THE USE OF STYRENE-BUTADIENE RUBBER IN OIL

WELL CEMENT PASTES

Fabrício de Campos Vitorino

Romildo Dias Toledo Filho

1
INTRODUCTION

2
Cementing

Challenges

• Brazilian pré-salt reservoirs;

• HT-HP oil wells;

• Ciclic Steam Injection stimulation wells;

• Design of ductile material;

• Adequate rheological properties;

• Durability under aggressive environment.

3
Thiercelin et.al. (1997)
STUDIES WITH SBR
POWDER

4
 Dosage
Reference Paste
• 0.35 w/c;
• 40% silica fume;
• 0.12% defoamer;
• 0.35% superplasticizer.
Polymer Powder Modified Cement Pastes
• Three fractions of polymer powder was added in to PR (6, 10 and 13 ) related to cementing
materials;
• In P6, P10 and P13 the superplasticizer content was reduced to 0.3, 0.3 and 0.28 respectively.

Materials PR P6 P10 P13

Cement (kg/cm3) 1016 955 914 884
Silica fume (kg/cm3) 406 382 366 353
Polymer (kg/cm3) - 34 57 75
Superplasticizer (kg/cm3) 16.7 14.2 14.2 13.3
Antifoam (kg/cm3) 1.7 1.7 1.7 1.7
Water (kg/cm3) 496 496 496 496 5
 -C2S
Materials Properties 200
C3 S

• Portland Cement Classe G; 150

C3 A
C4AF
Ca(SO4)2

Intensidade
• Density 3.25 g/cm3; CaSO4
100

Composição química do cimento classe G

50
Óxidos CaO SiO 2 Fe 2 O 3 SO 3 Al 2 O 3 K 2 O SrO TiO 2 MnO ZnO CuO
Teor (%) 70,2 16,0 5,6 3,9 3,2 0,5 0,3 0,2 0,1 0,1 0,0
0
10 20 30 40 50 60 70
Ângulo 2

80 100 0,5
100
D50= 15,63m TG
60 98 0,4
D80= 31,58 m
Fração acumulada (%)

75 mres.= 98,3%
80

Deriv. Massa (%/min)

40
Massa (%) 96 0,3
50 60

20
94 0,2
40
25
0
92 0,1
0 1000 2000 3000
DTG
20

0 0,0
90
0,1 1 10 100 100 200
0 300 400 500 600 700 800 900 1000
0 1000 2000 3000 6
Diâmetro (m) Temperatura (°C)
 50
Materials Properties Quartzo

• Silica fume; 40 Carbeto de sílicio

• Especific density 2,37 g/cm3. 30

Intensidade
20
Composição química da sílica ativa
Óxidos SiO 2 Al 2 O 3 SO 3 P 2 O 5 K 2 O CaO 10
Teor (%) 94,5 1,2 1,8 0,9 0,8 0,6

0
10 12 14 16 18 20 22 24 26 28 30 32 34 36 38
Ângulo 2
100 0,5
99 TG
mres.= 96,9%
98 0,4

Deriv. Massa (%/min)

97
D50 = 6,6 m
96 0,3

Massa (%) 95
94 0,2
93
92 0,1
DTG
91
90 0,0
100 200 300 400 500 600 700 800 900 1000
Temperatura (°C)
(BALTHAR, 2010) 7
Materials Properties

Tird generation superplasticizer Defoam

• Carboxilic ether based; • Specific density 1,00g/cm3.
• Total solids content 29,8%;
• Specific density 1,07g/cm3.

