GB2385325A - Cement comprising particulate phenol formaldehyde resin - Google Patents
Cement comprising particulate phenol formaldehyde resin Download PDFInfo
- Publication number
- GB2385325A GB2385325A GB0203505A GB0203505A GB2385325A GB 2385325 A GB2385325 A GB 2385325A GB 0203505 A GB0203505 A GB 0203505A GB 0203505 A GB0203505 A GB 0203505A GB 2385325 A GB2385325 A GB 2385325A
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- Prior art keywords
- cement
- phenol
- composition
- particulate
- linked
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/30—Condensation polymers of aldehydes or ketones
- C04B24/302—Phenol-formaldehyde condensation polymers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00663—Uses not provided for elsewhere in C04B2111/00 as filling material for cavities or the like
- C04B2111/00706—Uses not provided for elsewhere in C04B2111/00 as filling material for cavities or the like around pipelines or the like
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
A cement composition comprises cement; water; and a particulate, phenol-formaldehyde material. The particulate, phenol-formaldehyde material can be a partially or essentially fully cross-linked resin. Preferably, the particles have a highly cross-linked shell and a partially cross-linked interior. The particles may be spherical, plate-like, ribbon-like or fibrous and their size may vary from less than 10 microns up to 300 microns. The solid components of the cement composition are combined to optimise the packing volume fraction. The use of a solid particulate material means that it can contribute to the physical properties of the cement as well as to the chemical behaviour. Highly cross linked resins are preferred where chemical and physical stability are required. Material having a molecular weight of greater than 10,000 is often preferred. The cement composition can be used to cement oil, gas or geothermal wells where high temperatures, pressures and physical stresses are encountered and the cement is exposed to high salinity brines and hydrocarbon formation fluids.
Description
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RESIN CEMENTS The present invention relates to the use of phenol-formaldehyde resins in cements for use in oil wells or the like.
The use of resins, including phenol-formaldehyde resins, in cements has been previously proposed, particularly in an attempt to improve the physical performance of the set cement.
Phenol-formaldehyde resin chemistry is known to be highly resistant to chemical attack and stable at elevated temperatures. A well-known example of a phenolformaldehyde resin is Bakelite. Other examples illustrating the properties of such resins can be found in US 5,5782, 300 and SPE 39960. The chemistry of phenolformaldehyde resins includes that of resole resins, novolac resins, phenolic resins and similar resins. Such chemistry also includes phenol-formaldehyde-like resins such as acetylated novoloid fibres.
Certain applications of phenol-formaldehyde resins have been proposed in the field of cements. Examples include US 6,065, 539 and US 5,569, 324 in which liquid phenolformaldehyde resins, prior to significant cross-linking, are included in cement slurries.
Liquid, partially cross-linked resins have also been included in high solids concentration cements to give physical and chemical benefits to the resulting cement, as is described in Advanced Cement Based Materials, Volume 6, #2, August 1997 pp 45-52. However, such cements are not pumpable in the manner of oilfield cement slurries.
The use of solid resin materials in oilfield cement slurries is known, in particular for providing toughness to the resulting cement. Flexible materials, such as polyproylene and rubber have been included in oilfield cement slurries for use in cementing zones of wells subjected to extreme physical stresses such as perforation zones and junctions of multilateral wells. Examples of such uses are found in WO 00/37387 and WO 00/20350.
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Novoloid fibres (20mm x 20 um) have been included in oilfield cement slurries pumped to address lost circulation problems.
It is an object of the present invention to provide a cement slurry that is suitable for use in oilfield applications and which benefits from the properties of solid phenolformaldehyde materials.
In accordance with the present invention, there is provided a cement composition comprising : - cement ; - water ; and - a particulate, phenol-formaldehyde material.
Other additives commonly used in cements can be included in the composition according to requirements.
The particulate, phenol-formaldehyde material can be a partially or essentially fully cross-linked resin. The use of a solid particulate material means that it can contribute to the physical properties of the cement as well as to the chemical behaviour. Highly cross linked resins are preferred where chemical and physical stability are required.
Material having a molecular weight of greater than 10,000 is often preferred.
Examples of fully cross-linked phenol-formaldehyde resins are BellPearl R800 from Kanebo Ltd. , Maririn HF from GunEi Chemical, and Novoloid fibres from Nippon Kynol. An example of a partially cross-linked phenol-formaldehyde resin particulate material is BellPearl S899 from Kanebo Ltd.
