Cementing Additives

Client Cementing Seminar

Agenda
Additives Families

Slurry Properties

Laboratory Equipment & Tests

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Well Conditions
PROBLEM
WELL CONTROL
OVER PRESSURE
WEAK FORMATION

ADDITIVE CATEGORY

SLURRY PARAMETER

SOLUTIONS
EXTENDERS

DENSITY
WEIGHTING AGENTS
ACCELERATORS
THICKENING TIME
RETARDERS

PERMEABLE FORMATIONS
MUD REMOVAL
FRICTION PRESSURE
MIXABILITY/PUMPABILITY

FLUID STABILITY
FLUID LOSS CONTROL

FLAC
DISPERSANTS

RHEOLOGY
GELLING AGENTS

PLUGGING
LOST CIRCULATION
BRIDGING PROPERTIES
DENSITY
ABNORMAL AND SPECIAL CONDITION
HEAT RETROGRESSION
HYDRATION PRODUCT

LCM
EXTENTERS
SILICA

FOAMERS

STABILIZED FOAM CAPABILITY

FOAMING AGENTS AND STABILIZERS

FOAM

FOAMING TENDENCY

ANTI-FOAM

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TEMPERATURE

Cementing Additives
Extenders

Dispersants

Reduce slurry density

Improve mixability

Increase slurry yield

Reduced water slurries

Reduce friction pressure (Low Ty and Pv)

Weighting Agents

Increase slurry density

Accelerators and Retarders

Fluid Loss Control

Lost Circulation Material (LCM)

Change thickening time

Alter rate of compressive strength development

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Speciality Additives
Antifoam/ defoamer agents

Antisettling additives

Bonding agents

Expansive additives

Gas migration control additives

Thixotropic systems

Strength retrogression control

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Slurry Density

Lighter
More Water*
Absorbent
Light Material

Lower Density

Neat Cement
15.6 ppg Class A
15.8 ppg Class G
16.4 ppg Class H

Heavier
Less Water
Heavy Material
Dispersant

Higher Density

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Changing
of
slurry density

Classification of Extenders

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Water based extenders

Water
Clays (Bentonite)- check viscosity - D020, D128
Sodium silicates - need Ca++ to work - D075, D079
Low density solids
Pozzolans (Fly ashes, diatomaceous earth) - D035, D056, D061, D602
Kolite and Gilsonite - D042, D024
Microsilica - D154, D155
Very low density materials
Nitrogen - Foamed Cement:- need stabilizer
Ceramic microspheres, 5000 psi max - D124 (LITEFIL)

Ultra Lightweight Extenders

Foamed cement
Nitrogen injected into cement with foaming agent for stability

Very low densities (>6 lb/gal)

Good strength

LiteCRETE cement

Lightweight ceramic or glass spheres

Very low densities (> 6.7 lb/gal)

Extremely good mechanical properties

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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

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Commonly Used Weighting Agents

Additional Water

AGENT

SG

D031

Barite

4.22

0.0240

D076

Hematite

4.95

0.0023

D907

Cement

3.2

0.0529

D157

Mn3O4 (Mn tetraoxide)

4.7 - 4.9

gal/lb

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CODE

Thickening & Setting Time

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Control to
Allow time to complete job
Reduce chance for fluid/gas flow
Reduce WOC (reduce rig-time)
Affected by
Temperature
Pressure
Cement type (class and fineness)
Mixing and placement methods
Accelerators and Retarders
Other additives (salt, dispersant, fluid loss additives)

Accelerators
Shorten stage I and II and accelerate stages III and IV

Accelerators are used to enhance strength development

Primary usage is for low temperature applications where strength

development is slow

Reduce WOC time

Also to counteract retarding effect of other additives

I

II

III

IV

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Accelerators

Calcium chloride

Sodium chloride
D044, Sea water(3.5% BWOW)

Proprietary materials
D186 (Low temp cement set enhancer)

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S001(77% CaCl2 purity)

S002 (97% CaCl2 purity)
D077(Liquid CaCl2, 32-38% purity)

