WO2015143390A2 - Équipement en céramique dérivée de polymère pour l'exploration et la récupération de ressources - Google Patents

Équipement en céramique dérivée de polymère pour l'exploration et la récupération de ressources Download PDF

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Publication number
WO2015143390A2
WO2015143390A2 PCT/US2015/021861 US2015021861W WO2015143390A2 WO 2015143390 A2 WO2015143390 A2 WO 2015143390A2 US 2015021861 W US2015021861 W US 2015021861W WO 2015143390 A2 WO2015143390 A2 WO 2015143390A2
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Prior art keywords
equipment
polysilocarb
formulation
ceramic material
precursor
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PCT/US2015/021861
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English (en)
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WO2015143390A3 (fr
Inventor
Bruce A. BRICCO
Brian L. Benac
Walter J. SHERWOOD
Mark S. Land
Douglas M. DUKES
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Melior Innovations, Inc.
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Priority claimed from US14/268,150 external-priority patent/US9815943B2/en
Priority claimed from US14/634,814 external-priority patent/US10167366B2/en
Application filed by Melior Innovations, Inc. filed Critical Melior Innovations, Inc.
Publication of WO2015143390A2 publication Critical patent/WO2015143390A2/fr
Publication of WO2015143390A3 publication Critical patent/WO2015143390A3/fr

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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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • C04B35/571—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
    • C04B35/589—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained from Si-containing polymer precursors or organosilicon monomers
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B17/00—Drilling rods or pipes; Flexible drill strings; Kellies; Drill collars; Sucker rods; Cables; Casings; Tubings
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B17/00—Drilling rods or pipes; Flexible drill strings; Kellies; Drill collars; Sucker rods; Cables; Casings; Tubings
    • E21B17/01—Risers
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B33/00—Sealing or packing boreholes or wells
    • E21B33/10—Sealing or packing boreholes or wells in the borehole
    • E21B33/12—Packers; Plugs
    • E21B33/1208—Packers; Plugs characterised by the construction of the sealing or packing means
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3826—Silicon carbides
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/5216—Inorganic
    • C04B2235/524—Non-oxidic, e.g. borides, carbides, silicides or nitrides
    • C04B2235/5248—Carbon, e.g. graphite
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/616—Liquid infiltration of green bodies or pre-forms
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/94—Products characterised by their shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • the present disclosure relates to polymeric derived ceramic downhole apparatus and methods for making such apparatus.
  • the present disclosure relates to drilling activities and structure that utilize polymeric derived siloxane based ceramics.
  • the present disclosure further relates to creating wells, e.g.,
  • hydrocarbon producing wells water wells and geothermal wells, to increase and enhance the production from these wells by employing siloxane based polymeric derived ceramic downloading drilling apparatus.
  • natural resources In the production of natural resources from formations within the earth a well or borehole is drilled into the earth to the location where the natural resource is believed to be located.
  • These natural resources may be a hydrocarbon reservoir, containing natural gas, crude oil and combinations of these; the natural resource may be fresh water; it may be a heat source for geothermal energy; or it may be some other natural resource that is located within the ground.
  • These resource-containing formations may be a few hundred feet, a few thousand feet, or tens of thousands of feet below the surface of the earth, including under the floor of a body of water, e.g., below the sea floor. In addition to being at various depths within the earth, these formations may cover areas of differing sizes, shapes and volumes.
  • the volume or rate of flow e.g., gals per minute
  • the distance within the formation out from the well where the natural resources will flow into the well can be increase (e.g., the volume and area of the formation that can be drained by a single well is increased and it will thus take less total wells to recover the resources from an entire field)
  • the time period when the well is producing resources can be lengthened; the flow rate can be
  • Fluid communication between the formation and the well can be increased by the use of hydraulic fracturing techniques.
  • Hydraulic fracturing involves forcing fluids down a well under pressure causing the formation rock to fracture.
  • the fluid containing propping agents is forced into the fractures creating channels or flow paths that may have cross sections of a few microns, to several millimeters, and potentially larger.
  • the fractures may also extend out from the well in all directions for a few feet, several feet and tens of feet or further.
  • the fluid is flowed back out of the well leaving the propping agent in place.
  • the longitudinal axis of the well in the reservoir may be vertical or it may be on various angles (either slopping up or down) or horizontal.
  • the wells are typically essentially horizontal in the reservoir.
  • the section of the well located within the reservoir, i.e., the section of the formation containing the natural resources, can be called the pay zone.
  • Typical fluid volumes in fracturing treatment of a formation can range from a few thousand to millions of gallons. Proppant volumes can approach several thousand cubic feet.
  • an objective of a proppant fracturing is to create and enhance fluid communication between the wellbore and the hydrocarbons in the formation or reservoir. Proppant fracturing techniques are therefore used to create and enhance conductive pathways for the hydrocarbons to get from the reservoir to the wellbore.
  • one way of enhancing the efficacy of proppant fracturing techniques is to have uniform proppant distribution. In this manner a uniformly conductive fracture along the wellbore height and fracture half-length can be provided.
  • each section of the casing string is cemented (can be open hole, or slotted liner with external casing packers, as well as other borehole configurations) within the wellbore before the next section of the wellbore is drilled.
  • the completion process may begin.
  • the completion process comprises a number of steps. Hydraulic openings or perforations are typically created through the casing string, cement and a short distance into the desired formation by detonating shaped charges carried in a perforating gun.
  • the perforations allow production fluids from the subterranean formation to enter the interior of the wellbore.
  • the formation pressure must be controlled. Typically, this is achieved by loading a completion fluid into the wellbore during the completion process.
  • the completion fluid has a density sufficient to create pressure at the location or locations of the wellbore perforations, thereby preventing formation fluids from entering the wellbore.
  • a stimulation control treatment process may be performed.
  • a work string including a service tool, a gravel pack packer, a ported housing and port closure sleeve, a sealbore housings, a check valve, a wash pipe extending through the screen, a lower seal assembly and a sump packer may be run downhole.
  • a treatment fluid which may contain sand, gravel or proppants, is then pumped down the work string and either into the wellbore annulus, into the formation or both depending upon the desired results of the treatment process.
  • Downhole tooling and equipment conventionally are made from relatively expensive materials, and alternatively are desirable.
  • the materials are incapable of making non- reinforced structures having any usable strength; the process produces undesirable and hazardous byproducts, such as hydrochloric acid and sludge, which may contain magnesium; the process requires multiple solvent and reagent based reaction steps coupled with curing and pyrolizing steps; the materials are incapable of forming a useful prepreg; and their overall physical properties are mixed, e.g., good temperature properties but highly brittle.
  • the present disclosure is directed towards polymer derived ceramic downhole equipment and equipment for use in the exploration and recovery of natural resources.
  • one or more of completion assemblies, composite plugs, liner hanger systems, multilaterals, packer systems, subsurface systems and sucker rods, or components thereof can be partially or wholly formed from specifically selected polymer derived ceramic material. Relevant specifications, such as those required under ANSI/ADP are met utilizing contemplated ceramic material.
  • a system for the production of natural resources from formation within the earth comprises downhole equipment, wherein components of the downhole drilling equipment are formed at least in part from polymer derived ceramic material.
  • a method involving production of natural resources from formation within the earth comprises providing downhole equipment, wherein
  • components of the downhole drilling equipment are formed at least in part from polymer derived ceramic material.
  • a system for the production of natural resources from formation within the earth having: downhole equipment, wherein components of the downhole drilling equipment are formed at least in part from polymer derived ceramic material.
  • the present systems, methods and equipment having one or more of the following features: wherein the system includes a drill head formed from polymer derived ceramic material; wherein the system includes a drill pipe formed from polymer derived ceramic material; wherein the system includes a surface casing formed from polymer derived ceramic material; wherein the system includes a tubular casing formed from polymer derived ceramic material; wherein the system includes a completion assembly formed from polymer derived ceramic material; wherein the system includes a liner hanger assembly formed from polymer derived ceramic material; wherein the system includes one or multilateral assemblies formed from polymer derived ceramic material; wherein the system includes one or more packer assemblies formed from polymer derived ceramic material; wherein the system includes a sucker rod assembly formed from polymer derived ceramic material; wherein the polymer derived ceramic material is a polysilocarb derived ceramic material; wherein the polysilocarb formulation is a reaction type formulation; wherein the polysilocarb formulation is a reaction type formulation,
  • a down hole equipment for use in obtaining a natural resource from below a surface of the earth, the equipment having a component having a cured polysilocarb material.
  • the present systems, methods and equipment having one or more of the following features: wherein the equipment is a drilling head; wherein the equipment is a blow out preventer; wherein the equipment is a marine riser assembly; wherein the equipment is a well head; wherein the equipment is a derrick; wherein the derrick is on a drill ship; wherein the equipment is a submersible pump; wherein the component having a cured polysilocarb formulation is a surface; and, wherein the surface is an inner surface.
  • a down hole equipment for use in obtaining a natural resource from below a surface of the earth, the equipment having a component having a ceramic composite polysilocarb material.
  • a down hole equipment for use in obtaining a natural resource from below a surface of the earth, the equipment having a component having a coating having a polysilocarb derived material.
  • a method for obtaining a natural resource from a formation within the earth having: providing a downhole equipment, wherein a component of the downhole equipment comprises a polymer derived ceramic material; advancing the downhole equipment in a bore hole below the surface of the earth.
  • a method of making a component for a downhole equipment having: providing a polysilocarb formulation and forming the polysilocarb formulation into a component part of the downhole equipment.
  • the present systems, methods and equipment having one or more of the following features: curing the component part; machining the component part; pyrolizing the cured component part; pyrolizing the component part; re- infiltrating the pyrolized component part.
  • FIG. 1 is a cross-sectional view, depicting an embodiment of drilling a first section of a bore hole in accordance with the present inventions.
  • FIG. 2 is a cross-sectional view, depicting an embodiment of further drilling of a bore hole beyond a fresh water aquifer in accordance with the present inventions.
  • FIG. 3 is a cross-sectional view, depicting an embodiment of further drilling in accordance with the present inventions.
  • FIG. 4 is a cross-sectional view, depicting an embodiment of inserting a surface casing within a bore hole in accordance with the present inventions.
  • FIG. 5 is a cross-sectional view, depicting an embodiment of pumping cement within a bore hole in accordance with the present inventions.
  • FIG. 6 is an enlarged cross-sectional view, depicting insertion of casing within the bore hole
  • FIG. 7 is an enlarged cross-sectional view, depicting an embodiment further cementing and insertion of casing within the bore hole in accordance with the present inventions.
  • FIG. 8 is a cross-sectional view, depicting an embodiment of a kickoff point of a horizontal wellbore in accordance with the present inventions.
  • FIG. 9 is a cross-sectional view, depicting an embodiment to further drilling of a horizontal section of a wellbore
  • FIG. 10 is a cross-sectional view, depicting an embodiment of removal of drilling equipment from the horizontal section of the wellbore in accordance with the present inventions.
  • FIG. 1 1 is a cross-sectional view, depicting an embodiment of insertion of a casing within the horizontal section of a wellbore in accordance with the present inventions.
  • FIG. 12 is a cross-sectional view, depicting an embodiment of inserting cement along casing placed in a horizontal section of a wellbore in accordance with the present inventions.
  • FIG. 13 is a cross-sectional view, depicting an embodiment of further insertion of cement within horizontal section of a wellbore in accordance with the present inventions.
  • FIG. 14 is a cross-sectional view, depicting the final casing cemented within a horizontal section of a wellbore in accordance with the present inventions.
  • FIG. 15 is a cross-sectional view, depicting an embodiment of insertion of a perforating gun along the distal section of a horizontal wellbore in accordance with the present inventions.
  • FIG. 16 is a cross-sectional view, depicting an embodiment of the firing of the perforating gun shown in FIG. 15 in accordance with the present inventions.
  • FIG. 17 is a cross-sectional view, depicting an embodiment of holes formed within the horizontal section of a wellbore in accordance with the present inventions.
  • FIG. 18 is a cross-sectional view, depicting an embodiment of the formation of fractures within the earth along the horizontal rail bore in accordance with the present inventions.
  • FIG. 19 is a cross-sectional view, depicting an embodiment of the insertion of a plug along a horizontal section of a wellbore in accordance with the present
  • FIG. 20 is a cross-sectional view, depicting an embodiment of the insertion of another perforating gun proximal of the plug placed in a horizontal section of the wellbore in accordance with the present inventions.
  • FIG. 21 is a cross-sectional view, depicting an embodiment of fracturing caused proximal the placement of a plug within the horizontal section of a wellbore in accordance with the present inventions.
  • FIG. 22 is a cross-sectional view, depicting an embodiment of a plurality of plugs placed between fractures formed in a horizontal section of a wellbore in
  • FIG. 23 is an enlarged cross-sectional view, depicting an embodiment of drilled out plugs placed between fractures formed in a horizontal section of a wellbore in accordance with the present inventions.
  • FIG. 24 is a cross-sectional view, depicting an embodiment of the flow of material through the drilled out plugs placed in a horizontal section of a wellbore in accordance with the present inventions.
  • FIG. 25 is a cross-sectional view, depicting an embodiment of further flowing of material from the fracturing caused in the earth's adjacently horizontal wellbore in accordance with the present inventions.
  • FIG. 26 is a cross-sectional view, depicting an embodiment of a drill string including a drill head forming a wellbore in accordance with the present inventions.
  • FIG. 27 is a side and cross-sectional view, depicting an embodiment of a drill pipe in accordance with the present inventions.
  • FIG. 28 is a cross-sectional view, depicting an embodiment of a component of a hangar system in accordance with the present inventions.
  • FIG. 29 is a cross-sectional view, depicting an embodiment of components of a multi-lateral system in accordance with the present inventions.
  • FIG. 30 is a cross-sectional view, depicting an embodiment of packer assemblies placed within a wellbore in accordance with the present inventions.
  • FIG. 31 A is a side view, depicting an embodiment of a sucker rod structure in accordance with the present inventions.
  • FIG. 31 B is an enlarged side view of the embodiment of FIG. 31 A.
  • FIG. 32 is a cross-sectional view, depicting an embodiment of a structure of a perforating gun in accordance with the present inventions.
  • FIG. 33 is perspective partial cutaway view of an embodiment of a polymer derived riser assembly accordance with the present inventions.
  • FIG. 34 is a perspective partial cutaway view of a portion of an embodiment of a polymer derived riser assembly in accordance with the present inventions.
  • Embodiments of the present inventions relate to polymeric derived materials, and in particular, to polysilocarb derived materials for applications in downhole apparatus, equipment and components and methods for making and utilizing such apparatus.
  • embodiments of the present inventions relate to drilling activities and structure that utilize polymeric derived siloxane based ceramics and cured materials.
  • the present disclosure further relates to creating wells, e.g.,
  • hydrocarbon producing wells water wells, geothermal wells, and other natural resource providing wells, to increase and enhance the production from these wells by employing siloxane based polymeric derived ceramic down hole drilling apparatus, equipment and components.
  • Si silicon
  • a liquid material e.g., a plastic, a preceramic, and a pyrolized material, e.g., a ceramic.
  • the silicon based materials of the present inventions go against the general trends of the art of silicon chemistry and uses.
  • the art of silicon chemistry, and in particular organosilicon chemistry has moved toward greater and greater complexity in the functional groups that are appended to, and a part of, a silicon based polymeric backbone.
  • the processes that are utilized to make these polymers have moved toward greater and greater complexity.
  • the present inventions move away from this trend, by preferably functionalizing a silicon based polymeric backbone with simpler structures, such as phenyl, phenylethyl and smaller groups, and do so with processes that are simplified, e.g., solvent free, reduced solvent, lower cost starting materials, fewer steps, and reduction of reaction intermediates.
  • silicones as tacky, soft or liquid materials that are used with, on, or in conjunction with, other materials to enhance or provide a performance feature to those other materials.
  • Silicon based materials generally are not viewed as stand alone products, primary products, or structural elements.
  • the silicon based materials of the present inventions move away from this trend and understanding in the art.
  • the silicon based materials of the present inventions provide materials that, among other things, can function as stand alone products, primary products and structural elements.
  • the silicon based materials of the present invention can also function as composites, coatings, components, additives, material performance enhancers, and other applications and utilizations.
  • the present inventions provide a new material systems and platform having many varied formulations, applications and uses, which could not generally have been obtained with prior silicon based products, and in particular, could not generally have been obtained with prior silicon based products at acceptable costs, volumes, manufacturing conditions, handling requirements, or processing conditions among other things.
  • polysilocarb materials e.g., material containing silicon (Si), oxygen (O) and carbon (C), and materials that have been pyrolized from such materials.
  • Polysilocarb materials may also contain other elements.
  • Polysilocarb materials are made from one or more polysilocarb precursor formulation or precursor formulation.
  • the polysilocarb precursor formulation contains one or more functionalized silicon polymers, or monomers, as well as, potentially other ingredients, such as for example, inhibitors, catalysts, pore formers, fillers, reinforcers, fibers, particles, colorants, pigments, dies, polymer derived ceramics ("PDC”), ceramics, metals, metal complexes, and combinations and variations of these and other materials and additives.
  • functionalized silicon polymers or monomers
  • PDC polymer derived ceramics
  • the polysilocarb precursor formulation is then cured to form a solid or semi- sold material, e.g., a plastic.
  • the polysilocarb precursor formulation may be processed through an initial cure, to provide a partially cured material, which may also be referred to, for example, as a preform, green material, or green cure (not implying anything about the material's color).
  • the green material may then be further cured.
  • one or more curing steps may be used.