Particulate material having an highly cross-linked shell and an partially cross-linked interior can be used to provide delayed release of the reactive interior component into the cement composition, where it may react with other cement components.
The size and shape of the particulate material can be chosen according to requirements. In particular, when the cement composition is one having an engineered particle size distribution, the resin can comprise part or all of one or more of the
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particle size fractions. For example, resin particles can be obtained in sizes corresponding to a coarse particle size range ( 300 micron), medium particle size range ( : : : 30 micron) or fine particle size range ( < 10 micron). The solid components of the cement composition forming these fractions can be combined to optimise the packing volume fraction (PVF = portion of the volume occupied by particulate material that is occupied by solid material). This approach is describe in more detail in EP 0 621247 B, which describes a cement composition formed from particles having controlled particle size ranges or granulometries. By optimising the packing volume fraction of the particulate materials, cement slurries can be designed that have improved properties while remaining pumpable in normal field conditions.
Also, the particle size can be chosen to meet other requirements. For example, for squeeze cementing operations, the particulate components of the cement slurry should be as small as possible. In this case a particle size of less than 10 microns is preferred.
The particulate phenol-formaldehyde material preferably has a spherical particle shape (size in all dimensions is approximately the same). However, plate-like particles (size in and 2"d dimension size in 3rd dimension), ribbon structures (size in 1 sl dimension > size in second dimension > size in 3rd dimension), or fibre structures (size in I s'dimension size in 2nd and 3rd dimensions) are also possible.
Compositions of the present invention are particularly useful for cementing oil wells or the like when aggressive conditions are encountered, such as high temperatures or pressures, high salinity brines and hydrocarbon formation fluids, tectonic stresses, perforations or other physical stresses and the like. Such cement compositions also find uses in cementing pipes in geothermal wells which have to convey very high temperature water.
The present invention will now be described by way of examples and with reference to the following drawings, in which: Figure 1 shows the effect of ageing in diesel oil on phenol-formaldehyde resin fibres; Figure 2 shows the effect of ageing in steam on phenol-formaldehyde resin fibres ; Figure 3 shows the effect of heating on phenol-formaldehyde particles ; and
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Figures 4a and 4b show an experimental set-up for testing compositions according to the invention.
Example I In this example, the stability of phenol-formaldehyde resins in hydrocarbons at high temperature is demonstrated.
Phenol-formaldehyde fibres (Novoloid fibres from Nippon Kynol,-15 microns diameter, length-30 cm) are placed in diesel oil in a pressure vessel and heated to 450 F (232 C) and maintained at this temperature for three months. Periodically, the vessel is cooled and several fibres removed and their mechanical properties tested.
Figure 1 plots the development of Modulus, Strain and Fibre Diameter against time for this test. Each result is an average of 10 measurements on ten separate fibres. The results show that the fibres are essentially unaffected by exposure to the diesel oil, indicative of the stability of such materials in downhole environments.
Example 2 In this example, the stability of phenol-formaldehyde resins in water at high temperature is demonstrated.
Phenol-formaldehyde fibres (Novoloid fibres from Nippon Kynol,-15 microns diameter, length-30 cm) are placed in water in a pressure vessel and heated to 350 F (177 C) and maintained at this temperature for three months. Periodically, the vessel is cooled and the fibre removed and their mechanical properties tested. Figure 2 plots the development of Modulus, Strain and Fibre Diameter against time for this test. The results show that the fibres are essentially unaffected by exposure to the water, indicative of the stability of such materials in downhole environments.
Example 3 In this example, the stability of phenol-formaldehyde resins at high temperature is demonstrated.
Samples of highly cross-linked phenol-formaldehyde resins (BellPearl R800 and Maririn HF) having particle sizes of 8 microns and 300-850 microns respectively
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and a ground rubber product commonly used in oilfield cements (ground rubber particles having a particle size in the range of 250-425 microns) are subjected to thermogravimetric analysis with a heating rate of2. 5 C/min in a nitrogen atmosphere, rapid loss of weight indicating thermal degradation of the material. The results of the analysis are shown in Figure 3. The resin particles are much more stable than the rubber. Rapid weight loss for the resin occurs above 4000C compared to the 2500C for the rubber. Weight loss of the resin particles below 400 C is due to the increase in cross-linking level liberating water and sublimating trace amounts of salt remaining from the fabrication process. The larger particles are more susceptible to this as they are initially less cross-linked compared to the smaller particles.