Retardation of Cement Slurries

Applications
Intermediate and production strings

Squeeze and cement plugs

Used to provide sufficient time to place cement

Used at elevated temperature and where long pumping times are

needed

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Cement Retarders
Retarder

BHCT oF
100

D13/D81

100

D13/D81 with Dispersant

100

300

400

140
185
125

250

D800/D801 with D93/L10

250

D110

175

310
300
300

D110 with D93/L10

D28/D150

220

300

D28/D150 with D121

300

D28/D150 with D93

300

D74 - for RFC only

100

D161 UNISET HT
D177 UNISET LT

350
400

140

X
250

80

375

37%
NaCl

250

450

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D800/D801

200

Fresh Sea

Retarders
Possible negative effects on slurries
Gelation (ex. Lignosulfonates)

Dispersion

Increased fluid loss

Incompatibility

Slow the development of compressive strength

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AccuSET - D197
3rd generation retarder
1st generation - Lignosulfonate

2nd generation - UniSET

3rd generation - AccuSET

Main advantages

Low sensitivity to temperature variations

Shorter WOC times for long cement columns

Accelerated hydration rate

Lot to lot consistency

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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 slurry loses water

Differential pressure

Permeable medium (formation)

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Fluid Loss in Cement Slurries

Fluid loss stages
Dynamic fluid loss

Static fluid loss

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 poor quality cement

Annular Bridging

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Mechanisms

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Particle Plugging

Polymer Plugging

Acceptable Fluid Loss Limits

30 - 50
< 50
200 - 300
< 50

ml/30 min
ml/30 min
ml/30 min
ml/30 min

200
100 - 200
35 - 100
< 50

ml/30 min
ml/30 min
ml/30 min
ml/30 min

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Typical Values: (API test, 1000 psi)

Gas migration prevention
Liner cementing
Casing cementing
Horizontal well cementing
Squeeze Cementing
Formation with K < 1 md
Formation with 1<K<100 md
Formation with K>100 md
High density slurry

Dispersants with FLACs

Mechanism of action
Disperse cement grains
improve packing
Flocculate with salt
plugging action
FILTER CAKE

WITH DISPERSANT

RANDOM PACKING

ORDERED PACKING

HIGH PERMEABILITY

LOW PERMEABILITY

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WITHOUT DISPERSANT

reduce permeability

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

Reduce viscosity and yield point

Reduce friction pressures
Improve cement slurry mixability (lower Ty)
Reduced water slurries (density up to 18 lb/gal)
Improve efficiency of fluid loss control additives

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Why dispersants?

Types of Dispersants
D065, D080
D145A
D065A, D080A
D604M, D604AM
D081
D121
D185

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Sodium Polynapthalene Sulfonate (PNS)

Polymelamine Sulfonate (PMS)
Aromatic polymer
Organic polymer
Lignin Derivative/HydroxyCarboxylic Acid
Hydroxy Carboxylic Acid
Steric Effect dispersant

Dispersant Mechanism
+
- + -+
-+ + + + -+ + +
+
- - ++ - +- + -- +
+ + -+ - +
+
+ - +
+
- +
- +
- +
- + - +
+
+
+- +
+

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Aggregated

Dispersant Mechanism
-

+
-- - + - +
-- - - - +
+ +
+
+ + --+ -+ - + - - + -- +
+
+- - + --- +
+- - + - - + -- - + +
+
- - -+- - +
+
- +
- - +
+
-- +
+
+
+-

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Dispersant Mechanism

-- - - - +
-+ + - - -

--

+ - - +-+ - - ++ --

- +
- +- - +
+
- + - - - -+ - +
- - +
- +
+- - +
+
+- +
Dispersed
-

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+ +- -+
- + - - +- - +
-

-- - + - +
+ + --+

Anti Settling Additives

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Anti Settling Additives reduce

Free water
Sedimentation
Slurry instability
Compatible with all Cementing products and cement
No significant effects on slurry properties, except rheology
Temperature range: up to 300 deg F
Antisettling Agent
D153: 0.1 - 1.5 % BWOC
Liquid Antisettling Agent D162: 0.005 - 0.025 gal/sk

Lost Circulation Control

Granular

Flake/Laminar

Fibrous

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Reduce density
Reduce friction pressure
Add Particulate LCM

Granular Lost Circulation Materials

D042 - KOLITE* additive
Ground coal
SG - 1.3
Concentration - 5 - 25 lb/sk
Slurry stability is key

D024 - Gilsonite

Ground asphaltinic material

SG - 1.07
Similar to D42
Temperature limitation of 300oF due to softening
Mechanism
Bridging
Mixing difficulties at high concentrations

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Flake Lost Circulation Materials

D029 (Cellophane flake)
Concentration - 1/8 to 1/2 lb/sk

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D130 (Polyester flakes)

Concentration - 1/8 to 1/2 lb/sk
Mechanisms - Form mat on fractures, vugs, etc..
Handling - Mixing difficulties at high concentrations

Lost Circulation - Others

Other Treatments for Lost Circulation include:
Zonelock S and SC
InstanSeal
InstanSeal Cement
CemNET fibers
Losseal Fibers

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Lost Circulation - CemNET

Main Applications
New approach on controlling massive losses using fibers in cement.
Non formation damage has been reported.