  • the material may be "end cured," i.e., being cured to that point at which the material has the necessary physical strength and other properties for its intended purpose.
  • the amount of curing may be to a final cure (or "hard cure"), i.e., that point at which all, or essentially all, of the chemical reaction has stopped (as measured, for example, by the absence of reactive groups in the material, or the leveling off of the decrease in reactive groups over time).
  • a final cure or "hard cure”
  • the material may be cured to varying degrees, depending upon it's intended use and purpose. For example, in some situations the end cure and the hard cure may be the same.
  • the curing may be done at standard ambient temperature and pressure ("SATP", 1 atmosphere, 25° C), at temperatures above or below that temperature, at pressures above or below that pressure, and over varying time periods (both continuous and cycled, e.g., heating followed by cooling and reheating), from less than a minute, to minutes, to hours, to days (or potentially longer), and in air, in liquid, or in a preselected atmosphere, e.g., Argon (Ar) or nitrogen (N 2 ).
  • SATP standard ambient temperature and pressure
  • time periods both continuous and cycled, e.g., heating followed by cooling and reheating
  • time periods both continuous and cycled, e.g., heating followed by cooling and reheating
  • Argon Argon
  • N 2 nitrogen
  • the polysilocarb precursor formulations can be made into non-reinforced, non-filled, composite, reinforced, and filled structures, intermediates and end products, and combinations and variations of these and other types of materials. Further, these structures, intermediates and end products can be cured (e.g., green cured, end cured, or hard cured), uncured, pyrolized to a ceramic, and combinations and variations of these (e.g., a cured material may be filled with pyrolized beads derived from the same polysilocarb as the cured material).
  • the precursor formulations may be used to form a "neat” materials, (by “neat” material it is meant that all, and essentially all of the structure is made from the precursor material or unfilled formulation; and thus, there are no fillers or
  • reinforcements may be used to form composite materials, e.g., reinforced products. They may be used to form non-reinforced materials, which are materials that are made of primarily, essentially, and preferably only from the precursor materials, for example a pigmented polysiloxane structure having only precursor material and a colorant would be considered non-reinforced material.
  • the polysilocarb formulation can be, for example, sprayed, flowed, thermal sprayed, painted, molded, formed, extruded, spun, dropped, injected or otherwise manipulated into essentially any volumetric shape, including planer shape (which still has a volume, but is more akin to a coating, skin, film, or even a counter top, where the thickness is significantly smaller, if not orders of magnitude smaller, than the other dimensions), and combinations and variations of these.
  • volumetric shapes would include, for example, spheres, pellets, rings, lenses, disks, panels, cones, frustoconical shapes, squares, rectangles, trusses, angles, channels, hollow sealed chambers, hollow spheres, blocks, sheets, coatings, films, skins, particulates, beams, rods, angles, columns, fibers, staple fibers, tubes, cups, pipes, and combinations and various of these and other more complex shapes, both engineering and architectural.
  • ⁇ may be shaped into preforms, or preliminary shapes that correspond to, or with, a final product, such as for example use in or with, a break pad, a clutch plate, a break shoe, a motor, high temperature parts of a motor, a diesel motor, rocket components, turbine components, air plane components, space vehicle components, building materials, shipping container components, and other structures or components.
  • the polysilocarb precursor formulations may be used with reinforcing materials to form a composite material.
  • the formulation may be flowed into, impregnated into, absorbed by or otherwise combined with a reinforcing material, such as carbon fibers, glass fiber, woven fabric, non-woven fabric, copped fibers, fibers, rope, braided structures, ceramic powders, glass powders, carbon powders, graphite powders, ceramic fibers, metal powders, carbide pellets or
  • the reinforcing materials may be any of the high temperature resistant reinforcing materials currently used, or capable of being used with, existing plastics and ceramic composite materials.
  • the polysilocarb precursor formulation may be formulated for a lower temperature cure (e.g., SATP) or a cure temperature of for example about 100° F to about 400° F
  • the reinforcing material may be polymers, organic polymers, such as nylons, polypropylene, and polyethylene, as well as aramid fibers, such as NOMEX or KEVLAR.
  • the reinforcing material may also be made from, or derived from the same material as the formulation that has been formed into a fiber and pyrolized into a ceramic, or it may be made from a different precursor formulation material, which has been formed into a fiber and pyrolized into a ceramic.
  • a different precursor formulation material which has been formed into a fiber and pyrolized into a ceramic.
  • other porous, substantially porous, and non-porous ceramic structures derived from a precursor formulation material may be used.
  • the polysilocarb precursor formulation may be used to form a filled material.
  • a filled material would be any material having other solid, or semi-solid, materials added to the polysilocarb precursor formulation.
  • the filler material may be selected to provide certain features to the cured product, the ceramic product or both. These features may relate to or be aesthetic, tactile, thermal, density, radiation, chemical, magnetic, electric, and combinations and variations of these and other features. These features may be in addition to strength. Thus, the filler material may not affect the strength of the cured or ceramic material, it may add strength, or could even reduce strength in some situations.
  • the filler material could impart color, magnetic capabilities, fire resistances, flame retardance, heat resistance, electrical conductivity, anti-static, optical properties (e.g., reflectivity, refractivity and iridescence), aesthetic properties (such as stone like appearance in building products), chemical resistivity, corrosion resistance, wear resistance, abrasions resistance, thermal insulation, UV stability, UV protective, and other features that may be desirable, necessary, and both, in the end product or material.
  • filler materials could include copper lead wires, thermal conductive fillers, electrically conductive fillers, lead, optical fibers, ceramic colorants, pigments, oxides, dyes, powders, ceramic fines, PDC particles, pore-formers, carbosilanes, silanes, silazanes, silicon carbide, carbosilazanes, siloxane, powders, ceramic powders, metals, metal complexes, carbon, tow, fibers, staple fibers, boron containing materials, milled fibers, glass, glass fiber, fiber glass, and nanostructures (including
  • crushed, PDC particles e.g., fines or beads
  • a polysilocarb formulation can be added to a polysilocarb formulation and then cured to form a filled cured plastic material, which has significant fire resistant properties as a coating or structural material.
  • flame retardant As used herein, unless specifically provided otherwise, the terms flame retardant, fire retardant, flame resistant, fire resistant, flame protection, fire protection, flame suppression, fire suppression, and similar such terms are to be given their broadest possible meanings, and would include all burning, fire, combustion or flame related meanings that are found, described or set forth in standards, codes,
  • the fill material may also be made from, or derived from the same material as the formulation that has been formed into a cured or pyrolized solid, or it may be made from a different precursor formulation material, which has been formed into a cured solid or semi-solid, or pyrolized solid.
  • the polysilocarb formulation and products derived or made from that formulation may have metals and metal complexes.
  • metals as oxides, carbides or silicides can be introduced into precursor formulations, and thus into a silica matrix in a controlled fashion.
  • organometallic, metal halide (chloride, bromide, iodide), metal alkoxide and metal amide compounds of transition metals and then copolymerizing in the silica matrix is contemplated.
  • Cyclopentadienyl complexes that can be utilized with precursor formulations and in products, can include: bis-cyclopentadienyl metal complexes of first row transition metals (Titanium, Vanadium, Chromium, Iron, Cobalt, Nickel); second row transition metals (Zirconium, Molybdenum, Ruthenium, Rhodium, Palladium); third row transition metals (Hafnium, Tantalum, Tungsten, Iridium, Osmium, Platinum); Lanthanide series (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho); Actinide series (Ac, Th, Pa, U, Np).
  • first row transition metals Tianium, Vanadium, Chromium, Iron, Cobalt, Nickel
  • second row transition metals Zirconium, Molybdenum, Ruthenium, Rhodium, Palladium
  • third row transition metals Hafnium, Tantalum, Tung
  • Monocyclopentadienyl complexes may also be utilized to provide metal functionality to precursor formulations and would include monocyclopentadienyl complexes of: first row transition metals (Titanium, Vanadium, Chromium, Iron, Cobalt, Nickel); second row transition metals (Zirconium, Molybdenum, Ruthenium, Rhodium, Palladium); third row transition metals (Hafnium, Tantalum, Tungsten, Iridium, Osmium, Platinum) when preferably stabilized with proper ligands, (for instance Chloride or Carbonyl).
  • first row transition metals Tianium, Vanadium, Chromium, Iron, Cobalt, Nickel
  • second row transition metals Zirconium, Molybdenum, Ruthenium, Rhodium, Palladium
  • third row transition metals Hafnium, Tantalum, Tungsten, Iridium, Osmium, Platinum
  • Alky complexes of metals may also be used to provide metal functionality to precursor formulations and products.
  • the Si center has an alkyl group (ethyl, propyl, butyl, vinyl, propenyl, butenyl) which can bond to transition metal direct through a sigma bond. Further, this would be more common with later transition metals such as Pd, Rh, Pt, Ir.
  • Coordination complexes of metals may also be used to provide metal functionality to precursor formulations and products.
  • the Si center has an unsaturated alkyl group (vinyl, propenyl, butenyl, acetylene, butadienyl) which can bond to carbonyl complexes or ene complexes of Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni.
  • the Si center may also be attached to a phenyl, substituted phenyl or other aryl compound (pyridine, pyrimidine) and the phenyl or aryl group can displace carbonyls on the metal centers.
  • Metal alkoxides may also be used to provide metal functionality to precursor formulations and products.
  • Metal alkoxide compounds can be mixed with the Silicon precursor compounds and then treated with water to form the oxides at the same time as the polymer, copolymerize. This can also be done with metal halides and metal amides. Preferably, this may be done using early transition metals along with
  • Compounds where Si is directly bonded to a metal center which is stabilized by halide or organic groups may also be utilized to provide metal functionality to precursor formulations and products.
  • the metal and metal complexes may be the continuous phase after pyrolysis, or subsequent heat treatment.
  • Formulations can be specifically designed to react with selected metals to in s/fu form metal carbides, oxides and other metal compounds, generally known as cermets (e.g., ceramic metallic compounds).
  • the formulations can be reacted with selected metals to form in situ compounds such as mullite, alumino silicate, and others.
  • the amount of metal relative to the amount of silica in the formulation or end product can be from about 0.1 mole % to 99.9 mole %, about 1 mole % or greater, about 10 mole % or greater, about 20 mole percent or greater % and greater.
  • the forgoing use of metals with the present precursor formulas can be used to control and provide predetermined stoichiometries.
  • Filled materials would include reinforced materials.
  • cured, as well as pyrolized polysilocarb filled materials can be viewed as composite materials.
  • the polysilocarb would constitute the bulk or matrix phase, (e.g., a continuous, or substantially continuous phase), and the filler would constitute the dispersed (e.g., non-continuous), phase.
  • the ratio (either weight or volume) of polysilocarb to filler material could be from about 0.1 :99.9 to 99.9:0.1 . Smaller amounts of filler material or polysilocarb could also be present or utilized, but would more typically be viewed as an additive or referred to in other manners.
  • composite, filled material, polysilocarb filled materials, reinforced materials, polysilocarb reinforced materials, polysilocarb filled materials, polysilocarb reinforced materials and similar such terms should be viewed as non-limiting as to amounts and ratios of the material's constitutes, and thus in this context, be given their broadest possible meaning.
  • the polysilocarb precursor formulation may be specifically formulated to cure under conditions (e.g., temperature, and perhaps time) that match, e.g., are predetermined to match, the properties of the reinforcing material, filler material or substrate.
  • These materials may also be made from, or derived from, the same material as the polysilocarb precursor formulation that is used as the matrix, or it may be made from a different polysilocarb precursor formulation.
  • porous, substantially porous, and non-porous ceramic structures derived from a polysilocarb precursor formulation material may be used as filler or reinforcing material.
  • the polysilocarb precursor formulations may be used to coat or impregnate a woven or non-woven fabric, made from for example carbon fiber, glass fibers or fibers made from a polysilocarb precursor formulation (the same or different formulation), to from a prepreg material. Further, a polysilocarb precursor formulation may be used as an interface coating on the reinforcing material, for use either with a polysilocarb precursor formulation as the matrix material. Further, carbon fiber may be heat treated to about 1 ,400° to about 1 ,800° or higher, which creates a surface feature that eliminates the need for a separate interface coating, for use with polysilocarb precursor formulations.
  • Fillers can reduce the amount of shrinkage that occurs during the processing of the formulation into a ceramic, they can be used to provide a predetermined density of the product, either reducing or increasing density, and can be used to provide other customized and predetermined product and processing features. Fillers, at larger amounts, e.g., greater than 10%, can have the effect of reducing shrinkage during cure.
  • the filler can be evenly distributed in the precursor formulation, unevenly distributed, a predetermined rate of settling, and can have different amounts in different formulations, which can then be formed into a product having a predetermined amounts of filler in predetermined areas, e.g., striated layers having different filler concentration.
  • each filler particle may have a volume that is less than about 0.3%, less than about 0.2%, less than about 0.1 %, and less than about 0.05% of the volume of a product, intermediate or part.
  • the diameter of the filler should preferable be about 1/10 to about 1/20 of the diameter of the proppant particle, and more preferably the filler diameter should be less than about 1/20 of the diameter of the proppant particle.
  • the relative amount of filler used in a material should preferable be about 30% to about 65% of the volume of the sphere, e.g., volume %.
  • a small particulate filler e.g., fines, beads, pellets
  • at least about 2% to at least about 5 volume % can show an increase in the strength, although this may be greater or smaller depending upon other factors, such as the shape and volume of the product, later processing conditions, e.g., cure time, temperature, number of pyrolysis reinfiltrations.
  • cure time e.g., cure time
  • temperature e.g., number of pyrolysis reinfiltrations.
  • Such small particulate filled products in which appreciable strength benefits are obtained from the filler, and in particular an increase in strength of at least about 5%, at last about 10% and preferably at least about 20% would be considered to be reinforced products and materials.
  • volume % and “% volume” and similar such terms refer to the volume of a first component as a percentage of the volume of the total, e.g., formulation, material or product.
  • the polysilocarb structures, intermediates and end products, and combinations and variations of these may be machined, milled, molded, shaped, drilled or otherwise mechanically processed and shaped.
  • the precursor formulations are preferably clear or are essentially colorless and generally transmissive to light in the visible wavelengths. They may, depending upon the formulation have a turbid, milky or clouding appearance. They may also have color bodies, pigments or colorants, as well as color filler (which can survive pyrolysis, for ceramic end products, such as those used in ceramic pottery glazes). The precursor may also have a yellow or amber color or tint, without the need of the addition of a colorant.
  • the precursor formulations may be packaged, shipped and stored for later use in forming products, e.g., structures or parts, or they may be used directly in these processes, e.g., continuous process to make a product.
  • a precursor formulation may be stored in 55 gallon drums, tank trucks, rail tack cars, onsite storage tanks having the capable of holding hundreds of gals, and shipping totes holding 1 ,000 liters, by way of example. Additionally, in manufacturing process the formulations may be made and used in a continuous, and semi-continuous processes.
  • the present inventions provide substantial flexibility in designing processes, systems, ceramics, having processing properties and end product performance features to meet predetermined and specific performance criteria.
  • the viscosity of the precursor formulation may me predetermined by the formulation to match a particular morphology of the reinforcing material
  • the cure temperature of the precursor formulation may be predetermined by the formulation to enable a prepreg to have an extended shelf life.
  • the viscosity of the of the precursor formulation may be established so that the precursor readily flows into the reinforcing material of the prepreg while at the same time being thick enough to prevent the precursor formulation from draining or running off of the reinforcing material.
  • the formulation of the precursor formulation may also, for example, be such that the strength of a cured preform is sufficient to allow rough or initial machining of the preform, prior to pyrolysis.
  • Custom and predetermined control of when chemical reactions occur in the various stages of the process from raw material to final end product can provide for reduced costs, increased process control, increased reliability, increased efficiency, enhanced product features, and combinations and variation of these and other benefits.
  • the sequencing of when chemical reactions take place can be based primarily upon the processing or making of precursors, and the processing or making of precursor formulations; and may also be based upon cure and pyrolysis conditions. Further, the custom and predetermined selection of these steps, formulations and conditions, can provide enhanced product and processing features through chemical reactions, molecular arrangements and rearrangements, and microstructure arrangements and rearrangements, that preferably have been predetermined and controlled.
  • the process form making the present polysilocarb materials involves one or more steps.
  • the starting materials are obtained, made or derived.
  • Precursors are obtained or can be made from starting materials.
  • the precursors are combined to form a precursor formulation.
  • the precursor formulation is then shaped, formed, molded, etc. into a desired form, which form is then cured, which among other things transforms the precursor formulation into a plastic like material.
  • This cured plastic like material can then be pyrolyzed into a ceramic. It being understood, that these steps may not all be used, that some of these steps may be repeated, once, twice or several times, and that combinations and variations of these general steps may be utilized to obtain a desired product or result.
  • the process type and conditions and the precursors can be predetermined and preselected.
  • This regime of precursors and processes provides great flexibility to create custom features for intermediate, end and final products, and thus, typically, combinations and variations of them, can provide a specific predetermined product.
  • Factors such as cost, controllability, shelf life, scale up, manufacturing ease, etc., can also be considered.
  • precursor materials may be methyl hydrogen
  • siloxane backbone additives reactive monomers, hydrocarbons, reaction products of a siloxane backbone additive with a silane modifier or an organic modifier, and other similar types of materials, such as silane based materials, silazane based materials, carbosilane based materials, phenol/formaldehyde based materials, and combinations and variations of these and others.