Example 4 In this example, the ability of phenol-formaldehyde resins to provide flexibility to cement slurries is demonstrated.
The addition of flexible materials to oilfield cement slurries is well known, see for example WO 00/37387, WO/20350 and SPE 38598. While the materials proposed, ground rubber or polypropylene are effective in many cases, sustained high temperatures can cause problems. For example, polypropylene particles melt at 1660C and rubber degrades at 250 C (see above) and is attacked by solvents and hydrocarbons at lower temperatures.
Trimodal slurries A and B are prepared as summarised in Table 1 below. The slurries are identical in terms of volumes of solid constituents but Slurry A includes polypropylene particles (-200-800 microns diameter) and Slurry B includes phenolformaldehyde resin particles (Maririn HF 300-850 microns diameter).
TABLE 1 Slurry A Slurry B (Polypropylene) (Phenol-Formaldehyde) Cement (Class G) 333.68g/600ml 333.68g/600ml Micro-Silica 118.06g/600ml 118.06g/600ml Polypropylene particles 163.35g/600ml Phenol-Formaldehyde - 230.51g/600ml Antifoam 1.53g/600ml 1.70g/600ml Fluid Loss Additive 19.39g/600ml 21.47g/600ml Dispersant 2.23g/600ml 2.47g/600ml
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Porosity 45% Density12. 33 Ib/gal13. 25 lb/gal In both cases, equal volumes of flexible particles are added, density differences leading to the difference in mass and slurry density. The concentrations of antifoam, dispersant and fluid loss additive are added at a constant ratio per mass of solids.
Samples of each slurry are cured at 300 F and 3000psi for 3 days which is sufficient time for the maximum compressive strength to be obtained. After curing, cubes of set cement are crushed in a hydraulic press and the Young's modulus and maximum compressive strength measured. The results are shown in Table 2 below:
TABLE 2 Slurry A Slurry B Young's modulus 2059 + 647 MPa 1173 + 850 MPa Compressive Strength 22.3 + 0.8 MPa 16. 3 + 3. 2 MPa Compressive 0.011 0.014 Strength/Modulus The data show that compositions according to the invention can provide flexibility and strength at temperature.
Example 5 In this example, the ability of compositions including phenol-formaldehyde resin particles to pass through small gaps is demonstrated.
Fine ( < 20 micron) phenol-formaldehyde particles can be added to an optimised microcement composition without impacting the ability of the slurry to pass though small gaps (-120 microns width). In this example, a higly cross-linked phenol- formaldehyde resin (BellPearl R800 from Kanebo Ltd. , nominal particle size 8 microns) is included in a cement slurry. The particles are approximately spherical and so allow relatively easy mixing in slurries. Three sample slurries are prepared and summarised in Table 3 below. Slurry A is a basic microcement formulation, while Slurries B and C have a portion of the microcement replaced by quantities of resin particles. The dispersant and retarder are kept at a constant ratio with the cement whilst the fluid loss additive and antifoam agent are kept at a constant ratio with the total liquid volume of the slurry.
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TABLE 3 Slurry A Slurry B Slurry C Microcement 601.8g/600ml 361.08g/600ml 424.8g/600ml BellPearl R800103. 63g/600ml 121. 92g/600ml Retarder 1. 02g/600ml 0. 61g/600ml 0. 72g/600ml Dispersant45. 27g/600mt 27. 17g/600ml 31. 97g/600ml Fluid Loss Additive 141. 07g/600ml 141. 07g/600ml 128. 25g/600ml Antifoam 18. 28g/600ml 18. 28g/600ml 16. 61 g/600ml Water202. 73g/600m ! 217. 75g/600ml 191. 88g/600ml Porosity 66% 66% 60% Density 14. 0 ppg 12. 09 ppg 12. 74 ppg The properties of the slurries are tested in the setup shown in Figure 4. This comprises a permeable base block including a filter paper 10 and a Perspex plate 12 mounted above the base block 10 on spacers 14 mounted along parallel sides to leave a channel 16 of 120 micron thickness, 30mm width and 24.5 cm length therebetween. One end of the Perspex plate 12 is provided with an injection port 18 and the channel is closed at that end such that fluids injected into the channel have to pass along its length in order to flow out of the test setup.
