Cementing Additives

Module CF204
15 Sep 99

Well Conditions
ADDITIVE CATEGORY

PROBLEM

SLURRY PARAMETER

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.

SOLUTIONS

LCM
Extenders
Silica
Foaming agent &
stabilizers
Anti foamers

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)

Cement Additives

Accelerators and Retarders

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

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)

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

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 CS-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

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:

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
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

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

10

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

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
LITEPOZ 7 D61

14.7
13.6

10.8

TXI Cement D911

14.
13. 2

12

Trinity Lite-Wate Cement D49

11.9

Diacel D D56

15

Gilsonite D24

12

14.
5
13.
8
15

KOLITE D42

12

15

11

Expanded Perlite D72

10.6

Sodium Metasilicate D79

11

14.5

Sodium Silicate D75

11.5

14.5

LITEFIL D124
Foamed Cement
Microsilica D154 / D155

12

12
15

6
11

15

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

14

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)

15

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

16

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

17

Hydration of Cement
I

II

IV

hr

min

18

III

days

I.

PRE - INDUCTION PERIOD

II.

INDUCTION PERIOD

III.

ACCELERATION PERIOD

IV.

DECELERATION PERIOD

V.

DIFFUSION PERIOD

STAGES 1 and 2: Pre Induction and Induction

Periods

Ca

Al OH Ca Si
SO4

Seconds

ETTRINGITE

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

19

Retardation of cement slurries

Applications

Intermediate and production strings

Squeeze and cement plugs
High temperature and depth
Chemical Classes of retarders

20

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

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)

21

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

22

Cement Retarders
Retarder

BHCT oF
100

D13/D81

100

D13/D81 with Dispersant

100

D800/D801

200

300

185
250

D800/D801 with D93/L10

250
175

300

D28/D150

220

D28/D150 with D121

25

300
100

375

300
300

D28/D150 with D93

D161

310
300

D110 with D93/L10

D74

400

140

125

D110

Fresh Sea 37%

NaCl

350
400

140
250

450

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

26

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:

27

REDUCED
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

ING

Yield Value

Thickening Time (min)

160

Thickening Time versus Density

TI M
E

40

E
YIELD VALU

15.6

28

Slurry Density (ppg)

16.4

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)

30

Dispersants with FLACs

Mechanism of action

Disperse cement grains and improve packing --> reduced permeability

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

FILTER CAKE

RANDOM PACKING
HIGH PERMEABILITY

31

WITH DISPERSANT

ORDERED PACKING
LOW PERMEABILITY

Acceptable Fluid Loss Limits

Typical Values: (API, 1000 psi)
Prevention of gas channeling
Liner cementing
Casing cementing

30 - 50 ml/30 min
< 50 ml/30 min
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

32

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

33

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

34

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

35

Dispersant Action
SO33

C2SH- + Ca + - 03S
CEMENT

POLY
C2SH - + Ca + - 03S
DISPERSANT
MOLECULE

SO33

Amount of dispersant adsorbed depends on concentration

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

36

Slurry Density
CHANGING OF SLURRY DENSITY

LIGHTER

HEAVIER

MORE
WATER*

MORE
WATER

LIGHT

ABSORBANT

MATERIAL

HEAVY
MATERIAL

DISPERSANT

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

LESS
WATER

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

39

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

40

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

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:
High density

Preferred

Alternative

Low density

Alternative

Preferred

Settling Problems

Alternative

Preferred

Mixing Problems
(Rheology)

Preferred

Alternative

Use above 300F

Alternative

Preferred

41

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)
42