  • inhibitors such as cyclohexane, 1 -Ethynyl-1 -cyclohexanol (which may be obtained from ALDRICH), Octamethylcyclotetrasiloxane,
  • tetramethyltetravinylcyclotetrasiloxane (which may act, depending upon amount and temperature as a reactant or a reactant retardant (i.e., slows down a reaction to increase pot life), e.g., at room temperature it is a retardant and at elevated
  • polysilocarb precursor formulation e.g., an inhibited polysilocarb precursor formulation.
  • Other materials, as well, may be added to the polysilocarb precursor formulation, e.g., a filled polysilocarb precursor formulation, at this point in processing, including fillers such as SiC powder, carbon black, PDC particles, pigments, particles, nano-tubes, whiskers, or other materials, discussed in this specification or otherwise known to the arts. Further, a formulation with both inhibitors and fillers would be considered an inhibited, filled polysilocarb precursor formulation.
  • Precursors and precursor formulations are preferably non-hazardous materials. Generally they have flash points that are preferably above room and typical storage temperatures, are preferably noncorrosive, preferably have low vapor pressure, low or no odor, and may be non- or mildly irritating to the skin.
  • a catalyst may be used, and can be added at the time of, prior to, shortly before, or at an earlier time before the precursor formulation is formed or made into a structure, prior to curing.
  • Precursor formulations can have pot lives, that meet the needs of the manufacturing process. Generally, catalysts can be used and can be balance with, or used in conjunction with the inhibitor to have a predetermined and predictable shelf life, cure time, cure temperature profiles. These profiles can be tailored to the specific manufacturing processes, e.g., ship and hold for a month before curing, or ship hold and process directly from liquid to ceramic, or make and cure with minimal shipping or hold times.
  • the precursors may also be selected from the following:
  • methylhydrogen fluid This is a type of material commonly called methylhydrogen fluid, and has the formula below:
  • This may be called methyl terminated with dimethyl groups and has the formula below.
  • This may be called hydride terminated with dimethyl groups and has the formula below.
  • this precursor can improve as-cured toughness and decrease shrinkage and improve thermal stability of as-cured material
  • this precursor can improve as-cured toughness and decrease shrinkage and improve thermal stability of as-cured material; but, may allow for higher cross-link density
  • this precursor's tri-functionality can be used for controlled branching, as well as in some embodiments to reduced shrinkage.
  • this precursor's tri-functionality can be used for controlled branching, as well as in some embodiments to reduced shrinkage.
  • this precursor can be used to improve as cured toughness and decreased shrinkage; as well as providing the ability to improve crosslink density through branching if needed.
  • this precursor may provided for less shrinkage than the tetravinyl; but still can provide for high crosslink density due to high vinyl percentage, but primarily through 2-dimensional crosslinking, without any branching
  • this precursor may assist in decreasing the density by in-situ nano/micro pore formation.
  • this precursor may assist in decreasing the density by in-situ nano/micro pore formation.
  • this precursor can increase cure speed, decrease shrinkage slightly, and improves thermal /structural stability of cured and pyrolyzed material
  • embodiments of formulations for polysilocarb formulations may for example have from about 20% to about 99% MH, about 0% to about 30% siloxane backbone additives, about 1 % to about 60% reactive monomers, and, about 0% to about 90% reaction products of a siloxane backbone additives with a silane modifier or an organic modifier reaction products.
  • the precursor formulations are relatively, and essentially, shear insensitive, and thus the type of pumps or mixing are not critical. It is further noted that in higher viscosity formulations additional mixing time may be required.
  • Embodiments of processes can provide the ability to build custom precursor formulations that when cured can provide plastics having unique and desirable features such as high temperature, flame resistance and retardation, strength and other features.
  • the cured materials can also be pyrolized to form ceramics having unique features. This allows for the predetermined balancing of different types of functionality in the end product by selecting function groups for incorporation into the polymer that makes up the precursor formulation.
  • Embodiments of a preform can be cured in a controlled atmosphere, such as an inert gas, or it can be cured in the atmosphere.
  • the cure conditions e.g., temperature, time, rate, etc.
  • the cure conditions can be predetermined by the formulation and other processing conditions.
  • such conditions can be selected to match, the size of the preform, the shape of the preform, or the mold holding the preform to prevent stress cracking, off gassing, or other problems associated with the curing process.
  • the curing conditions may be such as to take advantage of, in a controlled manner, what may have been previously perceived as problems associated with the curing process.
  • off gassing may be used to create a foam material having either open or closed structure.
  • the porosity of the material may be predetermined such that, for example, a particular pore size may be obtained, and in this manner a filter or ceramic screen having predetermined pore sizes, flow
  • the preforms may be used as a stand alone product, an end product, a final product, or a preliminary product for which later machining or processing may be performed on.
  • the preforms may also be subject to pyrolysis, which converts the preform material into a ceramic.
  • the preform, or cured structure or cured material in some embodiments it is heated to above about 650° C to about 1 ,200° C. At these
  • temperatures typically all organic structures are either removed or combined with the inorganic constituents to form a ceramic.
  • the material is an amorphous glassy ceramic.
  • the material When heated above 1 ,200° C the material may from nano crystalline structures, or micro crystalline structures, such as SiC, Si3N 4 , SiCN, ⁇ SiC, and above 1 ,900° C an a SiC structure may form.
  • char yield or pyrolysis yield
  • Embodiments of formulations are capable of being air pyrolized to form a ceramic and to preferably do so at char yield in excess of at least about 80% and above 88%.
  • the initial or first pyrolysis step generally yields a structure that is not very dense. However, in some examples, such as the use of light weight spheres, the first pyrolysis may be sufficient.
  • a reinfiltration process that may be performed on the pyrolized material, to add in additional polysilocarb precursor formulation material, to fill in, or fill the voids and spaces in the structure.
  • This reinfiltrated material is they repyrolized.
  • This process of pyrolization, reinfiltration may be repeated, through one, two, three, and up to 10 or more times to obtain the desired density of the final product.
  • the viscosity of the formulation may be tailored to provide more efficient reinfiltrations, and thus, a different formulation may be used at later reinfiltration steps, as the voids or pores become smaller and more difficult to get the formulation material into it.
  • the high char yields, and other features of embodiments of the present invention enable the manufacture of completely closed structures, e.g., "helium tight" materials, with less than twelve reinfiltration steps, less than about 10 reinfiltrations steps and less than five reinfiltrations steps.
  • an initial inert gas pyrolysis may be performed with a high char yield formulation followed by four reinfiltration air pyrolysis steps.
  • Embodiments of the present inventions have the ability to utilize precursors that have impurities, high-level impurities and significant impurities.
  • precursors may have more than about 0.1 % impurities, more than about 0.5%, more than about 1 % impurities, more than about 5% impurities, more than about 10% impurities, and more than about 50% impurities.
  • the amounts of these impurities, or at least the relative amounts, so that the amount of actual precursor is known should preferably be determined by for example GPC (Gel Permeation Chromatography) or other methods of analysis. In this manner the formulation of the polysilocarb precursor formulation may be adjusted for the amount of impurities present.
  • GPC Gel Permeation Chromatography
  • the ability to use impure, lower purity, materials in embodiments of the present inventions provides the ability to greatly reduce the cost of the formulations and end products, e.g., cured preforms, cured parts, and ceramic parts or structures.
  • the ability to use impure, lower purity, materials in embodiments of the present inventions provides the ability to have end products, e.g., cured preforms, cured parts, and ceramic parts or structures, that have a substantially greater consistence from part to part, because variations in starting materials can be adjusted for during the formulation of each polysilocarb precursor formulation.
  • the equipment, processes and techniques to make the present inventions can be any of the systems, processes and techniques disclosed and taught in this specification, know to the art for molding, forming, extruding, coating, and assembling components, as well as, those disclosed and taught in US Patent Applications Serial Numbers 14/212,986, 14/268,150, 14/324,056, 14/514,257, 61/946,598 and 62/055,397 and 62/106,094, the entire disclosure of each of which are incorporated herein by reference.
  • polymer derived ceramic precursor formulations can generally be made by three types of processes, although other processes, and variations and combinations of these processes may be utilized. These processes generally involve combining precursors to form a precursor formulation.
  • One type of process generally involves the mixing together of precursor materials in preferably a solvent free process with essentially no chemical reactions taking place, e.g., "the mixing process.”
  • the other type of process generally involves chemical reactions, e.g., "the reaction type process,” to form specific, e.g., custom, precursor formulations, which could be monomers, dimers, trimers and polymers.
  • a third type of process has a chemical reaction of two or more components in a solvent free environment, e.g., "the reaction blending type process.”
  • the reaction blending type process essentially all, and preferably all, of the chemical reactions take place during subsequent processing, such as during curing, pyrolysis and both.
  • these terms - reaction type process, reaction blending type process, and the mixing type process - are used for convenience and as a short hand reference. These terms are not, and should not be viewed as, limiting.
  • the reaction process can be used to create a precursor material that is then used in the mixing process with another precursor material.
  • formulation from the reaction type process may be used in the mixing type process and the reaction blending process.
  • a formulation from the reaction blending type process may be used in the mixing type process and the reaction type process.
  • the precursors may be made by way of an alkoxylation type process, e.g., an ethoxylation process.
  • chlorosilanes are reacted with ethanol in the presences of a catalysis, e.g., HCI, to provide the precursor materials, which materials may further be reacted to provide longer chain precursors.
  • a catalysis e.g., HCI
  • Other alcohols e.g., methanol may also be used.
  • SiCI 4 , SiCI 3 H, SiCI 2 (CH 3 ) 2 , SiCI 2 (CH 3 )H, Si(CH 3 )3CI, Si(CH 3 )CIH are reacted with ethanol CH 3 CH 2 OH to form precursors.
  • phenols may be the source of the phenoxy group, which is substituted for a hydride group that has been placed on the silicon.
  • One, two or more step reactions may need to take place.
  • Precursor materials may also be obtained by way of an acetylene reaction route.
  • an acetylene reaction route In general there are several known paths for adding acetylene to Si-H.
  • tetramethylcyclotetrasiloxane can be reacted with acetylene in the presence of a catalyst to produce tetramethyltetravinylcyclotetrasiloxane.
  • This product can then be ring opened and polymerized in order to form linear vinyl, methylsiloxanes.
  • typical vinyl silanes can be produced by reacting methyl,dichlorosilane (obtained from the direct process or Rochow process) with acetylene.
  • vinyl monomers can then be purified (because there may be some scrambling) to form vinyl, methyl, dichlorosilane. Then the vinyl monomer can be polymerized via hydrolysis to form many cyclic, and linear siloxanes, having various chain lengths, including for example various
  • cyclotetrasiloxanes e.g., D 4 '
  • various cyclopentasiloxanes e.g., D 5 '
  • Continuous High Pressure Reactor (“CHPR") embodiments may be advantageous for, among other reasons: reaction conversion saving more acetylene needed in liquid phase; tube reactors providing pressures which in turn increases solubility of acetylene; reaction with hexyne saving concentration and time (e.g., 100 hours,); can eliminate homogeneous catalyst and thus eliminate hydrosilylation reaction with resultant vinyls once complete; and, using a heterogeneous (Solid) catalyst to maintain product integrity, increased shelf-life, increase pot-life and combinations and variations of these.
  • CPR Continuous High Pressure Reactor
  • the presence and quality of vinyl and vinyl conversions can be determined by, among other things,: FT-IR for presence of vinyl absorptions, decrease in SiH absorption ; 1 H NMR for presence of vinyls and decrease in SiH; 13 C NMR for presence of vinyls.
  • volume % and “% volume” and similar such terms refer to the volume of a first component as a percentage of the volume of the total, e.g., formulation, material or product.
  • Precursor materials may be methyl hydrogen, and substituted and modified methyl hydrogens, siloxane backbone additives, reactive monomers, reaction products of a siloxane backbone additive with a silane modifier or an organic modifier, and other similar types of materials, such as silane based materials, silazane based materials, carbosilane based materials, phenol/formaldehyde based materials, and combinations and variations of these.
  • the precursors are preferably liquids at room temperature, although they may be solids that are melted, or that are soluble in one of the other precursors.
  • the precursors are mixed together in a vessel, preferably at room
  • each precursor material is miscible with the others, e.g., they can be mixed at any relative amounts, or in any proportions, and will not separate or precipitate.
  • the "precursor mixture” or "polysilocarb precursor formulation” is compete (noting that if only a single precursor is used the material would simply be a "polysilocarb precursor” or a “polysilocarb precursor formulation” or a "formulation").
  • fillers and reinforcers may be added to the formulation.
  • essentially no, and more preferably no chemical reactions, e.g., crosslinking or polymerization takes place within the formulation, when the formulation is mixed, or when the formulation is being held in a vessel, on a prepreg, or over a time period, prior to being cured.
  • the precursors can be mixed under numerous types of atmospheres and conditions, e.g., air, inert, N 2 , Argon, flowing gas, static gas, reduced pressure, elevated pressure, ambient pressure, and combinations and variations of these.
  • atmospheres and conditions e.g., air, inert, N 2 , Argon, flowing gas, static gas, reduced pressure, elevated pressure, ambient pressure, and combinations and variations of these.
  • inhibitors such as cyclohexane, 1 -Ethynyl-1 -cyclohexanol (which may be obtained from ALDRICH), Octamethylcyclotetrasiloxane, and
  • tetramethyltetravinylcyclotetrasiloxane may be added to the polysilocarb precursor formulation, e.g., an inhibited polysilocarb precursor formulation. It should be noted that tetramethyltetravinylcyclotetrasiloxane may act as both a reactant and a reaction retardant (e.g., an inhibitor), depending upon the amount present and temperature, e.g., at room temperature it is a retardant and at elevated temperatures it is a reactant.
  • a reaction retardant e.g., an inhibitor
  • polysilocarb precursor formulation e.g., a filled polysilocarb precursor formulation
  • fillers such as SiC powder, carbon black, sand, polymer derived ceramic particles, pigments, particles, nano-tubes, whiskers, or other materials, discussed in this specification or otherwise known to the arts.
  • a formulation with both inhibitors and fillers would be considered an inhibited, filled polysilocarb precursor formulation.
  • polysilocarb precursor formulations may have shelf lives at room temperature of greater than 12 hours, greater than 1 day, greater than 1 week, greater than 1 month, and for years or more. These precursor formulations may have shelf lives at high temperatures, for example, at about 90° F, of greater than 12 hours, greater than 1 day, greater than 1 week, greater than 1 month, and for years or more.
  • the use of inhibitors may further extend the shelf life in time, for higher temperatures, and combinations and variations of these.
  • the use of inhibitors may also have benefits in the development of manufacturing and commercial processes, by controlling the rate of reaction, so that it takes place in the desired and intended parts of the process or manufacturing system.
  • shelf life should be given its broadest possible meaning, unless specified otherwise, and would include, for example, the formulation being capable of being used for its intended purpose, or performing, e.g., functioning, for its intended use, at 100% percent as well as a freshly made formulation, at least about 90% as well as a freshly made formulation, at least about 80% as well as a freshly made formulation, and at at least about 70% as well as a freshly made formulation.
  • Precursors and precursor formulations are preferably non-hazardous materials. They have flash points that are preferably above about 70° C, above about 80° C, above about 100° C and above about 300° C, and above. Preferably, they may be noncorrosive. Preferably, they may have a low vapor pressure, may have low or no odor, and may be non- or mildly irritating to the skin.
  • a catalyst or initiator may be used, and can be added at the time of, prior to, shortly before, or at an earlier time before the precursor formulation is formed or made into a structure, prior to curing.
  • the catalysis assists in, advances, and promotes the curing of the precursor formulation to form a preform.
  • pot life e.g., how long can the catalyzed formulation remain in its holding vessel before it should be used.
  • precursor formulations can have pot lives, for example, of from about 5 minutes to about 10 days, about 1 day to about 6 days, about 4 to 5 days, about 30 minutes, about 15 minutes, about 1 hour to about 24 hours, and about 12 hours to about 24 hours.
  • the catalyst can be any platinum (Pt) based catalyst, which can, for example, be diluted to a ranges of: about 0.01 parts per million (ppm) Pt to about 250 ppm Pt, about 0.03 ppm Pt, about 0.1 ppm Pt, about 0.2 ppm Pt, about 0.5 ppm Pt, about 0.02 to 0.5 ppm Pt, about 1 ppm to 200 ppm Pt and preferably, for some applications and embodiments, about 5 ppm to 50 ppm Pt.
  • Pt platinum
  • the catalyst can be a peroxide based catalyst with, for example, a 10 hour half life above 90 C at a concentration of between 0.1 % to 3% peroxide, and about 0.5% and 2% peroxide. It can be an organic based peroxide. It can be any organometallic catalyst capable of reacting with Si-H bonds, Si- OH bonds, or unsaturated carbon bonds, these catalysts may include: dibutyltin dilaurate, zinc octoate, peroxides, organometallic compounds of for example titanium, zirconium, rhodium, iridium, palladium, cobalt or nickel. Catalysts may also be any other rhodium, rhenium, iridium, palladium, nickel, and ruthenium type or based catalysts. Combinations and variations of these and other catalysts may be used.
  • Catalysts may be obtained from ARKEMA under the trade name LUPEROX, e.g., LUPEROX 231 ; and from Johnson Matthey under the trade names: Karstedt's catalyst, Ashby's catalyst, Speier's catalyst.
  • custom and specific combinations of these and other catalysts may be used, such that they are matched to specific formulations, and in this way selectively and specifically catalyze the reaction of specific constituents.
