Dowell

Cement Additives

Additives 1

Dowell

Well Conditions
ADDITIVE CATEGORY

PROBLEM Well control over pressure and weak formations Temperature Permeable formations Mud removal Friction pressure Mixability/Pumpability Lost circulation

SLURRY PARAMETER Density

SOLUTIONS Extenders Weighting agents Accelerators Retarders FLAC Dispersants Gelling Agents LCM Extenders Silica Foaming agent & stabilizers Anti foamers
Additives 2

Thickening time Fluid Stability Fluid loss control Rheology

Plugging/Bridging properties Density

Abnormal and specialized conditions: Hydration product Strength retrogression Foamers Stabilized foam capability Foam Foaming tendency

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 3

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 4

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 5

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 n

Prehydrated bentonite 2-3% 12.8 ppg Neat cement + 0.5-1% S1 15.8ppg

Additives 6

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 7

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 8

Dowell

Calcium Chloride
l S1, S2, D77
n Most active accelerator n Range 1-4% n Effect on Thickening Time

CaCl2
(%BWOC)

Thickening Time (h:mn) 91oF 103oF 113oF 4:00 1:17 1:15 3:30 1:11 1:02 2:32 1:10 0:58

0 2 4

Additives 9

Dowell

Compressive Strength
Compressive Strength at Temperature (psi) CaCl2 (%) 0 2 4 6 hr NS 125 125 60oF 12 hr 60 480 650 24 hr 415 1510 1570 6 hr 45 410 545 80oF 12 hr 370 1020 1245 24 hr 1260 2510 2890 6 hr 370 1110 1320 100oF 12 hr 840 2370 2560 24 hr 1780 3950 4450

Additives 10

Dowell

Secondary Effects of CaCl2

l Increased temperature
n Heat of solution of CaCl2 n Additional accelerating effect (on surface?) n Casing expansion

l Increased rheology (gelation) l Possible permeability increase

n Reduced sulfate resistance

Additives 11

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

Time to reach 100 Bc (hr)

136F (58C)
6

154F(68C)
4

179F (81C)
2

210F (99C)

10

15

20

25

30
Additives 12

NaCl in Mix Water (% BWOW)

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

l Chemical Classes of Retarders

n Lignosulphonates n Hydroxycarboxylic acids n Inorganic compounds n Cellulose derivatives n Blended retarders n Special materials n (Blend of above components)
Additives 13

(D13, D81, D800, D801) (D109, D110, D45) (D93, D74) (D8) (D28, D150, D121) (D161)

Dowell

Mechanisms of Retardation
l Factors affecting mechanism of action
n Chemical nature of retarder n Chemical composition of cement

l Theories of mechanism of action

n Adsorption theory n Precipitation theory n Nucleation theory n Complexation theory

l Possible negative effects on slurries

n Gelation n Dispersion n Increased fluid loss n Incompatibility
Additives 14

Dowell

Cement Retarders
Retarder BHCT oF 100 100 100 125 140 185 250 250 175 310 300 300 220 300 300 300 100 140 250 450 350 400 375 200 300 400 Fresh Sea 37% NaCl

D13/D81 D13/D81 with Dispersant D800/D801 D800/D801 with D93/L10 D110 D110 with D93/L10 D28/D150 D28/D150 with D121 D28/D150 with D93 D74 - for RFC only D161

X X X X X X X X X X X

X X X X X X X X X X X X X X

Additives 15

Dowell

Lignosulfonates
l Low to mid temperature use
n D13 (D81) <185oF n D800 (D801) 140o - 220oF

l Pulping by-product
n Variable performance

l Efficiency improved 150o - 175oF l Tendency to gel at higher concentrations l May require dispersion

Additives 16

Dowell

Hydroxycarboxylic Acid
l Powerful retarders
n D110 (D109) - 175o - 325oF n D45 (salt dispersant)

l Detrimental effect with lattices l Some dispersion l Recommended retarder for silicate extended slurry

Additives 17

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

l Sodium Chloride (D44)

n Retards at concentrations over 20% n May over-retard at low temperatures

l D74 - Retarder for RFC (D53 version)