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Completely compatible with all cement systems and additives.

CemNET - The product

Dimensions: 15-20 microns diameter and 12 mm long

Density similar to the cement

Flexible fiber

Compatible with:
All Schlumberger cementing additives
CemCRETE slurries

Temperature range from 50 to 500 degF

Typical Concentration: from 0.5 to 0.8 lb/sack

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Features and Benefits

Stabilizes with randomly oriented fibers

Properties increase combined the fibers with the WELBOND

systems

Uses physics mechanism of fibers for reinforcement

Enhance slurry set properties with tensile strength absorbing

impacts and maintaining the integrity of the cement while being
drilled.

No formation damage by the addition of the fiber.

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Antifoam Agents

Mechanism of action:
Lower surface tension
Reduces film and causes rupture
Types of antifoam agents
Polyglycol ethers
Silicones
Solid : D046 (0.2 lb/sk)
Liquid : D047 (0.05 gal/sk)

Liquid : D206 (0.01 - 0.02 gal/sk)

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Purpose
Allow true slurry density to be mixed and pumped
Prevent slurry gelation
Prevent pump cavitation (due to aeration)

Strength Retrogression
Above 230 deg F BHST unstabilized cement will undergo:

A reduction in strength
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An increase in permeability
Due to conversion of C-S-H gel to more crystalline CSH which is
calcium rich
Prevented by the addition of 35 - 40% BWOC silica reduces C/S ratio
of C-S-H gel
Ca to Si molar ratio close to 1:1

Strength Retrogression
1. CS and K - neat cement @ 230oC (450oF)

1 D30 @230oC(450oF)
2 D66 @230oC(450oF)
3 D66 @320oC(610oF)

1 D30 @230oC(450oF)
2 D66 @230oC(450oF)
3 D66 @320oC(610oF)

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1. Class G + 44% water

2. Class G + 38% water
3. Class H + 32% water
4. Extended cement

2. CS and K 16.0 lb/gal Class G

+ 35% silica

Sulfate Resistance < 3% C3A

Mg + Na sulfates in formation fluids react with Ca(OH)2 in cement to form:

Ca(OH)2 + MgSO4 + 2H2O CaSO4 . 2H2O + Mg(OH)2 Crystals of Mg(OH)2

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Ca(OH)2 + Na2SO4 + 2H2O CaSO4 . 2H2O + 2NaOH A solution of NaOH

Swelling occurs due to replacement of Ca(OH)2 by Mg(OH)2

Cement porosity increases since NaOH is much more soluble than Ca(OH)2
Ettringite formation after cement has set causes expansion and cracking of
cement (not a problem abouve 140 degF), lower C3A content
C3AH6 + 3 CaSO4.2H2O + Water C3A.3CaSO4.32H2O
C3A + 3 CaSO4.2H2O + Water C3A.3CaSO4.32H2O

Schlumberger OFS HPHT Definitions

Global HPHT Fields and Prospects
650

NAM
LAM

HPHT-hc

EAF
ME

ASIA

HTLP

Deep Gas

Salak mountain, West Java (Steam)

550

Typically
Thermal
Recovery
Ultra-HPHT
Of
Gulf of
South Umm Gudair Eocene (HO)
Heavy OilThailand

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Reservoir Temperature Deg F

South Sumatra - HO

Liaohe
(HO)

PDO Central Oman (HO)

Oxy South Oman (HO)
PDO South Oman (HO)

450

Tonpo

Krishna
Godawari

Scorpio (North Padre Island)

