WO2004101951A1 - Self adaptive cement systems - Google Patents
Self adaptive cement systems Download PDFInfo
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- WO2004101951A1 WO2004101951A1 PCT/EP2004/005478 EP2004005478W WO2004101951A1 WO 2004101951 A1 WO2004101951 A1 WO 2004101951A1 EP 2004005478 W EP2004005478 W EP 2004005478W WO 2004101951 A1 WO2004101951 A1 WO 2004101951A1
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- cement
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Classifications
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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
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/06—Inhibiting the setting, e.g. mortars of the deferred action type containing water in breakable containers ; Inhibiting the action of active ingredients
- C04B40/0675—Mortars activated by rain, percolating or sucked-up water; Self-healing mortars or concrete
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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
- C09K8/467—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 containing additives for specific purposes
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0049—Water-swellable 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0051—Water-absorbing polymers, hydrophilic polymers
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0062—Cross-linked polymers
-
- 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
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00146—Sprayable or pumpable mixtures
-
- 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
- C04B2111/00034—Physico-chemical characteristics of the mixtures
- C04B2111/00146—Sprayable or pumpable mixtures
- C04B2111/00155—Sprayable, i.e. concrete-like, materials able to be shaped by spraying instead of by casting, e.g. gunite
Definitions
- the present invention relates to adaptive cement systems.
- the invention relates to cement systems which are "self-healing", i.e. system which can adapt to compensate for changes or faults in the physical structure of the cement, or which adapt their structure after the setting phase of the cement in the cementing of oil, gas, water or geothermal wells, or the like.
- the invention concerns thus a well cementing composition
- a well cementing composition comprising a pumpable slurry of cement, water and a material that reacts and/or expands (swells) in contact with liquid or gaseous hydrocarbon.
- This behavior has the effect of making the cement self-healing in the event of physical failure or damage.
- Numerous materials can be added as additive to the cement matrix and available to react/expand upon contact with hydrocarbons. Examples of such materials include rubber, in particular styrene butadiene rubber and ground rubber, poly 2 2 1 bicyclo heptene (polynorbomene), alkylstyrene, crosslinked substituted vinyl acrylate copolymers and diatomaceous earth.
- the material can be of almost any shape and size: spherical, fiber-like, ovoid, mesh systems, ribbons, etc., which allows their easy incorporation in cement slurries of comprising solid materials in discrete particle size bands. From a mixing and pumping point of view, it is usually better to use granular particles having a dimension less than 850 ⁇ m.
- the cement composition of the present invention will expand upon contact with a liquid or gaseous hydrocarbon.
- this provides a method of cementing a well with a self- healing cement, in particular with a cement that will fill the micro-cracks or fractures in the cement matrix when underground hydrocarbon enters the fault in the cement matrix and thus prevents the onset of the permeability.
- the properties of expansion of the set cement in contact with oil or more generally with hydrocarbon can also repair the micro-annuli at the interface between the cement and the casing or formation, a property that is particularly interesting to prevent gas migration.
- the cement composition further comprises an additive having residual water-absorption properties after the setting of the cement, thereby susceptible to swell in contact with underground water.
- an additive having residual water-absorption properties after the setting of the cement, thereby susceptible to swell in contact with underground water.
- This type of additive are more specifically described in the International Patent Application also entitled “self-adaptive cement", claiming the same priority as the present invention and naming Sylvaine Leroy- Delage, Muriel Martin-Beurel, Keith Dismuke and Erik Nelson as inventors, and which is hereby incorporated by reference.
- Suitable additive includes in particular super-absorbent polymer preferably selected from the list consisting of polymethacrylate and polyacrylamide or a non-soluble acrylic polymers.
- the super-absorbent polymer is preferably added dry-blended with the cement, at concentrations ranging from 0.05% to 3.2% by weight of cement [0011]
- the hydrocarbon fluid is considered as a triggering event that will cause the final expansion of the cement during a cementing process.
- the composition of the present invention may be pumped in a given zone, allowed to set and the hydrocarbon fluid is pumped in the immediate vicinity of the set cement to promote its expansion and the complete filling of the area to be cemented.
- this method is particularly suitable for hard to cement zones, in particular zones that are too narrow for conventional cement to properly penetrate such as micro-fractures or other repair jobs.
