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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
SOLUTIONS Extenders Weighting agents Accelerators Retarders FLAC Dispersants Gelling Agents LCM Extenders Silica Foaming agent & stabilizers Anti foamers
Additives 2
Abnormal and specialized conditions: Hydration product Strength retrogression Foamers Stabilized foam capability Foam Foaming tendency
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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
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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
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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
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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
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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)
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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
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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
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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
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Additives 11
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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
136F (58C)
6
154F(68C)
4
179F (81C)
2
210F (99C)
10
15
20
25
30
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(D13, D81, D800, D801) (D109, D110, D45) (D93, D74) (D8) (D28, D150, D121) (D161)
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Mechanisms of Retardation
l Factors affecting mechanism of action
n Chemical nature of retarder n Chemical composition of cement
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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
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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
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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
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Cellulose
l CMHEC (D8) - Diacel LWL
n Sometimes used for retardation n Viscosifying n Effective to 250oF n Some fluid loss control
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Blended Retarders
l Generally lignosulfonate with other material
n D28 (D150) n D121
l Dispersing action as well, especially at high concentration l D121 erratic below 300oF l D121 may overdisperse
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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
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Applications
l Cementing Long Liners and Casing
n Single Stage vs. Two-Stage Jobs n Single Slurry Replacing a Lead and Tail Slurry
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8 7 6 5 4 3 2 1 0 0 2 4 6 8 10 12 D161 Conventional
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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
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3000 psi
10
Additives 25
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Slurry Density
CHANGING OF SLURRY DENSITY
ABSORBENT
LIGHT MATERIAL
LOWER DENSITY
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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
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Classification of Extenders
l Water absorbing extenders
n Clays (Bentonite) - D20, D128 n Chemical extenders (Silicates) - D75, D79
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Bentonitic Extenders
BENTONITE CLAY
BENEFICIATED (PEPTIZED)
NON - TREATED
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
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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 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
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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
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Point of Departure
20 100 68 100
Consistency (Bc)
80 60 40 20 0 0
470*
468*
20
40
60
80
120
140
160
180
200
Point of Departure is the time at which the slurry begins to increase in consistency.
Additives 32
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D75 Slurries
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
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
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Dowell
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
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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
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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
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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
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Additives 39
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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
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l Mechanisms
n Form mat on fractures, vugs, etc..
l Handling
n Mixing difficulties at high concentrations
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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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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
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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
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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
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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
Underdispersed
25
Yield value
15 20 20
Free water
10 15
10 5
10
Viscosity
5
0.00
0.05
0.10
0.15
0.20
0.25
D80 (gal/sk)
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Underdispersed
25
25
15 20
20
Viscosity
10 15
10 5
10
Free water
0.00
0.05
0.10
0.15
0.20
0.25
D604M (gal/sk)
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Additives 49
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l Static
n After placement n Loss is proportional to square root of time n Cake grows n May result in annular restrictions
u
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E YIELD VALU
40
15.6
16.4
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Yield Value
Additives 53
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Mechanisms
Particle Plugging
Polymer Plugging
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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
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FILTER CAKE
WITHOUT DISPERSANT WITH DISPERSANT
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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
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Slurry Density
Changing Slurry Density
Absorbent
Light Material
Heavy Material
Dispersant
Lower Density
Higher Density
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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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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
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Slurry Stability
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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
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