Mobile Bay
Victoria

Jackdaw

Xinjiang

BP Rahma

Elgin

Brides

350

HPHT

PDO Fakhr

Ultra
HPHT
Conventional
HPHT
HPLT

Khuff D
Huldra

Pemex South
UDW Angola

South Timballier

Thunder horse

250

Tubular Bells

Conventional
Mad Dog
Puma

150
0

5000

10000

15000

Jack

Kaskida

predominantly
Deepwater
GoM

20000

Reservoir Pressure

Blind Faith

Tahiti

25000

30000

35000

HPHT Challenges

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High Temperature
Chemical versatility
Must be able to design a stable and pumpable slurry at low and high temperature
Must be able to retard at high temperature and set at lower temperature
Chemical sensitivity
To small temperature variations
To cement brand/batches
To slurry density variations
To additive concentration
Limitation of laboratory testing & computer modeling
High Pressure
Chemical sensitivity
Narrow margins between frac and pore pressures
Accurate fluid density
Limited ECD - Low displacement rates & long Thickening times
High mud density
Difficult Mud removal (density and rheology hierarchy rules)
High amount of solids (stability and rheology)
High cement slurry density Slurry Batch mixing
Limitation of laboratory testing & computer modeling

Temperature determination: BHST

BHST determined from BHLT (bottom hole logging temperature)
Horner plot method
Tj = static reservoir temperature (BHST)
tk = Circulation time prior to shut down
t = Shut-in time
Tws = bottom hole shut in temperature at t

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BHST Correction factors

Time period
3 to 4 hrs
5 to 7 hrs
8 to 10 hrs
11 to 24 hrs
25 to 48 hrs
49 hrs onwards

Correction formula
BHLT X 1.08 = BHST
BHLT X 1.07 = BHST
BHLT X 1.06 = BHST
BHLT X 1.05 = BHST
BHLT X 1.02 = BHST
BHLT X 1.00 = BHST

log

Tj= Tws + A log(1+tk/t )

520
Temp. History (degF)
460
480
500
440
420

Expected BHCT (planned circulation time)

Maximum BHCT (result of minimum circulating rate and time, in
case of losses for example)
Minimum BHCT (result of maximum circulating rate and time, in
case of mechanical problem for example)

140

160

180

200

140

160

180

200

520

Geoth.Prof ile
A nnulus

440

Temp. History (degF)

460
480
500

Maximum BHCT = 437

deg F, no circulation

20

40

60

80

100
120
Time (min)

D epth = 28000 ft

510

Geoth.Profile
A nnulus

Minimum BHCT = 406

deg F, after 5 hrs
circulation

Temp. History (degF)

450
480

100
120
Time (min)

420

Temperature simulation matrix

80

390

60

420

Formation
BHST
Lithology

540

Casing
Configuration
(Liner, Stab-In, )
OD-Weight

Mud inlet temperature can be critical in HPHT

40

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Cement-Mud
Composition
Rheology
Flow Rate
Inlet temp

Wellbore
Well Trajectory
Open Hole Caliper
Previous Casing

20

Depth = 28000 ft

540

API BHCT does not apply for gradients above 1.9 degF /100 ft or for
TVD above 6705 m [22000 ft]
LWD/MWD temperatures should not be used as BHCT
CemCADE* Computer simulated BHCT & Maximum Dynamic BHP

Expected BHCT = 415

deg F, after 3 hrs
circulation

400

540

Temperature determination: BHCT

Depth = 28000 ft
Geoth.Prof ile
A nnulus

20

40

60

80

100
120
Time (min)

140

160

180

200

HPHT fluid design guidelines Cement slurry Stability &

Fluid Loss Control
STABILITY:

Conditioning in HPHT consistometer or cured in HPHT curing

chamber
If well deviation is below 15 deg Free Fluid test is run vertical
If well deviation is above 15 deg Free Fluid test is run at 45
deg
Free Fluid = Zero
(Static) Sedimentation test: less than 5 % deviation from
theoretical density
Go/No-Go Test Consistency spike after motor shut off: below
70 Bc Also simulates dropping the top plug or the shut down
period prior to sting-out of the liner and circulate/reverse
circulate
Dynamic Settling Test: The SG of cement is measured from the
top, middle and bottom of the consistometer cup after the
cement has set.
FLUID LOSS:
Conditioning with stirred fluid loss cell is mandatory.
API Fluid Loss < 50 mL/30min

Weight of
Sample (g)
18.11
14.81
14.72
16.73
14.36
16.4
16.01
19.04

Average Density:

S.G. of Slurry
3
(g/cm )
1.26
1.26
1.26
1.27
1.28
1.27
1.26
1.29

Density of
Slurry (ppg)
10.49
10.55
10.54
10.60
10.65
10.59
10.53
10.75

1.27

10.59

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Sample
Number
Top
1
2
3
4
5
6
7
Bottom
8

Weight of
Volume of
Removed
Water (g)
14.01
11.39
11.33
12.81
10.94
12.56
12.34
14.37

Go No Go test & Dynamic Sedimentation test: Stability at High Temperatures (1)

Strong dynamic settling !

