CN106232748A - Poly-silica material with carbon element, method and purposes - Google Patents

Poly-silica material with carbon element, method and purposes Download PDF

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Publication number
CN106232748A
CN106232748A CN201580021474.7A CN201580021474A CN106232748A CN 106232748 A CN106232748 A CN 106232748A CN 201580021474 A CN201580021474 A CN 201580021474A CN 106232748 A CN106232748 A CN 106232748A
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carbon
weight
poly
preparation
silica
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Inventor
安德鲁·R·霍普金斯
马克·S·兰德
沃尔特·J·舍伍德
蒂姆·C·穆勒尔
布里科·A·布里科
道格拉斯·M·杜克斯
布莱恩·L·比纳克
迈克尔·J·米勒
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Melior Innovations Inc
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Melior Innovations Inc
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Priority claimed from US14/212,896 external-priority patent/US9815952B2/en
Priority claimed from US14/268,150 external-priority patent/US9815943B2/en
Application filed by Melior Innovations Inc filed Critical Melior Innovations Inc
Publication of CN106232748A publication Critical patent/CN106232748A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
    • B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
    • B24D3/04—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0081—Composite particulate pigments or fillers, i.e. containing at least two solid phases, except those consisting of coated particles of one compound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24D—TOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D3/00—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
    • B24D3/02—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
    • B24D3/04—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic
    • B24D3/14—Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic ceramic, i.e. vitrified bondings
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • 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
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    • 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
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C04B2235/427—Diamond
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    • 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
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
    • C04B2235/483—Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes

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Abstract

Poly-silica carbon preparation, solidify and the material that is pyrolyzed and goods and the purposes of this material.Especially, poly-silicon-oxygen-carbon ceramic material and the goods of pyrolysis comprise these materials, wherein said pottery has the silicon of about 30 weight % to about 60 weight %, the oxygen of about 5 weight % to about 40 weight % and the carbon of about 3 weight % to about 35 weight %, and wherein the carbon that carbon is silicon bonding of 20 weight % to 80 weight % and the carbon of 80 weight % to about 20 weight % are free carbon.

Description

Poly-silica material with carbon element, method and purposes
The application: (i) is according to 35 U.S.C. § 119 (e) (1), it is desirable to date of filing is the 61/ of on February 28th, 2014 The rights and interests of 946,598 serial number U.S. Provisional Applications；(ii) according to 35 U.S.C. § 119 (e) (1), it is desirable to date of filing is 2015 The rights and interests of the 62/106,094th serial number U.S. Provisional Application on January 21, in；(iii) it is the submitted on May 2nd, 2014 The part continuation application of 14/268,150 serial number U.S. Patent application；And (iv) is the 14/th submitted on March 14th, 2014 The part continuation application of 212,896 serial number U.S. Patent applications, the complete disclosure of above-mentioned every part of application is by quoting also Enter herein.
Background of invention
Invention field
The present invention relates to poly-organic (polyorganic) compositions, structure and material；The ceramic precursor material that polymer is derivative Material and ceramic material；And the most poly-silica carbon (polysilocarb) compositions, structure and material.The invention still further relates to system Standby these compositionss, the method for structure and material.Serial No. 61/818,981,61/818,906,61/788,632,61/ The U.S. Patent Application Publication of 843,014 and 61/890808 and teach the ceramic material that polymer is derivative, above-mentioned every part of Shen Complete disclosure please is incorporated herein by.
By carbon silane or Polycarbosilane (Si-C), silane or polysilane (Si-Si), silazane or polysilazane (Si-N- Si), prepared by carborundum (SiC), carbon silazane or polycarbosilazanes (Si-N-Si-C-Si), siloxanes or polysiloxanes (Si-O) Or derivative material is known.The material of these general types has the biggest but unconsummated prospect；And fail to obtain Large-scale application or market accreditation.On the contrary, the narrowest, limited, small lot, high price and Gao Te have been become in their use The application of the opposite sex, such as the ceramic composition on rocket nozzle or the paster of space shuttle.Therefore, they fail acquisition and are widely used Pottery, and think that they obtain the most less accreditation and use, if yes, as plastic material, such as, cured but The plastic material not being pyrolyzed.
In degree more or less, all these materials and the method for preparing them all have one or more Shortcoming, including: such as, they are fairly expensive and are difficult to prepare, and have the cost of every pound of thousands of dollars；They need height Purity and the most highly purified parent material；Described method needs harmful organic solvent, such as, toluene, oxolane (THF) And hexane；Described material can not prepare the non-reinforcing structure with any usable intensity；Described method produces less desirable and has The by-product of evil, such as hydrochloric acid and mud, described by-product may contain magnesium；Described method need multiple based on solidification and heat Solve solvent and the reagent of the reactions steps that step combines；The preimpregnation material that described material can not be formed；And they All physical property is mixing, and such as, good temperature characterisitic is the most extremely fragile.
Therefore, although think that it has long-range prospect, but the material of these types fails to be applied on a large scale or city Field accreditation, and substantially remain in the Science Explorations stage.
General introduction
Therefore, to having performance characteristic and the feature of high cost-ceramic, but have more in preparation with in terms of using described material Low cost and the new material of greater flexibility have permanent and unsatisfied needs.Among others, the present invention is by providing this Goods manufacture, apparatus and method that literary composition is instructed, disclosed and claimed solve these demands.
Provide the derivative enhancing multiple grinding component of poly-silica carbon or cutting element；It has: body phase (bulk And cutting material phase)；Wherein said body derives autohemagglutination silica carbon preparation mutually.
Provide and there are the material of one or more following characteristics, method, goods: wherein said poly-silica carbon preparation is Response type preparation；Wherein said poly-silica carbon preparation is response type preparation, and wherein said preparation has at least one selected from following Precursor: phenyl triethoxysilane, phenyl methyl diethoxy silane, methyldiethoxysilane, vinyl methyl diethyl TMOS, trimethylethoxysilane, triethoxysilane and TES 40；Wherein said poly-silica carbon preparation is response type system Agent, the most described preparation has at least two selected from following precursor: phenyl triethoxysilane, phenyl methyl diethoxy silicon Alkane, methyldiethoxysilane, vinyl methyl diethoxy silane, trimethylethoxysilane, triethoxysilane and TES 40；Wherein said cutting material is selected from composite polycrystal-diamond, SiC, aluminium oxide and diamond；Wherein said cutting material is equal Even it is distributed in whole described component；Wherein said cutting material is evenly distributed in most of outer volume of described component, its Described in outer volume limit described component cumulative volume at least about 50%；Wherein said poly-silica carbon preparation is mixed type system Agent；Wherein said poly-silica carbon preparation is slurriable combination, and wherein said preparation has at least one selected from following precursor: first Base end-blocking vinyl polysiloxane, the vinyl polysiloxane of ethenyl blocking, hydride end-blocking vinyl polysiloxane, The dimethyl polysiloxane of ethenyl blocking, hydroxy-end capped dimethyl polysiloxane, phenyl end capped dimethyl polysiloxane, The phenethyl polysiloxanes of methyl blocking and tetravinyl cyclosiloxane；Wherein said poly-silica carbon preparation is substantially free of solvent.
Still further provides the structural building element of the poly-silica carbon preparation with solidification.
Provide and there are the material of one or more following characteristics, method, goods: there is the poly-of structure member and solidification Siloxane formulation；Wherein said structure member is selected from dry wall, slabby rocks, plasterboard, MDF plate, plywood, plastics and particle Plate；Have selected from paint, glue and the second component of plastics；And wherein said second component has the polysiloxanes system of solidification Agent；The polysiloxanes preparation of wherein said solidification is volume profiles；Wherein said poly-silica carbon preparation is response type preparation；Wherein Described poly-silica carbon preparation is slurriable combination；Wherein said poly-silica carbon preparation is slurriable combination, and wherein said preparation has Have at least one to be selected from following precursor: the vinyl polysiloxane of methyl blocking, the vinyl polysiloxane of ethenyl blocking, The vinyl polysiloxane of hydride end-blocking, the dimethyl polysiloxane of ethenyl blocking, the poly-silica of hydroxy-end capped dimethyl Alkane, phenyl end capped dimethyl polysiloxane, the phenethyl polysiloxanes of methyl blocking and tetravinyl cyclosiloxane；Wherein institute State poly-silica carbon preparation substantially free of solvent.
Still further provides the structural building element of the poly-silicon-oxygen-carbon ceramic with pyrolysis, described pottery has about 30 weights The amount silicon of % to about 60 weight %, the oxygen of about 5 weight % to about 40 weight % and the carbon of about 3 weight % to about 35 weight %, and And wherein the carbon that carbon is silicon bonding of 20 weight % to 80 weight % and the carbon of 80 weight % to about 20 weight % are free carbon.
Provide and there are the material of one or more following characteristics, method, goods: wherein said ceramic material has about The silicon of 40 weight % to about 50 weight %, and the carbon that the carbon of the most about 25 weight % to about 40 weight % is silicon bonding；Wherein Described ceramic material has about 40 weight % silicon to about 50 weight %, and the most about 55 weight % are to the carbon of about 75 weight % For free carbon；Wherein said ceramic material has about 20 weight % oxygen to about 30 weight %, and the most about 25 weight % are extremely The carbon of about 40 weight % is the carbon of silicon bonding；Wherein said ceramic material has about 20 weight % oxygen to about 30 weight %, and And the most about 55 weight % to the carbon of about 75 weight % be free carbon；Wherein said ceramic material has about 20 weight % to about 30 The carbon of weight %, and the carbon that the carbon of the most about 25 weight % to about 40 weight % is silicon bonding；Wherein said ceramic material has There is about 20 weight % carbon to about 30 weight %, and the carbon of the most about 55 weight % to about 75 weight % is free carbon.
Still further provides the method providing anti-flaming protection to construction package, described method has selection poly-silicon to be used The construction package that oxygen alkane preparation processes；By described polysiloxanes formulation application in described construction package；Described polysiloxanes preparation Can solidify to hard in the time response less than two days at 75f；Solidify described polysiloxanes preparation；Thus have described firmly The described construction package of the polysiloxanes application of solidification has the standard refractory test of at least about 1/2-h under ASTM E-119.
Provide and there are the material of one or more following characteristics, method, goods: thus there is the poly-silica of hard solidification The described construction package of alkane application has the standard refractory test of at least about 2-h under ASTM E-119；Thus there is hard solidification Polysiloxanes application described construction package have under ASTM E-119 at least about 4-h standard refractory test；Wherein institute State construction package selected from load bearing wall, masonry units, the composite component of structural material for building, non-load bearing wall, partition thing, Post, longeron, crossbeam, flat board, composite plate and for floor and the beam assembly on roof.
Further it is provided that the construction package of resistance to combustion, it has: construction package and the polysiloxanes preparation of hard solidification；Described poly-silicon Oxygen alkane preparation is the most halogen-free；The wherein said construction package of resistance to combustion exceedes at least about 1/2-h's under ASTM E-119 Standard refractory is tested.
Further it is provided that for the resistance to combustion outsourcing thing of construction package, it has: for resistance to combustion outsourcing thing and the leaching of construction package Enter the hard polysiloxanes preparation solidified in described outsourcing thing；Described polysiloxanes preparation is the most halogen-free.
Furthermore providing the plastic refractory with the first plastics and halogen-free flame-retardant, described fire retardant has hard solidification Polysiloxanes preparation；Described plastics can meet at least V0 grade under UL-94.
Furthermore providing the final products with poly-silica carbon preparation, described final products are selected from fiber, proppant, silicon Alkane cladding proppant, silane and antistatic additive cladding proppant, explosion-proof barriers, ballistic composite, structural elements, drag Car, movable building, transport container, friction member, lapping device, armored vehicle, flak jackets, insulator, paint, fireproof coating, Table top, gas extraction system, tubular structure, line insulators, conduit insulators, conduit lining, concrete and vapour barrier.
Further it is provided that final products, the most poly-silica carbon preparation has the pottery of pyrolysis, and described pottery has about 30 weights The amount silicon of % to about 60 weight %, the oxygen of about 5 weight % to about 40 weight % and the carbon of about 3 weight % to about 35 weight %, and And wherein the carbon that carbon is silicon bonding of 20 weight % to 80 weight % and the carbon of 80 weight % to about 20 weight % are free carbon.
Furthermore providing the method preparing goods, wherein said goods are selected from fiber, proppant, the support of silane cladding Agent, silane and the proppant of antistatic additive cladding, explosion-proof barriers, ballistic composite, structural elements, trailer, movable building, fortune Defeated container, friction member, lapping device, armored vehicle, flak jackets, insulator, paint, fireproof coating, table top, gas extraction system, Tubular structure, line insulators, conduit insulators, conduit lining, concrete and vapour barrier.Described method has: select poly- Silica carbon preparation, prepares described poly-silica carbon preparation, by processing described poly-silica carbon preparation as at least the 0.05% of goods Goods are prepared to 100%.
Further it is provided that have the product of the poly-silicon-oxygen-carbon ceramic of pyrolysis, described pottery has about 30 weight % to about The silicon of 60 weight %, about 5 weight % to the oxygen of about 40 weight % and the carbon of about 3 weight % to about 35 weight %, and wherein 20 Weight % to the carbon of 80 weight % is the carbon of silicon bonding and the carbon of 80 weight % to about 20 weight % is free carbon.
Accompanying drawing is sketched
Figure 1A is the perspective view of the embodiment of the poly-silica carbon structural member according to the present invention.
Figure 1B is the perspective view of the embodiment of the poly-silica carbon structural member according to the present invention.
Fig. 1 C is the perspective view of the embodiment of the poly-silica carbon structural member according to the present invention.
Fig. 1 D is the perspective view of the embodiment of the poly-silica carbon structural member according to the present invention.
Fig. 2 is the decomposition diagram of the embodiment of the poly-silica carbon building-supporting component according to the present invention.
Fig. 3 A is the side-looking of the embodiment of the armored vehicle with armour plate based on poly-silica carbon according to the present invention Figure.
Fig. 3 B is the front view of the vehicle of Fig. 3 A.
Fig. 4 is the perspective view of the embodiment of the poly-silica carbon modularized house unit according to the present invention.
Fig. 5 is the perspective view of the embodiment of the poly-silica carbon transport container according to the present invention.
Fig. 6 is the perspective view of the embodiment of the panel based on poly-silica carbon according to the present invention.
Fig. 7 is the perspective view of the embodiment of the poly-silica carbon flak jackets according to the present invention.
Fig. 8 is the perspective view of the embodiment of the poly-silica carbon rope according to the present invention.
Fig. 9 is the perspective view of the embodiment of the poly-silica carbon trailer according to the present invention.
Figure 10 is the perspective view of the embodiment of the poly-silica carbon emery wheel according to the present invention.
Figure 11 is the perspective view of the belt grinding machine of the embodiment with poly-silica carbon grinding belt according to the present invention.
Figure 12 is the perspective view of the poly-silica carbon pipe according to the present invention.
Figure 13 is the sectional view of the poly-silica carbon brake assemblies according to the present invention.
The description of preferred embodiment
Generally, the present invention relates to unique and novel silicon (Si) sill, described silica-base material is easily fabricated, process also And there is astonishing and beyond thought performance and application.These silica-base materials have as fluent material, the material of solidification The application of the material (such as pottery) of (such as plastics), preceramic materials and pyrolysis and use.
The silica-base material of the present invention is contrary with the general trend of chemistry of silicones and application.Generally, chemistry of silicones field, especially It is organosilicon chemistry field, advances towards the direction become increasingly complex in functional group, and described functional group is additional to silica-based poly- Compound main chain and be the part of silicon-based polymer main chain.Similarly, generally, the method court of these polymer it is used to prepare The direction become increasingly complex to advance.The present invention by preferably functionalization have more simple structure (such as phenyl, phenethyl and Less group) silicon-based polymer main chain and deviate from this trend, and with simplify technique (such as, solvent-free, reduce Solvent, the parent material of lower cost, less step and the minimizing of reaction intermediate) carry out.
Additionally, siloxanes (silicones) is considered as viscosity, flexibility or fluent material by generally this area, itself and other material Material be used together, be used on other material or be used in combination to strengthen with other material those other materials performance characteristic or Performance characteristic is provided for other material.Silica-base material has not conventionally considered as stand-alone product, primary product or structural detail.So And, the silica-base material of the present invention deviates from mutually with this trend in this area and understanding.Among others, the silica-base material of the present invention The material that can serve as stand-alone product, primary product and structural detail is provided.The silica-base material of the present invention is also used as being combined Material, coating, component, additive, material property reinforcing agent and other application and use.
Therefore, the invention provides new material system and the platform with many different formula, application and purposes, it leads to Chang Buneng obtains with existing silica-based products, among other things, be especially generally not capable of with acceptable cost, in batches, system Make condition, operation requires or process conditions obtain with existing silica-based products.
Generally, the present invention relates to " poly-silica carbon " material, such as, contain silicon (Si), oxygen (O) and the material of carbon (C), with And the material by this class materials pyrolysis.Poly-silica material with carbon element can also comprise other element.Poly-silica material with carbon element is by a kind of or many Plant poly-silica carbon precursor formulation or precursor formulation is made.The silicon that poly-silica carbon precursor formulation comprises one or more functionalizations gathers Compound or monomer, and other possible composition, such as: such as, inhibitor, catalyst, pore former, filler, reinforcing agent, fibre The derivative pottery (" PDC ") of dimension, granule, coloring agent, pigment, dyestuff, polymer, pottery, metal, metal complex and these Combination and modification and other material and additive.
Then, poly-silica carbon precursor formulation is cured to form solid or semisolid material, such as, plastics.Can pass through Initial solidification processes poly-silica carbon precursor formulation to provide partially cured material, and it is referred to as such as, preform (preform), green material (green material) or green firming body (are not meant as relevant to material color any Things).It is then possible to solidify this green material further.Therefore, it is possible to use one or more curing schedules.This material can By " finally solidification ", being i.e. cured to such point: at this point, described material has required physics for its intended purpose Intensity and other performance.The amount of solidification can reach finally to solidify (or " solidification firmly "), i.e. at this point, all or substantially All of chemical reaction has stopped (such as, as measured by there is not reactive group in material, or by reactivity The minimizing of group level off in time is measured).Therefore, and described material can be consolidated according to its desired use and purpose Change to different degree.Such as, in some cases, final solidification and hard solidification can be identical.