  • the use of these types of matched catalyst-formulations systems may be used to provide predetermined product features, such as for example, pore structures, porosity, densities, density profiles, high purity, ultra high purity, and other morphologies or features of cured structures and ceramics.
  • this mixing type process for making a precursor formulation preferably chemical reactions or molecular rearrangements only take place during the making of the starting materials, the curing process, and in the pyrolizing process. Chemical reactions, e.g., polymerizations, reductions, condensations, substitutions, take place or are utilized in the making of a starting material or precursor.
  • chemical reactions e.g., polymerizations, reductions, condensations, substitutions, take place or are utilized in the making of a starting material or precursor.
  • no and essentially no chemical reactions and molecular rearrangements take place.
  • polymerization, crosslinking or other chemical reactions take place primarily, preferably essentially, and more preferably solely during the curing process.
  • the precursor may be a siloxane backbone additive, such as, methyl hydrogen (MH), which formula is shown below.
  • MH methyl hydrogen
  • the MH may have a molecular weight ("mw” which can be measured as weight averaged molecular weight in amu or as g/mol) from about 400 mw to about 10,000 mw, from about 600 mw to about 3,000 mw, and may have a viscosity preferably from about 20 cps to about 60 cps.
  • the percentage of methylsiloxane units "X" may be from 1 % to 100%.
  • the percentage of the dimethylsiloxane units "Y” may be from 0% to 99%.
  • This precursor may be used to provide the backbone of the cross-linked structures, as well as, other features and characteristics to the cured preform and ceramic material. This precursor may also, among other things, be modified by reacting with unsaturated carbon compounds to produce new, or additional, precursors.
  • methyl hydrogen fluid has minimal amounts of "Y”, and more preferably "Y” is for all practical purposes zero.
  • the precursor may be a siloxane backbone additive, such as vinyl substituted polydimethyl siloxane, which formula is shown below.
  • This precursor may have a molecular weight (mw) from about 400 mw to about 10,000 mw, and may have a viscosity preferably from about 50 cps to about 2,000 cps.
  • the percentage of methylvinylsiloxane units "X" may be from 1 % to 100%.
  • the percentage of the dimethylsiloxane units "Y” may be from 0% to 99%.
  • X is about 100%.
  • This precursor may be used to decrease cross-link density and improve toughness, as well as, other features and characteristics to the cured preform and ceramic material.
  • the precursor may be a siloxane backbone additive, such as vinyl substituted and vinyl terminated polydimethyl siloxane, which formula is shown below.
  • This precursor may have a molecular weight (mw) from about 500 mw to about 15,000 mw, and may preferably have a molecular weight from about 500 mw to 1 ,000 mw, and may have a viscosity preferably from about 10 cps to about 200 cps.
  • the percentage of methylvinylsiloxane units "X" may be from 1 % to 100%.
  • the percentage of the dimethylsiloxane units "Y” may be from 0% to 99%.
  • This precursor may be used to provide branching and decrease the cure temperature, as well as, other features and characteristics to the cured preform and ceramic material.
  • the precursor may be a siloxane backbone additive, such as vinyl substituted and hydrogen terminated polydimethyl siloxane, which formula is shown below.
  • This precursor may have a molecular weight (mw) from about 300 mw to about 10,000 mw, and may preferably have a molecular weight from about 400 mw to 800 mw, and may have a viscosity preferably from about 20 cps to about 300 cps.
  • the percentage of methylvinylsiloxane units "X" may be from 1 % to 100%.
  • the percentage of the dimethylsiloxane units "Y” may be from 0% to 99%.
  • This precursor may be used to provide branching and decrease the cure temperature, as well as, other features and characteristics to the cured preform and ceramic material.
  • the precursor may be a siloxane backbone additive, such as allyl terminated polydimethyl siloxane, which formula is shown below.
  • This precursor may have a molecular weight (mw) from about 400 mw to about 10,000 mw, and may have a viscosity preferably from about 40 cps to about 400 cps.
  • the repeating units are the same.
  • This precursor may be used to provide UV curability and to extend the polymeric chain, as well as, other features and
  • the precursor may be a siloxane backbone additive, such as vinyl terminated polydimethyl siloxane, which formula is shown below.
  • This precursor may have a molecular weight (mw) from about 200 mw to about 5,000 mw, and may preferably have a molecular weight from about 400 mw to 1 ,500 mw, and may have a viscosity preferably from about 10 cps to about 400 cps.
  • the repeating units are the same.
  • This precursor may be used to provide a polymeric chain extender, improve toughness and to lower cure temperature down to for example room temperature curing, as well as, other features and characteristics to the cured preform and ceramic material.
  • the precursor may be a siloxane backbone additive, such as silanol (hydroxy) terminated polydimethyl siloxane, which formula is shown below.
  • This precursor may have a molecular weight (mw) from about 400 mw to about 10,000 mw, and may preferably have a molecular weight from about 600 mw to 1 ,000 mw, and may have a viscosity preferably from about 30 cps to about 400 cps.
  • the repeating units are the same.
  • This precursor may be used to provide a polymeric chain extender, a toughening mechanism, can generate nano- and micro- scale porosity, and allows curing at room temperature, as well as other features and characteristics to the cured preform and ceramic material.
  • the precursor may be a siloxane backbone additive, such as silanol (hydroxy) terminated vinyl substituted dimethyl siloxane, which formula is shown below.
  • This precursor may have a molecular weight (mw) from about 400 mw to about 10,000 mw, and may preferably have a molecular weight from about 600 mw to 1 ,000 mw, and may have a viscosity preferably from about 30 cps to about 400 cps.
  • the percentage of methylvinylsiloxane units "X" may be from 1 % to 100%.
  • the percentage of the dimethylsiloxane units "Y” may be from 0% to 99%.
  • This precursor may be used, among other things, in a dual-cure system; in this manner the dual-cure can allow the use of multiple cure mechanisms in a single formulation. For example, both condensation type cure and addition type cure can be utilized. This, in turn, provides the ability to have complex cure profiles, which for example may provide for an initial cure via one type of curing and a final cure via a separate type of curing.
  • the precursor may be a siloxane backbone additive, such as hydrogen (hydride) terminated polydimethyl siloxane, which formula is shown below.
  • This precursor may have a molecular weight (mw) from about 200 mw to about 10,000 mw, and may preferably have a molecular weight from about 500 mw to 1 ,500 mw, and may have a viscosity preferably from about 20 cps to about 400 cps.
  • the repeating units are the same.
  • This precursor may be used to provide a polymeric chain extender, as a toughening agent, and it allows lower temperature curing, e.g., room temperature, as well as, other features and characteristics to the cured preform and ceramic material.
  • the precursor may be a siloxane backbone additive, such as di-phenyl terminated siloxane, which formula is shown below.
  • R is a reactive group, such as vinyl, hydroxy, or hydride.
  • This precursor may have a molecular weight (mw) from about 500 mw to about 2,000 mw, and may have a viscosity preferably from about 80 cps to about 300 cps.
  • the percentage of methyl - R - siloxane units "X" may be from 1 % to 100%.
  • percentage of the dimethylsiloxane units "Y" may be from 0% to 99%.
  • This precursor may be used to provide a toughening agent, and to adjust the refractive index of the polymer to match the refractive index of various types of glass, to provide for example transparent fiberglass, as well as, other features and characteristics to the cured preform and ceramic material.
  • the precursor may be a siloxane backbone additive, such as a mono-ph terminated siloxane, which formulas are shown below.
  • R is a reactive group, such as vinyl, hydroxy, or hydride.
  • This precursor may have a molecular weight (mw) from about 500 mw to about 2,000 mw, and may have a viscosity preferably from about 80 cps to about 300 cps.
  • the percentage of methyl - R - siloxane units "X" may be from 1 % to 100%.
  • percentage of the dimethylsiloxane units "Y" may be from 0% to 99%.
  • This precursor may be used to provide a toughening agent and to adjust the refractive index of the polymer to match the refractive index of various types of glass, to provide for example transparent fiberglass, as well as, other features and characteristics to the cured preform and ceramic material.
  • the precursor may be a siloxane backbone additive, such as diphenyl dimethyl olysiloxane, which formula is shown below.
  • This precursor may have a molecular weight (mw) from about 500 mw to about 20,000 mw, and may have a molecular weight from about 800 to about 4,000, and may have a viscosity preferably from about 100 cps to about 800 cps.
  • the percentage of dimethylsiloxane units "X" may be from 25% to 95%.
  • the percentage of the diphenyl siloxane units "Y” may be from 5% to 75%.
  • This precursor may be used to provide similar characteristics to the mono-phenyl terminated siloxane, as well as, other features and characteristics to the cured preform and ceramic material.
  • the precursor may be a siloxane backbone additive, such as vinyl terminated diphenyl dimethyl polysiloxane, which formula is shown below.
  • This precursor may have a molecular weight (mw) from about 400 mw to about 20,000 mw, and may have a molecular weight from about 800 to about 2,000, and may have a viscosity preferably from about 80 cps to about 600 cps.
  • the percentage of dimethylsiloxane units "X" may be from 25% to 95%.
  • the percentage of the diphenyl siloxane units "Y” may be from 5% to 75%.
  • This precursor may be used to provide chain extension, toughening agent, changed or altered refractive index, and improvements to high temperature thermal stability of the cured material, as well as, other features and characteristics to the cured preform and ceramic material.
  • the precursor may be a siloxane backbone additive, such as hydroxy terminated diphenyl dimethyl polysiloxane, which formula is shown below.
  • This precursor may have a molecular weight (mw) from about 400 mw to about 20,000 mw, and may have a molecular weight from about 800 to about 2,000, and may have a viscosity preferably from about 80 cps to about 400 cps.
  • the percentage of dimethylsiloxane units "X" may be from 25% to 95%.
  • the percentage of the diphenyl siloxane units "Y” may be from 5% to 75%.
  • This precursor may be used to provide chain extension, toughening agent, changed or altered refractive index, and improvements to high temperature thermal stability of the cured material, can generate nano- and micro- scale porosity, as well as other features and characteristics to the cured preform and ceramic material.
  • the precursor batch may also contain non-silicon based cross-linking agents, be the reaction product of a non-silicon based cross linking agent and a siloxane backbone additive, and combinations and variation of these.
  • the non-silicon based cross-linking agents are intended to, and provide, the capability to cross-link during curing.
  • non-silicon based cross-linking agents that can be used include: cyclopentadiene (CP), methylcyclopentadiene (MeCP), dicyclopentadiene (“DCPD”), methyldicyclopentadiene (MeDCPD), tricyclopentadiene (TCPD), piperylene,
  • Some organic materials containing oxygen, nitrogen, and sulphur may also function as cross-linking moieties.
  • the precursor may be a reactive monomer. These would include molecules, such as tetramethyltetravinylcyclotetrasiloxane ("TV”), which formula is shown below.
  • TV tetramethyltetravinylcyclotetrasiloxane
  • This precursor may be used to provide a branching agent, a three- dimensional cross-linking agent, as well as, other features and characteristics to the cured preform and ceramic material. (It is also noted that in certain formulations, e.g., above 2%, and certain temperatures, e.g., about from about room temperature to about 60° C, this precursor may act as an inhibitor to cross-linking, e.g., in may inhibit the cross-linking of hydride and vinyl groups.)
  • the precursor may be a reactive monomer, for example, such as trivinyl cyclotetrasiloxane,
  • the precursor may be a silane modifier, such as vinyl phenyl methyl silane, diphenyl silane, diphenyl methyl silane, and phenyl methyl silane (some of which may be used as an end capper or end termination group).
  • silane modifiers can provide chain extenders and branching agents. They also improve toughness, alter refractive index, and improve high temperature cure stability of the cured material, as well as improving the strength of the cured material, among other things.
  • a precursor, such as diphenyl methyl silane may function as an end capping agent, that may also improve toughness, alter refractive index, and improve high temperature cure stability of the cured material, as well as, improving the strength of the cured material, among other things.
  • the precursor may be a reaction product of a silane modifier with a vinyl terminated siloxane backbone additive.
  • the precursor may be a reaction product of a silane modifier with a hydroxy terminated siloxane backbone additive.
  • the precursor may be a reaction product of a silane modifier with a hydride terminated siloxane backbone additive.
  • the precursor may be a reaction product of a silane modifier with TV.
  • the precursor may be a reaction product of a silane.
  • the precursor may be a reaction product of a silane modifier with a cyclosiloxane, taking into consideration steric hindrances.
  • the precursor may be a partially hydrolyzed tetraethyl orthosilicate, such as TES 40 or Silbond 40.
  • the precursor may also be a methylsesquisiloxane such as SR- 350 available from General Electric Company, Wilton, Conn.
  • the precursor may also be a phenyl methyl siloxane such as 604 from Wacker Chemie AG.
  • the precursor may also be a methyiphenySvinylsiloxane, such as H82 C from Wacker Chemie AG.
  • the precursors may also be selected from the following:
  • POLYDIMETHYLSILOXANE (OF1070) 70131 -67-8; SiSiB® OF1070 SILANOL TERMINATED PO LYD I M ETH YS I LOXAN E 70131 -67-8; OH-ENDCAPPED POLYDIMETHYLSILOXANE HYDROXY TERMINATED OLYDIMETHYLSILOXANE
  • a precursor may be a compound of the following general formula.
  • the R groups Ri, R 2 , R 3 , and R 4 may all be different, or one or more may be the same.
  • R 2 is the same as R 3
  • R 3 is the same as R 4
  • Ri and R 2 are different with R 3 and R 4 being the same, etc.
  • embodiments of formulations for polysilocarb formulations may for example have from about 0% to 50% MH, about 20% to about 99% MH, about 0% to about 30% siloxane backbone additives, about 1 % to about 60% reactive monomers, about 30% to about 100% TV, and, about 0% to about 90% reaction products of a siloxane backbone additives with a silane modifier or an organic modifier reaction products.
  • the formulations In mixing the formulations sufficient time should be used to permit the precursors to become effectively mixed and dispersed. Generally, mixing of about 15 minutes to an hour is sufficient. Typically, the precursor formulations are relatively, and essentially, shear insensitive, and thus the type of pumps or mixing are not critical. It is further noted that in higher viscosity formulations additional mixing time may be required.
  • the temperature of the formulations, during mixing should preferably be kept below about 45° C, and preferably about 10° C. (It is noted that these mixing conditions are for the pre-catalyzed formulations.)
  • reaction type process in general, a chemical reaction is used to combine one, two or more precursors, typically in the presence of a solvent, to form a precursor formulation that is essentially made up of a single polymer that can then be, catalyzed, cured and pyrolized.
  • This process provides the ability to build custom precursor formulations that when cured can provide plastics having unique and desirable features such as high temperature, flame resistance and retardation, strength and other features.
  • the cured materials can also be pyrolized to form ceramics having unique features.
  • reaction type process allows for the predetermined balancing of different types of functionality in the end product by selecting functional groups for incorporation into the polymer that makes up the precursor formulation, e.g., phenyls which typically are not used for ceramics but have benefits for providing high
  • a custom polymer for use as a precursor formulation is made by reacting precursors in a condensation reaction to form the polymer precursor formulation. This precursor formulation is then cured into a preform through a hydrolysis reaction. The condensation reaction forms a polymer of the type shown below.
  • Ri and R 2 may be the same or different.
  • the custom precursor polymers can have several different polymeric units, e.g., Ai , A 2 , A n , and may include as many as 10, 20 or more units, or it may contain only a single unit, for example, MHF made by the reaction process may have only a single unit.
  • Embodiments may include precursors, which include among others, a triethoxy methyl silane, a diethoxy methyl phenyl silane, a diethoxy methyl hydride silane, a diethoxy methyl vinyl silane, a dimethyl ethoxy vinyl silane, a diethoxy dimethyl silane.
  • the end units, Si End 1 and Si End 2 can come from the precursors of dimethyl ethoxy vinyl silane, ethoxy dimethyl phenyl silane, and trimethyl ethoxy silane. Additionally, if the polymerization process is properly controlled a hydroxy end cap can be obtained from the precursors used to provide the repeating units of the polymer.
  • the precursors are added to a vessel with ethanol (or other material to absorb heat, e.g., to provide thermal mass), an excess of water, and hydrochloric acid (or other proton source).
  • ethanol or other material to absorb heat, e.g., to provide thermal mass
  • hydrochloric acid or other proton source
  • This mixture is heated until it reaches its activation energy, after which the reaction typically is exothermic.
  • the water reacts with an ethoxy group of the silicon of the precursor monomer, forming a hydroxy (with ethanol as the byproduct). Once formed this hydroxy becomes subject to reaction with an ethoxy group on the silicon of another precursor monomer, resulting in a polymerization reaction.
  • This polymerization reaction is continued until the desired chain length(s) is built.
  • Control factors for determining chain length are: the monomers chosen (generally, the smaller the monomers the more that can be added before they begin to coil around and bond to themselves); the amount and point in the reaction where end cappers are introduced; and the amount of water and the rate of addition, among others.
  • the chain lengths can be from about 180 mw (viscosity about 5 cps) to about 65,000 mw (viscosity of about 10,000 cps), greater than about 1000 mw, greater than about 10,000 mw, greater than about 50,000 mw and greater.
  • the polymerized precursor formulation may, and typically does, have polymers of different molecular weights, which can be predetermined to provide formulation, cured, and ceramic product performance features.
  • the material Upon completion of the polymerization reaction the material is transferred into a separation apparatus, e.g., a separation funnel, which has an amount of deionized water that, for example, is from about 1 .2x to about 1 .5x the mass of the material.
  • This mixture is vigorously stirred for about less than 1 minute and preferably from about 5 to 30 seconds. Once stirred the material is allowed to settle and separate, which may take from about 1 to 2 hours.