Each cement slurry is injected into the system from a syringe at a fixed flow rate and a maximum injection pressure. Fluid loss occurs through the base block and filter paper 10. If the slurry contains particles that are too large, or if the fluid loss is not properly controlled, solids will build up in the channel and the maximum injection pressure will be reached and the test stopped. Non-optimised class G slurries cannot flow through this setup. All three slurries A-C pass this test demonstrating that the phenol-formaldehyde particles do not interfere with the capability of the slurry to penetrate small spaces.
Example 6 This example demonstrates the resistance to aging of compositions according to the invention.
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The slurries are prepared. Slurry A is a basic Class G cement slurry with cement and an antifoam agent. Slurry B is a conventional, flexible slurry containing rubber particles, a dispersing agent (polynaphthalene sulphonate), a retarder (lignosulphonate), and an antifoam agent (silicone). Slurry C is a phenolformaldehyde resin-containing composition according to the invention. As well as the cement and resin particles (highly cross-linked resin beads 300-800 microns in diameter), Slurry C also contains a dispersing agent and a fluid loss additive and micro-silica to prevent strength retrogression. The compositions are summarised in Table 4 below ("bwoc"= by weight of cement ;"gps"= gallons per sack):
TABLE 4 Slurry A Slurry B Slurry C Micro-Silica 35. 5% bwoc Phenol---69. 3% bwoc Formaldehyde Resin Rubber 30. 6% bwocDispersant 0. 037 gps 0. 067 gps Retarder - 0. 025 gps Antifoam 0.03 gps - Fluid Loss Additive - - 0.0674 gps Porosity 58% 45% 45% Density 1. 89/cm 1. 69/crin 1. 59 g/cm
Slurries A and B are cured in 5 cm cubic moulds at 77 C and 3000 psi for several days to set. Samples of Slurry C are cured in similar moulds under different conditions:
(i) 77 C atmospheric 2 days (ii) 150 C 3000 psi 3 days (iii) 250 C 3000 psi 3 days (iv) 300 C 3000 psi 3 days Compressive strength and Young's modulus are measured as before and summarised in Table 5 below:
TABLE 5 Conditions Young's Modulus Compressive Strength Slurry A 6275 MPa 36.6 MPa Slurry B 1615 MPa 10.1 MPa Slurry C (i) 1663 MPa 9.0 MPa
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(ii) 684 MPa 16. 4 MPa (iii) 1376 MPa 19. 4 MPa (iv) 1714 MPa 5. 5 MPa Under similar curing conditions, the resin system gives similar properties to a conventional rubber-based, flexible system with a Young's modulus that is about 1/4 of that of a comparable neat cement system. At elevated temperatures, the resin system retains good properties with low Young's modulus and a compressive strength of > 5MPa. Thus the flexibility is retained even under conditions in which conventional systems are unstable.
Claims (12)
- CLAIMS 1 In accordance with the present invention, there is provided a cement composition comprising: - cement ; - water ; and - a particulate, phenol-formaldehyde material.
- 2 A composition as claimed in claim 1, wherein the particulate, phenol- formaldehyde material is a partially or essentially fully cross-linked resin.
- 3 A composition as claimed in claim 2, wherein the particulate, phenol- formaldehyde material is a highly cross-linked resins having a molecular weight of greater than 10,000.
- 4 A composition as claimed in claim 1 or 2 wherein the particulate, phenol- formaldehyde material has a highly cross-linked shell and an partially cross- linked interior.
- 5 A composition as claimed in any preceding claim, wherein the particulate, phenol-formaldehyde material is provided with a discrete particle sizedistribution comprising one or more of a coarse particle size range (Z 300 micron), medium particle size range C : : 30 micron) or fine particle size range ( < 10 micron)
- 6 A composition as claimed in any preceding claim, wherein the solid components are combined to optimise the packing volume fraction.
- 7 A composition as claimed in any preceding claim, wherein the particulate, phenol-formaldehyde material has a particle size of less than 10 microns.
- 8 A composition as claimed in any preceding claim, wherein the shape of the particulate phenol-formaldehyde is spherical particle, plate-like, ribbon-like, or fibrous.<Desc/Clms Page number 11>
- 9 A method of cementing oil, gas or geothermal wells, comprising pumping a cement composition as claimed in any preceding claim into the well.