Solidification can complete under the following conditions: at standard ambient temperature and pressure (" SATP ", 1 atmospheric pressure, 25 DEG C) Under, at a temperature of temperature is higher or lower than being somebody's turn to do, under pressure is higher or lower than this pressure, and through extremely several points less than one minute Clock, to a few hours, to a couple of days (or may longer) different time sections (continuously and circulate, such as, after heating cooling and Reheat), in atmosphere, (such as, argon (Ar) or nitrogen (N in a liquid or in preliminary election atmosphere2))。
Poly-silica carbon precursor formulation can make non-reinforcing, non-filling, compound, that strengthen and the structure of filling, centre Body and final products, and these combination and other types of material and modification.Furthermore, it is possible to by these structures, intermediate and Final products solidification (such as, green compact solidification, final solidification or solidification firmly), uncured, pyrolysis are pottery and these group (such as, the material of solidification can be filled out with the pyrolysis globule derived from the poly-silica carbon identical with the material of solidification for conjunction and modification Fill).
Precursor formulation may be used for formed " pure " material (" pure " material refer to all and essentially all of structure by Precursor material or unfilled preparation are made；Therefore, there is not filler or reinforcing agent).Precursor formulation may be used for being formed again Condensation material, such as, the product of enhancing.Precursor formulation may be used for forming non-reinforcing material, described non-reinforcing material be mainly by, Substantially by and the material be the most only made up of precursor material, such as, the coloring only with precursor material and coloring agent gathers Siloxane structure will be considered as non-reinforcing material.
In terms of poly-silica carbon precursor formulation is made structure, parts, intermediate or final products, can be by poly-silica Carbon preparation such as, by spraying, stream is moulded, thermal spraying, paint are coated with, mold, shape, extrude, make up, droplet mould, inject in the way of or its Its mode operates into substantially any volume profiles, including flat shape (it still has a volume, but be more closely similar to coating, top layer, Film or even table top, if wherein thickness is unlike other size decimal order of magnitude, also than other much smaller size), and These combination and modification.These volume profiles will include: such as, spheroid, pellet, annular, eyeglass shape, disk, panel, cone Shape, conical butt, square, rectangle, pencil, dihedral, passage, hollow sealing room, hollow ball, bulk, lamellar, coating, Film, top layer, microgranule, beam-like, bar-shaped, dihedral, cylindricality, threadiness, chopped fiber shape, tubulose, cup-shaped, tubular, and these group Close and modification and other more complicated engineering and building shape.Additionally, they can be formed corresponding to or meet the preformation of finished product Type body or original shape, such as, send out for brake block, clutch plate, brake shoe, electromotor, the high-temperature component of electromotor, diesel oil Motivation, rocket part, turbine part, aircraft components, spacecraft component, construction material, transport container parts and other structure Or parts, or use in such ways.
Poly-silica carbon precursor formulation can be used together to form composite with reinforcing material.It is therefoie, for example, said preparation Can flow in reinforcing material, immerse in reinforcing material, be enhanced absorbed, or otherwise with reinforcing material group Closing, described reinforcing material is such as carbon fiber, glass fibre, fabric, non-woven fabrics, copper fiber, fiber, rope, braiding structure, pottery Porcelain powder, glass dust, carbon dust, graphite powder, ceramic fibre, metal powder, carbide pellet or component, chopped fiber, tow, above-mentioned material Nanostructured, PDC, meet other material any of the temperature requirement of method and final products, and these combination and change Type.It is therefoie, for example, reinforcing material can be any high temperature resistant reinforcing material used at present or can with existing plastics and Any high temperature resistant reinforcing material that ceramic composite is used together.Additionally, because poly-silica carbon precursor formulation can prepare use (such as, SATP) or the solidification temperature of e.g., from about 100 °F to about 400 °F is solidified, so reinforcing material is permissible in lower temperature Be polymer, organic polymer (such as nylon, polypropylene and polyethylene) and aramid fiber (such as NOMEX or KEVLAR)。
Reinforcing material can also by with formed fiber and be pyrolyzed into the identical material of preparation of pottery make or derived from This material, or its can by form fiber be pyrolyzed into pottery different precursor formulation materials make.Except available Make outside the ceramic fibre derived from precursor formulation material of reinforcing material, it is also possible to use derived from other of precursor formulation material Porous, the substantially porous and ceramic structure of atresia.
Poly-silica carbon precursor formulation may be used for forming packing material.Packing material has to add to poly-silica carbon by being Other solid of body preparation or any material of semisolid material.Can think that cured article, pottery produce with Selective filling material Product or both some feature is provided.These features can relate to or aesthetics, sense of touch, heat, density, radiation, chemistry, magnetic, electricity Feature and these combination and modification and further feature.These features can be feature in addition to intensity.Therefore, fill Material can not affect solidification or the intensity of ceramic material, and it can increase intensity, or even can be in some cases Reduce intensity.Packing material can give color, magnetic function, fire resistance, anti-flammability, thermostability, electric conductivity, antistatic, optics Performance (such as, reflectance, refractive index and iris), aesthetic properties (the such as stone shape outward appearance in building products), chemical resistance Rate, corrosion resistance, wearability, resistance to abrasion, heat insulation, UV stability, UV protect, and can be in final products or material Desired, necessary and expectation and the further feature of necessity.Therefore, packing material may include that and gives some instances, and copper is led Line, heat filling, conductive filler, lead, optical fiber, ceramic colorant, pigment, oxide, dyestuff, powder, ceramic fine particle, PDC granule, pore former, carbon silane, silane, silazane, carborundum, carbon silazane, siloxanes, powder, ceramic powders, metal, Metal complex, carbon, tow, fiber, chopped fiber, containing boron material, milled fibre, glass, glass fibre, fibrous glass and nanometer Structure (includes aforesaid nanostructured).For example, it is possible to the PDC granule (such as, particulate or globule) pulverized is added to poly-silicon In oxygen carbon preparation, then carrying out being cured to form the solidification plastic material of filling, described plastic material is as coating or structure Material has significant fire resistance.
As used herein, unless otherwise specifically stated, term fire retardant, fireproof agent, resistance to combustion, protection fire-resistant, anti-flaming, anti- Fire protection, press down combustion, press down fire and this type of similar term be endowed they most widely may implications, and be included within marking The all calcinations, fire, burning or the flame that have been found that, describe or propose in standard, specification, certification, regulation and criterion are relevant Implication, and alleviating, reduce and avoiding of fire, burning or smog will be included.
Packing material can also by make with the identical material of preparation forming solidification or pyrolysis solid or derived from This material, or it can be by the different solids forming solidification or the precursor formulation material of the solid of semisolid or pyrolysis Material is made.
Poly-silica carbon preparation and can have metal derived from the product of said preparation or the product prepared by said preparation And metal complex.Therefore, it can introduce in precursor formulation the metal as oxide, carbide or silicide, and because of This introduces in silica matrix in a controlled manner.Accordingly, it is considered to use organic metal, metal halide (chloride, bromination Thing, iodide), the metal alkoxide of transition metal and metal amide compounds, then by mixing in precursor formulation at dioxy SiClx substrate carries out copolymerization.
It is, for example possible to use the cyclopentadienyl compounds of transition metal.Can be by the cyclopentadienyl group of transition metal Compound is divided into two classifications: dicyclopentadiene base complex and new monocyclopentadienylcomplex complex.Cyclopentadienyl complexes is permissible Comprise C5H5、C5Me5、C5H4Me、CH5R5(wherein R=Me, Et, propyl group, isopropyl, butyl, isobutyl group, sec-butyl).At these Under the either case of situation, Si can directly can be connected with alkyl chain with cyclopentadienyl ligands bonding or Si center, its Then be connected with cyclopentadienyl ligands.
The cyclopentadienyl complexes that can be used together with precursor formulation and use in the product can include following Biscyclopentadienyl complex: the first row transition metal (titanium, vanadium, chromium, ferrum, cobalt, nickel), the second row transition metal (zirconium, Molybdenum, ruthenium, rhodium, palladium), the third line transition metal (hafnium, tantalum, tungsten, iridium, osmium, platinum), group of the lanthanides (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho), actinium series (Ac, Th, Pa, U, Np).
New monocyclopentadienylcomplex complex can be used for providing metal functionality into precursor formulation, and when conjunction is preferably used Suitable part (such as chloride or carbonyl) will include following biscyclopentadienyl complex when carrying out stable: first Row transition metal (titanium, vanadium, chromium, ferrum, cobalt, nickel)；Second row transition metal (zirconium, molybdenum, ruthenium, rhodium, palladium)；The third line transition metal (hafnium, tantalum, tungsten, iridium, osmium, platinum).
The alkyl complex of metal can be used for providing metal functionality into precursor formulation and product.At these alkyl networks In compound, Si center has and directly can be bonded alkyl (ethyl, propyl group, butyl, vinyl, propylene with transition metal by σ key Base, cyclobutenyl), described alkyl.Additionally, in the case of this transition metal (such as Pd, Rh, Pt, Ir) after arrangement relatively more Common.
The co-ordination complex of metal can be used for providing metal functionality into precursor formulation and product.It is coordinated network at these In compound, Si center has can be with the carbonyl complex of Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni or thiazolinyl The unsaturated alkyl (vinyl, acrylic, cyclobutenyl, acetylene, butadienyl) of complex bonding, described unsaturated alkyl.Si Center can also be connected with phenyl, substituted phenyl or other aryl compound (pyridine, pyrimidine), and phenyl or aryl Can be with the supercentral carbonyl of substituted metal.
Metal alkoxide can be used for providing metal functionality into precursor formulation and product.Metallic alkoxide compound can be with Silicon precursor compound mixes, and then processes to form oxide, simultaneously as polymer copolymerization with water.This can also use metal halogen Compound and metal amine compound complete.Preferably, this can use the transition metal and aluminum, gallium and indium arranged earlier above, arrangement Transition-metal Fe, Mn, Cu and alkaline-earth metal Ca, Sr, Ba, Mg after relatively complete.
Wherein Si also may be used with the compound of metal center (it carries out stablizing by halogenide or organic group) Direct Bonding Metal functionality is provided for for precursor formulation and product.
Moreover, it will be appreciated that metal and metal complex can be continuous phase after pyrolysis or heat treatment subsequently.Can Preparation is specifically designed to selected metal reaction to be formed in situ commonly referred to ceramic metal (such as, ceramic metallization Compound) metal carbides, oxide and other metallic compound.Described preparation can be with selected metal reaction with original position shape Become such as mullite, aluminosilicate and other.Relative to the amount of the silicon dioxide in preparation or end-product, the amount of metal is permissible It is about 0.1 mole of % to 99.9 mole of %, about 1 mole of % or more, about 10 moles of % or more, about 20 moles of % or more. Can be used for controlling and providing predetermined stoichiometry in conjunction with the aforementioned applications of the metal of precursor formulation of the present invention.
Packing material will include reinforcing material.In many cases, the poly-silica carbon of solidification and pyrolysis can be filled Material is considered as composite.Generally, under this view, poly-silica carbon will constitute body phase or substrate phase (such as, continuous or base This continuous print phase), and filler is by composition dispersion (such as, discontinuous) phase.
It should be noted, however, that material is referred to as " (filled) of filling " or " (reinforced) of enhancing " not Mean this material major part (by weight, stereometer, or in terms of both) be poly-silica carbon.Therefore, generally, poly-silica Carbon can be about 0.1:99.9 to 99.9:0.1 with the ratio (weight or volume) of packing material.Can also exist or use Lesser amount of packing material or poly-silica carbon, but it will more generally useful be considered additive or otherwise mention.Cause This, term composite, packing material, poly-silica carbon packing material, reinforcing material, poly-silica carbon reinforcing material, poly-silica carbon Should be regarded as non-in terms of quantity that packing material, poly-silica carbon reinforcing material and this type of similar term are constituted at material and ratio Restrictive, the most within a context, it is endowed the most possible implication.
Can specifically prepare poly-silica carbon precursor formulation with in the performance phase with reinforcing material, packing material or base material Solidify under coupling, the such as default condition (such as, temperature and possible time) matched.These materials can also by be used as The material that the poly-silica carbon precursor formulation of substrate is identical is made or derived from this material, or it can be by different poly-silica Carbon is made.In addition to the ceramic fibre of derivative autohemagglutination silica carbon precursor formulation material, derivative autohemagglutination silica carbon precursor formulation material Porous, substantially porous and atresia ceramic structure can serve as filler or reinforcing material.
Poly-silica carbon precursor formulation may be used for coating or dipping fabric or non-woven fabrics to form preimpregnation material, described Fabric is by such as carbon fiber, glass fibre or the fiber being made up of poly-silica carbon precursor formulation (identical or different preparations) Make.Additionally, poly-silica carbon precursor formulation can serve as the interface coating on reinforcing material, or with the poly-silicon as host material Oxygen carbon precursor formulation is used together.Furthermore, it is possible to carbon fiber to be heat-treated to about 1400 ° to about 1800 ° or higher temperature, this Create the surface character eliminating the needs to separating interface coating, to be used together with poly-silica carbon precursor formulation.
Filler can reduce the contraction occurred during preparation processing becomes pottery, and filler can be used for providing product Predetermined density, or reduce or increase density, and it is provided for other customization and predetermined product and technology characteristics.Filler The effect reducing the contraction during solidification can be had under larger quantities (such as, more than 10%).
According to concrete application, product or final use, filler can be evenly distributed in precursor formulation, uneven Ground distribution, the predetermined rate of settling and can have different amounts in different preparations, then described preparation can be formed There is the product of the filler of scheduled volume in presumptive area (there is the band layer of different packing densities).
Preferably for typical filling product, filler is substantially uniformly distributed, and is more preferably evenly distributed on In final products.Local stress or weak spot can be avoided by this way.Typically for non-reinforcing material, each filler The volume of grain can be less than about the 0.3% of volume, about 0.2%, about 0.1% and about 0.05% of product, intermediate or parts. Such as, such as fruit product be spherical and filler is also for spherical, and the diameter of filler should be preferably about the 1/ of proppant particles diameter 10 to about 1/20, it is highly preferred that the diameter of filler should be less than about the 1/20 of proppant particles diameter.Generally, fill out used by material The relative quantity of material should be preferably about 30% to about 65% (such as, volume %) of spheroid volume.
Generally, in the case of there is no fiber, fabric etc., when little granular filler (such as, particulate, globule, bead) is used In time increasing the purpose of intensity, typically at least about 2 volume % at least about 5 volume % can demonstrate that intensity increases, although root According to other factors, (shape of such as product and volume, (such as, hardening time, temperature, pyrolysis infiltrate post-treatment condition again (reinfiltration) quantity)) described amount can be bigger or the least.Generally, when level of filler from about 5 volume % with During upper increase, further benefits in strength will not be realized.(the most considerable benefits in strength derives from this type of little particles filled product Filler, particularly intensity add at least about 5%, at least about 10% and preferably at least about 20%) it is considered enhancing product Product and material.
As used herein, except as otherwise noted, term %, weight % and quality % are used interchangeably, and are to refer to as Weight for totally the first component of the percetage by weight of (such as, preparation, mixture, material or product).As made herein With, except as otherwise noted, " volume % " refers to " % volume " and this type of similar term as overall (such as, preparation, material Material or product) the volume of the first component of percentage by volume.
Each point during manufacture process, can to poly-silica carbon structure, intermediate and final products and these Combination and modification carry out machining, grind, mold, shape, hole or other machining and shaping.
Generally, term " about " means to contain ± variance of 10% or scope are the experiments relevant to the described value obtained Or instrumental error, and the biggest value.
Precursor formulation is preferably transparent or substantially colorless, and generally through the light in visible wavelength.According to preparation its Can have muddiness, emulsus or nebulous outward appearance.Precursor formulation can also have colour solid, pigment or coloring agent and have Color filler (for pottery final products, such as pottery bristol glaze used in those, described colour solid, pigment or coloring agent with And colored filler can tolerate pyrolysis).Precursor can also have yellow or amber tint or tone, and without adding Toner.
Precursor formulation can be packed, transports and stored, to be subsequently used for being formed product (such as, structure or parts), or Precursor formulation described in person is used directly for these processes (such as, continuous process) to prepare product.It is therefoie, for example, front system Agent can be stored in bucket, tank truck, the track nail car of 55 gallons, can accommodate the field tank of hundreds of gallons and accommodate 1,000 In the transport case risen.Additionally, in the fabrication process, preparation continuously and can be prepared and using in semi-continuous process.
Among other things, the present invention has processing characteristics and the method for final products performance characteristic, system, pottery in design Porcelain aspect provides great motility, to meet predetermined and specific performance standard.It is therefoie, for example, the viscosity of precursor formulation Can make a reservation for mate the specific modality of reinforcing material by formula, the solidification temperature of precursor formulation can be come pre-by formula It is fixed, so that preimpregnation material can have the pot-life of prolongation.The viscosity of precursor formulation can be set up, so that precursor is prone to stream Enter in the reinforcing material of preimpregnation material, the most sufficiently thick to prevent precursor formulation from flowing away from reinforcing material or running off.Before The formula of body preparation it may also is that: such as so that it is the most right that the intensity of the preform of solidification be enough to allow Preform carries out rough or preliminary mechanical processing.
In each stage of the process from parent material to final finished, customization that when chemical reaction occurs and predetermined control System can provide the cost of reduction, the process control of enhancing, the reliability of raising, the efficiency of raising, the product feature of enhancing and These combination and modification and other benefit.The sequence when chemical reaction occurs can be based primarily upon processing or the system of precursor Standby and the processing of precursor formulation or preparation；It can also be based on solidification and pyrolytical condition.Additionally, these steps, preparation and bar The customization of part and predetermined selection can be passed through chemical reaction, molecules align and rearrangement and microstructure arrangement and reset (preferably Through predetermined and control) product and the machining feature of enhancing are provided.