- alkylstyrene which is available in bead form from Imtech Imbibitive Technologies Corp. under the name: Imbiber Beads. These are cross-linked alkylstyrene polymers engineered to absorb a broad range of organic chemicals (hence hydrocarbons).
- the beads are solid, spherical beads of approx. 200 - 300 microns diameter. They are unaffected by water but when placed in contact with liquid organic materials will absorb up to 27 times the volume of organic liquid and expand up to three times the original diameter, depending on the liquid and other environmental variable such as temperature, pressure, etc. The organic liquid is held in the organic structure and is not released under pressure.
- polymer capable of absorbing hydrocarbons are polymers used for hydrocarbons spills are for instance poly 221 bicyclo heptene ⁇ olynorbornene, e.g. Norsorex®AP XI from ATOFINA) or INIPOL ®AB40 from CECA.
- Norsorex NS or Norsorex APX1 grades from Norsorex are available (Norsorex NS or Norsorex APX1 for instance).
- the behavior in oil may vary from simple gelling effect without expansion to gelling and expansion.
- Norsorex® is a white polymer powder, it is hydrophobic and oleophilic and has a low density (0.96 g/cm 3 ). It is insoluble and inert in water. It has been developped by ATOFINA to absorb high quantities of various hydrocarbons including for instance naphtenic oil, kerosene aromatic oil.
- ground rubber is obtained by recycling tires. The recycling process is a series of shredding and special grinding operations to remove metal and fiber. These particles contain a certain amount of carbon black.
- Two sources have been tested: ground rubber from ATR (American Tyre Recycler) and ECORR RNM 45 from Rubber Ressources. Density of such products is between 1.1 -1.2 g/cm 3 . It has been patented that the use of ground rubber particles in cement formulations improved the cement mechanical properties by decreasing the value of the Young's modulus and by improving the behavior under shock. These ground rubber particles also have self healing effect and lead to expansion properties in contact with hydrocarbon.
- resins such as precrosslinked substituted vinyl acrylate copolymers in dry powder form.
- Pliolite family developed by Eliokem. These resins are available in different range with different behavior in terms of swelling effect in organic fluids. They produce soft colloidal microgels in organic fluids. They should be slowly added to the fluid under shear to ensure complete gel development. They are already used in oilfield in organic based drilling fluids as primary fluid loss control additives with secondary rheological contribution. They are suitable for HTHP wells since they are heat stable up to 500°F. They are insoluble in water and are able to swell in various aromatics and aliphatic fluids.
- Materials such as diatomaceous earth or perlite can also be used in an absorbent, swelling role. Diatomite it is a soft bulky solid material (88% silica) composed of skeletons of small prehistoric aquatic plants related to algae. They are available in powder, its specific gravity is between 1.9 and 2.35. This powder is able to absorb 1.5 to 4 times its weight of water and also has high oil absorption capacity it is used as absorbent in industry. The particle size is an important factor because this material is able to swell in water and also in oil.
- the absorbent materials are typically dry blended with the cement and any other solid components before transport to the well-site, mixing with water and placement in the well.
- the sizes and quantities will be selected to allow even dispersion through the cement matrix.
- a range of materials and/or particle sizes can be used to permit extended behavior over a period of time. However for some material it could be necessary to prehydrate the material in mix water before adding the cement.
- Figures 1 to 8 are plots of the development of the linear expansion (in %) with time (in days) for different systems according to the present inveniton Testing procedure
- Tests have been carrying out by incorporating powders of various types of polymers as solid additives in cement slurries.
- the cement slurries are then placed in annular expansion cell to study the expansion behavior when the cement set and also the behavior after setting when it is in contact with hydrocarbon.
- the comparison between tests is made by changing the polymer nature.
- Several polymer concentrations have been tested, ranging from 10% to 50% BVOB (by volume of blend). All designs are based on fresh water and black Dyckerhoff North cement. Most slurries include fine crystalline silica (noted fine silica).
- the slurries were optimized with the mere objective of obtaining stability. Focus was to get acceptable plastic viscosity (PV) and yield stress (TY) at mixing time and after 20 minutes of conditioning. Free water and sedimentation tests were also carried out. Mixing and test procedure was according to API Spec 10.
- the linear expansion of the cement slurries is measured with a device consisting of a bottom plate, a split expandable ring with two attached pins and a top plate.
- the expandable ring is placed between the two plates, and a screw fixes the two plates together.
- the outside diameter of the expandable ring grows and the distance between the attached pins increases.
