce friction pressures
n Improve cement slurry mixability
n Reduced water slurries (density up to 18.0 lb/gal)
n Improve efficiency of fluid loss additives
Additives
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Dowell
Dispersants
l TIC* Additive
l Superplasticizers
n PNS - D65, D80, D604M, D604AM
n PMS - D145
l Plasticizers
n Cement retarders (D13, D81, D800, D801)
n Mud thinners
* Mark of Schlumberger
Additives
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Dowell
Dispersant Action
SO3
C2SH- +Ca+ -0
3S
CEMENT
C2SH- +Ca+ -0
3S
SO3
Dispersant
Molecule
• Amount of dispersant adsorbed depends on concentration
• Cement grain surfaces become uniformly negative
• Like signs repel one another ---> dispersion
Additives
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Dowell
Use of TIC D80 in ETD
20 30 30
Underdispersed Overdispersed
20 20
10 10
5
Plastic Viscosity Viscosity
5 (Cp) 5
D80 (gal/sk)
25
Yield value 25
15 Acceptable Range
Yield Value (lb/100ft2)
20 20
Viscosity
Free Water
10 15 15 (%)
10 10
5
Plastic Viscosity
Free water
5 (Cp) 5
D604M (gal/sk)
Additives
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Dowell
Dynamic vs. Static Fluid Loss
l Dynamic
n Placement
n Loss is proportional to time
n Filter cake reaches pseudo-stable thickness
n Density increases
n Slurry properties change
l Static
n After placement
n Loss is proportional to square root of time
n Cake grows
n May result in annular restrictions
u Causes loss of hydrostatic pressure
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Dowell
Effect of Fluid Loss
l Damage to some formations by filtrate
l Gas migration through thick filter cake and through
poor quality cement
l Other properties:
REDUCED INCREASED
n
n Slurry yield n
n Hydrostatic
n
n Free water n
n Slurry density
n
n Thickening time n
n Plastic viscosity
n
n Settling n
n Yield point
n
n Bulk Shrinkage n
n Compressive strength
n
n Mud removal efficiency (?) n
n Bonding
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Dowell
Thickening Time versus Density
160
Thickening Time (min)
TH
ICK
EN
ING
Yield Value
TIM
E
E
YIELD VALU
40
Additives
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Dowell
Mechanisms
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Dowell
FLAC* Additives
l Particulate -
n Gel - D20
n Latex - D600 (MT,M-HD,L) D134(HT,HD,L)
n Microgels - D300, D500(AD,LT,L)
l Water Soluble Polymers
n Cellulose Derivative
u D60, D59(MT,ND,S) D112(MT,LD,S)
n Non-Ionic Polymer
u D127(LT,S) B30(LT,S) D159(L-MT,AD,L) D160(L-MT,AD,S)
n Anionic Polymer
u D603(MT,ND,L) D143, D158(M-HT,HD,L), D156(LT,AD,S)
n Cationic Polymer - D73.1(M-HT,ND,L)
n FLAC Enhancer - D136 (below 200oF)
* Mark of Schlumberger
Additives
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Dowell
Dispersant Effect on Fluid Loss
Mechanism of action
•• Disperse cement grains and improve packing --> reduced permeability
•• Flocculate w/salt ---> plugging action
FILTER CAKE
WITHOUT DISPERSANT WITH DISPERSANT
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Dowell
Acceptable Fluid Loss Limits
l Gas zones 30 - 50 mL/30 min
l Liner < 50 mL/30 min
l Casing 200 - 300 mL/30 min
l Horizontal well <50 mL/30 min
l High density slurries: <50 mL/30 min
l Squeeze :
n Formation with K < 1 md 200 mL/30 min
n Formation with K 1 md - 100 md 100 - 200 mL/30 min
n Formation with K > 100 md 35 - 100 mL/30 min
Lighter Heavier
More Less Less
Water* Water Water
Light Heavy
Absorbent Dispersant
Material Material
Lower Higher
Density Density
15.6 Class A
Neat Cement 15.8 Class G
16.4 Class H
* D124 and Foamed Cement are exceptions
Additives
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Dowell
Weighting Agents
l Requirements
n High specific gravity
n Compatible particle size and distribution (settling)
n Low water adsorption (efficiency)
n Availability and acceptable cost
n Purity and consistency of product
n Inert
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Dowell
Strength Retrogression
Above 230oF cement undergoes:
n Reduction in strength
n Increase in permeability
l Due to crystalline changes in CSH gel
CSH gel ---------> alpha dicalcium silicate
amorphous crystalline
strong, impermeable weak, permeable
C/S = 1.5 C/S = 2.0
l Prevented by addition of 30 - 40% BWOC silica (reduces C/S
ratio of C-S-H gel)
CSH gel + silica ---------> Tobermorite
C/S = 0.8
Tobermorite ---------> Xonotlite + Gyrolite
C/S + 1.0 C/S + 0.8
Care should be given to production temperatures
Additives
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Dowell
D30 Silica Sand & D66 Silica Flour
D30 D66
NAME SILICA SAND SILICA FLOUR
Particle size US Mesh 70 - 200 > 200
±10% + 12%
Additional Water 1.12 gal/sk 1.34 gal/sk
Specific gravity 2.63 2.63
Applications:
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Dowell
Slurry Stability
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Dowell
Antifoam Agents
l Purpose
n Prevent slurry gelation
n Allow true slurry density to be mixed and pumped
n Prevent pump cavitation (due to aeration)
l Mechanism of action:
n Lower surface tension
n Reduces film and causes rupture
l Types of antifoam agents
n Polyglycol ethers
Solid : D46 (0.2 lb/sk)
Liquid : D47 (0.05 gal/sk)
n Silicones
Liquid : D144 (0.01 - 0.02gal/sk)
Liquid : M45 (0.05 gal/sk)
Additives
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Dowell