Generally, the method form of the poly-silica material with carbon element of the preparation present invention comprises one or more steps.Obtain, preparation or Person derives parent material.Obtain precursor or precursor can be prepared by parent material.It is combined forming precursor formulation to precursor.So After by precursor formulation molding, shape, molding etc. becomes desired form, then solidifies this form, among other things, also by front Body preparation is transformed into quasi-plastic property material.Then the quasi-plastic property materials pyrolysis of this solidification can be become pottery.Should be appreciated that these walk Suddenly can not all use, some in these steps can be repeated once, twice or several times, it is possible to use these are general The combination of step and modification obtain required product or result.
Special process according to product and desired character, precursor and raw material, can make a reservation for and preliminary election technology type and condition And precursor.The biggest motility that this solution provides of precursor and technique thinks that intermediate, final products and finished product are formed The feature of customization, therefore, usual combinations thereof and modification can provide specific predetermined prod.It is also contemplated that such as become The factors such as basis, controllability, pot-life, expansion, easy manufacture.
In embodiments, precursor material can be Methyl Hydrogen Polysiloxane Fluid (methyl hydrogen) and replace and modified Methyl Hydrogen Polysiloxane Fluid, siloxane main chain additive, reactive monomer, hydro carbons, siloxane main chain additive and silane modifier Or the material of the product of organic modifiers and other similar type (such as based on silane material, based on silazane Material, material based on carbon silane, based on phenol/formaldehyde materials) and these combination and modification and other material.
Additionally, inhibitor is such as, hexamethylene, 1-acetenyl-1-Hexalin (it can obtain from ALDRICH), prestox ring four (according to consumption and temperature, it can be as reactant or reaction blocker for siloxanes, t etram-ethyltetravinylcyclotetrasiloxane (reaction of i.e. slowing down is to increase storage period), such as, at room temperature it is blocker, and at high temperature it is reactant), can add To described poly-silica carbon precursor formulation, the such as poly-silica carbon precursor formulation suppressed.Can also be when this of processing by other Material adds to described poly-silica carbon precursor formulation (such as, the poly-silica carbon precursor formulation of filling), and other material described includes Such as SiC powder, carbon black, PDC granule, pigment, granule, nanotube, the filler of whisker or discussed in this description or another Other material the most known in the art.Additionally, the preparation with inhibitor and filler will be considered as inhibition, filling poly- Silica carbon precursor formulation.
Precursor and precursor formulation are preferably innocuous materials.Generally, they have preferably above room temperature and typically store temperature The flash-point of degree, its preferred non-corrosiveness, it is therefore preferred to have low-vapor pressure, light abnormal smells from the patient or odorlessness, and can be to skin Skin is non-stimulated or minimal irritation.Catalyst can be used, and catalyst can be before curing in described precursor formulation Formed or when being prepared to structure, before, somewhat before or add before the time earlier.Precursor formulation can have full The storage period that foot manufacture process needs.Generally, it is possible to use catalyst, and catalyst can balance each other with inhibitor (balance with) or be used together with inhibitor, to have predetermined and predictable pot-life, hardening time, solid Change temperature curve.These curves may adapt to specific manufacturing process, transports the most before curing and stores one month, or Person transports preservation and is directly processed into pottery from liquid, or prepares and solid with the shortest haulage time or the time of storage Change.
In this mixed type technique of preparation precursor formulation, it is preferable that chemical reaction or molecular rearrangement occur over just In the preparation process of precursor, in the solidification process of preform and in pyrolytic process.Therefore, in the preparation of precursor occur or Person utilizes chemical reaction (such as, be polymerized, reduce, be condensed, replace).In preparing poly-silica carbon precursor formulation, it is preferable that do not have And there is no that chemical reaction and molecular rearrangement occur.The ceramic existing method derivative relative to preparing polymer, Preparation precursor formulation during avoid to polymerization or other reaction demand and do not utilize polymerization or other reaction These embodiments of the mixed type technique of the present invention provide significant advantage.Preferably, these mixed types preparation and In the embodiment of technique, be polymerized, cross-link or other chemical reaction mainly, preferably substantially and the most only Occur in the preform during solidification process.
Described precursor can also be selected from following:
The polymethyl hydrogen siloxane fluid 63148-57-2 of HF2020 trimethyl silyl end-blocking
This is the material that a class is commonly referred to Methyl Hydrogen Polysiloxane Fluid fluid, and has following formula:
The methyl hydrogen siloxane dimethylsiloxane copolymer 68037-of HF2050 TMS end-blocking 59-2
What it can be referred to as methyl blocking has dimethylated group (methyl terminated with Dimethyl groups), and there is following formula.
In some embodiments, this precursor can reduce heat release and reduce contraction.
The methyl hydrogen siloxane dimethylsiloxane copolymer 69013-23-6 of HF2060 hydride end-blocking
It can be referred to as hydride end-blocking there is dimethylated group (hydride terminated with Dimethyl groups), and there is following formula.
In some embodiments, this precursor can reduce heat release and reduce contraction, and provides branching-point.
The polydiphenylsiloxane of HF2038 hydrogen end-blocking
In some embodiments, this precursor can improve solidification toughness and reduce the material shrinking and improving solidification Heat stability.
The methyl hydrogen siloxane dimethylsiloxane copolymer 115487-49-5 of HF2068 hydride end-blocking
In some embodiments, this precursor can improve solidification toughness and reduce the material shrinking and improving solidification Heat stability；But higher crosslink density can be allowed.
HF2078 hydride end-blocking poly-(phenyl-dimethyl siloxy) siloxanes (phenyl silsesquioxane, Hydrogen end-blocking) 68952-30-7
In some embodiments, the three-functionality-degree of this precursor may be used for controlling branch, and in some embodiments In be used for reducing contraction.
Vinyl methyl-dimethyl polysiloxane copolymer the 68083-of VF6060 vinyl-dimethyl base end-blocking 18-1
In some embodiments, the three-functionality-degree of this precursor may be used for controlling branch, and in some embodiments In be used for reducing contraction.
The dimethyl diphenyl polysiloxane copolymer 68951-96-2 of VF6862 vinyl-dimethyl base end-blocking
In some embodiments, this precursor may be used for improving solidification toughness and reducing contraction.
The dimethyl-methyl vinyl-diphenyl polysiloxane copolymer of VF6872 vinyl-dimethyl base end-blocking
In some embodiments, this precursor may be used for improving solidification toughness and reducing contraction；If desired, also by Cladodification provides the ability improving crosslink density.
PC9401 1,1,3,3-tetramethyl-1,3-divinyl disiloxane 2627-95-4
In some embodiments, this precursor can provide the contraction more less than tetravinyl；But due to high ethylene Base percentage ratio, it still can be provided high crosslink density, but mainly be cross-linked by two dimension, without any branch.
Polydimethylsiloxane (OF1070) 70131-67-8 of PF1070 silanol end-blocking
In some embodiments, this precursor can help to reduce density by the formation of in-situ nano/micron openings.
The polydimethylsiloxane 70131-67-8 of silanol end-blocking
The polydimethylsiloxane 73138-87-1 of OF1070 OH-end-blocking
Hydroxy-end capped polydimethylsiloxane
In some embodiments, this precursor can help to reduce density by the formation of in-situ nano/micron openings.
The polydimethylsiloxane 68083-19-2 of VF6030 ethenyl blocking
In some embodiments, this precursor can increase curing rate, slightly reduces contraction, and improve solidification and Heat/the structural stability of the material of pyrolysis.
The polydimethylsiloxane fluid 70900-21-9 of HF2030 hydrogen end-blocking
Generally, the embodiment of the formula of poly-silica carbon preparation can have, the MH of e.g., from about 20% to about 99%, about The siloxane main chain additive of 0% to about 30%, the reactive monomer of about 1% to about 60% and the silicon of about 0% to about 90% Oxygen alkane main chain additive and silane modifier or the product with organic modifiers.
When mixing described preparation, need the sufficient time to allow described precursor effectively mix and disperse.Generally, before described Body preparation is the most substantially sheared insensitive, and therefore pump or mixed type are not crucial.It is further noted that more Full-bodied preparation may need extra incorporation time.The embodiment of method can provide the precursor formulation manufacturing customization Ability, described precursor formulation can provide has unique and required feature (such as high temperature, anti-flammability and resistance to combustion when solidification Property, intensity and further feature) plastics.The material of solidification can also carry out being pyrolyzed to form the pottery with specific characteristic.This Constitute by selecting functional group to mix and the polymer of precursor formulation allows the different types of functionality in final products Predetermined balance.The embodiment of preform can solidify in such as the controlled atmosphere of noble gas or it can be in an atmosphere Solidification.Predetermined condition of cure, such as, temperature, time, speed etc. can be come by preparation and other processing conditions.For example, it is possible to Select this type of condition to mate the size of preform, the shape of preform or to accommodate the mould of preform, to prevent Stress fracture, aerofluxus or the other problem relevant with solidification process.Additionally, condition of cure can be: utilize it with control mode The front things that may have been considered as the problem relevant with solidification process.It is therefoie, for example, aerofluxus may be used for generation has opening Structure or the foamed materials of enclosed construction.Furthermore, it is possible to the porous of predetermined material, so that such as can obtain specific Aperture, and can prepare by this way there is preset aperture, the filter of flow behavior or ceramic screen.
The preform of the preform of non-reinforcing, pure preform or enhancing may be used as stand-alone product, final Product, finished product or follow-up it can be carried out the preliminary product of machining or process.Preform can also stand pyrolysis, this Preform material is changed into pottery.
When being pyrolyzed the material of preform, the structure of solidification or solidification, in some embodiments, it is heated to surpass Cross about 650 DEG C to about 1200 DEG C.At these tem-peratures, usual all organic structures or be removed, or combine shape with inorganic constituents Become pottery.Generally at a temperature of 650 DEG C to 1200 DEG C, material is amorphous glass state pottery.When being heated to more than 1200 DEG C Time, material can form such as SiC, Si3N4, the nanocrystalline structure of SiCN, β SiC or micro-crystal structure, and exceed 1900 DEG C can form α SiC structure.
During being pyrolyzed, material is lost by aerofluxus.Amount at the last surplus material of pyrolysis setting is referred to as carbon residue Rate (or pyrolysis rate).Preparation in embodiment can air thermal dissociation to form pottery, and exceed at least about 80% and The most so carry out under the carbon yield of more than 88%.Initially or first pyrolysis step generally produces structure less closely.But, In certain embodiments, the use of such as light ball, described pyrolysis first can be sufficient for.Therefore, in some embodiments In can have can pyrolysis material on carry out infiltrate (reinfiltration) process again, to add extra poly-silica carbon Precursor formulation material is to insert or the hole in interstitital texture and space.Then the material that this infiltrates again is pyrolyzed again. This pyrolysis, the process infiltrated again can be repeated once, twice, three times and up to 10 times or more times to obtain the institute of finished product Need density.Additionally, about the preparation in embodiment of the present invention, the viscosity of described preparation can customize to provide the most again Infiltration, therefore, it can be used for by different preparations in follow-up immersion step again, owing to hole or hole become more and more less And it is more difficult to make formulation materials enter.High fixing carbon in embodiment of the present invention and further feature, enabling with few In 12 immersion step, less than about 10 times immersion step and immersion step manufacture is completely enclosed again less than five times knots more again Structure, such as " helium sealing " (helium tight) material.So that it takes up a position, for example, can carry out the most lazy with high fixing carbon preparation Property gas pyrolysis, carry out subsequently four times infiltrating air thermal dissociation step again.
Embodiment of the present invention have the ability utilizing the precursor containing impurity, high level impurity and notable impurity.Cause This, described precursor can have the impurity more than about 0.1%, impurity more than about 0.5%, more than about 1%, miscellaneous more than about 5% Matter, the impurity more than about 10% and the impurity more than about 50%.Use have the material of impurity time, the amount of these impurity or At least relative quantity, it should preferably measured by such as GPC (gel permeation chromatography) or other analysis method, in order to Solve the amount of actual precursor.By this way, for the amount of impurity existed, described in adjustable, poly-silica carbon precursor formulation joins System.Ceramic other method derivative relative to preparing polymer, embodiment of the present invention utilize the impurity material of reduced levels The ability of material, the most impure material and the most impure material provides significant advantage.Among other things, this carries Two significant advantages are supplied.First, use ability impure, relatively low-purity material to provide in embodiments of the invention Be greatly lowered described preparation and final products (such as, the preform of solidification, the parts of solidification and ceramic component or Structure) the ability of cost.Second, use ability impure, relatively low-purity material to carry in embodiments of the invention Supply that there are such final products (such as, the preform of solidification, the parts of solidification and ceramic component or structure) Ability, the various piece of described final products has the most higher concordance, because in each poly-silica carbon precursor formulation During preparation, the change of parent material can be adjusted.
Constitute the equipment of the present invention, method and technology can be this disclosure and any system of teaching, method and Technology, molding known in the art, shape, extrude, coating, build-up member, and in Serial No. 14/212,986,14/ 268,150, the U.S. Patent application of 14/324,056,14/514,257,61/946,598,62/055,397 and 62/106,094 Disclosed in and teaching those, the complete disclosure of each patent application is incorporated herein by.
Should be appreciated that in this specification, the use of title is in order at purpose clear, that quote, and enter never in any form Row limits.Therefore, described under title method, compositions and disclosure should be in conjunction with this specification including various embodiment Full content understand.In this specification, the use of title should not limit the protection domain that the present invention provides.
Obtain the conventional method of poly-silica carbon precursor
Generally, the ceramic precursor preparation that polymer is derivative, the most poly-silica carbon precursor formulation, generally can be by three kinds The method of type prepares, although other method and the modification of these methods and combination can also be used.These methods are usually directed to In conjunction with precursor to form precursor formulation.A type of method is usually directed to precursor material in preferred solvent-free process, basic On do not have chemical reaction occur in the case of mix, such as " mixed type technique ".Another type of method generally relates to And chemical reaction (such as, " response type technique "), to form the precursor formulation specifically such as customized, described precursor formulation is permissible For monomer, dimer, trimer and polymer.The method of the third type has two kinds or more kinds of in solvent-free environment The chemical reaction of component, such as " reaction admixing type technique " (the reaction blending type process).Generally, In hybrid technique, essentially all and the most all chemical reaction all occurs in subsequent process, such as, occurs solid Change, be pyrolyzed and during both.
Should be appreciated that these terms-response type technique, reaction admixing type technique and mixed type technique are in order to easy-to-use Quote with as shorthand.These terms not and are not construed as limiting.For example, it is possible to be used for producing precursor by response type technique Material, is then used for described precursor material and another precursor material in mixed type technique.
In addition to other place, this specification describes these technology types under its respective title.Should be appreciated that Under teaching to a kind of technique under one title, with another title, the teaching to another technique can be suitable for each other, and is suitable for In other parts, embodiment and the teaching of this specification, vice versa.Can by the parent material of a type of technique or Person's precursor material is in another type of technique.Moreover, it will be appreciated that the technique described under these titles should be in conjunction with this The full content of description is understood (including various embodiment and embodiment).
Should be appreciated that the combination of these techniques and modification may be used for obtaining precursor formulation and obtain intermediate, final Product and finished product.According to specific technique and the desired feature of product, for precursor and the parent material of a kind of technology type May be used in other technique.Preparation from described mixed type technique can be in response type technique or reaction admixing type technique In be used as precursor or component.Similarly, the preparation from response type technique may be used for mixed type technique and reaction admixing type In technique.Similarly, the preparation carrying out autoreaction admixing type technique may be used in mixed type technique and response type technique.Therefore, Preferably, can in conjunction with and utilize from the optimum performance of other technique and feature with provide cost benefit and effective technique with And final products.These techniques provide the biggest motility and think that intermediate, final products and finished product produce the feature of customization, Therefore, any one in these techniques and combinations thereof can provide specific predetermined prod.Selecting which kind of technique it is Time preferably, it is contemplated that the factors such as such as cost, controllability, pot-life, expansion, easy manufacture.
In addition to commercially available, precursor can also be prepared by alkoxylate type technique (such as, ethoxylation technique).? In this technique, chlorosilane and ethanol react in the presence of catalyst (such as HCl), to provide precursor material, and described material Can react to provide the precursor of more long-chain further.Other alcohols (such as methanol) can also be used.It is therefoie, for example, SiCl4、SiCl3H、SiCl2(CH3)2、SiCl2(CH3)H、Si(CH3)3Cl、Si(CH3) ClH and ethanol CH3CH2OH reacts with shape Become precursor.Wherein in some reactions, phenols can be the source of the phenoxy group replacing the hydride group being positioned on silicon.May Need a step, two steps or more multistep reaction.
Precursor material can also be obtained by acetylene reaction route.Typically, there are some known routes for by acetylene It is added to Si-H.It is therefoie, for example, tetramethyl-ring tetrasiloxane can in the presence of a catalyst with acetylene reaction, to produce four Methyl tetravinyl cyclotetrasiloxane.Then this product can be carried out open loop and polymerization, in order to form the vinyl of straight chain Methylsiloxane.It is alternatively possible to by by dimethyl dichlorosilane (DMCS) (being obtained by direct technique or Rochow technique) and second Alkyne reaction produces typical vinyl silanes.Then these monomers can be purified (because there may be some chaff interferences Matter) to form vinyl methyl dichlorosilane.It is then possible to make polymerization of vinyl monomer to form many ring-type silicon via hydrolysis Oxygen alkane and linear siloxanes, described siloxanes has various chain length, including the most various cyclotetrasiloxanes (such as, D4') and each Plant D5 (such as, D5’).But, these routes are expensive, and therefore the parent material for lower cost is originated and deposited In demand that is long-term and that increase to produce vinyl silanes.Before making the present invention, it is not regarded as that MHF may be used for Addition on acetylene work Skill is to obtain vinyl silanes.MHF is more less expensive, in addition to other side, by second than vinyl, methyl (straight chain or ring-type) Alkynes is added to MHF so that vinyl meets long-term needs to provide more cost-efficient material and relatively cheap cost. When carrying out this additive reaction, in addition to other side, it is considered as and controls following variable: feed (D4', straight-chain methyl hydrogen silicon Oxygen alkane fluid)；Temperature；Acetylene and the ratio of Si-H；(Karstedt catalyst, DBT Laureate, without catalysis for homogeneous catalyst Agent, has the Karstedt catalyst of inhibitor)；Loaded catalyst (carbon carries Pt, carrying alumina Pt and carrying alumina Pd)；Stream Speed (liquid feedstock, acetylene feed)；Pressure；And catalyst concn.Table A and table B provide Addition on acetylene to MHF (ring-type and Straight chain) the embodiment of embodiment of reaction.Table A is batch (-type) acetylene reaction.Table B is continuous way acetylene reaction.Should manage Solve, it is possible to use batch (-type), continuous way, the counter-current flow of MHF and acetylene charging, the circulation continuously of one way material and these group Conjunction and modification and other technique are to realize higher conversion ratio.
