Cementing Additives

Well Conditions
ADDITIVE CATEGORY

PROBLEM
Well control
over pressure and
weak formations

Density

Extenders
Weighting agents

Temperature

Thickening time

Accelerators
Retarders

Permeable formations

Fluid Stability
Fluid loss control

FLAC

Mud removal
Friction pressure
Mixability/Pumpability

Rheology

Dispersants
Gelling Agents

Lost circulation

Plugging/Bridging properties
Density

Abnormal and specialized conditions:

Heat retrogression
Hydration product
Foamers
Stabilized foam capability
Foam
Foaming tendency
Etc.
2

SOLUTIONS

SLURRY PARAMETER

LCM
Extenders
Silica
Foaming agent &
stabilizers
Anti foamers

Cementing additives
z Accelerators and retarders
Change thickening time
Alter rate of compressive strength development

z Extenders
Reduce slurry density
Increase slurry yield

z Weighting agents
Increase slurry density

z Dispersants
Improve mud removal
Improve mixability / reduced water slurries
Reduce friction pressure (Lower ty and Pv)

z Fluid Loss Control

z Lost Circulation Material (LCM)
3

Cement Additives
z Accelerators and Retarders
z Change thickening time
z Alter rate of compressive strength development

z Extenders
z Reduce slurry density
z Increase slurry yield

z Weighting Agents

Specialty:

d e n s i t yz Antifoam/defoamer agents
z Bonding agents
z Dispersants
z Expansive additives
z Improve mud removal
z Gas migration control additives, etc.
z Improve mixability
z Thixotropic systems
z Reduce friction pressure
z In c r e a s e

z Fluid Loss Control

z Lost Circulation Material
4

Antifoam Agents
z

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)

Conductor pipe
z Prevents washing out under rig
z Customer wants short rig downtime
z Quick setting cement - rapid

development of compressive
strength
z Accelerated slurries, e.g.:
Neat cement + NaCl (D44) 3-5%
Neat Cement + CaCl2 (S1) 2-4%
Neat cement + seawater

z Cemented with stab-in or just driven

Accelerators
z 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 CS-H gel structure
z Can be used to offset retarding effects of other additives
z 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)
z D44 - NaCl - <10%BWOW
z Seawater

Check consistency - near river mouths

z D77 - CaCl2 in liquid form - 0.2 to 0.4 gps
z ARCTIC SET For Low Temperature
7

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

Time to reach 100 Bc

Slurry consistency (hr)

136F (58C)

154F(68C)

179F (81C)
210F (99C)

10

15

20

25

NaCl IN MIX WATER (% BWOW)

30

Surface Casings
z Unconsolidated zones
z Low Temperatures (New challenge in

deep O/S - temperature very low)

z Large volumes of slurry
z Light weight slurries
z Strong slurry at shoe
z 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
9

Slurry Density
CHANGING OF SLURRY DENSITY

LIGHTER
MORE
WATER*

ABSORBANT

LIGHT
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
10

Classification of Extenders
z 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)

z 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.

z Very low density materials

Nitrogen - FOAM CEMENT - need stabilizer
Ceramic microspheres - D124 (LITEFIL) - Max 5000 psi / no VIP

11

Cement Extenders
Extender or
Lightweight System

Slurry Density (lb/gal)

9
10 11 12 13 14

Bentonite

15

11.2
12

LITEPOZ 3 D35

14.7
13.6

10.8

LITEPOZ 7 D61
TXI Cement D911

14.2

12

Trinity Lite-Wate Cement D49

13.7

11.9

Diacel D D56

14.5

11

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
Foamed Cement
Microsilica D154 / D155
12

15

12
15

6
11

15

Bentonitic Extenders
BENTONITE CLAY

BENEFICIATED (PEPTIZED)

MONTMORILLONITE - D20
(FRESH)

NON - TREATED

ATTAPULGITE - D128
(SEA)

General properties:

13

Water based extender

SG = 2.65

Dry blended or pre-hydrated

Concentration range, 0-20% BWOC
Density range, 11.5 - 15 ppg

Economical and widely available

Decreases compressive strength,
increases permeability
Viscosifies slurries (Lots of solids)

Chemical Extenders
z Sodium silicates and metasilicates
React with cations in the cement (Ca2+, 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

z D79, SODIUM METASILICATE - dry

z D75, SODIUM SILICATE - liquid
14

Lightweight Aggregates
z

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)

15

Ultra Lightweight Extenders

z Ceramic microspheres, LITEFIL D124 (Limit 4500 psi)
Ceramic or glass microspheres
Inert
Density range: 8.5 lb/gal to 14.5 lb/gal

z Foamed cement systems

Nitrogen injected into slurry with foamer
Very low densities achieved > 6.0 lb/gal
Good mechanical properties

16

Intermediate Casings
z

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

17

Hydration of Cement
I

II

IV

hr

min

18

III

days

I.I.