  • the polymer is the higher density material and is removed from the vessel. This removed polymer is then dried by either warming in a shallow tray at 90° C for about two hours; or, preferably, is passed through a wiped film distillation apparatus, to remove any residual water and ethanol.
  • sodium bicarbonate sufficient to buffer the aqueous layer to a pH of about 4 to about 7 is added. It is further understood that other, and commercial, manners of mixing, reacting and separating the polymer from the material may be employed.
  • a catalyst is used in the curing process of the polymer precursor formulations from the reaction type process.
  • the same polymers, as used for curing the precursor formulations from the mixing type process can be used. It is noted that, generally unlike the mixing type formulations, a catalyst is not necessarily required to cure a reaction type polymer. Inhibitors may also be used. However, if a catalyst is not used, reaction time and rates will be slower.
  • the curing and the pyrolysis of the cured material from the reaction process is essentially the same as the curing and pyrolysis of the cured material from the mixing process and the reaction blending process.
  • the reaction type process can be conducted under numerous types of atmospheres and conditions, e.g., air, inert, N 2 , Argon, flowing gas, static gas, reduced pressure, ambient pressure, elevated pressure, and combinations and variations of these.
  • atmospheres and conditions e.g., air, inert, N 2 , Argon, flowing gas, static gas, reduced pressure, ambient pressure, elevated pressure, and combinations and variations of these.
  • reaction blending type process precursor are reacted to from a precursor formulation, in the absence of a solvent.
  • an embodiment of a reaction blending type process has a precursor formulation that is prepared from MHF and Dicyclopentadiene ("DCPD"). Using the reactive blending process a MHF/DCPD polymer is created and this polymer is used as a precursor formulation.
  • DCPD Dicyclopentadiene
  • a sealable reaction vessel with a mixer, can be used for the reaction.
  • the reaction is conducted in the sealed vessel, in air; although other types of atmosphere can be utilized.
  • the reaction is conducted at atmospheric pressure, but higher and lower pressures can be utilized.
  • the reaction blending type process can be conducted under numerous types of atmospheres and conditions, e.g., air, inert, N 2 , Argon, flowing gas, static gas, reduced pressure, ambient pressure, elevated pressure, and combinations and variations of these.
  • the temperature of the reaction vessel is controlled to, maintain a predetermined temperature profile over time, and to manage the temperature increase that may be accompanied by an exotherm.
  • the temperature of the reaction vessel is regulated, monitored and controlled throughout the process.
  • the temperature profile can be as follows: let temperature reach about 80° C (may take -15- 40 min, depending upon the amount of materials present); temperature will then increase and peak at -104° C, as soon as temperature begins to drop, the heater set temperature is increased to 100° C and the temperature of the reaction mixture is monitored to ensure the polymer temp stays above 80° C for a minimum total of about 2 hours and a maximum total of about 4 hours. After 2-4 hours above 80° C, the heater is turned off, and the polymer is cooled to ambient. It being understood that in larger and smaller batches, continuous, semi-continuous, and other type processes the temperature and time profile may be different.
  • Industrial factory automation and control systems can be utilized to control the reaction, temperature profiles and other processes during the reaction.
  • Table C sets forth various embodiments of reaction blending processes. [00222] Table C
  • the degree of polymerization is the number of monomer units, or repeat units, that are attached together to form the polymer.
  • /mol refers to the molar equivalents.
  • Grams/mole of vinyl refers to the amount of a given polymer needed to provide 1 molar equivalent of vinyl functionality.
  • VH refers to methyl vinyl fluid, a linear vinyl material from the ethoxy process, which can be a substitute for TV.
  • the numbers "0200” etc. for VT are the viscosity in centipoise for that particular VT.
  • Precursor formulations including the polysilocarb precursor formulations from the above types of processes, as well as others, can be cured to form a solid, semi- sold, or plastic like material.
  • the precursor formulations are spread, shaped, or otherwise formed into a preform, which would include any volumetric structure, or shape, including thin and thick films.
  • the polysilocarb precursor formulation may be processed through an initial cure, to provide a partially cured material, which may also be referred to, for example, as a preform, green material, or green cure (not implying anything about the material's color). The green material may then be further cured. Thus, one or more curing steps may be used.
  • the material may be "end cured,” i.e., being cured to that point at which the material has the necessary physical strength and other properties for its intended purpose.
  • the amount of curing may be to a final cure (or "hard cure"), i.e., that point at which all, or essentially all, of the chemical reaction has stopped (as measured, for example, by the absence of reactive groups in the material, or the leveling off of the decrease in reactive groups over time).
  • the material may be cured to varying degrees, depending upon its intended use and purpose. For example, in some situations the end cure and the hard cure may be the same. Curing conditions such as atmosphere and temperature may affect the
  • composition of the cured material is a composition of the cured material.
  • the precursor formulation e.g., polysilocarb formulation
  • the precursor formulation can be, for example, formed using the following techniques: spraying, spray drying, atomization, nebulization, phase change separation, flowing, thermal spraying, drawing, dripping, forming droplets in liquid and liquid-surfactant systems, painting, molding, forming, extruding, spinning, ultrasound, vibrating, solution polymerization, emulsion polymerization, micro-emulsion
  • volumetric shapes may include for example, the following: spheres, pellets, rings, lenses, disks, panels, cones, frustoconical shapes, squares, rectangles, trusses, angles, channels, hollow sealed chambers, hollow spheres, blocks, sheets, coatings, films, skins, particulates, beams, rods, angles, slabs, columns, fibers, staple fibers, tubes, cups, pipes, and combinations and various of these and other more complex shapes, both engineering and architectural.
  • the forming step, the curing steps, and the pyrolysis steps may be conducted in batch processes, serially, continuously, with time delays (e.g., material is stored or held between steps), and combinations and variations of these and other types of processing sequences.
  • the precursors can be partially cured, or the cure process can be initiated and on going, prior to the precursor being formed into a volumetric shape.
  • These steps, and their various combinations may be, and in some embodiments preferably are, conducted under controlled and predetermined conditions (e.g., the material is exposed to a predetermined atmosphere, and temperature profile during the entirely of its processing, e.g., reduced oxygen, temperature of cured preform held at about 140° C prior to pyrolysis).
  • system, equipment, or processing steps, for forming, curing and pyrolizing may be the same equipment, continuous equipment, batch and linked equipment, and combinations and variations of these and other types of industrial processes.
  • a spray drying technique could form cured particles that are feed directly into a fluidized bed reactor for pyrolysis.
  • the polysilocarb precursor formulations can be made into neat, non- reinforced, non-filled, composite, reinforced, and filled structures, intermediates, end products, and combinations and variations of these and other compositional types of materials. Further, these structures, intermediates and end products can be cured (e.g., green cured, end cured, or hard cured), uncured, pyrolized to a ceramic, and combinations and variations of these (e.g., a cured material may be filled with pyrolized material derived from the same polysilocarb as the cured material).
  • the precursor formulations may be used to form a "neat” material, (by “neat” material it is meant that all, and essentially all of the structure is made from the precursor material or unfilled formulation; and thus, there are no fillers or
  • the polysilocarb precursor formulations may be used to coat or impregnate a woven or non-woven fabric, made from for example carbon fiber, glass fibers or fibers made from a polysilocarb precursor formulation (the same or different formulation), to from a prepreg material.
  • the polysilocarb precursor formulations may be used to form composite materials, e.g., reinforced products.
  • the formulation may be flowed into, impregnated into, absorbed by or otherwise combined with a reinforcing material, such as carbon fibers, glass fiber, woven fabric, grapheme, carbon nanotubes, thin films, precipitates, sand, non-woven fabric, copped fibers, fibers, rope, braided structures, ceramic powders, glass powders, carbon powders, graphite powders, ceramic fibers, metal powders, carbide pellets or components, staple fibers, tow, nanostructures of the above, polymer derived ceramics, any other material that meets the temperature requirements of the process and end product, and combinations and variations of these.
  • a reinforcing material such as carbon fibers, glass fiber, woven fabric, grapheme, carbon nanotubes, thin films, precipitates, sand, non-woven fabric, copped fibers, fibers, rope, braided structures, ceramic powders, glass powders, carbon powders, graphite powders, ceramic fibers, metal powders, carbide pellets or components, staple fiber
  • the reinforcing material may also be made from, or derived from the same material as the formulation that has been formed into a fiber and pyrolized into a ceramic, or it may be made from a different precursor formulation material, which has been formed into a fiber and pyrolized into a ceramic.
  • the polysilocarb precursor formulation may be used to form a filled material.
  • a filled material would be any material having other solid, or semi-solid, materials added to the polysilocarb precursor formulation.
  • the filler material may be selected to provide certain features to the cured product, the ceramic product and both. These features may relate to, or be, for example, aesthetic, tactile, thermal, density, radiation, chemical, cost, magnetic, electric, and combinations and variations of these and other features. These features may be in addition to strength. Thus, the filler material may not affect the strength of the cured or ceramic material, it may add strength, or could even reduce strength in some situations.
  • the filler material could impart color, magnetic capabilities, fire resistances, flame retardance, heat resistance, electrical conductivity, anti-static, optical properties (e.g., reflectivity, refractivity and iridescence), aesthetic properties (such as stone like appearance in building products), chemical resistivity, corrosion resistance, wear resistance, reduced cost, abrasions resistance, thermal insulation, UV stability, UV protective, and other features that may be desirable, necessary, and both, in the end product or material.
  • filler materials could include carbon black, copper lead wires, thermal conductive fillers, electrically conductive fillers, lead, optical fibers, ceramic colorants, pigments, oxides, sand, dyes, powders, ceramic fines, polymer derived ceramic particles, pore-formers, carbosilanes, silanes, silazanes, silicon carbide, carbosilazanes, siloxane, powders, ceramic powders, metals, metal complexes, carbon, tow, fibers, staple fibers, boron containing materials, milled fibers, glass, glass fiber, fiber glass, and nanostructures (including nanostructures of the forgoing) to name a few.
  • the polysilocarb formulation and products derived or made from that formulation may have metals and metal complexes. Filled materials would include reinforced materials. In many cases, cured, as well as pyrolized polysilocarb filled materials can be viewed as composite materials. Generally, under this view, the polysilocarb would constitute the bulk or matrix phase, (e.g., a continuous, or substantially continuous phase), and the filler would constitute the dispersed (e.g., non- continuous), phase.
  • the filler can be evenly distributed in the precursor formulation, unevenly distributed, distributed over a predetermined and controlled distribution gradient (such as from a predetermined rate of settling), and can have different amounts in different formulations, which can then be formed into a product having a predetermined amounts of filler in predetermined areas (e.g., striated layers having different filler concentration).
  • a predetermined and controlled distribution gradient such as from a predetermined rate of settling
  • the ratio (either weight or volume) of polysilocarb to filler material could be from about 0.1 :99.9 to 99.9:0.1 .
  • the polysilocarb precursor formulations may be used to form non-reinforced materials, which are materials that are made of primarily, essentially, and preferably only from the precursor materials; but may also include formulations having fillers or additives that do not impart strength.
  • the curing may be done at standard ambient temperature and pressure ("SATP", 1 atmosphere, 25° C), at temperatures above or below that temperature, at pressures above or below that pressure, and over varying time periods.
  • SATP standard ambient temperature and pressure
  • the curing can be conducted over various heatings, rate of heating, and temperature profiles (e.g., hold times and temperatures, continuous temperature change, cycled temperature change, e.g., heating followed by maintaining, cooling, reheating, etc.).
  • the time for the curing can be from a few seconds (e.g., less than about 1 second, less than 5 seconds), to less than a minute, to minutes, to hours, to days (or potentially longer).
  • the curing may also be conducted in any type of surrounding environment, including for example, gas, liquid, air, water, surfactant containing liquid, inert atmospheres, N 2 , Argon, flowing gas (e.g., sweep gas), static gas, reduced O2, reduced pressure, elevated pressure, ambient pressure, controlled partial pressure and combinations and variations of these and other processing conditions.
  • gas e.g., sweep gas
  • static gas e.g., static gas
  • reduced O2 reduced pressure
  • elevated pressure elevated pressure
  • ambient pressure controlled partial pressure and combinations and variations of these and other processing conditions.
  • the furnace, containers, handling equipment, atmosphere, and other components of the curing apparatus and process are clean, essentially free from, and do not contribute any elements or materials, that would be considered impurities or contaminants, to the cured material.
  • the curing environment e.g., the furnace, the atmosphere, the container and combinations and variations of these can have materials that contribute to or effect, for example, the composition, catalysis, stoichiometry, features, performance and combinations and variations of these in the preform, the ceramic and the final applications or products.
  • the curing takes place at temperatures in the range of from about 5°C or more, from about 20°C to about 250°C, from about 20°C to about 150°C, from about 75°C to about 125°C, and from about 80°C to 90°C.
  • temperatures in the range of from about 5°C or more, from about 20°C to about 250°C, from about 20°C to about 150°C, from about 75°C to about 125°C, and from about 80°C to 90°C.
  • rate of temperature change over time e.g., ⁇ degrees/time
  • hold times e.g., hold times, and temperatures
  • the cure conditions may be dependent upon, and in some embodiments can be predetermined, in whole or in part, by the formulation to match, for example the size of the preform, the shape of the preform, or the mold holding the preform to prevent stress cracking, off gassing, or other
  • the curing conditions may be such as to take advantage of, preferably in a controlled manner, what may have previously been perceived as problems associated with the curing process.
  • off gassing may be used to create a foam material having either open or closed structure.
  • curing conditions can be used to create or control the microstructure and the nanostructure of the material.
  • the curing conditions can be used to affect, control or modify the kinetics and thermodynamics of the process, which can affect morphology, performance, features and functions, among other things.
  • a cross linking reaction takes place that provides in some embodiments a cross-linked structure having, among other things, an -Ri-Si-C-C-Si-O-Si-C-C-Si-R2- where Ri and R2 vary depending upon, and are based upon, the precursors used in the formulation.
  • Ri and R2 vary depending upon, and are based upon, the precursors used in the formulation.
  • the cured materials may have a cross-linked structure having 3-coordinated silicon centers to another silicon atom, being separated by fewer than 5 atoms between silicons.
  • some formulations may exhibit an exotherm, i.e., a self heating reaction, that can produce a small amount of heat to assist or drive the curing reaction, or that may produce a large amount of heat that may need to be managed and removed in order to avoid problems, such as stress fractures.
  • a self heating reaction i.e., a self heating reaction
  • During the cure off gassing typically occurs and results in a loss of material, which loss is defined generally by the amount of material remaining, e.g., cure yield.
  • Embodiments of the formulations, cure conditions, and polysilocarb precursor formulations of embodiments of the present inventions can have cure yields of at least about 90%, about 92%, about 100%.
  • the materials may have cure yields above 100%, e.g., about 101 -105%, as a result of oxygen being absorbed from the air.
  • this shrinkage may be, depending upon the formulation, cure conditions, and the nature of the preform shape, and whether the preform is reinforced, filled, neat or unreinforced, from about 20%, less than 20%, less than about 15%, less than about 5%, less than about 1 %, less than about 0.5%, less than about 0.25% and smaller.
  • Curing of the preform may be accomplished by any type of heating apparatus, or mechanisms, techniques, or morphologies that has the requisite level of temperature and environmental control, for example, heated water baths, electric furnaces, microwaves, gas furnaces, furnaces, forced heated air, towers, spray drying, falling film reactors, fluidized bed reactors, lasers, indirect heating elements, direct heating, infrared heating, UV irradiation, RF furnace, in-situ during emulsification via high shear mixing, in-situ during emulsification via ultrasonication.
  • heated water baths for example, heated water baths, electric furnaces, microwaves, gas furnaces, furnaces, forced heated air, towers, spray drying, falling film reactors, fluidized bed reactors, lasers, indirect heating elements, direct heating, infrared heating, UV irradiation, RF furnace, in-situ during emulsification via high shear mixing, in-situ during emulsification via ultrasonication.
  • the cured preforms may be used as a stand alone product, an end product, a final product, or a preliminary product for which later machining or processing may be performed on.
  • the preforms may also be subject to pyrolysis, which converts the preform material into a ceramic.
  • the preform, or cured structure, or cured material In pyrolizing the preform, or cured structure, or cured material, it is heated to about 600° C to about 2,300° C; from about 650° C to about 1 ,200° C, from about 800°C to about 1300°C, from about 900°C to about 1200°C and from about 950°C to 1 150°C. At these temperatures typically all organic structures are either removed or combined with the inorganic constituents to form a ceramic. Typically at temperatures in the about 650° C to 1 ,200° C range the resulting material is an amorphous glassy ceramic.
  • the material When heated above about 1 ,200° C the material typically may from nano crystalline structures, or micro crystalline structures, such as SiC, Si3N , SiCN, ⁇ SiC, and above 1 ,900° C an a SiC structure may form, and at and above 2,200° C a SiC is typically formed.
  • the pyrolized, e.g., ceramic materials can be single crystal, polycrystalline, amorphous, and combinations, variations and subgroups of these and other types of morphologies.
  • the pyrolysis may be conducted under many different heating and
  • the pyrolysis may have various heating ramp rates, heating cycles and environmental conditions.
  • the temperature may be raised, and held a predetermined temperature, to assist with known transitions (e.g., gassing, volatilization, molecular rearrangements, etc.) and then elevated to the next hold temperature corresponding to the next known transition.