Table A: batch (-type) acetylene reaction
Table B: continuous way acetylene reaction
(D4' be tetramethyl tetrahydride cyclotetrasiloxane)
In addition to other reason, continuous high pressure reactor (" CHPR ") embodiment can be favourable for following reasons : reaction conversion ratio saves acetylene required in more liquid phases；Tubular reactor provides then increases the pressure of the dissolubility of acetylene Power；Concentration and time (such as, 100 hours) are saved in reaction with hexin；Homogeneous catalyst can be got rid of, therefore once complete, Eliminate the hydrosilylation reactions with gained vinyl；And use heterogeneous (solid) catalyst to maintain that product is complete, to increase Add the pot-life, increase storage period and these combination and modification.
Process Addition on acetylene reaction in various condition time, some factors may is that by dilution acetylene and reduction urge The crosslinking of agent concentration is slow；And relative to less molecule, the conversion ratio of bigger straight chain molecule (uses heterogeneous catalysis Agent) can be lower.
Among other things, the existence of vinyl and quality and vinyl conversion rate can be determined by following: FT- IR is for determining the existence that vinyl absorbs, and SiH absorbs minimizing；1H NMR reduces for the existence and SiH determining vinyl ；13C NMR is for determining the existence of vinyl.
As used herein, except as otherwise noted, term %, weight % and quality % are interchangeably used, and refer to Weight as totally the first component of the percent of (such as, preparation, mixture, material or product) weight.Such as this paper institute Using, except as otherwise noted, term " volume % " refers to " % volume " and this type of similar term as (the most such as, Preparation, material or product) the volume of the first component of percentage by volume.
Mixed type technique
Precursor material can be that Methyl Hydrogen Polysiloxane Fluid and replacement and the Methyl Hydrogen Polysiloxane Fluid of modification, siloxane main chain add Agent, reactive monomer, siloxane main chain additive and silane modifier or the product of organic modifiers and other phase Like the material of type, such as based on silane material, based on polysilazane material, based on carbon silane material, based on phenol/formaldehyde Material, and the combination of these materials and modification.The most described precursor is at room temperature liquid, although they can be to be melted Solid, or solid solvable in one of other precursor.But (, in such cases it should be appreciated that when a kind of precursor When dissolving another kind of, it is still not considered the term " solvent " as used in prior art processes, described prior art work Skill uses non-composition (non-constituent) solvent, such as, will not form a part for end product or the molten of component Agent, the solvent being considered garbage and solvent that both have concurrently).
Described precursor the most at room temperature mixes.Preferably, a small amount of solvent and the most solvent-free (such as water, organic solvent, polar solvent, non-polar solven, hexane, THF, toluene) is added into this mixture of precursor material In.Preferably, every kind of precursor material is miscible with other material, and such as, they can be with Arbitrary Relative amount or arbitrary proportion Mixing, and will not be layered or precipitate.Now, described " precursor mixture " or " poly-silica carbon precursor formulation " is complete (note: if only using single precursor, described material will be only " poly-silica carbon precursor " or " poly-silica carbon precursor formulation " Or " preparation ").Although complete, but filler and reinforcing agent can be added to described preparation.Excellent at described preparation Select in embodiment, when described preparation is mixed, or when described preparation be just placed in container, be placed on preimpregnation material or Before being cured keep a period of time time, there is no in described preparation and more preferably do not have chemical reaction (such as crosslinking or Person is polymerized) occur.
Can polytype atmosphere and under the conditions of mix precursor, such as air, inert atmosphere, N2, argon, flowing gas Body, gas at rest, decompression, high pressure, ambient pressure and these combination and modification.
Additionally, can be by inhibitor such as hexamethylene, 1-acetenyl-1-Hexalin (it can obtain from ALDRICH), prestox Cyclotetrasiloxane, t etram-ethyltetravinylcyclotetrasiloxane add to described poly-silica carbon precursor formulation, the such as poly-silicon suppressed Oxygen carbon precursor formulation.Should be appreciated that t etram-ethyltetravinylcyclotetrasiloxane can be as reaction according to the amount existed and temperature Thing and reaction blocker (such as, inhibitor), such as, at room temperature it is blocker, and at high temperature it is reactant.Also may be used So that other material is added to described poly-silica carbon precursor formulation, such as, the poly-silica carbon precursor of filling when this of processing Preparation, other material described includes filler, the derivative ceramic particle of such as SiC powder, carbon black, sand, polymer, pigment, Grain, nanotube, whisker or other material discussed in this description or the most known in the art.Additionally, have inhibitor With the preparation of filler by poly-silica carbon precursor formulation that be considered as inhibition, that fill.
According to precursor concrete in described poly-silica carbon precursor formulation and their relative quantity, poly-silica carbon precursor formulation exists Can have under room temperature more than 12 hours, more than 1 day, more than 1 week, more than 1 month and several years or longer storage life Limit.These precursor formulation at high temperature can have more than 12 hours, more than 1 day (such as, under about 90 °F), more than 1 week, big In 1 month and several years or longer pot-life.The use of inhibitor can extend the storage life under higher temperature further Between Xian Shi, and these combination and modification.The use of inhibitor can also by control reaction rate and be of value to manufacture and The development of business process, so that it betides technique or the expectation part of the system of manufacture and desired part.
As used herein, except as otherwise noted, term " pot-life " should give its wide significance as far as possible, and Including such as can with 100% percentage ratio as the preparation of brand-new, at least about 90% the same, at least about with the preparation of brand-new 80% as the preparation of brand-new and about 70% with the preparation of brand-new the same for its intended purpose or carry out (such as, running) The preparation of its desired use.
Precursor and precursor formulation are preferably innocuous materials.They have preferably from about more than 70 DEG C, more than about 80 DEG C, about 100 With more than about 300 DEG C and higher flash-point more than DEG C.Preferably, they are noncorrosive.Preferably, they can have low Vapour pressure, can have the lightest abnormal smells from the patient or an odorlessness, and can to skin non-stimulated or minimal irritation.
Catalyst or initiator can be used, and can be formed in described precursor formulation before curing or be made When standby one-tenth structure, it is added into before before, somewhat before or earlier.Described catalyst helps, advance, promote described before Body preparation be cured to form preform.
After adding described catalyst, precursor formulation is referred to as " storage period ", example for solidifying the most useful period As, how long the preparation of described catalysis can keep before it should be used in accommodating container.According to concrete preparation, the most just If using inhibitor and use, the amount just used, holding conditions (such as temperature, low O2Atmosphere) and potential its Its factor, the storage period of precursor formulation can be such as, about 5 minutes to about 10 days, about 1 day to about 6 day, about 4 days to 5 days, about 30 minutes, about 15 minutes, about 1 hour to about 24 hour and about 12 hours to about 24 hours.
Described catalyst can be any catalyst based on platinum (Pt), and it can such as be diluted to: the most every million points It (ppm) 0.01 part of Pt to about 250ppm Pt, about 0.03ppm Pt, about 0.1ppm Pt, about 0.2ppm Pt, about 0.5ppm Pt, about 0.02 to 0.5ppm Pt, about 1ppm to 200ppm Pt, it is preferable that for some application and embodiment, about 5ppm extremely 50ppm Pt.Described catalyst can be under the concentration of 0.1% to 3% peroxide and about 0.5% to 2% peroxide in There is when more than 90 DEG C the catalyst based on peroxide of such as 10 hour half-life.It can be based on organic peroxide Compound.It can be any organo-metallic catalyst that can react with Si--H bond, Si-OH key or unsaturated carbon bond, these Catalyst may include that dibutyl tin laurate, zinc octoate, peroxide and such as titanium, zirconium, rhodium, iridium, palladium, cobalt or nickel Organo-metallic compound.Catalyst can also be other rhodium any, rhenium, iridium, palladium, cobalt, nickel and ruthenium type catalyst or based on Their catalyst.These combination and modification and other catalyst can also be used.Trade name can be obtained from ARKEMA Catalyst for LUPEROX (such as, LUPEROX 231)；And obtain trade name Karsted from Johnson Matthey Family name's catalyst, AshbyShi catalyst, the catalyst of SpeierShi catalyst.
In addition it is possible to use the customization of these and other catalyst and particular combination so that by them and specific preparation Coupling, and the most optionally and specifically it is catalyzed the reaction of special component.Additionally, the catalysis of the coupling of these types The use of agent-formulation system is provided for predetermined product feature, such as, consolidated structures and the pore structure of pottery, porous Property, density, Density Distribution, high-purity, ultra-high purity and other form or feature.
In this mixed type technique for preparing precursor formulation, it is preferable that chemical reaction or molecular rearrangement are only sent out Raw during the preparation of parent material, in solidification process and pyrolytic process.The preparation of parent material or precursor occurs Or utilize chemical reaction (such as, be polymerized, reduce, be condensed, replace).System before preparing poly-silica carbon by mixed type technique During agent, preferably without and there is no that chemical reaction and molecular rearrangement occur.Avoid during preparation precursor formulation To polymerization or other reaction demand and do not utilize polymerization or other reaction the present invention mixed type technique these implement Scheme provides significant advantage relative to the existing method preparing the derivative pottery of polymer.Preferably, in these mixed types Preparation and technique embodiment in, be polymerized, cross-link or other chemical reaction mainly, preferably substantially and more preferably During occurring over just solidification process.
Described precursor can be siloxane main chain additive, and such as, Methyl Hydrogen Polysiloxane Fluid (MH), its formula is as follows.
MH can have about 400mw, and to about 10000mw, about 600mw to the molecular weight of about 3000mw, (" mw " can be as weight Average molecular weight is measured in units of amu or g/mol), and there is the preferably from about 20cps viscosity to about 60cps.Methyl The percent of siloxane unit " X " can be 1% to 100%.The percent of dimethyl siloxane units " Y " can be 0% to 99%.This precursor may be used for the preform to solidification and the main chain of ceramic material offer cross-linked structure and further feature And characteristic.Among other things, this precursor can also be modified by reacting with undersaturated carbon compound, new to produce Type or other precursor.Generally, Methyl Hydrogen Polysiloxane Fluid fluid (MHF) has minimal amount of " Y ", more preferably for all reality Purpose " Y " is 0.
Described precursor can be siloxane main chain additive, and such as, the polydimethylsiloxane of vinyl substituted, its formula is such as Shown in lower.
This precursor can have the molecular weight (mw) of about 400mw to about 10000mw, and can have preferably from about The viscosity of 50cps to about 2000cps.The percent of methyl vinyl siloxane unit " X " can be 1% to 100%.Dimethyl The percent of siloxane unit " Y " can be 0% to 99%.Preferably, X is about 100%.This precursor may be used for reducing to be handed over Join density and improve toughness and provide further feature and characteristic to preform and the ceramic material of solidification.
Described precursor can be siloxane main chain additive, such as, and vinyl substituted and the poly dimethyl of ethenyl blocking Siloxanes, its formula is as follows.
This precursor can have the molecular weight (mw) of about 500mw to about 15000mw, and can preferably have about The molecular weight of 500mw to 1000mw, and can have the preferably from about 10cps viscosity to about 200cps.Methyl ethylene silica The percent of alkane unit " X " can be 1% to 100%.The percent of dimethyl siloxane units " Y " can be 0% to 99%. This precursor is provided for branch and reduces solidification temperature, and provides other to preform and the ceramic material of solidification Features and characteristics.
Described precursor can be siloxane main chain additive, such as, and vinyl substituted and the polydimethylsiloxanes of hydrogen end-blocking Alkane, its formula is as follows.
This precursor can have the molecular weight (mw) of about 300mw to about 10000mw, and can preferably have about The molecular weight of 400mw to 800mw, and can have the preferably from about 20cps viscosity to about 300cps.Methyl vinyl silicone The percent of unit " X " can be 1% to 100%.The percent of dimethyl siloxane units " Y " can be 0% to 99%.This Plant precursor be provided for branch and reduce solidification temperature, and provide other special to preform and the ceramic material of solidification Seek peace characteristic.
Described precursor can be siloxane main chain additive, and such as, the polydimethylsiloxane of allyl capped, its formula is such as Shown in lower.
This precursor can have the molecular weight (mw) of about 400mw to about 10000mw, and can have preferably about The viscosity of 40cps to about 400cps.Repetitive is identical.This precursor is provided for UV curability and extends poly- Close chain, and provide further feature and characteristic to preform and the ceramic material of solidification.
Described precursor can be siloxane main chain additive, and such as, the polydimethylsiloxane of ethenyl blocking, its formula is such as Shown in lower.
This precursor can have the molecular weight (mw) of about 200mw to about 5000mw, and can preferably have about 400mw To the molecular weight of 1500mw, and can have the preferably from about 10cps viscosity to about 400cps.Repetitive is identical.This Plant precursor to be provided for polymeric chain growing agent, improve toughness and solidification temperature is reduced to such as cold curing, Yi Jixiang The preform of solidification and ceramic material provide further feature and characteristic.
Described precursor can be siloxane main chain additive, such as, and the polydimethylsiloxane that silanol (hydroxyl) blocks, its Formula is as follows.
This precursor can have the molecular weight (mw) of about 400mw to about 10000mw, and can preferably have about The molecular weight of 600mw to 1000mw, and can have the preferably from about 30cps viscosity to about 400cps.Repetitive is identical 's.This precursor is provided for polymeric chain growing agent, toughening mechanisms, can produce nanoscale and micron-sized hole and permit Permitted at room temperature to solidify, and provided further feature and characteristic to preform and the ceramic material of solidification.
Described precursor can be siloxane main chain additive, such as, and the diformazan of the vinyl substituted that silanol (hydroxyl) blocks Radical siloxane, its formula is as follows.
This precursor can have the molecular weight (mw) of about 400mw to about 10000mw, and can preferably have about The molecular weight of 600mw to 1000mw, and can have the preferably from about 30cps viscosity to about 400cps.Methyl ethylene silica The percent of alkane unit " X " can be 1% to 100%.The percent of dimethyl siloxane units " Y " can be 0% to 99%. Among other things, this precursor may be used for double cure system；The most double solidifications can allow in unitary agent Use multiple curing mechanism.It is, for example possible to use condensed type solidification and add-on type solidify both.This provides then has complexity The ability of cure profile, it such as can provide the initial solidification via a type of solidification and the solidification via independent type Final solidification.
Described precursor can be siloxane main chain additive, such as, and the polydimethylsiloxane that hydrogen (hydride) blocks, its Formula is as follows.
This precursor can have the molecular weight (mw) of about 200mw to about 10000mw, and can preferably have about The molecular weight of 500mw to 1500mw, and can have the preferably from about 20cps viscosity to about 400cps.Repetitive is identical 's.This precursor is provided for polymeric chain growing agent, can serve as toughener, and it allows lower temperature solidification, example As, room temperature, and provide further feature and characteristic to preform and the ceramic material of solidification.
Described precursor can be siloxane main chain additive, and such as, the siloxanes of diphenyl end-blocking, its formula is as follows.
The most now R is reactive group, such as, and vinyl, hydroxyl or hydride.This precursor can have about The molecular weight (mw) of 500mw to about 2000mw, and can have the preferably from about 80cps viscosity to about 300cps.Methyl-R-silicon The percent of oxygen alkane unit " X " can be 1% to 100%.The percent of dimethyl siloxane units " Y " can be 0% to 99%.This precursor is provided for toughener and for adjusting the refractive index of polymer to mate various types of glass Refractive index, for provide the most transparent glass fibre and to solidification preform and ceramic material provide further feature and Characteristic.
Described precursor can be siloxane main chain additive, and such as, single phenyl end capped siloxanes, its formula is as follows.
Wherein R is reactive group, such as, and vinyl, hydroxyl or hydride.This precursor can have about 500mw To the molecular weight (mw) of about 2000mw, and can have the preferably from about 80cps viscosity to about 300cps.Methyl-R-siloxanes The percent of unit " X " can be 1% to 100%.The percent of dimethyl siloxane units " Y " can be 0% to 99%.This Plant precursor and be provided for toughener and for adjusting the refractive index refractive index with the various types of glass of coupling of polymer, For providing the most transparent glass fibre and providing further feature and characteristic to preform and the ceramic material of solidification.
Described precursor can be siloxane main chain additive, such as, diphenyldimethyl polysiloxanes, the following institute of its formula Show.
This precursor can have the molecular weight (mw) of about 500mw to about 20000mw, and can preferably have about The molecular weight of 800mw to about 4000mw, and can have the preferably from about 100cps viscosity to about 800cps.Dimethyl siloxane The percent of unit " X " can be 25% to 95%.The percent of diphenylsiloxane unit " Y " can be 5% to 75%.This Kind of precursor be provided for single phenyl end capped type siloxane as characteristic and to the preform of solidification and ceramic material Material provides further feature and characteristic.
Described precursor can be siloxane main chain additive, such as, and the diphenyldimethyl polysiloxanes of ethenyl blocking, Its formula is as follows.
This precursor can have the molecular weight (mw) of about 400mw to about 20000mw, and can have about 800 to about The molecular weight of 2000, and can have the preferably from about 80cps viscosity to about 600cps.The hundred of dimethyl siloxane units " X " Mark can be 25% to 95%.The percent of diphenylsiloxane unit " Y " can be 5% to 75%.This precursor is permissible For provide chain growth, toughener, change or the refractive index that changes and the high high-temp stability of material improving solidification, with And provide further feature and characteristic to preform and the ceramic material of solidification.
Described precursor can be siloxane main chain additive, such as, and hydroxy-end capped diphenyldimethyl polysiloxanes, its Formula is as follows.
This precursor can have the molecular weight (mw) of about 400mw to about 20000mw, and can have about 800 to about The molecular weight of 2000, and can have the preferably from about 80cps viscosity to about 400cps.The hundred of dimethyl siloxane units " X " Mark can be 25% to 95%.The percent of diphenylsiloxane unit " Y " can be 5% to 75%.This precursor is permissible For provide chain growth, toughener, change or the refractive index that changes and the high high-temp stability of material improving solidification, can To produce nanoscale and micron-sized hole and to provide further feature and characteristic to preform and the ceramic material of solidification.