PRE
PRE -- INDUCTION
INDUCTION PERIOD
PERIOD

II.
II.

INDUCTION
INDUCTION PERIOD
PERIOD

III.
III.

ACCELERATION
ACCELERATION PERIOD
PERIOD

IV.
IV.

DECELERATION
DECELERATION PERIOD
PERIOD

V.
V.

DIFFUSION
DIFFUSION PERIOD
PERIOD

STAGES 1 and 2: Pre Induction and Induction Periods

Ca

Al OH Ca Si
SO4

Seconds

ETTRINGITE
ETTRINGITE

Hours
C - S - H Gel
PROTECTIVE LAYERS STOPS REACTIONS ???? - PUMPING TIME
19

Retardation of cement slurries

z

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

20

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

z Retarders : Theories of mechanism of action

Adsorption theory
Precipitation theory
Nucleation theory
Complexation theory

z Possible negative effects on slurries

21

Gelation
Dispersion
Increased fluid loss
Incompatibility
Slows the development of the compressive strength (D028)

Mechanisms of Retardation
z 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

z Precipitation theory
Ca and OH react with Retarder to Precipitate an Impermeable Layer

z Nucleation theory
Retarder Adsorbs to Poison Nucleation and Growth Sites

z Complexation theory
Retarder Complexes with Ca to Minimise the Driving Force for Reaction
and Prevent Formation of Nucleation Sites
22

Properties of Individual Retarders

z Lignosulphonates (Low to Medium Temperatures)

Most Common Retarders Derived from Wood Pulp

Active Ingredients Alcohols and Carbohydrates
MW 20,000 to 30,000
Work Better with Low C3A which Consumes Retarder
D800/D801 higher temperature stability than D13/D81
Work by Adsorption and Nucleation

z Carboxylic Acids (Medium to High Temperatures)

23

Carboxyl and OH groups strongly Complex Calcium

Work by Nucleation
Powerful Retarders: Easily over-retard at T < 90oC
D110 and D109 Different Dilutions of Same Chemical
Very sensitive to concentration

Properties of Individual Retarders

24

Blended
D28: Sugars plus Lignin Amine
z High Temperature Applications
z Strongly Complexing
z Works by Complextation and Nucleation Poisoning
z Can Separate Into IndividualComponents
D121: Mixed Dispersant and Retarder
z Lignosulphonate and HydroxyCarboxylic Acid
z High Temperature Applications often with D028

Inorganic Retarders (Mid to High Temperature)

D93 - Borax
z A retarder: Adsorption ?
z A Retarder Aid by Stabilizing Other Retarders
D161 - A New High Temperature Retarder (Blend) - Impart viscosity
build up.

Cement Retarders
Retarder

BHCT oF
100

D13/D81

100

D13/D81 with Dispersant

100

D800/D801

200

300

185
250
250

D800/D801 with D93/L10

175

300

D28/D150

220

300

D28/D150 with D93

300
100

375

300

D28/D150 with D121

D161

25

310
300

D110 with D93/L10

D74

400

140

125

D110

Fresh Sea 37%

NaCl

350
400

140

X
250

450

Fluid Loss in Cement Slurries

z Definition:
Filtrate (aqueous solution) lost to the formation
Filter cake deposited at formation face
Cement particles left in annulus

z Why cement loses water:

Differential pressure
Permeable medium (formation)
Water/cement ratio > hydration needs

z Fluid loss stages:

Dynamic fluid loss
Static fluid loss
26

Effect of Fluid Loss on Slurry Properties

z

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

27

Slurry yield
Free water
Thickening time
Settling
Bulk Shrinkage
Mud removal efficiency

INCREASED

Hydrostatic (psi/ft)
Slurry density
Plastic viscosity
Yield point
Compressive strength
Bonding

TH
ICK

EN
IN

GT
IM
E

Yield Value

Thickening Time (min)

160

Thickening Time versus Density

40

E
YIELD VALU

15.6
28

Slurry Density (ppg)

16.4

Mechanisms of Fluid Loss Control

z Reduce cement filter cake permeability

Particulate materials to fill voids

Polymer particles to plug pores
Polymer film over cement particles/pores
Change cement particle distribution with dispersants
z Increase viscosity of aqueous phase

Addition of water soluble polymers

Also reduce filter cake permeability
Effect small compared to permeability reduction
29

Additives for Fluid Loss Control

z

Particulate FLACs
D20, D600, D134
z Latex FLAC
D600 (MT,AD,L), D134
z Cationic Polymer
D73.1 (MT-HT,ND,L)