- the linear expansion of the slurry is calculated from the difference of the readings by multiplying this value times a constant corresponding to the circumference of the mold.
- the curing process includes two steps: first, the slurry is put in water bath during at least 7 days at the selected temperature to follow the linear expansion versus the time, this step can be prolonged if necessary to reach a flat level of expansion; then the set sample is then transferred in oil to record expansion versus time.
- This two-step curing procedure simulates setting of the cement matrix in the well followed by contact with oil due to loss of zonal isolation (either cracks or creation of a micro-annuli).
- Tests were performed with three different oils: an oil consisting from 60 to 100% of aliphatic hydrocarbons (not 01), with a flash point of 113°C; diesel (02) - tested only at room temperature due to a flash point below 60°C; and a dearomatized hydrocarbon fluid having a flash point of 103 °C (03). Samples were cured in molds at 60 °C in a water bath under atmospheric pressure for one week. Cylinders (1-inch diameter, 2-inch long) were then cored and the cores placed in oil.
- Example 1 ground rubber
- GR1 particles are commercialized by American Tyre Recycler under the name "Rubber 40 mesh” have a density of 1.2 g/cm 3 and an average particle size of 425 ⁇ .
- GR2 are commercialized by Rubber Ressources, under the product name ECORR RNM 45. The density is 1.2 g/cm 3 , the average particle size 355 ⁇ .
- Both are ground rubber obtained by a recycling process involving a series of shredding and special grinding operations to remove metal and fiber. These particles are black and contain a certain amount of carbon black. Recycled rubber has the advantage of being flexible and cheap.
- Figure 1 is a plot of the linear expansion along time (in days) for slurry A2, when exposed to the dearomatized oil. Note that virtually no expansion was observed on reference cores put in water. The open circles correspond to the tests performed at room temperature while the full squares are for the test at 60 °C. Expansion is observed with oil and the expansion level increases with temperature (0.26% at room temperature and up to 0.9% at 60 °C. It should be observed that for clarity purpose, the value of only one test have been reported in this figure 1 - and in all other similar figures - while the result data given in table 2 - or in corresponding similar tables - are average based on several tests and consequently, do not necessarily match in values.
- figure 2 shows the linear expansion vs. time for slurry Al (full squares) and A2 (full triangles) upon exposition to the aliphatic hydrocarbon oil 01, at 60 °C.
- the expansion reaches 0.7% at 20 % BVOB instead of 0.1% at 10 % BVOB.
- Imbiber beads® are cross-linked alkylstyrene polymers engineered to absorb a broad range of organic chemicals.
- the beads are solid, spherical particles that are approximatively 200-300 microns in diameter. Typical application of such beads is too prevent spills from escaping into the environment. They are unaffected by water, and once contact has been made with a adequate liquid organic the beads will absorb up to 27 volumes of the organic liquid and swell up to 3 diameters depending on the liquid and on other variables such as temperature. The liquid is held in the molecular structure, the imbiber bead will not release the liquid due to compression. Its density is 1.12 g/cm3.
- Beads Bl are made exclusively of alkylstyrene.
- Beads B2 are a mixture at a 50:50 weight ratio of alkylstyrene beads and sand.
- the compositions of the tested slurries are shown in table 6. Note that for slurries A17 and A29, the concentration of beads is given by weight of cement and not by weight of blend as for slurries A30 and A31.
- Fluorinated resins like poly 221 bicyclo heptene (polynorbomene) are used for hydrocarbon spills are commercial products include for instance Norsorex® AP XI available from ATOFINA, Paris, France and INIPOL AB 40 available from CECA, Paris, France. Depending on the specific grade, the behavior in oil varies form simple gelling to gelling with expansion.
- Norsorex AP XI is a white polymer powder, made from particles ranging from about 0.5mm to about 1mm, having a density of 0.96g cm 3 .
- Table 8 recaps some slurries designs and rheological properties. Expansion tests results are displayed table 9.
- Test compositions are provided Table 10. Note that the resins are prehydrated in water during 5 minutes at 4000 rpm. Rheological properties could not be measured due to unstable readings. Expansion levels are reported table 11
- composition of slurry A28 is shown table 12, expansion levels table 13.