The most various cyclosiloxane can be used as reactive molecule.They can be by following nomenclature or formula It is described: DxD* y, wherein " D " represents dimethylsiloxy units, and " D*" represent substituted methyl siloxy units, its In "*" group can be vinyl, pi-allyl, hydride, hydroxyl, phenyl, styryl, alkyl, cyclopentadienyl group or its Its organic group, X is 0-8, y >=1, and x+y is 3-8.
Precursor batch can also comprise non-silicon-based cross-linking agent, it is possible to for non-silicon-based cross-linking agent and siloxane main chain additive Product, and these combination and modification.Non-silicon-based cross-linking agent purport during curing provides the ability of crosslinking.Such as, may be used With use non-silicon-based cross-linking agent include: cyclopentadiene (CP), methyl cyclopentadiene (MeCP), bicyclopentadiene (" DCPD "), Methyl dicyclopentadiene (MeDCPD), three cyclopentadiene (TCPD), piperylene, divinylbenzene, isoprene, norborneol two Alkene, vinyl norbornene, acrylic norborene, isopropenylnorbornene, methyl ethylene norborene, bicyclo-nonyl two Alkene, methyl bicyclic nonadiene, allene, 4 vinyl cyclohexene, 1,3-heptadiene, cycloheptadiene, 1,3-butadiene, ring pungent two Alkene and isomer thereof.Generally, comprise two (or more) to react with Si-H, the Si-OH in precursor or other Si key Any hydrocarbon of unsaturated C=C key can serve as cross-linking agent, described.Some organic materials comprising oxygen, nitrogen and sulfur are also used as Crosslink part.
Described precursor can be reactive monomer.These will include molecule such as t etram-ethyltetravinylcyclotetrasiloxane (" TV "), its formula is as follows.
This precursor be provided for branching agent, three-dimensional cross-linked dose and to solidification preform and ceramic material carry For further feature and characteristic.(should also be noted that: in some preparation, such as higher than 2%, and at a temperature of some, e.g., from about room temperature To about 60 DEG C, this precursor can serve as the inhibitor of crosslinking, for example, it is possible to suppression hydride and the crosslinking of vinyl).
Described precursor can be reactive monomer, such as, and trivinyl cyclotetrasiloxane,
Divinyl cyclotetrasiloxane,
Trivinyl list hydride cyclotetrasiloxane,
Divinyl dihydride cyclotetrasiloxane,
And hexamethyl cyclotetrasiloxane, such as,
Described precursor can be silane modifier, such as vinylphenyhnethylsilane, diphenyl silane, diphenyl methyl Silane and phenyl methyl silane (some of them can serve as end-capping reagent or terminal group).These silane modifiers can provide chain Growing agent and branching agent.Among other things, they also improve toughness, change the height of the material of refractive index, improvement solidification The intensity of the material of temperature solidification stability and improvement solidification.Among other things, precursor such as diphenylmethylsilane Can play the effect of end-capping reagent, it can also improve toughness, changes refractive index, and the hot setting of the material improving solidification is stable Property, and improve the intensity of the material of solidification.
Described precursor can be the product of silane modifier and the siloxane main chain additive of ethenyl blocking.Described Precursor can be the product of silane modifier and hydroxy-end capped siloxane main chain additive.Described precursor can be silane The product of the siloxane main chain additive that modifying agent blocks with hydride.Described precursor can be silane modifier and TV Product.Described precursor can be the product of silane.In view of sterically hindered, described precursor can be silane modifier Product with cyclosiloxane.Described precursor can be the tetraethyl orthosilicate of partial hydrolysis, such as TES40 or Silbond 40.Described precursor can also be methyl silsesquioxane (methylsesquisiloxane), such as can be from General Electric Company, the SR-350 that Wilton, Conn obtain.Described precursor can also be phenyl methyl silica Alkane, such as, from the 604 of Wacker Chemie AG.Described precursor can also be methyl phenyl vinyl siloxanes, such as, H62C from Wacker Chemie AG.
Described precursor can also be selected from following:
HF2020, the Methyl Hydrogen Polysiloxane Fluid fluid 63148-57-2 of TMS end-blocking； The methyl hydrogen siloxane dimethylsiloxane copolymer 68037-59-2 of HF2050 TMS end-blocking； The methyl hydrogen siloxane dimethylsiloxane copolymer 69013-23-6 of HF2060 hydride end-blocking；HF2038 hydrogen seals The polydiphenylsiloxane of end；The methyl hydrogen siloxane dimethylsiloxane copolymer of HF2068 hydride end-blocking 115487-49-5；Poly-(pheiiyldimetliyl siloxy) siloxanes phenyl silsesquioxane of HF2078 hydride end-blocking Alkane, the 68952-30-7 of hydrogen end-blocking；The poly-silica of vinyl methyl dimethyl of VF6060 vinyl-dimethyl base end-blocking Alkyl copolymer 68083-18-1；The dimethyl diphenyl polysiloxane copolymer of VF6862 vinyl-dimethyl base end-blocking 68951-96-2；The dimethyl-methyl vinyl-diphenyl polysiloxanes of VF6872 vinyl-dimethyl base end-blocking is altogether Polymers；PC9401 1,1,3,3-tetramethyl-1,3-divinyl disiloxane 2627-95-4； Polydimethylsiloxane (OF1070) 70131-67-8 of PF1070 silanol end-blocking；Poly-the two of OF1070 silanol end-blocking Methylsiloxane 70131-67-8；Polydimethylsiloxane (hydroxy-end capped polydimethylsiloxane) 73138-of OH end-blocking 87-1；The polydimethylsiloxane 68083-19-2 of VF6030 ethenyl blocking；AndHF2030 hydrogen seals The polydimethylsiloxane fluid 70900-21-9 of end.
Therefore, in addition to the precursor of aforementioned type, it is contemplated that precursor can also is that the compound of below general formula.
Wherein end-capping reagent E1 and E2It is selected from: such as, trimethyl silicane (-Si (CH3)3), dimethyl-silicon hydroxyl (-Si (CH3)2OH), dimethyl-silicon hydride (-Si (CH3)2H), dimethyl ethenyl silicon (-Si (CH3)2(CH=CH2))、(-Si(CH3)2 (C6H5)) and dimethyl alkoxyl silicone (-Si (CH3)2(OR).R group R1、R2、R3And R4Can be different from, or one or Multiple can be identical.It is therefoie, for example, R2With R3Identical, R3With R4Identical, R1And R2Difference and R3With R4Identical, etc.. Described R group is selected from such as hydrogen (-H), methyl (Me) (-C), ethyl (-C-C), vinyl (-C=C), alkyl (-R) (CnH2n+1), pi-allyl (-C-C=C), aryl (' R), phenyl (Ph) (-C6H5), methoxyl group (-O-C), ethyoxyl (-O-C-C), Siloxy (-O-Si-R3), alkoxyl (-O-R), hydroxyl (-O-H), phenethyl (-C-C-C6H5) and aminomethyl phenyl-ethyl (-C-C (-C)(-C6H5)。
Generally, the embodiment of the formula of poly-silica carbon preparation can such as have about 0% to 50% MH, about 20% to The MH of about 99%, the siloxane main chain additive of about 0% to about 30%, the reactive monomer of about 1% to about 60%, about 30% to The TV of about 100% and the siloxane main chain additive of about 0% to about 90% and silane modifier or anti-with organic modifiers Answer product.
When mixing described preparation, the time of abundance should be used to allow precursor effectively mix and disperse.Generally, about 15 points The mixing of Zhong Zhiyi hour is enough.Generally, precursor formulation is insensitive for relatively and substantially shearing, therefore pump or mixed The type closed not is crucial.Shall also be noted that and may need extra incorporation time in the preparation of viscosity higher.Mixed During conjunction, the temperature of preparation should be preferably maintained below about 45 DEG C, and preferably from about 10 DEG C.(it should be noted that, these mixing conditions It is the preparation for pre-catalysis).
Response type technique
Generally, in response type technique, the most in the presence of the solvent use chemical reaction combine one, two kinds or More kinds of precursors, the precursor formulation being substantially made up of single polymers with formation, then described precursor formulation can be urged Change, solidify and be pyrolyzed.Process provides the ability of the precursor formulation setting up customization, the precursor formulation of described customization is being cured Time the plastics with unique and desired feature (such as high temperature, anti-flammability and flame resistance, intensity and further feature) can be provided. Also can be by the materials pyrolysis of solidification to form the pottery with specific characteristic.This response type technique forms precursor by selecting to mix Functional group in the polymer of preparation (such as, it is generally not used for pottery but is of value to the phenyl that high temperature capabilities is provided for plastics, with And general do not provide high-temperature characteristic for plastics but the styrene of benefit is provided for pottery), thus allow the difference in final products The predetermined balance of the function of type.
Generally, react the polymer preparing the customization as precursor formulation by making precursor carry out in the condensation reaction, To form polymer precursor preparation.Then by hydrolysis, this precursor formulation is solidified into preform.Described condensation reaction Form the polymer of type shown below.
The wherein R in polymerized unit1And R2Can be hydrogen (-H), methyl (Me) (-C), ethyl (-C-C), vinyl (-C= C), alkyl (-R) (CnH2n+1), unsaturated alkyl (-CnH2n-1), cycloalkyl (-CnH2n-1), pi-allyl (-C-C=C), cyclobutenyl (-C4H7), pentenyl (-C5H9), cyclopentenyl (-C5H7), methyl cyclopentene base (-C5H6(CH3)), norbornene (-CXHY, Wherein X=7-15 and Y=9-18), aryl (' R), phenyl (Ph) (-C6H5), cycloheptenyl (-C7H11), cyclo-octene base (- C8H13), ethyoxyl (-O-C-C), siloxy (-O-Si-R3), methoxyl group (-O-C), alkoxyl (-O-R), hydroxyl (-O-H), benzene Ethyl (-C-C-C6H5), aminomethyl phenyl-ethyl (-C-C (-C) (-C6H5)) and ethenylphenyl-ethyl (-C-C (C6H4(-C= C)))。R1And R2Can be identical or different.(such as, the precursor polymer of customization can have several different polymerized unit A1、A2、An), and can include up to 10,20 or more unit, or it can only comprise single unit, such as, The MHF prepared by course of reaction can only have single unit.
Embodiment can include precursor, and among other things, described precursor also includes triethoxy methyl silicane, diethyl Epoxide aminomethyl phenyl silane, diethoxymethyl hydrosilanes, diethoxymethylvinylschane, dimethylethyloxy ethylene Base silane, di ethoxy di methyl-monosilane, ethyoxyl dimethylphenylsilaneand, diethoxy dihydro silane, triethoxy benzene Base silane, diethoxy hydrogenation trimethicone, diethoxymethyl trimethicone, trimethylethoxysilane, two Diethylamino phenyl TMOS, dimethylethyloxy hydride siloxane and these combination and modification and other precursor, including this Other precursor described in description.
Terminal units, Si end 1 and Si end 2 can come from dimethylethyloxy vinyl silanes, ethyoxyl dimethyl Phenyl silane and the precursor of trimethylethoxysilane.If additionally, suitably control polymerization process, polymerization can be provided from being used for The precursor of the repetitive of thing obtains hydroxy-end capped (end cap).
Generally, by precursor and ethanol (or other material, to absorb heat, such as, to provide caloic), the water of excess, with And hydrochloric acid (or other proton source) adds in container together.Being heated by this mixture, until it reaches activation energy, hereafter reaction is logical It it is often heat release.Generally, in the reaction, water reacts with the ethyoxyl of the silicon of precursor monomer, forms hydroxyl (using ethanol as pair Product).Once being formed, this hydroxyl becomes the object reacted with the ethyoxyl on the silicon of another precursor monomer, causes polyreaction. Proceed this polyreaction, until the chain length needed for building.
Among other things, for determining that the governing factor of chain length is: selected monomer (generally, starts to enclose at it Around wound on itself and before being bonded to self, monomer is the least can add the most)；Amount in the reaction introducing end-capping reagent And point；And the amount of water and adding rate etc..Therefore, to can be about 180mw (viscosity about 5cps) to about 65000mw (viscous for chain length Spend about 10000cps), greater than about 1000mw, greater than about 10000mw, greater than about 50000mw and bigger.Additionally, before Ju He Body preparation and generally can have the polymer of different molecular weight really, and described molecular weight can be scheduled thinks preparation, solid Change and ceramic product provides performance characteristic.
Once polyreaction completes, and transfers the material to segregation apparatus (such as, separatory funnel), its deionized water having Amount for example, this quality of materials about 1.2 again to about 1.5 times.This mixture is stirred vigorously and is approximately less than 1 minute, and preferably It is about 5 seconds to 30 seconds.Once stirring, described material can settle and separate, and this may need about 1 hour to 2 hours.Polymer Become more highdensity material, and remove from container.Then by the polymer of this removal by tray at 90 DEG C Heat about two hours and be dried；Or preferably, by scraped film type distilling apparatus, to remove water and the ethanol of any remnants. Alternatively, interpolation be enough to be buffered to water layer pH the sodium bicarbonate of about 4 to about 7.It is also understood that and can use mixing, reaction Other and commercial system with isolating polymer from material.
Preferably, the solidification process from the polymer precursor preparation of response type technique uses catalyst.Can make With the polymer identical with the precursor formulation carrying out Self-mixing technique for solidification.It should be noted that, generally and slurriable combination not With, catalyst is optional for curing reaction type polymer.Inhibitor can also be used.But, if not using catalysis Agent, response time and speed will be slower.From response type technique solidification material solidification and pyrolysis with carry out Self-mixing work The solidification of material of the solidification of skill and reaction admixing type technique and be pyrolyzed substantially the same.
Can multiple atmosphere and under the conditions of carry out response type technique, such as air, inert atmosphere, N2, argon, flowing gas Body, gas at rest, decompression, ambient pressure, high pressure and these combination and modification.
Reaction admixing type technique
In reaction admixing type technique, precursor is made to be reacted to form precursor formulation under solvent-free.Such as, reaction admixing type The embodiment of technique has the precursor formulation prepared by MHF and bicyclopentadiene (" DCPD ").Response type is used to blend technique, Produce MHF/DCPD polymer, and this polymer is used as precursor formulation.(it can be used alone to form solidification or heat The product solved, or it is used as precursor in mixing or course of reaction).Use known molecular amount and the MHF of hydride equivalent quality； " P01 " (P01 is by Pt (0) tetravinyl cyclotetrasiloxane (such as, tetramethyl four of 2% in tetravinyl cyclotetrasiloxane Vinyl cyclotetrasiloxane) complex, with Pt (0) complex of tetravinyl cyclotetrasiloxane 20 times to 0.1% of dilution.With this The mode of kind is that the body catalyst of every 1% load provides 10ppm Pt catalyst)；The MHF parent material of 0.20wt% (has The active equivalents known) (40% to 90%)；And the bicyclopentadiene purity of 83% (have >) of 10% to 60%.Described In the embodiment of technique, can be used for reacting by the sealable reaction vessel with blender.In atmosphere in sealing Container reacts；Although other type of atmosphere can be used.Preferably, under atmospheric pressure react, but permissible Use higher and lower pressure.Furthermore, it is possible to polytype atmosphere and under the conditions of carry out react admixing type technique, such as Air, inert atmosphere, N2, argon, flowing gas, gas at rest, decompression, ambient pressure, high pressure and these combination and change Type.
In embodiments, 850 grams of MHF (the 85% of total polymeric blends) added to reaction vessel and add Heat is to about 50 DEG C.Once reach this temperature, close heater, and the MHF in reaction vessel adds the P01 of 0.20 weight % Platinum catalyst.Generally, when adding catalyst, formation bubble and temperature will be begun to ramp up about 2-20 DEG C.
When temperature begins to decline, the DCPD (15wt% of total polymeric blends) of about 150g is added to reacting appearance Device.Temperature may decline other amount again, e.g., from about 5-7 DEG C.
Now, in course of reaction, control the temperature in reaction vessel to maintain predetermined temperature curve in time, and Management may increase with the temperature of heat release.Preferably, during whole, regulate, be monitored and controlled the temperature of reaction vessel.
In the embodiment of the MHF/DCPD embodiment of course of reaction, temperature curve can be such that and allows temperature reach About 80 DEG C (may spend～15-40min, depend on the amount of the material existed)；Then temperature will increase and peak value is～104 DEG C, once temperature begins to decline, and heater just arranges temperature and increases to 100 DEG C, and monitor the temperature of reactant mixture with Guarantee polymer temperature 80 DEG C minimum the most about 2 hours maintained above and at most the most about 4 hours.2-4 more than 80 DEG C After hour, close heater, and polymer is cooled to ambient temperature.Should be appreciated that in bigger and less batch, company In technique continuous, semicontinuous and other type of, temperature and time curve can be different.
In fairly large, it is possible to use the operation of commercial operation, intermittent operation, continuous way and these combination.Can With the reaction being used for controlling in course of reaction by industrial plant automatization and control system, temperature curve and other technique.
Table C lists reaction and blends the various embodiments of technique.
Table C
In above table, " degree of polymerization " is for be joined together to form the monomeric unit of polymer or the number of repetitive Amount." equivalent _/mol " refers to molar equivalent." gram/mol vinyl " refers to provide the vinyl-functional institute of 1 molar equivalent The amount of the given polymer needed." VMH " refers to methyl ethylene fluid, from the straight chain type ethylene base material of ethyoxyl process Material, it can be the replacement of TV.The numeral " 0200 " etc. of VT is the viscosity in terms of centipoise for specific VT.