- 10 A method as claimed in claim 9 wherein the composition is pumped into a portion of the well in which aggressive conditions are encountered.
- 11 A method as claimed in claim 10, comprising pumping the composition into a region of high temperatures or pressures, high salinity brines and hydrocarbon formation fluids, tectonic stresses, perforations or other physical stresses.
- 12 A method as claimed in claim 9,10 or 11, wherein the cement composition is pumped around the outside of a pipe or casing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0203505A GB2385325B (en) | 2002-02-14 | 2002-02-14 | Resin cements |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0203505A GB2385325B (en) | 2002-02-14 | 2002-02-14 | Resin cements |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB0203505D0 GB0203505D0 (en) | 2002-04-03 |
| GB2385325A true GB2385325A (en) | 2003-08-20 |
| GB2385325B GB2385325B (en) | 2004-08-11 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0203505A Expired - Fee Related GB2385325B (en) | 2002-02-14 | 2002-02-14 | Resin cements |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2385325B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2407317A (en) * | 2003-10-20 | 2005-04-27 | Schlumberger Holdings | A well cement composition with controlled physical properties |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55121939A (en) * | 1979-03-06 | 1980-09-19 | Showa Denko Kk | Manufacture of reinforced concrete product |
| US4297414A (en) * | 1978-07-07 | 1981-10-27 | Mitsui Petrochemical Industries, Ltd. | Reinforcing material for hydraulic substances and method for the production thereof |
| US4339273A (en) * | 1980-02-22 | 1982-07-13 | Ametex Ag | Process for producing a fiber-reinforced, hydraulically setting composition, the composition produced and the use thereof |
| US4460730A (en) * | 1982-05-14 | 1984-07-17 | Kanebo, Ltd. | Composition containing a powder of an inorganic material |
| JPH01203249A (en) * | 1988-02-08 | 1989-08-16 | Ohbayashi Corp | Lightweight soil cement |
| US5458195A (en) * | 1994-09-28 | 1995-10-17 | Halliburton Company | Cementitious compositions and methods |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU751965A1 (en) * | 1972-10-30 | 1980-07-30 | Куйбышевский политехнический институт им.В.В.Куйбышева | Method of preparing cementing compositions |
| SU838090A1 (en) * | 1978-08-25 | 1981-06-17 | Всесоюзный Научно-Исследовательскийинститут По Креплению Скважин И Буро-Вым Pactbopam | Plugging material |
-
2002
- 2002-02-14 GB GB0203505A patent/GB2385325B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4297414A (en) * | 1978-07-07 | 1981-10-27 | Mitsui Petrochemical Industries, Ltd. | Reinforcing material for hydraulic substances and method for the production thereof |
| JPS55121939A (en) * | 1979-03-06 | 1980-09-19 | Showa Denko Kk | Manufacture of reinforced concrete product |
| US4339273A (en) * | 1980-02-22 | 1982-07-13 | Ametex Ag | Process for producing a fiber-reinforced, hydraulically setting composition, the composition produced and the use thereof |
| US4460730A (en) * | 1982-05-14 | 1984-07-17 | Kanebo, Ltd. | Composition containing a powder of an inorganic material |
| JPH01203249A (en) * | 1988-02-08 | 1989-08-16 | Ohbayashi Corp | Lightweight soil cement |
| US5458195A (en) * | 1994-09-28 | 1995-10-17 | Halliburton Company | Cementitious compositions and methods |
Non-Patent Citations (2)
| Title |
|---|
| WPI Abstract Accession No.1980-78126C & JP 55121939 A * |
| WPI Abstract Accession No.1989-280794 & JP 01203249 A * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2407317A (en) * | 2003-10-20 | 2005-04-27 | Schlumberger Holdings | A well cement composition with controlled physical properties |
| WO2005040549A1 (en) * | 2003-10-20 | 2005-05-06 | Services Petroliers Schlumberger | Cementing composition with controlled mechanical properties |
| GB2407317B (en) * | 2003-10-20 | 2006-04-12 | Schlumberger Holdings | Cementing composition |
| US7470322B2 (en) | 2003-10-20 | 2008-12-30 | Schlumberger Technology Corporation | Cementing composition with controlled mechanical properties |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2385325B (en) | 2004-08-11 |
| GB0203505D0 (en) | 2002-04-03 |
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| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20110214 |