Additives 18

Dowell

Cellulose
l CMHEC (D8) - Diacel LWL
n Sometimes used for retardation n Viscosifying n Effective to 250oF n Some fluid loss control

l Other fluid loss additives

n D59, D60, D112

Additives 19

Dowell

Blended Retarders
l Generally lignosulfonate with other material
n D28 (D150) n D121

- 220o - +300oF - 250o - 350oF

l Dispersing action as well, especially at high concentration l D121 erratic below 300oF l D121 may overdisperse

Additives 20

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

l Effective in Fresh Water, Seawater, and Salt Water l Liquid

Additives 21

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 22

Dowell

D161 Setting Characteristics

oF RatioRatio of TTR psi @ 320 of 50 TTR 50 psi @ 320oF oF to TTto @TT 350 @ 350oF

8 7 6 5 4 3 2 1 0 0 2 4 6 8 10 12 D161 Conventional

Thickening Time @ 350oF

Additives 23

Dowell

CS to TT Ratio
D161 D121/D28
D66 (%BWOC) D47 (gps) D158 (gps) Disp (% or gps) Retarder (% or gps) D93 (%BWOC) 35 0.05 0.5 0.06 1.25 --5:27 TTR 50 psi TTR 500 psi 8:18 10:10 1.5 35 0.05 0.5 1.00 1.50 --3:32 19:03 21:48 5.4 35 0.05 0.5 1.00 2.00 --4:12

D93/D110
35 0.05 0.5 0.06 0.24 0.40 4:12 35 0.05 0.5 0.06 0.40 0.40 8:53

Thickening Time (hr:min) at 350oF: Compressive Strength (hr:min) at 320oF:

25:46 35:52 30:13 28:59 38:45 33:27 6.1 8.5 3.4

Ratio of TTR 50 psi @ 320oF toTT @ 350oF

Dyckerhoff Red Label at 16.0 ppg

Additives 24

Dowell

Compressive Strength Development

22 20 18 16 14 12 10 8 6 4 2 0 2 3 4 5 6 7 8 9

3000 psi

Time to reach compressive strength at 320F (hr)

500 psi 50 psi

10

Thickening time @ 350F (hr)

Additives 25

Dowell

Slurry Density
CHANGING OF SLURRY DENSITY

LIGHTER MORE WATER*

ABSORBENT

LIGHT MATERIAL

LOWER DENSITY

15.6 Class A Neat Cement 15.8 Class G 16.4 Class H

* D124 and Foamed Cement are exceptions
Additives 26

Dowell

Cement Extenders
Extender or Lightweight System 6 7 8 Slurry Density (lb/gal) 9 10 11 12 13 14 11.5 12 10.8 12 11 10.6 12 12 11 11.5 9 6 11 10.5 12.5
Additives 27

15 15 14.7

Bentonite LITEPOZ* 3 D35 LITEPOZ 7 D61 TXI Lightweight Cement Diacel D D56 Expanded Perlite D72 Gilsonite D24 KOLITE* D42 Sodium Metasilicate D79 Sodium Silicate D75 LITEFIL* D124 Foamed Cement Microsilica LiteCRETE* Cement
* Mark of Schlumberger
Dowell

13.6 14.2 14.5 13.8 15 15 14.5 14.5 12 15 15

Classification of Extenders
l Water absorbing extenders
n Clays (Bentonite) - D20, D128 n Chemical extenders (Silicates) - D75, D79

l Low density solids

n Pozzolans (Fly ashes) - D35, D56, D61, D602 n KOLITE* and gilsonite - D42, D24 n Expanded perlite - D72 n Silica fume (Microsilica) - D154, D155

l Very low density materials

n Nitrogen - Foamed Cement n Ceramic microspheres - D124 (LITEFIL*)
* Mark of Schlumberger
Additives 28

Dowell

Bentonitic Extenders
BENTONITE CLAY

BENEFICIATED (PEPTIZED)

NON - TREATED

MONTMORILLONITE - D20 (FRESH)

ATTAPULGITE - D128 (SEA)

General properties:
n n n n n n n n n n

Water based extender n n SG = 2.65 n n Dry blended or pre-hydrated Concentration range, 0-20% BWOC n n Density range, 11.5 - 15 ppg n n