Solidification and pyrolysis
Can will include that poly-silica carbon precursor formulation and other precursor formulation from above type of technique are carried out It is cured to form solid, semisolid or quasi-plastic property material.Generally, carry out stretching, shape or being additionally formed by precursor formulation Preform, described preform will include any volume structure or shape, including thin film and thick film.When solidification, permissible Processing poly-silica carbon precursor formulation to provide partially cured material by initial solidification, it is referred to as, such as, and preformation Type body, green material or green firming body (being not meant as anything relevant with material color).Then can be by described Green material solidifies further.Therefore, it is possible to use one or more curing schedules.This material can by " finally solidification ", i.e. by Being cured to such point: at this point, described material has required physical strength for its intended purpose and other performance.Gu The amount changed can reach finally to solidify (or " solidification firmly "), i.e. at this point, and all or essentially all of chemical reaction is Stop (such as, as measured by material does not exist reactive group, or by the minimizing of reactive group in time in Plateau is measured).Therefore, described material can be cured in various degree according to its desired use and purpose.Such as, In some cases, final solidification and hard solidification can be identical.The condition of cure of such as atmosphere and temperature can affect solid The composition of the material changed.
When precursor formulation being prepared as structure or preform, described precursor formulation (such as, poly-silica carbon preparation) Techniques below can be used to be formed: such as, spray, be spray-dried, be atomized, gasify, phase transformation separation, flowing, thermal spraying, lead Draw, instil, form drop at liquid and liquid surface system, paint is coated with, mold, shape, extrude, weave, ultrasonic, vibrate, solution Polymerization, emulsion polymerization, micro-emulsion polymerization, the alternate manner of injection, injection moulding or operation become substantially any volume shape Shape.These volume profiles can include following: such as, spheroid, pellet, annular, eyeglass shape, disk, panel, taper, butt circle Taper, square, rectangle, pencil, dihedral, passage, hollow sealing room, hollow ball, bulk, lamellar, coating, film, top layer, micro- Grain, beam-like, bar-shaped, dihedral, cylindricality, threadiness, chopped fiber shape, tubulose, cup-shaped, tubular, and these combination and modification and Other more complicated engineering and building shape.
Forming step, curing schedule and pyrolysis step can postpone (such as, material quilt in batch process over time Store or keep between the steps) and carry out constantly, continuously, and these combination and modification and other type of processing Sequentially.Furthermore, it is possible to carry out partially cured by precursor, or before described precursor forms volume profiles, solidification can be started Technique and always carrying out.These steps and their various combinations can and the most preferably controlled and Carry out under predetermined condition (such as, material is exposed under predetermined atmosphere and temperature curve in its whole courses of processing, such as, The oxygen reduced, the temperature solidifying preform before pyrolysis is maintained at about 140 DEG C).It is also understood that for shaping, solidifying With hot analytical system, equipment or procedure of processing can be same equipment, continuous device, interval and connect equipment and these Combination with other type of industrial process and modification.It is therefoie, for example, spray drying technology can be formed is fed directly to fluidisation Bed reactor is for the granule of the solidification of pyrolysis.
Poly-silica carbon precursor formulation can be made pure, non-reinforcing, non-filling, compound, that strengthen and fill Structure, intermediate and final products, and these combination and modification and the material of other component type.Additionally, these knots Structure, intermediate and final products can be cured (such as, green solidification, final solidification or solidification firmly), uncured, be pyrolyzed For pottery and these combination and modification, (such as, the material of solidification can be with derived from the poly-silicon identical with the material of solidification The material of the pyrolysis of oxygen carbon is filled).
Precursor formulation may be used for formed " pure " material (" pure " material refer to all and essentially all of structure by Precursor material or unfilled preparation are made；Therefore, there is not filler or reinforcing agent).
Poly-silica carbon precursor formulation may be used for coating or dipping by such as carbon fiber, glass fibre or by poly-silica carbon Fiber that precursor formulation (identical or different preparations) is made and the fabric made or non-woven fabrics, to form preimpregnation material.Cause This, poly-silica carbon precursor formulation may be used for forming composite, such as, the product of enhancing.Such as, said preparation can flow into increasing In strong material, in immersion reinforcing material, it is enhanced absorbed or combines with reinforcing material otherwise, described enhancing Material is such as carbon fiber, glass fibre, fabric, Graphene, CNT, thin film, precipitate, sand, non-woven fabrics, copper fibre Dimension, fiber, rope, braiding structure, ceramics, glass dust, carbon dust, graphite powder, ceramic fibre, metal powder, carbide pellet or The derivative pottery of component, chopped fiber, tow, the nanostructured of above-mentioned material, polymer, meet the temperature of method and final products Other material any required, and these combination and modification.Reinforcing material can also by with form fiber and be pyrolyzed into pottery The material that the preparation of porcelain is identical is made or derived from this material, or it can be formed fiber by different and be pyrolyzed into pottery Precursor formulation material make.Poly-silica carbon precursor formulation may be used for forming packing material.Packing material has interpolation by being Other solid to poly-silica carbon precursor formulation or any material of semisolid material.Can be with Selective filling material with to solid Change product, ceramic product and both some feature is provided.These features can relate to or such as aesthetics, sense of touch, heat, close Degree, radiation, chemistry, cost, magnetic, electricity and these combination and modification and further feature.These features can be except intensity it Outer feature.Therefore, packing material can not affect the material of solidification or the intensity of ceramic material, and it can increase intensity, or Person even can reduce intensity in some cases.Packing material can give color, magnetic function, fire resistance, anti-flammability, heat-resisting Property, electric conductivity, antistatic, optical property (such as, reflectance, refractive index and iris), aesthetic properties are (such as in building products Stone shape outward appearance), chemical resistance rate, corrosion resistance, wearability, cost reduction, resistance to abrasion, heat insulation, UV stability, UV protect Protect, and can in final products or material desired, necessary and expectation and the further feature of necessity.Therefore, fill Material may include that and gives some instances, carbon black, copper conductor, heat filling, conductive filler, lead, optical fiber, ceramic colorant, The derivative ceramic particle of pigment, oxide, sand, dyestuff, powder, ceramic fine particle, polymer, pore former, carbon silane, silane, Silazane, carborundum, carbon silazane, siloxanes, powder, ceramic powders, metal, metal complex, carbon, tow, fiber, short fibre Tie up, containing boron material, milled fibre, glass, glass fibre, fibrous glass and nanostructured (including aforesaid nanostructured).
Poly-silica carbon preparation and can have metal derived from the product of said preparation or the product prepared by said preparation And metal complex.Packing material will include reinforcing material.In many cases, can be by solidification and the poly-silica carbon of pyrolysis Packing material is considered as composite.Generally, according to this viewpoint, poly-silica carbon general's composition body phase or substrate phase are (such as, continuously Or substantially continuous phase), and filler is by composition dispersion (such as, discontinuous) phase.According to specific application, product or Final use, filler can be evenly distributed in precursor formulation, distribution unevenly, with predetermined and controlled distribution ladder Degree (such as, the rate of settling with predetermined) is distributed and can have different amounts in different preparations, and described preparation is then Presumptive area (such as, there is the band layer of different packing densities) can be formed at there is the product of the filler of scheduled volume.So And, it should be noted that material is referred to as " filling " or " enhancing " and is not meant to the major part of this material (by weight, Stereometer, or in terms of both) it is poly-silica carbon.Therefore, generally, poly-silica carbon can with the ratio (weight or volume) of packing material With about 0.1:99.9 to 99.9:0.1.
Poly-silica carbon precursor formulation may be used for forming non-reinforcing material, described non-reinforcing material be mainly by, substantially By and the material be the most only made up of precursor material；But it is also possible to include the preparation with filler or additive, described Filler or additive do not give intensity.
Solidification can complete under the following conditions: at standard ambient temperature and pressure (" SATP ", 1 atmospheric pressure, 25 DEG C) Under, at a temperature of temperature is higher or lower than being somebody's turn to do, under pressure is higher or lower than this pressure, and in the different time periods.Permissible Through different heating, (such as, retention time and temperature, continuous print variations in temperature, the circulation of the rate of heat addition and temperature curve Variations in temperature (such as, heating, then maintain, cool down, reheating etc.)) solidify.Hardening time can be several seconds (such as, Less than about 1 second, less than 5 seconds) to less than one minute, to several minutes, to a few hours, to a couple of days (or may longer).All right Solidifying in any kind of surrounding, described surrounding includes such as, gas, liquid, empty gas and water, comprises liquid The surfactant of body, inert atmosphere, N2, argon, flowing gas (such as, purging gas), gas at rest, the O of reduction2, subtract Pressure, high pressure, ambient pressure, restricted partial pressure and these combination and modification and other processing conditions.For high-purity Material, other parts of smelting furnace, container, processing equipment, atmosphere and solidification equipment and technique be clean, there is no with And do not provide and be considered to be impurity or any element of pollutant or material for the material of solidification.In embodiments, Curing environment (such as, smelting furnace, atmosphere, container and these combination and modification) can have and contributes to or affect preforming Such as forming in body, pottery and final application or product, be catalyzed, stoichiometry, feature, performance and these combination and change The material of type.
Preferably, in the embodiment of solidification process, solidification betide about 5 DEG C or higher, about 20 DEG C to about 250 DEG C, At a temperature of about 20 DEG C to about 150 DEG C, about 75 DEG C to about 125 DEG C and about 80 DEG C to 90 DEG C.Although can use higher and more Low temperature and various heating curves (such as, the time dependent speed of temperature (" temperature rate ", such as, Δ degree/time Between), retention time and temperature).
Condition of cure, such as, temperature, time, temperature rate can completely or partially depend on preparation, and at some Embodiment is completely or partially made a reservation for by preparation, with coupling such as, the size of preform, the shape of preform, or Keep the mould of preform, to prevent stress fracture, aerofluxus or other phenomenon relevant with solidification process.Additionally, solidified bars Part can be for example, it is preferable to may have been considered as the thing of the problem relevant with solidification process before utilizing in a controlled manner Thing.It is therefoie, for example, aerofluxus may be used for producing the foamed materials with open architecture or enclosed construction.Similarly, solidified bars Part may be used for producing or controlling micro structure and the nanostructured of described material.Generally, can be used for condition of cure affecting, Controlling or change kinetics and the thermodynamics of described process, among other things, condition of cure can affect form, property Energy, feature and function.
When solidifying poly-silica carbon precursor formulation, crosslinking reaction, this provides in certain embodiments except having Also there is outside other side-R1-Si-C-C-Si-O-Si-C-C-Si-R2-cross-linked structure, wherein R1And R2According to and based on In described preparation use precursor and change.Solidification material embodiment in, they can have containing 3 and another The cross-linked structure at the silicon center of silicon atom coordination, described silicon center is by separating less than 5 atoms between silicon.
During solidification process, some preparations can show heat release (that is, self-heating reaction), and described heat release can produce on a small quantity Heat with help or drive curing reaction, maybe can produce may need management and go divided by avoiding problem (such as, stress cutting Split) substantial amounts of heat.During curing, generally there is aerofluxus, and cause material unaccounted-for (MUF), generally by remaining quantity of material (example As, solidify yield) determine this loss.The preparation of embodiment of the present invention, condition of cure and poly-silicon carbonic ether precursor formulation Can have at least about 90%, the curing degree of about 92%, about 100%.It is true that with air curing, the curing degree of material can surpass Crossing 100%, such as, about 101%-105%, this is because absorb the result of oxygen from air.Additionally, during curing, material Whether material would generally shrink, be enhancing according to preparation, condition of cure and the character of preform shape and preform, fill , pure or non-reinforcing, this contraction can be 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 less.
The solidification of preform can any kind of heater of temperature and environmental Kuznets Curves by having desired level Or mechanism, technology or form complete, the water-bath such as heated, electric furnace, microwave oven, gas smelting furnace, smelting furnace, the sky of forced action type heating Gas, tower, spray drying, falling film reactor, fluidized-bed reactor, laser instrument, indirect heating element heater, directly heat, infrared add Heat, UV radiation, RF stove, in emulsion process via the in-situ solidifying of high shear mixing, in emulsion process via ultrasonic former Position solidification.
The preform of solidification be no matter non-reinforcing, pure, fill or strengthen may be used as independent product Product, final products, finished product or the preliminary product of machining or process can be carried out subsequently.Preform can also be made through being heated Solving, this makes preform material change into pottery.
In the material of pyrolysis preform or the structure of solidification or solidification, it is heated to about 600 DEG C to about 2300 ℃；About 650 DEG C to about 1200 DEG C, about 800 DEG C to about 1300 DEG C, about 900 DEG C to about 1200 DEG C and about 950 DEG C to 1150 DEG C. At these tem-peratures, usual all organic structures or be removed, or combine with inorganic constituents to form pottery.Generally about 650 DEG C at a temperature of 1200 DEG C, the material obtained is amorphous glass pottery.When being heated to about more than 1200 DEG C, described material Material can generally form nanocrystalline structure or micro-crystal structure such as SiC, Si3N4, SiCN, β SiC, and at 1900 DEG C Time above, α SiC structure can be formed, and 2200 DEG C and above time, be usually formed α SiC.The such as ceramic material of pyrolysis Can be monocrystalline, polycrystalline, unbodied and the combination of form, modification and the subgroup of these and other type.
Can be pyrolyzed under many different heating and environmental condition, among other things, described condition is excellent Choosing includes thermal control, dynamics Controlling and these combination and modification.Such as, described pyrolysis can have various heating lifting Temperature speed, heat cycles and environmental condition.In some embodiments, temperature can raise and keep predetermined temperature, to help In known transformation (such as, exit, volatilize, molecular rearrangement etc.), then it is increased to next corresponding to next known transformation and protects Hold temperature.Pyrolysis can betide reducing atmosphere, oxidizing atmosphere, low O2, rich in gas (such as, in flame or With flame direct neighbor), inert atmosphere, N2, argon, air, decompression, ambient pressure, high pressure, flowing gas (such as, purge gas Body, has e.g., from about 15.0GHSV to about 0.1GHSV, about 6.3GHSV to about 3.1GHSV and the flow velocity of about 3.9GHSV), quiet In state gas and these combination and modification.
Can last and preferably result in time period being pyrolyzed completely of preform and be pyrolyzed.For high-purity material, molten Other parts of stove, container, processing equipment and pyrolysis installation be clean, there is no and do not provide be considered for The material of pyrolysis is impurity or any element of pollutant or material, and the constant flow rate of " purging " gas can produce at volatile matter Period helps purging smelting furnace.In embodiments, pyrolysis environment (such as, smelting furnace, atmosphere, container and these combination and change Type) can have contribute to or affect in pottery and final application or product such as composition, stoichiometry, feature, performance with And these combination and the material of modification.
During being pyrolyzed, material may be lost by aerofluxus.The remaining material when pyrolysis step or loop ends Amount is referred to as carbon yield (or pyrolysis rate).The preparation of the embodiment of invention formulation and poly-silica carbon precursor formulation are for SiOC Formation can have at least about 60%, about 70%, about 80% and at least about 90%, at least about 91% and higher carbon yield. It is true that with air thermal dissociation, described material can have the carbon yield far above 91%, and it can be close to 100%.In order to avoid Material (notes: generally at air thermal dissociation, is pyrolyzed at inert atmosphere, the oxygen atmosphere of reduction, substantially inert atmosphere, minimum oxygen Atmosphere and these combination and modification are carried out) in degraded, it is possible to use particularly customized preparation.For example, it is possible to by phenyl The high preparation of (at least about 11 weight % and the phenyl of preferably at least about 20 weight %) of content, allyl content are high (at least about 15% to about 60%) preparation is used for air thermal dissociation to alleviate the degraded of described material.
In some embodiments with in some purposes, the initially or first pyrolysis step forming SiOC generally produces Structure less closely, for example, it may be possible to not up to density needed for desired use.But, in certain embodiments, such as light weight The use of type spheroid, proppant, pigment etc., described pyrolysis first can be enough and enough.Therefore, generally Impregnation process again can be carried out, to add extra poly-silica carbon precursor formulation material to insert or to fill knot on pyrolytic material Hole in structure and space.Then this material infiltrated again can be carried out solidification and be pyrolyzed again.(in some embodiments In, the material infiltrated again is solidified, but is not pyrolyzed).This pyrolysis, the process infiltrated again can be repeated once, two Secondary, three times and up to 10 times or more times to obtain the desired density of finished product.In some embodiments, the most antipyretic, Si-O-C pottery exists graphene-structured, graphite-structure, amorphous carbon structure and these combination and modification.By producing The distribution of the silicon matter of the SiOxCy structure composition of SiO4, SiO3C, SiO2C2, SiOC3 and SiC4 is to be selected by precursor and to add Different ratio that work history causes and formed.Carbon generally bonding and/or and silicon atom bonding between adjacent carbon.Generally, In ceramic state, carbon non-principal and oxygen atom ligand, therefore oxygen is main and silicon is coordinated.Temperature required and ring can maintained Any heater that border controls is pyrolyzed.It is therefoie, for example, can with gas furnace, electric furnace, directly heat, indirectly heating, Fluid bed, kiln, tunnel oven, box kiln, shuttle kiln, coking type device, laser instrument, microwave oven and these combination and change Type and other heater that can obtain the temperature that pyrolysis needs and system complete pyrolysis.
In each stage of the process from raw material to final finished, chemical reaction, arrange and reset the customization when occurred The cost of reduction, the process control of enhancing, the reliability of raising, the efficiency of raising, the product of enhancing can be provided with predetermined control Purity that product feature increases and these combination and modification and other benefit.These change the sequence that when occurs can be based on The processing of precursor or preparation, and the processing of precursor formulation or preparation；And it can also be based on solidification and pyrolytical condition.This Outward, customization and the predetermined selection of these steps, preparation and condition can be by various transformations (such as, chemical reaction；Molecules align And rearrangement；And microstructured ar-rangement and rearrangement) product and the machining feature of enhancing are provided.
Each point during manufacture process, the ceramic structure (such as, poly-silica carbon structure) that polymer can be derived, Intermediate and final products and these combination and modification carry out machining, grind, mold, shape, hole, etch or it Its machining and shaping.
Disclosed United States Patent (USP) Shen in Publication No. 2014/0343220,2014/0274658 and 2014/0326453 Please, and the U.S. Patent application of Serial No. 61/946,598,62/055,397 and 62/106,094 describes initial material Material, precursor formulation, poly-silica carbon precursor formulation, and prepare, prepare, formed, solidify and pyrolytic precursors material is to form polymerization The method of material, structure and pottery that thing is derivative, the complete disclosure of each application is incorporated herein by.
In the ceramic preferred embodiment that poly-silica carbon is derivative, table 1 shows Si, O, the C's for pottery total amount Amount.