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Go-noGo

Go No Go test & Dynamic Sedimentation test: Stability at High Temperatures (2)

Go-noGo
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Dynamic Sedimentation test

Summary:
Successful HPHT cementing requires:
Accurate well data
Accurate temperature prediction
Optimized fluid design for mud, spacer, cement
Ensuring job execution meets with design
Design:
Temperature prediction is critical
Placement technique optimized
Fluid design
Mud removal

Contingency planning
Execution:
HPHT Experience, use trained personnel
Meeting rig conditions with laboratory design
Ensure slurry quality with QA/QC procedures

Ensure strict control of ALL the steps during the entire process

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All lab testing to reflect actual field conditions, and equipment limitations

Depleted Reservoirs & Mature Fields: Challenges

Mud Losses
Cost of fluids

Reservoir Damage due to losses

Isolation requirements

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Require very light weight cements

Good mechanical properties

Well Control Issues

This image cannot currently be
displayed.

Environmental compliance
Extra cement mixed for returns to
surface
48

System Application Ranges (CemCRETE)

High Density
Particle

Light
Particle

Flexible
Additive

25
lb/gal

Light
Particle

7.5
lb/gal

49

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Sand

Conventional cement properties

vs. CemCRETE technology
160
0.2

Fluid Loss (mL)

140

Permeability (mD)

0.18

120
0.16
0.14

100

0.12

80

0.1

60

0.08

70

0.04
0.02
0

Lightweight

Conventional

40

60

20

50

Lightweight

40

Conventional

30
20

4000

10

24 hr Compressive Strength (psi)

0

3500

Lightweight

3000
2500

Conventional

CemCRETE

2000

40

30

1500

25

1000

20

500
0

Lightweight

Conventional

Conventional
cements

Acid Solubility (wt %)

35

15
10
5
0

50

Lightweight

Conventional

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Solid Fraction (%)

0.06

Ultra LiteCRETE

Density Range: 7.5 8.7 ppg

6.7 7.5

8.0

8.7

Ultra LiteCRETE
51

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The ultra lightweight production quality cementing system

Systems as low as 6.7 ppg were pumped

Ultra LiteCRETE
Features & Applications
Extremely fractured or depleted
formations

Production liners/casing

Cement to surface
Production quality

Density: 7.5 8.7 ppg

Temperature: 80 392 degF

Compressive > 1000 psi

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Ultra LiteCRETE

52

Basics of Slurry Density

SG - 3.2

CEMENT
CEMENT

SG - 1.0

SG - SG
1.0- 1.0
Slurry weight - 1.9

What if this
becomes 1.0?

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SG - 1.0

CEMENT

Job execution: Solid Fraction Monitoring

Acquisition

Tub level

Slurry rate

Mixer
Mixing Water
Rate

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Gate
Control

Control
Valve

6 bbl tub
NRD

Slurry density

54

Equipment Requirements vs Foam

Unfoamed cement
Bleedoff w/Choke
Well

Cement Unit

Foamer
Pump

N2
Tank

Flow line to pit w/Choke

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Check Valve

Foam
Generator
NRD

N2 Isolation
Valve

Recirc.
Tub
Cement
Mixer

Cement
Silo

Bleedoff
w/N2 Choke

Check Valve
Popoff Valve
Micromotion Flowmeter

N2 Pump
N2
Tank

Process
Control
Computer

Foamed cement

Operational Challenges comparison vs Foam

Criteria

Foamed Cement

CemCRETE Systems

a
a
a

a
a

X
X

Risk to personnel

X
X
X
X
X
X

a
a
a
a
a
a

Quality of blend

Quality of mixed slurry

X
X

a
a

Mixing
Returns to surface
Dry blend
Site bulk storage
Space on location
Mobilization
Gas availability
Personnel training
Danger of N2 spillage

Risk of operational failure

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X
X
X

Equipment