  • the pyrolysis may take place in reducing atmospheres, oxidative atmospheres, low O2, gas rich (e.g., within or directly adjacent to a flame), inert, N 2 , Argon, air, reduced pressure, ambient pressure, elevated pressure, flowing gas (e.g., sweep gas, having a flow rate for example of from about from about 15.0 GHSV to about 0.1 GHSV, from about 6.3 GHSV to about 3.1 GHSV, and at about 3.9 GHSV), static gas, and combinations and variations of these.
  • gas rich e.g., within or directly adjacent to a flame
  • inert e.g., N 2 , Argon
  • air reduced pressure
  • ambient pressure e.g., elevated pressure
  • flowing gas e.g., sweep gas, having a flow rate for example of from about from about 15.0 GHSV to about 0.1 GHSV, from about 6.3 GHSV to about 3.1 GHSV, and at about 3.9 GHSV
  • static gas e.g.
  • the pyrolysis is conducted over a time period that preferably results in the complete pyrolysis of the preform.
  • the furnace, containers, handling equipment, and other components of the pyrolysis apparatus are clean, essentially free from, free from and do not contribute any elements or materials, that would be considered impurities or contaminants, to the pyrolized material.
  • a constant flow rate of "sweeping" gas can help purge the furnace during volatile generation.
  • the pyrolysis environment e.g., the furnace, the atmosphere, the container and combinations and variations of these, can have materials that contribute to or effect, for example, the composition, stoichiometry, features, performance and combinations and variations of these in the ceramic and the final applications or products.
  • embodiments of the present formulations can have char yields for SiOC formation of at least about 60%, about 70%, about 80%, and at least about 90%, at least about 91 % and greater.
  • the materials may have char yields well above 91 %, which can approach 100%.
  • specifically tailored formulations can be used.
  • formulations high in phenyl content (at least about 1 1 %, and preferably at least about 20% by weight phenyls), formulations high in allyl content (at least about 15% to about 60%) can be used for air pyrolysis to mitigate the degradation of the material.
  • the initial or first pyrolysis step for SiOC formation in some embodiments and for some uses, generally yields a structure that is not very dense, and for example, may not reached the density required for its intended use. However, in some examples, such as the use of lightweight spheres, proppants, pigments, and others, the first pyrolysis may be, and is typically sufficient. Thus, generally a reinfiltration process may be performed on the pyrolized material, to add in additional polysilocarb precursor formulation material, to fill in, or fill, the voids and spaces in the structure. This reinfiltrated material may then be cured and repyrolized.
  • the reinfiltrated materials is cured, but not pyrolized.
  • This process of pyrolization, reinfiltration may be repeated, through one, two, three, and up to 10 or more times to obtain the desired density of the final product.
  • Si-O-C ceramic upon pyrolization, graphenic, graphitic, amorphous carbon structures and combinations and variations of these are present in the Si-O-C ceramic.
  • a distribution of silicon species, consisting of SiOxCy structures, which result in SiO4, SiO3C, SiO2C2, SiOC3, and SiC4 are formed in varying ratios, arising from the precursor choice and their processing history.
  • Carbon is generally bound between neighboring carbons and/or to a Silicon atom. In general, in the ceramic state, carbon is largely not coordinated to an oxygen atom, thus oxygen is largely coordinated to silicon
  • the pyrolysis may be conducted in any heating apparatus that maintains the request temperature and environmental controls.
  • pyrolysis may be done with gas fired furnaces, electric furnaces, direct heating, indirect heating, fluidized beds, kilns, tunnel kilns, box kilns, shuttle kilns, coking type apparatus, lasers, microwaves, and combinations and variations of these and other heating apparatus and systems that can obtain the request temperatures for pyrolysis.
  • Custom and predetermined control of when chemical reactions, arrangements and rearrangements, occur in the various stages of the process from raw material to final end product can provide for reduced costs, increased process control, increased reliability, increased efficiency, enhanced product features, increased purity, and combinations and variation of these and other benefits.
  • the sequencing of when these transformations take place can be based upon the processing or making of precursors, and the processing or making of precursor formulations; and may also be based upon cure and pyrolysis conditions. Further, the custom and predetermined selection of these steps, formulations and conditions, can provide enhanced product and processing features through the various transformations, e.g., chemical reactions; molecular arrangements and rearrangements; and microstructure arrangements and
  • the polymer derived ceramic structures e.g., polysilocarb structures, intermediates and end products, and combinations and variations of these, may be machined, milled, molded, shaped, drilled, etched, or otherwise mechanically processed and shaped.
  • embodiments of the pyrolized polysilocarb ceramics can have about 30% to about 60% Si, can have about 5% to about 40% O, and can have about 3% to about 35% carbon. Greater and lesser amounts are also contemplated.
  • the type of carbon present in preferred embodiments of the polysilocarb derived ceramics can be free carbon, (e.g., turbostratic, amorphous, graphenic, graphitic forms of carbon) and Carbon that is bound to Silicon.
  • free carbon e.g., turbostratic, amorphous, graphenic, graphitic forms of carbon
  • Carbon that is bound to Silicon.
  • Embodiments having preferred amounts of free carbon and Silicon-bound-Carbon (Si-C) are set forth in Table 2.
  • polysilocarb derived ceramics can have from about 20% free carbon to about 80% free carbon, and from about 20% Si-C bonded carbon to about 80% Si-C bonded carbon. Greater and lesser amounts are also contemplated.
  • embodiments of the pyrolized polysilocarb ceramics can have other elements present, such as Nitrogen and Hydrogen.
  • Embodiments can have the amounts of these other materials as set out in Table 3. (Note that these are typical for embodiments of net materials. If fillers, additives, or other materials are combined with or into the precursor formulation; then such materials can generally be present to a greater or lesser extent in the pyrolized ceramic material)
  • these articles can be hard cured polysilocarb materials, pyrolized polysilocarb materials, pyrolized materials that are reinfiltrated to a very high density, filled and unfilled polysilocarb materials, ready to press sintered SiC (which is derived from polysilocarb materials as disclosed and taught in US Patent Application Serial No.
  • a polysilocarb formulation using the mixing type method is formulated.
  • the formulation is made by mixing together at room temperature 70% of the MHF precursor and a molecular weight of about 800 and 30% of the allyl terminated precursor having a molecular weight of about 500 in a vessel and placing in storage for later use.
  • the polysilocarb formulation has good shelf life and room temperature and the precursors have not, and do not react with each other.
  • the polysilocarb formulation has a viscosity of about 12 cps.
  • a polysilocarb formulation using the mixing type method is formulated.
  • the formulation is made by mixing together at room temperature 60% of the MHF precursor and a molecular weight of about 800 and 40% of the vinyl terminated precursor having a molecular weight of about 9,400 in a vessel and placing in storage for later use.
  • the polysilocarb formulation has good shelf life and room temperature and the precursors have not, and do not react with each other.
  • the polysilocarb formulation has a viscosity of about 200 cps.
  • EXAMPLE 3 A polysilocarb fornnulation using the mixing type method is formulated.
  • the formulation is made by mixing together 50% of the MH precursor having a molecular weight of about 800 and 50% of the vinyl terminated precursor having a molecular weight of about 800 in a vessel and placing in storage for later use.
  • the polysilocarb formulation has good shelf life and room temperature and the precursors have not, and do not react with each other.
  • the polysilocarb formulation has a viscosity of about 55 cps.
  • a polysilocarb formulation using the mixing type method is formulated.
  • the formulation is made by mixing together 40% of the MH precursor having a molecular weight of about 1 ,000 and 60% of the vinyl terminated precursor having a molecular weight of about 500 in a vessel and placing in storage for later use.
  • the polysilocarb formulation has good shelf life and room temperature and the precursors have not, and do not react with each other.
  • the polysilocarb formulation has a viscosity of about 25 cps.
  • a polysilocarb formulation using the mixing type method is formulated.
  • the formulation is made by mixing together 30% of the MHF precursor having a molecular weight of about 800 and 70% of the vinyl terminated precursor having a molecular weight of about 500 in a vessel and placing in storage for later use.
  • the polysilocarb formulation has good shelf life and room temperature and the precursors have not, and do not react with each other.
  • the polysilocarb formulation has a viscosity of about 10 cps.
  • the polysilocarb formulation of Example 1 has 40% of an about 80 micron to about 325 mesh SiC filler added to the formulation to make a filled polysilocarb formulation, which can be kept for later use.
  • the polysilocarb formulation of Example 2 has 30 % of an about 80 micron to about 325 mesh SiC filler added to the formulation to make a filled polysilocarb formulation, which can be kept for later use.
  • a polysilocarb formulation using the mixing type method is formulated.
  • the formulation is made by mixing together 10% of the MHF precursor having a molecular weight of about 800 and 73% of the styrene (phenylethyl) precursor (having 10% X) and a molecular weight of about 1 ,000, and 16% of the TV precursor, and 1 % of the OH terminated precursor, having a molecular weight of about 1 ,000 in a vessel and placing in storage for later use.
  • the polysilocarb formulation has good shelf life and room temperature and the precursors have not, and do not react with each other.
  • the polysilocarb formulation has a viscosity of about 72 cps.
  • a polysilocarb formulation using the mixing type method is formulated.
  • the formulation is made by mixing together 0-90% of the MH precursor having a molecular weight of about 800, and 0-90% of the styrene precursor (having 10% X) and a molecular weight of about 1000, and 0-30% of the TV precursor, and 0-30% of the vinyl terminated precursor having a molecular weight of about 9400 and 0-20% of the OH terminated precursor, having a molecular weight of about 800 in a vessel and placing in storage for later use.
  • the polysilocarb formulation has good shelf life and room temperature and the precursors have not, and do not react with each other.
  • the polysilocarb formulation has a viscosity of about 100 cps.
  • a polysilocarb formulation using the mixing type method is formulated.
  • the formulation is made by mixing together 70% of the MHF precursor and 30% of the vinyl terminated precursor having a molecular weight of about 500 and about 42% of a submicron and a 325 mesh silica in a vessel and placing in storage for later use.
  • the polysilocarb formulation has good shelf life and room temperature and the precursors have not, and do not react with each other.
  • the polysilocarb formulation has a viscosity of about 300 cps.
  • a polysilocarb formulation using the mixing type method is formulated.
  • the formulation is made by mixing together 20-80% of the MH precursor having a molecular weight of about 800, and 0-10% of the TV precursor, and 5-80% of the vinyl terminated precursor having a molecular weight of about and about 500 of submicron, 325 mesh, and 8 micron SiC in a vessel and placing in storage for later use.
  • the polysilocarb formulation has good shelf life and room temperature and the precursors have not, and do not react with each other.
  • the polysilocarb formulation has a viscosity of about 300 cps.
  • a precursor formulation of having 75% MHF, 15% TV, and 10% VT is formed using the mixing type process and stored.
  • Example 12a The cured material of Example 12a is pyrolized to form a polysilocarb derived ceramic composite material.
  • Example 12 1 % catalyst (10 ppm platinum and 0.5% LUPEROX 231 peroxide) is added to the formulation of Example 12, and the polysilocarb formulation is formed into a prepreg having carbon fiber reinforcement. The prepreg curing is done in Argon and at 200° C for 2 hours. The hard cured preform are pyrolized at 1000° C under vacuum for 5 hours.
  • a polysilocarb precursor formulation having 70% MHF, 20% TV, and 10% VT is formed using the mixing type process and placed in a container.
  • EXAMPLE 15 [00296] 1 % catalyst (10 ppm platinum and 0.5% LUPEROX 231 peroxide) is added to the precursor formulation of Example 14. The catalyzed precursor is then impregnated into a reinforcing material and cured to form a composite.
  • Example 15 The cured material of Example 15 is pyrolized to form a polysilocarb derived ceramic composite material.
  • Example 14 1 % catalyst (10 ppm platinum and 0.5% LUPEROX 231 peroxide) is added to the formulation of Example 14, and the polysilocarb formulation is formed into a prepreg having carbon fiber reinforcement. The prepreg curing is done in Argon and at 200° C for 2 hours. The hard cured preform are pyrolized at 1000° C under vacuum for 5 hours.
  • Example 16b The pyrolized preform of Example 16b, is infused with a polysiloxane precursor formulation and pyrolized.
  • the pyrolized preform of Example 17 is re-infused with a polysiloxane precursor formulation and pyrolized.
  • FIG. 38 135.00 20.1 % 210.35 0.64 41 .1 1 % 0.64 1 .28
  • a polysilocarb formulation is combined with a reinforcing material to form a preform, which is partially or completely cured to form a reinforced composite material in the shape of a component part.
  • the component part is cured, and preferably hard cured.
  • the hard cured component part is pyrolized to form a polysicocarb derived reinforced composite component part, which is taken through from two to five
  • the end reinforced component part is ready for further processing, e.g., machining to tolerances, assembly steps, integration steps, or use.
  • the polysicocarb derived ceramic component part may find applications, or be designed for use in, or as, among other things components of and the embodiments illustrated in the figures of this specification.
  • the use of the polysilocarb derived ceramic composite component parts can provide several features, including among other things, high temperature resistance, corrosion resistance, UV resistance, lightweight, low cost (significantly lower, by as much as several orders of magnitude over silicon carbide and conventional polymer derived ceramics), increased strength to weight rations (e.g., stronger and lighter, same strength and lighter, stronger and same weight), and fire resistance.
  • EXAMPLE 31 [00330] The polysilocarb derived ceramic composite component parts of Example 30 where the polysilocarb formulation includes a vinyl terminated siloxane.
  • Example 30 The polysilocarb derived ceramic composition component parts of Example 30 where the polysilocarb formulation is 60% MHF, 20% TV, 5% Vt and 10% MVF (a reacted formulation of all vinylmethyldiethoxysilane, e.g., the formulations of Examples 66-68)
  • Example 30 The polysilocarb derived ceramic composite component parts of Example 30 where the polysilocarb formulation includes about 10% of the vinyl terminated siloxane.
  • a polysilocarb formulation is combined with a reinforcing material to form a precursor, which is partially or completely cured to form a reinforced composite material in the shape of a component part.
  • the component part is cured, and preferably end cured.
  • the end component part is ready for further processing, e.g., machining to tolerances, assembly steps or use.
  • the polysicocarb derived plastic component part may find applications, or be designed for use in, or as, among other things things components of and the embodiments illustrated in the figures of this specification.
  • polysilocarb derived reinforced composite component parts can provide several features, including among other things, higher temperature resistance (including the ability to retain, or substantially maintain structural integrity during exposure to higher temperatures), include increased strength to weight rations (e.g., stronger and lighter, same strength and lighter, stronger and same weight), light weight, low cost, UV resistance, corrosion resistance, fire resistance, and fire retardation.
  • higher temperature resistance including the ability to retain, or substantially maintain structural integrity during exposure to higher temperatures
  • increased strength to weight rations e.g., stronger and lighter, same strength and lighter, stronger and same weight
  • light weight e.g., low cost
  • UV resistance e.g., UV resistance, corrosion resistance, fire resistance, and fire retardation.
  • Example 34 The polysilocarb derived ceramic composite component parts of Example 34 where the polysilocarb formulation includes a vinyl terminated siloxane.
  • Example 34 The polysilocarb derived ceramic composition component parts of Example 34 where the polysilocarb formulation is 60% MHF, 20% TV, 5% Vt and 10% MVF (a reacted formulation of all vinylmethyldiethoxysilane, e.g., the formulations of Examples 66-68).
  • Example 34 The polysilocarb derived ceramic composite component parts of Example 34 where the polysilocarb formulation includes about 10% of the vinyl terminated siloxane.
  • a polysilocarb formulation is combined with a reinforcing material to form a precursor to a reinforced composite, which is cured to form a reinforced composite material in the shape of a component part.
  • the component part is cured, and preferably hard cured.
  • the hard cured component part is pyrolized to form a polysicocarb derived composite component part, which is then infiltrated with a polysilocarb formulation, which is then cured.
  • This material can be referred to as a polysilocarb plastic-ceramic, or plastic-ceramic, reinforced structure is ready for further processing, assembly steps or use, such as in the components of, and the embodiments illustrated in the figures of this specification.
  • a polysilocarb formulation is formed into the shape of a larger internal diameter (from about 5 inches to about 36 inches, or larger) tube structure.
  • This tube structure is reinforced with reinforcing material arranged to provide both hoop strength (e.g., burst and crush) and axial strength (e.g., bending, elongation, and compression).
  • the thickness of the wall of the tube is dependent upon the end use requirements, the reinforcement material, and whether the material is a plastic, ceramic or plastic-ceramic. By way of example, the thickness could range from about less than a 1 ⁇ 4 inch to 5 inches or more.
  • the tube structures can be subject to: further processing, e.g., machining to specification; the incorporation of end assemblies, e.g., flanges, couplings, joints, connectors; the incorporation of secondary lines
  • tube-in-tube structure e.g., a double walled pipeline
  • break detection devices in for example the form of wires, or optical fibers, could be incorporated into the wall of the tube structure during formation.
  • These tube structures provide many features include increased strength to weight rations (e.g., stronger and lighter, same strength and lighter, stronger and same weight).
  • the polysilocarb tube structure of EXAMPLE 39 is a marine riser for off shore hydrocarbon exploration and production activities. Each riser section is about 75 feet long and the riser sections are capable of being assembled into a deep sea rise that can extend down from the surface to the sea floor for depth of more than 5,000 ft, 10,000 ft, 15,000 ft, 20,000 ft or more.
  • the riser has is substantially less dense than traditional steel risers.
  • the riser wall can have a density of less than about 5 g/cm 3 , and less than about 3 g/cm 3 , which is substantially less than the density of steel, which is about 7.8 g/cm 3 .