Table 1
Generally, the embodiment of the poly-silicon-oxygen-carbon ceramic of pyrolysis can have the Si of about 30% to about 60%, can have The O of about 5% to about 40% and can have the carbon of about 3% to about 35%.It is also contemplated for bigger and less amount.
Be present in the type of the carbon in the preferred embodiment of the derivative pottery of poly-silica carbon can be free carbon (such as, Random layer, amorphous, the carbon of Graphene, form of graphite), and the carbon being bonded with silicon.Table 2 shows the free carbon with preferred amounts Embodiment with the carbon (Si-C) of silicon bonding.
Table 2
Embodiment % free carbon %Si-C type
1 64.86 35.14
2 63.16 36.85
3 67.02 32.98
4 58.59 41.41
5 65.70 31.66
6 62.72 30.82
7 61.68 34.44
8 69.25 27.26
9 60.00 27.54
Generally, the embodiment of the pottery that poly-silica carbon is derivative can have the free carbon of about 20% to about 80% free Carbon and about 20% Si-C bonding carbon to about 80% Si-C bonding carbon.It is also contemplated for bigger and less amount.
Generally, can there is other element, such as nitrogen and hydrogen in the embodiment of the poly-silicon-oxygen-carbon ceramic of pyrolysis.Embodiment Can have the amount of these other materials gone out as shown in table 3.(note: these are typical cases for the embodiment of virgin material 's.If filler, additive or other material being combined with precursor formulation or being combined into precursor formulation；Then this type of material is usual Can be present in more or less in the ceramic material of pyrolysis).
Table 3
With reference to Figure 1A to Fig. 1 D, it is provided that the various embodiment party of the structure of the structure member prepared by poly-silica material with carbon element Case.Performance requirement (such as, load, stress, strain, impulsive force, environment etc.) according to these components, they can be hard solidification Poly-silica material with carbon element, the poly-silica material with carbon element of pyrolysis, the material infiltrated to the most highdensity pyrolysis again, fill and be not filled by Poly-silica material with carbon element, be prone to SiC (its derivative Serial No. 62/055,397,62/055,461 and 62/ freely of extruding sintering With the poly-silica material with carbon element instructed disclosed in the U.S. Patent application of 112,025, the complete disclosure of each application is by quoting It is expressly incorporated herein) and these combination, modification and composite and other material (such as, in addition to other material, metal, Steel, aluminum, metal matrix composite, plastics, carbon fiber and timber).In figure ia, it is shown that there is the post 100 of web 101 and lead to Cross the embodiment that connector 103 is fixed to the I-beam 102 of post 100.In fig. ib, it is shown that the enforcement of I-beam joint 104 Scheme, two of which I-beam 105,106 is fixed by connector or joint 107.I-beam 105 have web 108 and Top flange 120 and lower flange 121.I-beam 106 has web 109 and top flange and lower flange (unnumbered).In fig. 1 c, Providing post and the embodiment of I-beam structure 110, described I-beam structure 110 has center square column or a stake 111, and described 111 There is central opening space 112.I-beam 113a, 113b, 113c, 113d are fixed to post 111.In Fig. 1 D, it is provided that post and beam The embodiment of structure 114, described 114 have circular central post or stake 115, and described 115 have circular central opening 116.I type Beam 117a, 117b, 117c are attached to post 115.Described structure can be by known means such as metal, composite or poly- The silica carbon edge of a wing and bolt and other known technology for attachment structure component carry out being attached or fixing.
With reference to Fig. 2, it is shown that the embodiment of building structural element 200.Performance requirement according to these components is (such as, Load, stress, strain, impulsive force, environment etc.), they can be the poly-silica material with carbon element of hard solidification, the poly-silica carbon material of pyrolysis Material, infiltrate to the most highdensity pyrolysis again material, filling and unfilled poly-silica material with carbon element, be prone to extruding sintering SiC (disclosed in the U.S. Patent application of its derivative Serial No. 62/055,397,62/055,461 and 62/112,025 freely and The poly-silica material with carbon element of teaching, the complete disclosure of each application is incorporated herein by) and these combination, modification and multiple (such as, in addition to other material, metal, steel, aluminum, metal matrix composite, plastics, carbon are fine for condensation material and other material Peacekeeping timber).Described structure can by known means such as metal, composite or the poly-silica carbon edge of a wing and bolt with And other known technology being used for attachment structure component carries out being attached or fixing.Described building-supporting component 200 has post 201, Described post 201 has on pedestal or pad 202 and is fixed to pedestal or the web 203 of pad 202.Grit 204,205 (is used for supporting Unshowned sidewall, it can also be prepared by poly-silica material with carbon element) attachment post 201.Roof transversal I type beam 206 is attached to post 201 And supported by post 201.Roof purlin 207,208,209 is attached to transversal I type beam 206 and supports unshowned roofing board or structure Part, described roof purlin can also be prepared by poly-silica material with carbon element.
With reference to Fig. 3 A and Fig. 3 B, it is provided that have the embodiment of the armored vehicle 300 of anterior 301.Described vehicle is permissible Having car body panel or the armour plate being incorporated in car body panel or being in car body panel, described car body panel prevents or buffers ballistic body (such as, bullet, projectile, shrapnel and explosion energy and explosive force).Performance requirement according to these components (such as, load, Stress, strain, impulsive force, environment etc.), they can be the poly-silica material with carbon element of hard solidification, the poly-silica material with carbon element of pyrolysis, again Infiltrate material, filling and unfilled poly-silica material with carbon element to the most highdensity pyrolysis, be prone to SiC (its that extruding sinters Disclosed in the U.S. Patent application of derivative Serial No. 62/055,397,62/055,461 and 62/112,025 freely and teaching Poly-silica material with carbon element, the complete disclosure of each application is incorporated herein by) and these combination, modification and composite And other material (such as, in addition to other material, metal, steel, aluminum, metal matrix composite, plastics, carbon fiber and timber). In the embodiment of armored vehicle 300, there is armour 305 based on relatively low poly-silica carbon, the bottom of its protection vehicle, There is coaming plate 304 and poly-silica carbon hood assembly 307 on rear side of door-plate 302 based on poly-silica carbon, door-plate 303, poly-silica carbon.
With reference to Fig. 4, it is provided that can serve as the poly-silica carbon of such as house, residence, office, business or other purpose The embodiment of movable building 400.Performance requirement according to building, its panel and structural elements (such as, load, stress, is answered Change, impulsive force, environment etc.), they can be the poly-silica material with carbon element of hard solidification, the poly-silica material with carbon element of pyrolysis, again infiltrate to The material of the most highdensity pyrolysis, filling and unfilled poly-silica material with carbon element, be prone to extruding sintering SiC (its derived from As disclosed in the U.S. Patent application of Serial No. 62/055,397,62/055,461 and 62/112,025 and teaching poly-silica Material with carbon element, the complete disclosure of each application is incorporated herein by) and these combination, modification and composite and its Its material (such as, in addition to other material, metal, steel, aluminum, metal matrix composite, plastics, carbon fiber and timber).Move Dynamic building 400 has upper side wall 401a, 401b (for upper strata or secondth floor), and described upper side wall has window 402, and downside Wall 401c, 401d (for lower floor or firstth floor).Building 400 has door 403 and awning 404.
These buildings can build or be easily assembled in a certain place or position (such as, disaster scene).Except often Beyond other benefit of rule building, poly-silica carbon building can be relatively light, and preferably substantially builds than by the contrast that steel is standby Build lighter.
With reference to Fig. 5, it is provided that the embodiment of poly-silica carbon transport container 500.According to transport container, its panel, suspension ring, The performance requirement (such as, load, stress, strain, impulsive force, environment etc.) of locking device and structural elements, they can be hard The poly-silica material with carbon element of solidification, the poly-silica material with carbon element of pyrolysis, the material infiltrated to the most highdensity pyrolysis again, filling and not The poly-silica material with carbon element filled, SiC (its derivative Serial No. 62/055,397,62/055,461 freely being prone to extruding sintering With 62/112, with the poly-silica material with carbon element instructed disclosed in the U.S. Patent application of 025, the complete disclosure of each application is passed through It is incorporated herein by reference) and these combination, modification and composite and other material (such as, in addition to other material, gold Genus, steel, aluminum, metal matrix composite, plastics, carbon fiber and timber).Described transport container 500 has top board 501, sidewall 502, pedestal 503 and be formed at lifting opening or the suspension ring 504,505 of pedestal 503.Described container 500 has and comprises locking The door 506,507 of mechanism.Among other benefits, poly-silica carbon vessel can be lighter relative to conventional vessel, and preferably ground In basis lighter than by the similar containers that steel is standby.
With reference to Fig. 6, it is provided that the embodiment of tier building plate 600.One layer, two-layer, three layers or all layers (602,603, 604,605,606,607,608,609), according to performance requirement (such as, load, stress, strain, fire resistance, the impact of panel Power, environment etc.), described layer can be poly-silica material with carbon element, the poly-silica material with carbon element of pyrolysis of hard solidification, infiltrate to the highest The material of the pyrolysis of density, filling and unfilled poly-silica material with carbon element, it is prone to SiC (its derivative sequence freely of extruding sintering Number be 62/055,397,62/055,461 and 62/112,025 U.S. Patent application disclosed in and the poly-silica carbon material of teaching Material, the complete disclosure of each application is incorporated herein by) and these combination, modification and composite and other material Material (such as, in addition to other material, metal, steel, aluminum, metal matrix composite, plastics, carbon fiber, paper and timber).This Outward, surface 601 and 610 can be coated with poly-silica material with carbon element.
With reference to Fig. 7, it is provided that the embodiment of flak jackets 700 (such as, bullet-proof vest), its by shellproof based on poly-silica The material of carbon is made.Flak jackets 700 has and prevents or buffer ballistic body (such as, bullet, projectile, shrapnel and Explosive Energy Amount and explosive force) component.Performance requirement (such as, load, stress, strain, impulsive force, environment etc.) according to these components, They can be poly-silica material with carbon element, the poly-silica material with carbon elements of pyrolysis of hard solidification, infiltrate to the most highdensity pyrolysis Material, filling and unfilled poly-silica material with carbon element, be prone to extruding sintering SiC (its derivative Serial No. 62/055 freely, 397,62/055,461 and 62/112, disclosed in the U.S. Patent application of 025 and the poly-silica material with carbon element of teaching, each application complete Portion's disclosure is incorporated herein by) and these combination, modification and composite and other material (such as, except Outside other material, metal, steel, aluminum, metal matrix composite, plastics, carbon fiber and timber).
With reference to Fig. 8, it is provided that by the enforcement of the poly-silica carbon rope 800 of fiber 801,802 based on poly-silica carbon preparation Scheme.Performance requirement (such as, load, stress, strain, impulsive force, environment etc.) according to rope, described fiber can be hard solid Change poly-silica material with carbon element, the poly-silica material with carbon element of pyrolysis, the material, the filling that infiltrate to the most highdensity pyrolysis again and do not fill out The poly-silica material with carbon element filled, SiC (its derivative Serial No. 62/055,397,62/055,461 and freely being prone to extruding sintering With the poly-silica material with carbon element instructed disclosed in the U.S. Patent application of 62/112,025, the complete disclosure of each application is by drawing With being expressly incorporated herein) and these combination, modification and composite and other material (such as, in addition to other material, gold Genus, steel, metal matrix composite, plastics, nylon, carbon fiber and natural fiber).
With reference to Fig. 9, it is provided that have the embodiment of the trailer 900 of framework 901 based on poly-silica carbon.According to trailer Performance requirement (such as, load, stress, strain, impulsive force, environment etc.), described framework can be the poly-silica carbon material of hard solidification Material, poly-silica material with carbon element, the material infiltrated to the most highdensity pyrolysis again, filling and the unfilled poly-silica carbon material of pyrolysis Expect, be prone to SiC (U.S. of its derivative Serial No. 62/055,397,62/055,461 and 62/112,025 freely of extruding sintering With the poly-silica material with carbon element instructed disclosed in state's patent application, the complete disclosure of each application is incorporated herein by) and These combination, modification and composite and other material (such as, in addition to other material, metal, steel, aluminum, Metal Substrate Nanocrystal composition, plastics, carbon fiber and timber).
With reference to Figure 10, it is provided that the embodiment of abrasion device 1000 (such as, emery wheel).Can by poly-silica carbon or based on Poly-silica carbon prepares the abrasive media of described device and support member or structure member.Performance requirement according to abrasive member (such as, load, stress, strain, impulsive force, environment etc.), backing material can be the poly-silica material with carbon element of hard solidification, pyrolysis Poly-silica material with carbon element, the material infiltrated to the most highdensity pyrolysis again, filling and unfilled poly-silica material with carbon element, it is prone to crowded SiC (the U.S. Patent application of its derivative Serial No. 62/055,397,62/055,461 and 62/112,025 freely of pressure sintering Disclosed and the poly-silica material with carbon element of teaching, the complete disclosure of each application is incorporated herein by) and these combination, Modification and composite and other material (such as, in addition to other material, metal, steel, aluminum, metal matrix composite, are moulded Material, carbon fiber, natural fiber and timber).
With reference to Figure 11, it is provided that the embodiment of abrasion device 1100 (such as, belt grinding machine), it has driving lapping tape The driving wheel 1101 of 1102, described lapping tape 1102 has abrasive material based on poly-silica carbon.Performance according to abrasive material Require (such as, load, temperature, material etc. to be ground), abrasive material can be pyrolyzed poly-silica material with carbon element, again infiltrate to The material of the most highdensity pyrolysis, filling and unfilled poly-silica material with carbon element, be prone to extruding sintering SiC (its derived from As disclosed in the U.S. Patent application of Serial No. 62/055,397,62/055,461 and 62/112,025 and teaching poly-silica Material with carbon element, the complete disclosure of each application is incorporated herein by) and these combination, modification and composite and its Its material (such as, metal, coarse sand, diamond and grinding-material and abrasive material).
With reference to Figure 12, it is provided that the embodiment of poly-silica carbon pipe 1200.Described pipe 1200 has outer surface 1201, interior table Face 1202, circular wall 1203 and opening or passage 1204.Performance requirement according to described pipe (such as, load, stress, strain, Impulsive force, environment etc.), it can be poly-silica material with carbon element, the poly-silica material with carbon element of pyrolysis of hard solidification, infiltrate to the highest The material of the pyrolysis of density, filling and unfilled poly-silica material with carbon element, it is prone to SiC (its derivative sequence freely of extruding sintering Number be 62/055,397,62/055,461 and 62/112,025 U.S. Patent application disclosed in and the poly-silica carbon material of teaching Material, the complete disclosure of each application is incorporated herein by) and these combination, modification and composite and other material Material (such as, in addition to other material, metal, steel, aluminum, metal matrix composite, plastics and carbon fiber).
With reference to Figure 13, it is provided that the embodiment of braking automobile assembly.Described brake assemblies has piston 1301, clamp 1302, first brake sheet 1303a, the second brake block 1303b, rotor 1304, wheel hub 1305 and brake cable 1306.Except described Beyond 1303a, 1303b and rotor 1304, other parts of brake assemblies can also be prepared by material based on poly-silica carbon.Root According to the performance requirement (such as, load, stress, strain, impulsive force, environment etc.) of described parts, it can be the poly-silicon of hard solidification Oxygen material with carbon element, the poly-silica material with carbon element of pyrolysis, the material infiltrated to the most highdensity pyrolysis again, filling and unfilled poly-silicon Oxygen material with carbon element, be prone to extruding sintering SiC (its derivative Serial No. 62/055,397,62/055,461 and 62/112 freely, With the poly-silica material with carbon element instructed disclosed in the U.S. Patent application of 025, the complete disclosure of each application is incorporated by reference into Herein) and these combination, modification and composite and other material (such as, in addition to other material, metal, steel, Aluminum, metal matrix composite, plastics and carbon fiber).
Embodiment
There is provided following example with explanation the technique of the present invention, precursor, poly-silica carbon preparation, preimpregnation material, solidification pre- The various embodiments of molded body, application, instrument, unit and pottery.These embodiments for illustrative purpose, should not It is considered and does not additionally limit the scope of the invention.Unless otherwise indicated, the percent used is whole preparation, preforming Body or the percetage by weight of structure.
Embodiment 1
Preparation uses the poly-silica carbon preparation of mixed method.By at room temperature by 70% and molecular weight be about The precursor of the allyl capped of the MHF precursor of 800 and the molecular weight about 500 of 30% is mixed together to prepare institute in a reservoir State preparation, and stored for future use.Described poly-silica carbon preparation at room temperature has the good pot-life, and And described precursor does not has and will not react with each other.Described poly-silica carbon preparation has the viscosity of about 12cps.
Embodiment 2
Preparation uses the poly-silica carbon preparation of mixed method.By at room temperature by 60% and molecular weight be about The precursor of the ethenyl blocking of the MHF precursor of 800 and the molecular weight about 9400 of 40% is mixed together to preparation in a reservoir Described preparation, and stored for future use.Described poly-silica carbon preparation at room temperature has the good pot-life, And described precursor does not has and will not react with each other.Described poly-silica carbon preparation has the viscosity of about 200cps.
Embodiment 3
Preparation uses the poly-silica carbon preparation of mixed method.By the molecular weight of 50% is about 800 MH precursor and The precursor of the ethenyl blocking of the molecular weight of 50% about 800 is mixed together to prepare described preparation in a reservoir, and will It stores for future use.Described poly-silica carbon preparation at room temperature has the good pot-life, and described precursor does not has Have and will not react with each other.Described poly-silica carbon preparation has the viscosity of about 55cps.
Embodiment 4
Preparation uses the poly-silica carbon preparation of mixed method.By the molecular weight of 40% is about 1000 MH precursor and The precursor of the ethenyl blocking of the molecular weight of 60% about 500 is mixed together to prepare described preparation in a reservoir, and will It stores for future use.Described poly-silica carbon preparation at room temperature has the good pot-life, and described precursor does not has Have and will not react with each other.Described poly-silica carbon preparation has the viscosity of about 25cps.