8
 100
Materials Properties
• SBR Polymer Powder; 75
D50= 141,3 m
D80= 324,4 m

Massa passante (%)

• Specific density 1,78 g/cm3.
Polímero SBR em Pó 50
Razão estireno/butadieno 83 %
Aparência Pó branco levemente amarelado
Teor de umidade 1% 25
Tg 48 °C
Impurezas 6%
0
1 10 100 1000 10000
Tamanho de partículas (m)

100 2,0
TG

80
1,5

Deriv. Massa (%/min)

60

Massa (%)
1,0

40

0,5
20

DTG
0,0
0
100 200 300 400 500 600
Temperatura (°C)
9
PROCEDURES

10
Mixing Path

Mixing energy = 5,9 kJ/kg

8 days curing in
74°C. Heating
hate 0.33°C/min

11
• Hydration kinectics determination using ultrasound pulse
equipament

• UCA equipament – Chandler

Engineering;
• Heating rate: 23 to 54 °C in 45 min –
54 to 74 °C in 195 min;
• Pressure 20,7 MPa ;
• Curing time - 216 hours.

12
Rocha (2011)
 • Hydration kinectics determination using ultrasound pulse equipament

Adapdado de Odler (1988)

Período pós-aceleração
3500
B
Pulso Ultrassônico (m/s)

Período de
3000 aceleração

2500
Período de indução
2000
A
1500
Pré-estágio
PR de aceleração
1000
0,01 0,1 1 10 100
log Tempo (h)

Identified periods according Odler (1988)

• 1 – K2SO4 dissolution; • 3 – Dormant period; • 5 – Aft formation;
• 2 – Early C3S and C3A • 4 – Intermediate reactions • 6 – Coversion of Aft in AFm.
hydrarion; period, C-S-H formation;
• Hydration kinectics determination using ultrasound pulse equipament
Período pós-aceleração
3500
B

Período de aceleração
3000
Pulso Ultrassônico (m/s)

2500

Período de indução
2000 Ponto (h) Inclinação
Pré-estágio Pastas
PR de aceleração A B P61
Reta Reta 2
1500 A PR 1,19 5,83 3600,00 2227,00
P6 1,13 5,17 3388,00 3298,00
3500 P10 1,23 5,23 3193,00 3481,00
P13 1,28 5,15 3130,00 3557,00
3000

2500

2000
P10 P13
1500
0,01 0,1 1 10 100 0,01 0,1 1 10 100

log Tempo (h)

 Hydration products analyses

• X ray diffraction;

• D8 Focos Bruker diffractometer;

• Cu radiation (Cukα, λ = 1,5418 Å);

• Operating 40 kV and 40 mA;

• Step width 0,02º/s;

• Scanning donne in 2θ range from 10 ° to

70 °.

15
 300 1 dia
Hydration products analyses
200

100
PR
• X ray diffraction;
300

200
Ferrita
100 Ca(OH)2
P6
Intensidade

Etringita
300 Tobermorita
300 9 diaAlita
200
200 Belita
100 Aluminato
P10
100
PR
300
300
200
200
Intensidade
100
P13
100
P6
0
PR 10 15 20 25 30 35 40 45 50 55 60 300
65 70
200
Ângulo 2
100
Ferrita P10
300
18
Ca(OH)2
P6 Etringita 200
16 100
Tobermorita P13
14 Alita 0
Belita 10 15 20 25 30 35 40 45 50 55 60 65 70
12
Aluminato Ângulo 2
 Hydration products analysis

• Thermal analysis.

• SDQ 600 equipament;

• Nitrogen flow - 100 ml/min;

• Heating rate - 10 °C/min;

• First 60 min an isothermal temperature (35°C)

employeed;

• Phases quantification related to inicial cement

mass basis (Dweck et al.,2009).

17
 115 1 dia de cura
H2O Tobermorita e
Ca(OH)2 total (%) H2O total combinada (%)
PR Pasta Etringita (%)
Massa (%)

110 P6 1 dia 9 dias 1 dia 9 dias 1 dia 9 dias

P10 PR 5,8 14,6 12,9 0,0 11,4 21,3
P13 P6 6,5 14,5 16,2 9,1 12,9 22,4
105 P10 6,4 16,3 16,5 13,5 12,8 24,5
P13 7,3 14,3 19,8 16,8 14,3 23,2
100
Deriv. Massa (%/min)

0,8

0,6

0,4
115
0,2 9 dia de cura
PR

Massa (%)
0,0 110
P6
P10
100 200 300 400 500 600 700 800 900
105 1000 P13
Temperatura (°C)
100
Hydration products analysis
Deriv. Massa (%/°min)

0,8

115
• 1Thermal analysis.
dia de cura 0,6

0,4
PR
110 0,2
P6
0,0
105 P10
P13 100 200 300 400 500 600 700 800 900 1000
100
Temperatura (°C)
 Hydration products analysis

• Scanning Electron Microscopy.