- the tested formulation A28 shows expansion in contact with oil 03 at room temperature, contrary to other tested products, the expansion level is decreased by temperature since it is below 0.1% at 60 °C and reached between 0.6 % and 1.6 % with large dispersion in measurement at room temperature
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- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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Abstract
Description
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2524977A CA2524977C (en) | 2003-05-14 | 2004-05-14 | Self adaptive cement systems |
EP04732993.3A EP1625279B1 (en) | 2003-05-14 | 2004-05-14 | Self adaptive cement systems |
US10/556,990 US20070137528A1 (en) | 2003-05-14 | 2004-05-14 | Self adaptive cement systems |
NO20055405A NO20055405L (en) | 2003-05-14 | 2005-11-15 | Self-adjusting cement systems |
US12/907,958 US8551244B2 (en) | 2003-05-14 | 2010-10-19 | Self adaptive cement systems |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US47034103P | 2003-05-14 | 2003-05-14 | |
US60/470,341 | 2003-05-14 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/556,990 A-371-Of-International US20070137528A1 (en) | 2003-05-14 | 2004-05-14 | Self adaptive cement systems |
US12/907,958 Continuation US8551244B2 (en) | 2003-05-14 | 2010-10-19 | Self adaptive cement systems |
Publications (1)
Publication Number | Publication Date |
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WO2004101951A1 true WO2004101951A1 (en) | 2004-11-25 |
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Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2004/005124 WO2004101463A2 (en) | 2003-05-14 | 2004-05-12 | Compositions and methods for treating lost circulation |
PCT/EP2004/005479 WO2004101952A1 (en) | 2003-05-14 | 2004-05-12 | Self adaptive cement systems |
PCT/EP2004/005478 WO2004101951A1 (en) | 2003-05-14 | 2004-05-14 | Self adaptive cement systems |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
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PCT/EP2004/005124 WO2004101463A2 (en) | 2003-05-14 | 2004-05-12 | Compositions and methods for treating lost circulation |
PCT/EP2004/005479 WO2004101952A1 (en) | 2003-05-14 | 2004-05-12 | Self adaptive cement systems |
Country Status (7)
Country | Link |
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US (2) | US20070204765A1 (en) |
EP (4) | EP1625280A2 (en) |
AT (1) | ATE401490T1 (en) |
CA (3) | CA2524966C (en) |
DE (1) | DE602004015098D1 (en) |
NO (3) | NO20055348L (en) |
WO (3) | WO2004101463A2 (en) |
Cited By (56)
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US6983799B2 (en) | 2003-02-27 | 2006-01-10 | Halliburton Energy Services, Inc. | Method of using a swelling agent to prevent a cement slurry from being lost to a subterranean formation |
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US7617870B1 (en) | 2008-05-14 | 2009-11-17 | Halliburton Energy Services, Inc. | Extended cement compositions comprising oil-swellable particles and associated methods |
US7690429B2 (en) | 2004-10-21 | 2010-04-06 | Halliburton Energy Services, Inc. | Methods of using a swelling agent in a wellbore |
US7717180B2 (en) | 2006-06-29 | 2010-05-18 | Halliburton Energy Services, Inc. | Swellable elastomers and associated methods |
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CA2524977A1 (en) | 2004-11-25 |
EP1623089B1 (en) | 2008-07-16 |
US20070204765A1 (en) | 2007-09-06 |
NO20055348L (en) | 2005-12-13 |
NO20055405D0 (en) | 2005-11-15 |
NO20055348D0 (en) | 2005-11-11 |
EP2199539A1 (en) | 2010-06-23 |
EP1625280A2 (en) | 2006-02-15 |
EP1625279A1 (en) | 2006-02-15 |
CA2524514A1 (en) | 2004-11-25 |
ATE401490T1 (en) | 2008-08-15 |
US8551244B2 (en) | 2013-10-08 |
WO2004101463A2 (en) | 2004-11-25 |
US20110120715A1 (en) | 2011-05-26 |
CA2524966C (en) | 2012-09-11 |
CA2524514C (en) | 2012-03-20 |
EP1623089A1 (en) | 2006-02-08 |
WO2004101952A1 (en) | 2004-11-25 |
WO2004101463A3 (en) | 2005-01-06 |
DE602004015098D1 (en) | 2008-08-28 |
EP1625279B1 (en) | 2016-06-22 |
CA2524966A1 (en) | 2004-11-25 |
WO2004101463B1 (en) | 2005-02-17 |
CA2524977C (en) | 2012-03-20 |
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NO20055405L (en) | 2005-12-13 |
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