Economical and widely available Decreases compressive strength, increases permeability Viscosifies slurries Provides fluid loss control
Additives 29

Dowell

Bentonite (D20)
l Allow addition of extra water, yet control free water
Optimum water content must be determined n Starting point - 5.3% additional water per 1% bentonite
n

l Additional water means

Reduced cost (increased yield) n Reduced strength n Increased permeability n Reduced resistance to chemical attack by brines
n

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 30

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

l D79, Sodium Metasilicate - dry l D75, Sodium Silicate - liquid

Additives 31

Dowell

Point of Departure
20 100 68 100
Consistency (Bc)

Class G + 2% D79 (12.5 ppg)

Schedule 4g6 (118oF) 245* 170*

80 60 40 20 0 0

470*

468*

20

40

60

80

100 Time (min)

120

140

160

180

200

* 24 hr compressive strength (psi) of slurry removed and cured at 170oF

Point of Departure is the time at which the slurry begins to increase in consistency.
Additives 32

Dowell

D75 Slurries

Class G + 0.28 gps D75 @ 12.5 ppg

Shear 24 hr Compressive Strength (min) (psi) 20 650 90 640 140 470 260 200
POD is 90 minutes - plateau of 40 Bc at 150 minutes Test at 131oF

Class G + 0.24 gps D75 @ 13.0 ppg

D109 POD Time to 70 Bc (gps) (hr:mn) (hr:min) 0 1:50 +4:00 0.04 2:00 3:15 0.07 4:10 5:35
Tests at 118oF

Additives 33

Dowell

Silicate Slurry Design

l Point of departure is the thickening time
n Optimize D75/D110

l Use D110 (D109) as retarder (erratic behavior with lignosulfonates) l Calcium chloride has little effect on compressive strength l Mixing
n Do not mix D75 with any other liquid additive n Add CaCl2, then D75, then D110 if using fresh water n Keep water/D75 solution agitated (keep gel suspended)

Additives 34

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 35

Dowell

Pozzolans
l Naturally occurring
n Volcanic ashes n Diatomaceous earth (D61)

l Artificial
n Fly ash
u u

Type F (D35, D48) - most common Type C (D132) - more reactive (cementitious)

l Key Properties
n React with Ca(OH)2
u u

Contribute strength Reduce permeability

n Increased brine resistance

Additives 36

Dowell

Microsilica (silica fume)

l l l l l l l l l l Amorphous sub-micron spheres Pozzolanic properties (reactive) Low bulk density (<15 lb/ft3) Provides some slurry stability Frequently blended with other lightweight additives (HiLITE blend with D124) Bulk blending is difficult with dry material Liquid can be stored with minimal agitation Concentration up to 20% Dispersant is required to effectively disperse in water and prevent gelation Additives n D154 - dry n D155 - liquid
Additives 37

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

l Foamed cement systems

n Nitrogen injected into slurry with foamer n Very low densities > 6.0 lb/gal n Good mechanical properties
* Mark of Schlumberger
Additives 38

Dowell

Lost Circulation Control

l Reduce density l Reduce friction pressure l Add LCM
n Granular n Flake

Additives 39

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 40

Dowell

Flake Lost Circulation Materials

l D29 (Cellophane flake)
n Concentration - 1/8 to 1/2 lb/sk

l D130 (Polyester flakes)

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 41

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)

Additives 42

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 43

Dowell

Dispersants
l Cement slurry rheology n Volume of particles / total volume n Particle interactions n Aqueous phase rheology Change with dispersants 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 44

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

l Organic salts and acids

n D45 n D121
* Mark of Schlumberger
Additives 45

Dowell

Dispersant Action
C2SHCEMENT
+Ca+ -0 3S

SO3

C2SH-

+Ca+

-0

3S

Dispersant Molecule Amount of dispersant adsorbed depends on concentration Cement grain surfaces become uniformly negative Like signs repel one another ---> dispersion

SO3

Additives 46

Dowell

Use of TIC D80 in ETD

20 30 30

Underdispersed
25

Overdispersed Acceptable Range

25

Yield value

Yield Value ( /100ft2)

15 20 20

Free water
10 15

Free Water 15 (%)