• Quanta 200 equipament;

• Secondary electrons and backscattered mode

images;

• High and low vacuum mode;

• Energy-dispersive X-ray fluorescence

spectrometer coupled - Bruker Nano GmbH .

19
 Scanning Electron Microscopy (SEM)

1 day curing High Vacuun

20
 Scanning Electron Microscopy (SEM)
9 days curing Low Vacuun

1
2

3
Point 3
Point 2 Element [wt.%]
Element [wt.%] Carbon 52,71
Poit 1 Carbon 1,97 Oxygen 39,30
Element [wt.%] Oxygen 48,81 Calcium 20,23
Carbon 80,81 Calcium 28,52 Iron 0,31
Oxygen 17,42 Iron 1,80 Silicon 11,77
Calcium 0,74 Silicon 15,12 Aluminium 2,43
Iron 0,47 Aluminium 1,21 Magnesium 1,90
Silicon 0,24 Magnesium 1,27 Potassium 0,34
Aluminium 0,33 Potassium 0,53 Sulfur 0,41

21
 THE EFFORTS AT FIUBA
The investigation on chemical interaction between SBR polymer and a cement paste,
submitted to high temperature wet cure (74°C).

Techniques employeed:

• Fourier Transform Infrared Spectroscopy (FTIR);

• Dynamic Mechanical Analysis (DMA);
• Thermogravimetric Analysis (TGA);
• Differential Scanning Calorimetry (DSC);

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OTHER RESEARCH
LINES

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 FIBERS REINFORCED COMPOSITES
Development of Fiber Reinforced Cement pastes for use in HTHP oil wells

• Wollastonite microfiber

24
 FIBERS REINFORCED COMPOSITES
Development of Fiber Reinforced Cement pastes for use in HTHP oil wells
• Flexible steel fibers;
• Hybrid composites using Wollastonite and flexible fibers.

25
THE NUMATS/LABEST
INFRAESTRUCTURE

26
Sub-Laboratory of Macro-Structures - Reaction Plate

27
Sub-Laboratory of
Mechanical
Properties

28
 Sub-Laboratory of
Creep and
Shrinkage
Compresive Creep

Creep – Direct Tensile Flexural Creep

29
Sub-Laboratory of Cementing Oil Wells

30
Sub-Laboratory of Cementing Oil Wells

31
 Sub-Laboratory of Analytical Techniques

• DRX Brooker D8 Focus with furnace system for tests at

temperatures up to 1500oC
 Sub-Laboratory of Analytical Techniques

• Shimadzu EDX-D20 X-ray spectrophotometer for chemical

analysis of liquids and solids
 Sub-Laboratory of Analytical Techniques

• Sedigraph III Micrometrics • BET Micrometrics ASAP 2020

particles up to 0,1 µm surface area analyzer
 Sub-Laboratory of Analytical Techniques

• Laser Malvern MAetersizer 2000

particle size analyzer – particles up • Gas Pycnometer
to 0,1 µm
 Sub-Laboratory of Analytical Techniques

• Dynamic Ultra-Micro Hardness • Shimadzu MCT Micro

Tester Shimadzu DUH 511 Compression Tester
 Sub-Laboratory of Analytical Techniques

• Thermal Analysis

TA SDT Q600 TA DTA-TGA e DS DSC Q20P at pressures up to 2MPa

Other sub-laboratories:
• Sub-laboratory of durability;
• Sub-laboratory of rheology;
• Sub-Laboratory of Thermal Properties;
• Sub-Laboratory of High Temperatures;
• Sub-Laboratory Numerical Modeling;

38
Gracias!!

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