  • the reduced density of the polysilocarb riser reduces the amount of flotation needed, and thus reduces the over all outer diameter of the as deployed riser.
  • the smaller outer diameter provides the advantage of reducing the amount of surface area that is subject to currents and thus reduces the stresses placed upon the riser.
  • a polysilocarb formulation is coated onto the surface of a pipe and soft cured.
  • the polysilocarb formulation can be net or it can be filled, for example, with pyrolized polysilocarb ceramic fines. This process is repeated until the desired thickness of the coating is obtained. Once the desired thickness of the coating has been obtained the soft cured layers are end cured.
  • a coating along the exterior of the pipe can provide thermal insulation to the pipe, as well as, corrosion resistance.
  • An internal coating to the pipe may also provide thermal insulation for the materials in the pipe, and provides corrosion resistance. The corrosion resistance provided by the cured polysilocarb internal coating can enable the replacement of more expensive stainless steel and other high priced alloys with lower priced metals.
  • FIGS. 1 to 34 there are illustrated embodiments of the present polymer derived ceramic structures for the drilling, completion, production and other processes for conventional and unconventional oil and natural gas wells.
  • Shale reservoirs are usually one mile or more below the surface of the earth, well below any underground source of drinking water, which is typically no more than 300 to 1000 feet below the surface.
  • the rig is in constant operation 24 hours a day, 7 days a week for approximately 21 to 28 days.
  • a protective mat can be placed to cover the pad site.
  • a typical well is drilled in several stages starting with a large diameter drill bit and then successively smaller drill bits as the drilling is advanced.
  • Such drill bits can be manufactured from polymer derived ceramic materials.
  • the cutters, or cutting members can be made from abrasive materials derived from the present polysilocarb precursors, including SiC (the making and use of polysilocarb derived abrasives, including SiC, abrasive members, and cutters, etc., are disclosed and taught in US Patent Application Serial Numbers 14/634,814 and
  • nested protective casing is cemented into place.
  • casing can be formed from polymer derived ceramic materials. This will protect ground water and maintain the integrity of the well. Initially, prior to removing in the drilling rig, a large diameter hole is drilled for the first 50 to 80 feet.
  • a hole 50 is drilled straight down using fresh water based fluids which cools the drill bit 52, carries the rock cuttings back to the surface, and stabilizes the wall of the wellbore.
  • a series of compressors and boosters generate the air that is used to move the rock cuttings and fresh water into steel bins.
  • the rock cuttings are then disposed of within regulation guidelines and permits.
  • the drill pipe 56 is removed and replaced with pipe called surface casing 58 (See FIGS. 2-4). Again, the drill pipe can be formed from polymer derived ceramic material.
  • cement 60 is pumped down the casing 62 (FIG. 4).
  • a blowout preventer (not shown) is installed after the surface casing has been cemented.
  • the blowout preventer is a series of high-pressure safety valves and seals attached to the top of the casing to control well pressure and prevent surface releases.
  • additional casing sections 64, 66 may be run and like surface casing are then cemented in place to ensure no movement of fluids or gas between those layers and the ground water sources (See FIGS. 6 and 7).
  • a small drilling assembly is passed down through the surface casing.
  • the bit drills through float equipment and cement continuing its journey to the natural gas target area as deep as 8000 feet below the surface.
  • What makes drilling for hydrocarbons in a shale formation unique is the horizontal drilling approach.
  • Vertical drilling continues to a depth called the kickoff point 70. This is where the wellbore begins curving to become horizontal (FIGS. 8 and 9).
  • One of the advantages of horizontal drilling is that it is possible to drill several wells from only one drilling pad minimizing the impact to the surface environment.
  • the drill pipe is removed leaving the bore 50 (FIG. 10) and additional casing 72 is inserted through the full length of the wellbore (FIG.
  • drilling mud helps to stabilize the hole, cool the drill bit and control the downhole pressure. A few 100 feet above the target shale, the drilling assembly comes to a stop. Drilling continues horizontally through the shale at lengths greater than 4000 feet from the point where it entered the formation. Once drilling is completed, the equipment is retracted to the surface. Once the drilling is finished and the final casing 72 has been installed (FIG. 14) the drilling rig is removed and preparations are made for the well completion.
  • the first step in completing a well is the creation of a connection between the final casing 72 and the reservoir rock.
  • a smaller diameter casing called production casing is installed throughout the total length of the well.
  • production casing can be formed from polymer derived ceramics.
  • the production casing is cemented and secured in place by pumping cement down through the end of the casing.
  • the cement is pumped around the outside casing wall through approximately 2500 feet above the producing shale formation or to the surface.
  • the cement creates a seal to ensure that formation fluids can only be produced via the production casing.
  • the well is pressure tested to ensure its integrity for continued drilling.
  • a cross section of the well below surface builds several protective layers of cement and conductor or surface casing.
  • a perforating gun 74 which is equipped with shaped explosive charges down to the rock layer containing oil or natural gas.
  • the structure of the perforating gun can be formed at least in part from polymer derived ceramic material.
  • This perforating gun is then fired which creates holes 76 through the casing, cement and into the target rock (FIGS. 15 and 16). These perforating holes 76 connect the reservoir and the wellbore. Since the perforations are only a few inches long and are performed often more than a mile underground, the entire process is imperceptible on the surface.
  • the perforation gun is then removed in preparation for the next step - hydraulic fracturing.
  • the drilling process further involves the pumping of a mixture of mostly water and sand plus a few chemicals under controlled conditions into deep underground reservoir formations.
  • the chemicals are generally used for friction reduction, to keep bacteria from forming and to help carry the sand. These chemicals typically range in concentrations from 0.1 to 0.5% by volume and help to improve the performance of the stimulation.
  • This stimulation fluid is sent to trucks that pump the fluid into the wellbore and out through the perforations that were earlier formed.
  • This process creates fractures 80 in the oil and gas reservoir rock (FIGS. 17, 18).
  • the sand and the frac fluid remain in these fractures in the rock and keeps them open when the pump pressure is relieved. This allows the previously trapped oil or natural gas to flow to the wellbore more easily.
  • This initial stimulation segment is then isolated with a specially designed plug 82 also contemplated to be formed from polymer derived ceramic material and the perforating guns are used to perforate the ground (FIGS. 19-21 ). This area is then hydraulically fractured in the same manner. This process is repeated along the entire horizontal section of the well, which can extend several miles (FIG. 22). Once the stimulation is complete the isolation plugs are drilled out and production begins (FIGS. 23-24). Initially water, and then natural gas or oil flows into the horizontal casing and up the wellbore (FIG. 25).
  • Wells will be filled with cement and pipes cut off 3 to 6 feet below ground level. All surface equipment will be removed and all pads will be filled in with dirt or replanted. The land can then be used again by the land owner for other activities and there will be virtually no visional signs that a well was once there.
  • FIG. 26 depicts a drill string in the process of being cemented in place during one drilling pass into earth.
  • Each of the components of the drill strings can be formed from one or more of the polymer derived ceramic materials disclosed herein.
  • a borehole 102 can be drilled through the earth including a target geological formation.
  • the borehole is created with a milled tooth rotary drill bit 106 having milled ceramic roller cones 108, 1 10.
  • FIG. 26 shows a section view of a drill string in the process of being cemented in place during one drilling pass into formation.
  • a standard water passage 1 14 is shown through the rotary cone drill bit.
  • the threads 1 16 on rotary drill bit 106 are screwed into a latching subassembly 1 18.
  • the latching sub assembly is a relatively thick-walled pipe having some functions similar to a standard drill collar. This thick walled pipe can also be formed from a ceramic material.
  • FIG. 26 corresponds to the situation where cement is in the process of being forced from the surface through a valve assembly.
  • the top level of cement in the well is designated as element 140.
  • cement fills the annulus of the borehole.
  • mud fills the annulus of the borehole.
  • cement is present at position 142 and drilling mud is present at position 144 in FIG. 26.
  • Relatively thin-wall casing, or drill pipe, designated as element 146 in FIG. 26, is attached to the latching sub.
  • the bottom male threads of the drill pipe 148 are screwed into the female threads 150 of the latching sub.
  • Drilling mud is wiped off the walls of the drill pipe in the well with a bottom wiper plug 152.
  • the bottom wiper plug can be fabricated from polymer derived ceramic material in the shape shown.
  • Portions 154 and 156 of an upper seal of the bottom wiper plug are shown in a ruptured condition in FIG. 26. Initially, they sealed the upper portion of the bottom wiper plug. Under pressure from cement, the Bottom Wiper Plug is pumped down into the well until a lower lobe of the bottom wiper plug 158 latches into place into recession 160. After the bottom wiper plug latches into place, the pressure of the cement ruptures the upper seal of the bottom wiper plug.
  • a bottom wiper plug lobe 162 is shown in FIG. 26. Such lobes provide an efficient means to wipe the mud off the walls of the drill pipe while the Bottom Wiper Plug is pumped downhole with cement.
  • a top wiper plug 164 is being advanced downhole by water 166 under pressure in the drill pipe. As the Top Wiper Plug 164 is pumped down under water pressure, the cement remaining in region 168 is forced downward through the bottom wiper plug, through the valve assembly, through the water passages of the drill bit and into the annulus in the well.
  • a top wiper plug lobe 170 provides an efficient means to wipe the cement off the walls of the drill pipe while the top wiper plug is advanced downhole with water.
  • the yield load of the weld zone between members in tension shall be greater than the yield load of the drill-pipe body as given by Equation:
  • /Adp is the cross-sectional area of the drill-pipe body based on the specified dimensions of the pipe body
  • Ymin is the specified minimum yield strength of the drill-pipe body
  • Yw is the weld zone minimum yield strength (determined by the manufacturer based on the design).
  • /AW 0,7854 X D 2 te,min - d 2 te,max
  • c/te,max is the maximum allowable inside diameter specified by the drill-pipe manufacturer
  • Dte,min is the minimum allowable outside diameter specified by the drill-pipe manufacturer.
  • the guided-bend specimens can have no open discontinuity in the weld zone exceeding 3 mm (0,125 in) measured in any direction on the convex surface of the specimen after bending. Open discontinuities occurring on the corner of the specimen during testing shall not be considered unless there is definite evidence that they result from lack of fusion, inclusions or other internal discontinuities.
  • the dimensions of the drill-pipe body can correspond with the ANSI/APF requirements.
  • the configuration of a drill-pipe body 180 can correspond to FIG. 27.
  • the internal upset taper area 182 of the drill-pipe body shall have a smooth profile.
  • the internal upset configuration shall have no sharp corners or drastic changes of section that can cause a 90° hook-type tool to hang up.
  • the outside-diameter tolerances of the drill-pipe body can further be in accordance with the requirements of ANSI/ADP.
  • the outside-diameter tolerances behind the length, M eu apply to the outside diameter of the drillpipe body immediately behind the upset for a distance of approximately 127 mm (5 in) for sizes smaller than label 1 : 6-5/8 and a distance approximately equal to the outside diameter for label 1 : 6- 5/8. Measurements shall be made with calipers or snap gauges.
  • the wall thickness 184 at any place on the pipe body shall not be less than the specified thickness minus 12.5 %.
  • the drill-pipe body can be supplied in lengths and tolerances as specified in the purchase agreement. The lengths and tolerances should be such that the required final length of drill-pipe is achievable.
  • the mass of a drill pipe shall conform to the calculated mass for the end finish and dimensions specified, within the tolerances stipulated as follows. Calculated mass, WL, expressed in kilograms (pounds), of a piece of drill-pipe body of length Lpe shall be determined in accordance with: where
  • W pe is the non-upset pipe mass per unit length, expressed in kilograms per meter (pounds per foot);
  • Lpe is the length of drill-pipe body, expressed in meters (feet); e w is the drill-pipe-body mass gain due to end finishing. Mass tolerance is as follows: - single lengths: +6,5 -3,5%
  • Deviation from straight or chord height of a drill pipe shall not exceed either of the following: a) 0,2 % of the total length of the drill-pipe body measured from one end to the other b) 3,2 mm (1/8 in) maximum drop in the transverse direction in a length of 1 ,5 m (5 ft) from each end.
  • the outside and inside surfaces of the upset shall be aligned with the outside surface of the pipe body.
  • the total indicator reading shall not exceed 2,4 mm (0.093 in) for the outside surface and 3,2 mm (0.125 in) for the inside surface.
  • the minimum pipe-body elongation, e, in a 50,8 mm (2.0 in) gauge length, expressed in percent rounded to the nearest 0,5 % for elongations less than 10 % and to the nearest unit percent for elongations of 10 % and greater, shall be that determined by where
  • / is a constant equal to 1 944 (625 000);
  • A is the cross-sectional area of the tensile-test specimen, expressed in square millimeters (square inches), based on the specified outside diameter or nominal specimen width and specified wall thickness, rounded to the nearest 10 mm2 (0.01 in2), or 490 mm2 (0.75 in2) whichever is smaller;
  • L/dp is the minimum specified tensile strength, in megapascals (pounds per square inch).
  • the casing hanger can include a fluid port wherein the fluid port provides fluidic access to an outer annulus by allowing fluid to pass through the casing hanger, a landing sub attached to the casing hanger, and an isolation device attached to the landing sub wherein the isolation device is adapted to allow fluidic isolation of a portion of the landing sub from a portion of the outer annulus of the wellbore.
  • This structure too can be formed from polymer derived ceramic material.
  • FIG. 28 depicts a cross-sectional view of reverse circulation cementing apparatus 200 interacting with casing string 205 in a wellbore in accordance with one embodiment of the present invention.
  • the casing hanger 210 may be attached to landing sub 230 by collar 215 or any attachment means known in the art. Although landing sub 230 is illustrated as a separate piece from casing hanger 210, landing sub 230 may be integral to casing hanger 210 in certain embodiments.
  • the landing sub 230 may seat against ground 225, or any other support structure near the ground, to provide support for reverse circulation cementing apparatus 200.
  • the casing hanger 210 may include a fluid port 220.
  • the fluid port 220 may be used, among other things, to introduce cement slurry compositions to an outer annulus 250 by way of a fluid conduit 223.
  • the fluid port 220 may be integral to the casing hanger 210.
  • An isolation device 240 may provide fluidic isolation of outer annulus 250. In this way, fluid introduced into outer annulus 250 is prevented from exiting outer annulus 250 by leakage around landing sub 230.
  • the fluid insertion tube 245 may be any means for inserting fluid.
  • the isolation device 240 may be any device that provides at least partial fluidic isolation of outer annulus 250.
  • isolation device 240 may comprise a ceramic cup or basket, or a retrievable ceramic packer.
  • the isolation device 240 is shown as an inflatable tube.
  • the inflatable tube may be expanded or inflated with a fluid.
  • the fluid may be a hardening material such as polymer derived ceramic, which may be settable and capable of permanently hardening in a portion of outer annulus 250.
  • Insertion tube 245 may be used to introduce the material into isolation device 240 as necessary.
  • a sealing mandrel 260 may be attached to the casing hanger 210 by any means known in the art.
  • the sealing mandrel 260 may be integral to the casing hanger 210.
  • the sealing mandrel 260 is shown as attached to casing hanger 210 via a load bearing ring 270.
  • the load-bearing ring 270 is in turn attached to turnbuckles 263 and 265 via bolt 267.
  • the sealing mandrel 260 may also be attached to a casing string 205 via casing collars 272 and 274. In this way, sealing mandrel 260 may support the weight of the casing string 205.
  • Downhole tubing and casing are also subject to ANSI/API specifications, the contents of which are incorporated by reference in their entirety. Again, such structure is intended to be formed from the polymer derived ceramic material disclosed herein.
  • e k x A 0 2 / U° 9
  • e the minimum gauge length extension in 50,8 mm (2.0 in), expressed in percent, rounded to the nearest 0,5 % below 10 % and to the nearest unit percent for 10 % and larger;
  • A is the cross-sectional area of the tensile test specimen, expressed in square millimeters (square inches), based on specified outside diameter or nominal specimen width and specified wall thickness, rounded to the nearest 10 mm2 (0.01 in2), or 490 mm2 (0.75 in2) whichever is smaller;
  • U is the minimum specified tensile strength, in megapascals (pounds per square inch).
  • the yield strength shall be the tensile stress required to produce the elongation under load required.
  • the masses determined shall conform to the calculated masses for the endfinish.
  • WL is the calculated mass of a piece of pipe of length L, in kilograms (pounds); wpe is the plain-end mass in kilograms per metre (pounds per foot);
  • Lef is the length of pipe, including end-finish, in meters (feet), as defined in 8.6;
  • /cm is the mass correction factor: 1 ,000 for carbon steels; 0,989 for martensitic chromium steels; em is the mass gain due to end-finishing, in kilograms (pounds).
  • Casing, tubing and pup joints shall be furnished in lengths conforming to requirements. Length determination shall be in meters and hundredths of a meter (feet and tenths of a foot). The accuracy of length-measuring devices for lengths of product less than 30 m (100 ft) shall be ⁇ 0,03 m ( ⁇ 0.1 ft).
  • FIG. 29 an approach is depicted which has resulted in the construction and completion of a main or parent wellbore 312 and a lateral or branch wellbore 314.
  • This approach has been duplicated from U.S. Patent No. 6,907,930.
  • the wellbores 312, 314 intersect at an intersection 316, which is formed by positioning a milling/drilling whipstock (not shown in FIG. 80) in the main wellbore 312 below the intersection, and then using the whipstock to laterally deflect mills, drills, etc. to cut through casing 318 lining the main wellbore and drill the branch wellbore extending outwardly from the intersection.