10 5

10

Plastic Viscosity 5 (Cp)

Viscosity
5

0.00

0.05

0.10

0.15

0.20

0.25

D80 (gal/sk)

Note: ETD Cement at 185F

Additives 47

Dowell

Use of TIC D604M in ETD

20 30 30

Underdispersed
25

Yield value Acceptable Range

25

Yield Value (lb/100ft2)

15 20

20

Viscosity
10 15

Free Water 15 (%)

10 5

10

Plastic Viscosity 5 (Cp)

Free water

0.00

0.05

0.10

0.15

0.20

0.25

D604M (gal/sk)

Note: ETD Cement at 185F

Additives 48

Dowell

Fluid Loss in Cement Slurries

l Definition:
n Filtrate lost to the formation n Filter cake deposited at formation face n Cement particles left in annulus

l Why cement loses water:

n Differential pressure n Permeable medium (formation)

l Fluid loss stages:

n Dynamic n Static

Additives 49

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

Additives 50

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 n n Slurry yield n n Free water n n Thickening time n n Settling n n Bulk Shrinkage n n Mud removal efficiency (?) INCREASED n n Hydrostatic n n Slurry density n n Plastic viscosity n n Yield point n n Compressive strength n n Bonding

Additives 51

Dowell

Thickening Time versus Density

160

Thickening Time (min)

E YIELD VALU

40

15.6

Slurry Density (ppg)

16.4
Additives 52

Dowell

Yield Value

TH ICK EN ING TIM E

Mechanisms of Fluid Loss Control

l Reduce cement filter cake permeability
n Particulate materials to fill voids n Polymer particles to plug pores n Change cement particle distribution with dispersants

l Increase viscosity of aqueous phase

n Water soluble polymers n Small effect compared to permeability reduction

Additives 53

Dowell

Mechanisms

Particle Plugging

Polymer Plugging
Additives 54

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 55

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

RANDOM PACKING HIGH PERMEABILITY

ORDERED PACKING LOW PERMEABILITY

Additives 56

Dowell

Acceptable Fluid Loss Limits

l Gas zones l Liner l Casing l Horizontal well l High density slurries: l Squeeze :
n Formation with K < 1 md n Formation with K 1 md - 100 md n Formation with K > 100 md

30 - 50 mL/30 min < 50 mL/30 min 200 - 300 mL/30 min <50 mL/30 min <50 mL/30 min
200 mL/30 min 100 - 200 mL/30 min 35 - 100 mL/30 min

Neat cement = +1000 mL/30 min

Additives 57

Dowell

Slurry Density
Changing Slurry Density

Lighter More Water*

Heavier Less Water

Less Water

Absorbent

Light Material

Heavy Material

Dispersant

Lower Density

Higher Density

15.6 Class A Neat Cement 15.8 Class G 16.4 Class H

* D124 and Foamed Cement are exceptions
Additives 58

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

l Commonly used weighting agents

Code D31 D76 D157 Agent Barite Hematite MicroMax Cement SG 4.33 4.95 4.80 3.15 Additional water 0.024 gal/lb 0.0023 gal/lb 0.0011 gal/lb 0.049 gal/lb
Additives 59

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 strong, impermeable C/S = 1.5 crystalline weak, permeable 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 60

Dowell

D30 Silica Sand & D66 Silica Flour

NAME Particle size US Mesh Additional Water Specific gravity Applications: High density Low density Settling Problems Mixing Problems (Rheology) Use above 300F
Dowell

D30 SILICA SAND 70 - 200 10% 1.12 gal/sk 2.63

D66 SILICA FLOUR > 200 + 12% 1.34 gal/sk 2.63

Preferred Alternative Alternative Preferred Alternative

Alternative Preferred Preferred Alternative Preferred

Additives 61

Antisettling Agent D153

l Controls free water and/or sedimentation l Compatible with all Dowell products and cements l No significant effects on slurry properties, except rheology l Dry-blend or prehydrated (preferred), fresh or sea water l Temperature range: less than 302oF (150oC) l Concentration: 0.1 to 1.5%BWOC (depending on density)
Additives 62

Dowell

Slurry Stability

Additives 63

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 64

Dowell