Water Soluble Polymers

z

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

30

Dispersants with FLACs

Mechanism of action

Disperse cement grains and improve packing --> reduced permeability

Flocculate w/salt ---> plugging action
WITHOUT DISPERSANT

31

FILTER CAKE

WITH DISPERSANT

RANDOM PACKING

ORDERED PACKING

HIGH PERMEABILITY

LOW PERMEABILITY

Acceptable Fluid Loss Limits

Typical Values: (API, 1000 psi)
z

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

For squeeze cementing

z
32

< 50 ml/30 min

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

Production Casings
z

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

33

Dispersants
z

Cement slurry rheology

Volume of particles / total volume
Inter-particle interactions
Aqueous phase rheology

Change with dispersants

z

34

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

Dispersants
z

Types:
z Superplasticizers
D65
D80 - D80A
D604M - D604 AM
D145A (the only one for D300 to work)

z Plasticizers
Lignosulphonates
Cement retarders (D13 , D 81 , D800, D801)
Mud Thinners

z Organic salts and acids

D45, D121
35

Dispersant Action
SO33

C2SH- + Ca + - 03S
CEMENT

POLY
C2SH - + Ca + - 03S
DISPERSANT
MOLECULE

SO33

z Amount of dispersant adsorbed depends on concentration

z Cement grain surfaces become uniformly negatively
z Alike signs repel one another ---> dispersion

36

Workable Range of D80 Dispersant ETD vs DTD Cements

20

D80

30
UNDERDISPERSED

25

30
OVERDISPERSED

25

YIELD VALUE

Yield Value (lb/100ft 2 )

15
20

10

20

FREE WATER

15

15
FREE
WATER (%)

10

10

VISCOSITY

PLASTIC VISCOSITY
(cp)15

0.00

0.05

0.10

0.15

D80 (gal/sk)

NOTE: WITH ETD CEMENT AT 186F

37

0.20

0.25

Slurry Density
CHANGING OF SLURRY DENSITY

LIGHTER

HEAVIER

MORE
WATER*

ABSORBANT

MORE
LESS
WATER WATER

LIGHT
MATERIAL

HEAVY

DISPERSANT

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
38

Weighting Agents
z

Requirements

High specific gravity

Compatible particle size and distribution (settling)
Low water adsorption (efficiency)
Availability and acceptable cost
Purity and consistency of product
Inert
z Commonly used weighting agents
Code
Agent
SG
Additional water
D31
D76
(D907
D157
39

BARITE
HEMATITE
CEMENT3.20
Manganese O (Mn3 O4)

4.22
0.024 gal/lb
4.95
0.0023 gal/lb
0.0529 gal/lb)
Mg tetraoxide

Strength Retrogression
z Above 230 oF BHST unstabilized cement will undergo:

A reduction in strength
An increase in permeability
z Due to structural change in C-S-H gel
z Prevented by the addition of 30 - 40% BWOC silica reduces

C/S ratio of C-S-H gel)

40

D30 Silica Sand & D66 Silica Flour

NAME
Particle size
-US Mesh
Add. Water
Specific gravity

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

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

Applications:

41

High density

Preferred

Alternative

Low density

Alternative

Preferred

Settling Problems

Alternative

Preferred

Mixing Problems
(Rheology)

Preferred

Alternative

Use above 300F

Alternative

Preferred

Antisettling Agent D153

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

density)

42

New Fluid Loss Additives D159/D160

z

Adjustable fluid loss control

Accelerating effect at low temperature, less than 140 F

Working temperature range in fresh water: up to 230 F

Density range: 12.5 to 18 ppg

Concentration range:
D159: 0.3 to 0.7 gps (depending on density)
D160: 0.5 to 1.5%BWOC

Salt up to 15%BWOW

Incompatible with S1; erratic results with D110; best extended with D20

43

New Fluid Loss Additive D300

44

Adjustable fluid loss control

Low cost

No retarding effect at low temperatures

Working temperature range in fresh water: up to 230 F

Density range: 12.5 to 15.8 ppg

Concentration range: 0.35 to 1.1 gps (same for any density)

Salt up to 10%BWOW

Compatible with S1; best extended with D75

Incompatible with D80 and D20

New HT Retarder D161

z

Medium to high temperature retarder

Low costs - reduced WOC

Controllable and predictable thickening times

Reproducible lab tests
Rapid compressive strength development
Less sensitive to small concentration/mixing errors

Working temperature range: 250 to 450 F (fresh water)

Density range: 14 to 18 ppg

Concentration range: 0.6 to 2.5 gps

Synergetic effect with D158/D159

Incompatible with D600 and D134

45