  • a milling/drilling whipstock not shown in FIG. 80
  • Such downhole components are contemplated to be formed at least in part from polymer derived ceramic material. Techniques of forming wellbore intersections are well known to those skilled in the art. In one specific approach, both the wellbore 314 and the lower portion of the wellbore 312 could branch outwardly from the upper portion of the wellbore 312.
  • the milling/drilling whipstock is retrieved from the well, and the lower portion of the wellbore 312 is completed as shown in FIG. 29.
  • a gravel packing assembly 320 is installed in the wellbore 312, and the wellbore is gravel packed about the assembly to provide sand control.
  • the assembly 320 as depicted in FIG. 29 includes one or more well screens 322, a packer 324 and a slurry discharge device 326 interconnected in a tubular string 328. Again, one or more of these structures are contemplated to be formed from ceramic material.
  • the elements of the gravel packing assembly 320 can be arranged as depicted in FIG. 29, with the discharge device 326 positioned between the packer 324 and the screens 322, but other configurations may be utilized, if desired.
  • the packer 324 is set in the casing 318 below the intersection 316, and gravel and/or proppant 330 is discharged into an annulus 332 between the assembly 320 and the wellbore 312, using techniques well known to those skilled in the art.
  • the lower portion of the wellbore 312 is gravel packed in keeping with the principles of the invention.
  • a formation fracturing operation or other stimulation operation could be performed in the lower portion of the wellbore 312.
  • the screens 322 could be installed in the lower portion of the wellbore 312 without gravel packing or fracturing, the screens could be expanded in the lower portion of the wellbore as described below, or the lower portion of the wellbore could be completed in some other manner, if desired.
  • a deflector 334 is installed in the wellbore 312 below the intersection 316.
  • a tubular tailpipe 336 attached to the deflector 334 is stung into an upper end of the assembly 320 and is sealingly engaged therewith, for example, with seals 338 received in seal bores 340.
  • a passage 342 formed through the deflector 334 is in sealed communication with the interior of the assembly 320 via the tailpipe 336.
  • Both the deflector and tailpipe can be formed from ceramic material.
  • the branch wellbore 314 is completed and the wellbore intersection 316 is isolated from fluid flows in the wellbores 312, 314 in only a single trip into the well.
  • another gravel packing assembly 344 is attached to a tubular leg 346 of a wellbore connector 348 and conveyed into the well.
  • an outer tubing string 456 may include one or more packers 444, 446, 448, 450 that provide zonal isolation for the production of hydrocarbons in certain zones of interest within wellbore 432 (See FIG. 30 reproduced from U.S. Patent No. 8,267,173).
  • the packers 444, 446, 448, 450 isolate zones of the annulus between wellbore 432 and outer tubing string 456.
  • These packers irrespective of their configuration, can be formed at least in part from ceramics.
  • pack slurries also known as proppant slurries, may be pumped into the isolated zones provided
  • a string connects the pump, located down hole, to the drive system, located at the surface.
  • Conventional sucker rods are elongated rods, 20 feet to 30 feet in length.
  • Traditional drive string typically consisted of a sequence of conventional sucker rods 480 with connecting mechanisms 482 at each end of each conventional sucker rod which permit end-to-end interconnection of adjacent rods (See FIGS 31 A, 31 B).
  • a continuous sucker rod is a unitary rod, consisting of one elongated continuous piece of material. Thus, a continuous sucker rod does not have the numerous interconnection points found in the interconnected conventional sucker rods.
  • each interconnection point between two successive conventional sucker rods is a source of potential weakness and excess wear on the adjacent tubing and casing.
  • increased costs can be associated with continuous sucker rod.
  • the rods are contemplated to be formed from polymer derived ceramic.
  • the length of a drive string can vary from anywhere from as little as 500 feet to as much as 10,000 feet or more, depending on the depth of the well and desired location of the pump down hole.
  • a continuous sucker rod is typically produced and stored for sale on large transport reels. These transport reels have a maximum diameter of about 19 to 20 feet and the diameter may be as small as 9-10 feet. (The desired maximum diameter is limited by transport issues).
  • a full reel can carry continuous sucker rod with lengths of over 6,000 feet depending on the diameter of the rod.
  • One approach to manipulating a continuous sucker rod is set forth in U.S. 8,281 ,477. Such an approach can be adopted to create a continuous sucker rod out of polymer derived ceramic.
  • a perforating assembly is employed to create fractures within the wells of a wellbore.
  • the perforating assembly can be formed at least in part from ceramic material.
  • a perforating assembly 538 is preferably positioned within a casing 534 prior to the installation of a tubing string assembly 540. This is achieved by running the perforating assembly 538 downhole on a conveyance such as a wireline, a coiled tubing or preferably an electric wireline with logging capabilities such that the precise location for positioning the perforating assembly 538 within the casing 534 can be determined.
  • tubing string assembly 540 is run downhole until the downhole end of the tubing string assembly 540 contacts the uphole end of the perforating assembly 538.
  • Tubing string assembly 540 is then partially retrieved uphole to the location depicted in FIG. 83 such that the shock created when the perforating assembly 538 is fired does not affect any of the components of the tubing string assembly 540.
  • the perforating assembly 538 may initially be coupled to the downhole end of a tubing string assembly 540 such that only a single run is required for the installation of the downhole completion system of the present invention.
  • the perforating assembly 538 is disconnected from the tubing string assembly 540 such that the tubing string assembly 540 may be partially retrieved uphole to the location depicted in FIG. 32. Once the perforating assembly 538 and the tubing string assembly 540 are in this position, the completion of the well may begin.
  • the illustrated perforating assembly 538 includes a perforating gun 552 and an auto release gun hanger 554.
  • perforating gun 552 includes a plurality of shaped charges contained within a charge carrier such that when the shaped charges are detonated, each shaped charge creates a jet that blasts through a scallop or recess in the charge carrier, creates a hydraulic opening through casing 534 and cement 536 and then penetrates formation 514 forming a perforation 555 therein.
  • Perforating gun 552 may be activated by any suitable signaling process, however, perforating gun 552 is preferably a pressure activated perforating gun.
  • perforating assembly 538 may alternatively be a disappearing perforating gun that disintegrates upon firing or may be retrievable uphole via wireline or other suitable conveyance through tubing string assembly 540 after firing.
  • FIG. 33 there is shown an embodiment of a polymer derived riser assembly, and preferably a reinforced polysilocarb derived riser assembly.
  • This riser assembly may be made from cured reinforced polysilocarb material, e.g., a hard cured composite, it may be made from reinforced pyrolized material, e.g., a ceramic
  • a dynamically positioned (DP) drill ship 700 having a drill floor, a derrick 702 above the drill floor 701 , and moon pool 703 (as seen by the cutaway in the figure showing the interior of the drill ship 700) below the drill floor 701 and other drilling and drilling support equipment and devices utilized for operation, which are known to the offshore drilling arts, but are not shown in the figure.
  • DP dynamically positioned
  • the structural above deck components (as well as other components) and in particular the heavier structural above deck components, such as the derrick, and the drill floor support, can be made from reinforced polymer derived structures, reinforced polymer derived ceramic structures and combinations and variations of these; and in particular, polysilocarb derived ceramic composite structures. These structures and materials can be considerably lighter than steel, of equal or superior strength, and thus, the use of these lighter components can enhance the stability of the drill ship, among other advantages. Additionally, polysilocarb derived materials can function as fire resistant and retardant coatings and layers.
  • the drill ship 700 includes a polysilocarb derived riser assembly 704.
  • any other type of offshore drilling rig, vessel or platform including FPSOs, or GGSOs may be utilized and thus may include a polysilocarb derived riser assembly 704.
  • the polysilocarb derived riser assembly 704 as shown in this figure, is deployed and connecting drill ship 700 with a borehole 724 that extends below the seafloor 723.
  • the polysilocarb derived riser assembly is a drilling riser BOP package with the BOP positioned at or near the seafloor, typically attached to a wellhead, as seen for example in some drilling activities.
  • Embodiments of polysilocarb derived riser assemblies have applications for other types of risers, riser-BOP packages and activities.
  • polysilocarb derived riser assemblies have applications in relation to drilling, workover, servicing, testing, intervention and completing activities. They also have applications where a BOP is not employed, were drilling is done in the riser, where the riser is a production riser, and other configurations known to, or later developed by the art.
  • the polysilocarb derived riser assembly 704 has a polysilocarb derived riser 705, e.g., a composite polymer derived material, and a BOP stack 720.
  • the upper portion i.e., the portion of the riser when deployed that is closest to the surface of the water 725, of riser 705, is connected to the drillship 700 by tensioners that are attached to tension ring.
  • the upper section of the riser 705 may have a diverter and other components (not shown in this figure) that are commonly utilized and employed with risers and are well known to those of skill in the art of offshore drilling.
  • the polysilocarb derived riser 705 extends from the moon pool 703 of drill ship 700 and is connected to BOP stack 720.
  • the polysilocarb derived riser 705 is made up of riser sections, e.g., 707, 709, 71 1 , 713, that are connected together, by riser couplings, e.g., 706, 708, 710, 712, 714, and lowered through the moon pool 703 of the drill ship 700.
  • riser couplings e.g., 706, 708, 710, 712, 714
  • the polysilocarb derived riser 705 may also be referred to as a riser string.
  • riser sections may be made from polymer derived material (such as cured reinforced polysilocarb material, e.g., a hard cured composite, reinforced pyrolized material, e.g., a ceramic composite, and combinations and variations of these).
  • polymer derived material such as cured reinforced polysilocarb material, e.g., a hard cured composite, reinforced pyrolized material, e.g., a ceramic composite, and combinations and variations of these.
  • the riser-BOP connecter 715 is associated with flex joint 716, which may also be referred to as a flex connection or ball joint.
  • polymer derived material such as cured reinforced polysilocarb material, e.g., a hard cured composite, reinforced pyrolized material, e.g., a ceramic composite, and combinations and variations of these).
  • the BOP stack 720 may be characterized as having two component assemblies: an upper component assembly 717, which may be referred to as the lower marine riser package (LMRP), and a lower component assembly 718, which may be referred to as the lower BOP stack or the BOP proper.
  • the upper component assembly 717 has a frame 719 that houses an annular preventer.
  • the lower component assembly 718 has a frame 721 that houses an annular preventer, a first ram preventer, a second ram preventer, and a third ram preventer.
  • the BOP stack 720 has a wellhead connecter 735 that attaches to wellhead 736, which is associated with borehole 724.
  • the riser has an internal cavity, not shown in FIG. 33 that is in fluid and mechanical communication with an internal cavity, not shown in FIG. 33, in the BOP stack.
  • These internal cavities can be coated with, or made up entirely or in part of polymer derived materials, and in particular polysilocarb derived materials, as well as, polysilocarb pigment based coatings, which are taught and disclosed in US Patent Application Serial No. 14/634,819, the entire disclosure of which is incorporated herein by reference.
  • the riser BOP package provides, in an embodiment a polysilocarb derived cavity or channel, putting the drill ship 700 in fluid and mechanical communication with the borehole.
  • this channel has an interior surface that is made from a polysilocarb derived material, e.g., neat, reinforced, a jacket, an inner sleeve, a layer, a coating, or as a pigment in a coating, to name a few.
  • a polysilocarb derived material e.g., neat, reinforced, a jacket, an inner sleeve, a layer, a coating, or as a pigment in a coating, to name a few.
  • the polysilocarb derived materials, and coatings and paints based upon or utilizing these materials have excellent corrosion and abrasion resistance.
  • the flow fluids such as the hydrocarbon stream, the drilling fluids, or other fluids flowing through the riser, or other tubulars, valves, pipes, etc.
  • polysilocarb materials and coatings can be used to provide enhanced abrasion resistance, and mitigate, or manage the adverse effects of the abrasive fluid.
  • the abrasion resistant and corrosion resistant features of the polysilocarb derived materials also find applications in BOP components and surfaces, and other components and surfaces of the drilling rig.
  • the BOP stack frames 719, 721 protect the BOP, and may have lifting and handling devices, a control and connection module, and other equipment and devices utilized in subsea operation, which are known to the offshore drilling art, but are not shown in the figure.
  • the internal cavity in the stack goes through the stack from its top (closest to the surface of the water 725) to its bottom (closest to the sea floor 723).
  • This cavity for example, could be about 18 3/4" in diameter and has a cavity wall, which as discussed above may have a polysilocarb derived inner surface.
  • 21 riser typically, in deep sea drilling operations a 21 " riser and an 18 3/4" BOP are used.
  • the term “21 riser” can be considered as generic and covers risers wherein the large central tube has an outer diameter in the general range of 21 " and would include for example a riser having a 21 1/4" outer diameter.
  • Wall thickness for the polysilocarb derived central tube of 21 " risers can range from about 5/8" to 7/8" , about 1 ⁇ 4" to about 1 ⁇ 2", less than 1 ⁇ 2", and smaller and larger sizes.
  • Polysilocarb derived risers and BOPs can vary in size, type and configuration. Polysilocarb derived risers can have outer diameters ranging from about 13 3/8" to about 24".
  • polysilocarb derived risers Because of the reduced weight and equal or increased strength of polysilocarb derived risers they can have diameters larger than 24", e.g., 30", 36" 40" and greater. Further because of the reduced weight, less buoyancy control components will be needed for the riser, enabling smaller as deployed outer diameters, which reduces the effect of currents on the deployed riser. This it is contemplated that as deployed polymer derived risers can have, the above mentioned diameters, and wall thickness of less than about 7/8", and less then about 1 ⁇ 2" , yet have lengths of greater than about 5,000 ft, greater than about 10,000 ft., greater than 15,000 ft., and greater than about 20,000 ft.
  • the sections of the riser are typically stored vertically on the offshore drilling rig. Once the drilling rig has reached a drilling location the riser and BOP package are deployed to the seafloor.
  • the BOP stack is prepared and positioned under the drill floor and under the rotary table.
  • a spider and gimbal are also positioned with respect to the rotary table.
  • the lower most section of the riser that attaches to the BOP is moved into the derrick and lowered by the hoisting apparatus in the derrick through the spider and down to the BOP below the drill floor where it is connected to the BOP.
  • the riser and BOP are then lowered to a point where the upper coupling of the riser section is at a height above the drill floor were it can be readily connected to the next section of riser.
  • the spider holds the riser in this position.
  • the two sections and the BOP are then lowered, and this process is repeated until sufficient sections of riser have been added and lowered to enable the BOP to reach and be landed on (attached to) the wellhead at the seafloor.
  • FIG. 34 there are shown exemplary embodiment of a riser having a flanged coupling, such as an HMF coupling.
  • the riser and coupling are are polysilocarb derived components and surfaces.
  • a flanged coupling is shown for illustrative purposes, the teachings and embodiments would cover all types of riser connections, including various types of couplings that use mechanical means, such as, flanges, bolts, clips, bowen, lubricated, dogs, keys, threads, course threads, pins and other means of attachment known to the art or later developed by the art.
  • riser couplings would include flange-style couplings, which use flanges and bolts; dog-style, which use dogs in a box that are driven into engagement by an actuating screw; and key-style, which use a key mechanism that rotates into locking engagement.
  • the flange components would be polysilocarb derived reinforced ceramic composite structures.
  • riser section center tube 800 would have a flange attached to its upper end and that riser section center tube 803 would have a flange attached to its lower end.
  • Polysilocarb derived ceramic flange 801 is attached to upper flange 802 by bolts and nuts, e.g., 804, 805, 806.
  • Also associated with the riser sections 800, 803 and extending through the flanges 801 , 802 are a choke line 810, a booster line (not shown), a kill line (not shown), a hydraulic line (not shown) and blanks (e.g., open unfilled holes in the flange) 814.
  • Flange 801 has an outer surface 816, a mating surface 835 and a shoulder surface 836.
  • Flange 802 has an outer surface 817, a mating surface 837 and a shoulder surface 838.
  • these components of the riser center tube, flanges, and their respective and various surfaces can be made from, or coated with, polysilocarb derived materials, e.g., neat, reinforced, a jacket, an inner sleeve, a layer, a coating, or as a pigment in a coating, to name a few.
  • polysilocarb derived materials e.g., neat, reinforced, a jacket, an inner sleeve, a layer, a coating, or as a pigment in a coating, to name a few.

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  • Manufacturing & Machinery (AREA)
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Abstract

L'invention concerne un appareil et un procédé pour le développement d'un équipement de fond de trou en céramique dérivée de polymère comprenant une structure de complétion, des bouchons d'isolement, des systèmes de suspension, des colonnes montantes marines, des colonnes montantes, des ensembles de packers et des tiges de pompage. Dans diverses approches, un ou plusieurs éléments, surfaces ou structures de fond de trou peuvent prendre la forme d'un matériau en céramique dérivée de polymère, et, en particulier, d'un matériau dérivé de polysilocarb et d'un matériau en céramique dérivée de polysilocarb.
PCT/US2015/021861 2014-03-21 2015-03-20 Équipement en céramique dérivée de polymère pour l'exploration et la récupération de ressources WO2015143390A2 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US201461968774P 2014-03-21 2014-03-21
US61/968,774 2014-03-21
US14/268,150 US9815943B2 (en) 2013-03-15 2014-05-02 Polysilocarb materials and methods
US14/268,150 2014-05-02
US14/634,814 2015-02-28
US14/634,814 US10167366B2 (en) 2013-03-15 2015-02-28 Polysilocarb materials, methods and uses

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DK2636843T3 (en) * 2010-12-17 2015-01-19 Welltec As Well Completion

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