Embodiment 5
Preparation uses the poly-silica carbon preparation of mixed method.By the molecular weight of 30% is about 800 MHF precursor and The precursor of the ethenyl blocking of the molecular weight of 70% about 500 is mixed together to prepare described preparation in a reservoir, and will It stores for future use.Described poly-silica carbon preparation at room temperature has the good pot-life, and described precursor does not has Have and will not react with each other.Described poly-silica carbon preparation has the viscosity of about 10cps.
Embodiment 6
The poly-silica carbon preparation of embodiment 1 has about 80 microns of 40% in interpolation extremely described preparation to about 325 purposes SiC filler, the poly-silica carbon preparation filled with preparation, it can preserve for future use.
Embodiment 7
The poly-silica carbon preparation of embodiment 2 has about 80 microns of 30% in interpolation extremely described preparation to about 325 purposes SiC filler, the poly-silica carbon preparation filled with preparation, it can preserve for future use.
Embodiment 8
Preparation uses the poly-silica carbon preparation of mixed method.By the molecular weight of 10% is about 800 MHF precursor and 73% and molecular weight be about 1000 styrene (phenethyl) precursor (there is the X of 10%), the TV precursor and 1% of 16% The precursor of OH end-blocking of molecular weight about 1000 be mixed together in a reservoir prepare described preparation, by it and store Come for future use.Described poly-silica carbon preparation at room temperature has a good pot-life, and described precursor does not has and will not React with each other.Described poly-silica carbon preparation has the viscosity of about 72cps.
Embodiment 9
Preparation uses the poly-silica carbon preparation of mixed method.By the molecular weight of 0-90% is about 800 MH precursor, 0-90%'s and molecular weight be about 1000 styrene precursors (there is the X of 10%), the TV precursor of 0-30%, 0-30% point The precursor of ethenyl blocking of son amount about 9400 and the molecular weight of 0-20% are about the precursor of the OH end-blocking of 800 in a reservoir It is mixed together to prepare described preparation, by it and store for future use.Described poly-silica carbon preparation at room temperature has There is the good pot-life, and described precursor does not has and will not react with each other.Described poly-silica carbon preparation has about 100cps Viscosity.
Embodiment 10
Preparation uses the poly-silica carbon preparation of mixed method.By by the MHF precursor of 70% and the molecular weight of 30% being The precursor of the ethenyl blocking of about 500 and the silicon dioxide of the submicron of about 42% and 325 mesh mix in a reservoir Prepare described preparation, and stored for future use.Described poly-silica carbon preparation at room temperature has good guarantor Deposit the time limit, and described precursor does not has and will not react with each other.Described poly-silica carbon preparation has the viscosity of about 300cps.
Embodiment 11
Preparation uses the poly-silica carbon preparation of mixed method.Before the molecular weight of 20-80% is about the MH of 800 Body, the TV precursor of 0-10%, the precursor of the ethenyl blocking with molecular weight of 5-80% and the submicron of about 500,325 mesh And the SiC of 8 microns is mixed together to prepare described preparation in a reservoir, and stored for future use.Described poly- Silica carbon preparation at room temperature has the good pot-life, and described precursor does not has and will not react with each other.Described poly-silicon Oxygen carbon preparation has the viscosity of about 300cps.
Embodiment 12
The platinum catalyst of 40ppm is added to the poly-silica carbon preparation of embodiment 6, and the preparation that these are catalyzed by Drip (such as, being instilled by the drop of preparation) to add to the hot bath of 50-120 DEG C to solidify described preparation.In hot bath Time is about 1-2 minute.Then the droplet structure of solidification is pyrolyzed at 950 DEG C about 60 minutes.Described hot formal similarity is empty Bulbus cordis body, it has the density of below about 1g/cc, the diameter of about 60 microns to about 2mm and the crushing strength of about 0.5-2ksi.
Embodiment 13
Mixed type technique is used to form the precursor formulation of the VT with the MHF of 75%, the TV of 15% and 10%, and by it Store.
Embodiment 14a
Catalyst (10ppm platinum and the LUPEROX231 peroxide of 0.5%) by 1% adds the precursor to embodiment 13 In preparation.Then the precursor of catalysis impregnated to reinforcing material and carry out being cured to form composite.
Embodiment 14b
The curing materials of embodiment 14a is pyrolyzed, the ceramic composite derivative to form poly-silica carbon.
Embodiment 14c
Catalyst (10ppm platinum and the LUPEROX231 peroxide of 0.5%) by 1% adds the precursor to embodiment 13 In preparation.Use tower molding and cure system, by the poly-silica carbon preparation of catalysis from the sonic nozzle shape that internal diameter is 0.180 inch Becoming drop, described drop falls into from nozzle and passes through the solidification tower of 8 feet.The temperature of tower top is 495-505 DEG C, the temperature at the bottom of tower Degree is 650 DEG C.Discrete temperature district is not had in tower.It is to be realized by convection current that the air-flow of tower rises.Catch tray is maintained 110 DEG C. Molding and solidification are carried out in atmosphere.From dish, remove preforming pearl, and rear (firmly) solidifies 2 hours in the air of 200 DEG C. The preform support agent firmly solidified is pyrolyzed 2 hours in argon gas atmosphere at 1000 DEG C.Curing degree is 99% to 101%.Carbon residue Rate is 86%.
Embodiment 14d
Catalyst (10ppm platinum and the LUPEROX231 peroxide of 0.5%) by 1% adds the preparation to embodiment 13 In, described poly-silica carbon preparation is configured to have carbon fiber reinforced preimpregnation material.Preimpregnation material is solidificated in argon 200 Carry out at DEG C 2 hours.The preform firmly solidified is pyrolyzed 5 hours at 1000 DEG C under vacuo.
Embodiment 15
Mixed type technique is used to form the poly-silica carbon precursor formulation of the VT with the MHF of 70%, the TV of 20% and 10%, And place it in container.
Embodiment 16a
Catalyst (10ppm platinum and the LUPEROX231 peroxide of 0.5%) by 1% adds the precursor to embodiment 15 In preparation.Then the precursor of catalysis impregnated to reinforcing material and solidify, to form composite.
Embodiment 16b
Carry out the material of the solidification of embodiment 16a being pyrolyzed to form the ceramic composite that poly-silica carbon is derivative.
Embodiment 16c
Catalyst (10ppm platinum and the LUPEROX231 peroxide of 0.5%) by 1% adds the preparation to embodiment 15 In, described poly-silica carbon preparation is configured to have carbon fiber reinforced preimpregnation material.Preimpregnation material is solidificated in argon 200 At DEG C, 2 are carried out hour.The preform firmly solidified is pyrolyzed 5 hours at 1000 DEG C under vacuo.
Embodiment 17
Use tower molding and cure system, in the future Self-mixing technique and have 70% MHF, the TV of 20%, 10% The poly-silica carbon preparation of the catalyst (10ppm platinum and the LUPEROX231 peroxide of 0.5%) of VT and 1% from internal diameter is The sonic nozzle of 0.180 inch is formed as drop, and described drop falls into from nozzle and passes through the solidification tower of 8 feet.The temperature of tower top Degree is for 495-505 DEG C, and the temperature at the bottom of tower is 650 DEG C.Discrete temperature district is not had in tower.It is real by convection current that the air-flow of tower rises Existing.Catch tray is maintained 110 DEG C.Molding and solidification are carried out in atmosphere.From dish, remove preform support agent, and make its At 200 DEG C, (firmly) solidifies 2 hours afterwards in atmosphere.The preforming pearl firmly solidified is pyrolyzed 2 hours at 1000 DEG C under vacuo. Curing degree is 99% to 101%.Carbon yield is 86%.
Embodiment 18a
The preform of the pyrolysis of embodiment 16c is injected silicone precursor preparation and is pyrolyzed.
Embodiment 18b
The preform of the pyrolysis of embodiment 18a is injected silicone precursor preparation and is pyrolyzed.
Embodiment 19
Use response type technique, use formula as below to prepare precursor formulation.The temperature of reaction is remained 21 little at 61 DEG C Time.
Embodiment 20
Use response type technique, use formula as below to prepare precursor formulation.The temperature of reaction is remained 21 little at 72 DEG C Time.
Embodiment 21
Use response type technique, use formula as below to prepare precursor formulation.The temperature of reaction is remained 21 little at 61 DEG C Time.
Embodiment 22
Use response type technique, use formula as below to prepare precursor formulation.The temperature of reaction is remained 21 little at 72 DEG C Time.
Embodiment 23
Use response type technique, use formula as below to prepare precursor formulation.The temperature of reaction is remained 21 little at 61 DEG C Time.
Embodiment 24
Use response type technique, use formula as below to prepare precursor formulation.The temperature of reaction is remained 21 little at 72 DEG C Time.
Embodiment 25
Use response type technique, use formula as below to prepare precursor formulation.The temperature of reaction is remained 21 little at 72 DEG C Time.
Embodiment 26
Use response type technique, use formula as below to prepare precursor formulation.The temperature of reaction is remained 21 little at 61 DEG C Time.
Embodiment 27
Use response type technique, use formula as below to prepare precursor formulation.The temperature of reaction is remained 21 little at 61 DEG C Time.
Embodiment 28
Use response type technique, use formula as below to prepare precursor formulation.The temperature of reaction is remained 21 little at 61 DEG C Time.
Embodiment 29
Use response type technique, use formula as below to prepare precursor formulation.The temperature of reaction is remained 21 little at 61 DEG C Time.
Embodiment 30
Poly-silica carbon preparation and reinforcing material are combined to form preform, described preform is carried out partly or It is fully cured to form the composite of the enhancing of the shape of component parts.Component parts is solidified, and preferably carries out Hard solidification.The enhancing carrying out the component parts firmly solidified being pyrolyzed to form poly-silica carbon derivative is combined component parts so that it is warp Go through and infiltrate again for two to five times, solidify and pyrolysis cyclical.Prepare to be used for processing (such as machine further by final enhancing component parts Tool is machined to tolerance), number of assembling steps, integrated step or use.The derivative ceramic component parts of poly-silica carbon can apply, Or it is designed for or conduct: among other things, friction member, such as brake, brake block, brake disc and clutch Device；Construction material, such as crossbeam, longeron, post, I-beam, passage, pilaster (such as, 2 × 4 replacing parts (replacement)), wall Plate, roof, cover plate and floor；Aviation component, such as, high temperature engineering part, aircraft ring frames component, crust or outer covering, Driving cabin parts, seat frame, passenger compartment parts, carpet and fabric；Equipment (including automobile) parts, such as, pipe, rod, fixed The framing component of system, hollow, rectangular pipe, hollow octagonal tube, polygon rod, plate, fire wall, lining, seat component, buffer part Part, polygon hollow pipe, round tube, passage, I-beam, band and joint；And consumer goods, including consumption electronic products, electricity Device, furniture and house articles for use.The use of the Ceramic Composite component parts that poly-silica carbon is derivative can provide some features, except other Heat-resisting quantity, corrosion resistance, uv-resistance, lightweight, the low cost (polymer relative to carborundum with routine is included beyond aspect Derivative pottery, significantly reduces the most several order of magnitude), the intensity that increases and the ratio of weight (such as, higher and lighter, Intensity is identical and lighter, higher and weight is identical) and fire resistance.
Embodiment 31
The Ceramic Composite component parts that the poly-silica carbon of embodiment 30 is derivative, wherein said poly-silica carbon preparation includes ethylene The siloxanes of base end-blocking.
Embodiment 32
The Ceramic Composite component parts that the poly-silica carbon of embodiment 30 is derivative, wherein said poly-silica carbon preparation is 60% MHF, 20%TV, 5%Vt and 10%MVF (preparation of the reaction of all vinyl methyl diethoxy silanes, such as, embodiment The preparation of 66-68).
Embodiment 33
The Ceramic Composite component parts that the poly-silica carbon of embodiment 30 is derivative, wherein said poly-silica carbon preparation includes about The siloxanes of the ethenyl blocking of 10%.
Embodiment 34
Poly-silica carbon preparation is combined to form precursor with reinforcing material, described precursor is partly or completely solidified To form the composite of the enhancing of the shape of component parts.Component parts is solidified, and the most finally solidifies. Prepare to be used for processing (such as machining is to tolerance), number of assembling steps or use further by final composition component.Poly- The plastics component parts that silica carbon derives can be applied or be designed for or conduct: among other things, Building wood Material, such as beam, crossbeam, post, I-beam, passage, 2 × 4 replacing parts, wallboard, cover plate and floor；Aviation component, such as, driving cabin Parts, seat component, passenger compartment parts；Part of appliance, such as, pipe, rod, the framing component of customization, hollow, rectangular pipe, hollow eight Limit shape pipe, polygon row hollow pipe excellent, polygon, round tube, passage, I-beam, band, joint.The enhancing that poly-silica carbon derives is combined The use of component parts can provide some features, includes that heat-resisting quantity (is included in and is exposed to higher temperatures among other things Keep or substantially maintain the ability of structural intergrity during degree), including the intensity increased and weight ratio (such as, more By force and lighter, intensity is identical and lighter, higher and weight is identical), lightweight, low cost, uv-resistance, corrosion resistance, Fire resistance and anti-flammability.
Embodiment 35
The Ceramic Composite component parts that the poly-silica carbon of embodiment 30 is derivative, wherein said poly-silica carbon preparation includes ethylene The siloxanes of base end-blocking.
Embodiment 36
The Ceramic Composite component parts that the poly-silica carbon of embodiment 30 is derivative, wherein said poly-silica carbon preparation is 60% MHF, 20%TV, 5%Vt and 10%MVF (preparation of the reaction of all vinyl methyl diethoxy silanes, such as, embodiment The preparation of 66-68).
Embodiment 37
The Ceramic Composite component parts that the poly-silica carbon of embodiment 30 is derivative, wherein said poly-silica carbon preparation includes about The siloxanes of the ethenyl blocking of 10%.
Embodiment 38
By poly-silica carbon preparation with reinforcing material combination to be formed as precursor strengthening composite, it is cured to form The composite of the enhancing of the shape of component parts.Component parts is solidified, and the most firmly solidifies.To firmly solidify Component parts carry out being pyrolyzed forming the compound component parts that poly-silica carbon is derivative, then it is carried out with poly-silica carbon preparation Infiltration, then solidifies.This material can be referred to as poly-silica carbon plastics-pottery or plastics-pottery, and the structure of enhancing is accurate It is ready for use on process, number of assembling steps or use further.
Embodiment 39
The Ceramic Composite component parts that the poly-silica carbon of embodiment 30-38 derives is to have to be distributed in its total The grinding of cutting material or cutting element.Preferable cutting part is for having cutting or abrasive material (such as, polycrystalline diamond Composite sheet (PDC), aluminium oxide or diamond) cutting wheel, described cutting or abrasive material be uniformly distributed in whole cutting wheel In.By this way when described foot wheel abrasion, cutting material is exposed to continuing on the described surface taken turns, and ought described take turns by When using and wear and tear, cutting material preferably continues to be exposed to the described surface taken turns with the amount (if any) varied less On.
Embodiment 40
Poly-silica carbon preparation is solidified into the pearl of volume profiles.The pearl that the poly-silica carbon finally solidified is derivative is such as added Add to: paint, glue, plastics and construction material (such as, dry wall, thin slabstone, plasterboard, MDF plate, plywood, plastics and particle Plate).If located in or close to the surface of shape, the pearl that the poly-silica carbon of final solidification is derivative can provide as additive, Among other things, bonding (such as, as binding agent), resistance to water, fire resistance, anti-flammability, fire prevention and intensity；And it is resistance to Abrasion, wearability, corrosion resistance and uv-resistance.
In addition to pearl, poly-silica carbonaceous additive can be fine powder, particulate, the form of powder or other dispersible shape Formula.Dispersible form can be obtained by the consolidated structures ground or crushing is bigger.If causing described structure in solid Rupture during change, broken or complete under conditions of rupturing, they can also be obtained by solidification process.Can also be passed through other Process technology (such as, spray solidification or be dried) obtains these dispersible forms.
Embodiment 41
Poly-silica carbon preparation is solidified into the pearl of volume profiles.Then carry out described pearl being pyrolyzed to form poly-silica The ceramic bead that carbon is derivative.Ceramic bead derivative for poly-silica carbon is added extremely: such as, paint, glue, plastics and construction material (example As, dry wall, thin slabstone, plasterboard, MDF plate, plywood, plastics and flakeboard).Among other things, described pottery gathers Silica carbon pearl can provide fire resistance, anti-flammability, fire prevention and intensity as additive.
In addition to pearl, poly-silica carbonaceous additive can be fine powder, particulate, the form of powder or other is dispersible Form.Dispersible form can be obtained by grinding or crush bigger solidification or hot formal similarity.If causing State structure rupture during solidification or pyrolysis, broken or complete under conditions of rupturing, they can also be by solidification or be pyrolyzed Journey obtains.
Embodiment 42
By poly-silica carbon formulation application in the structure member (such as, beam, crossbeam, post) of high-rise.Described preparation Viscosity adheres to (such as, will not significantly drip or flow) until solidification process for making liquid preparation keep with structural construction parts Complete.Described preparation was further designed under environmental condition within the time less than two days solidification, is preferably hard solidification. If (need faster hardening time, or if it is desire to than the higher temperature of thermal source that can use to guarantee firmly to solidify, can With adjust described preparation and both).
Coating provides flameproof protection to structural construction parts, so that the construction package of poly-silica carbon coating meets or exceedes The requirement of ASTM E-119, the complete disclosure of ASTM E-119 is incorporated herein by.These coating or UV are stably , corrosion-resistant and be waterproof.
Therefore, these coating can apply to the assembly of such as masonry units and the composite component of the structural material of building Or be used together, including knee wall and other wall with the composite component of the assembly of such as masonry units and the structural material of building And partition thing, post, longeron, crossbeam, flat board and compoboard, and for floor and the beam assembly on roof, and constituted Other assembly of permanent global facility of building and construction unit.Therefore, these coating can give or provide to The standard combustion testing performance of few about 1/2-h, about 2-h, about 4-h and about 6-h or longer exposes.
This poly-silica carbon protective coating is Halogen, and such as, it does not comprise any halogen.Therefore, described protectiveness Coating can be substantially free of halogen, i.e. the amount of halogen is the lowest so that it is can that its level exposes for people in any aerofluxus That accept or admissible；Halogen can be substantially free of, i.e. the amount of halogen is the lowest so that making them in any aerofluxus Existence can not test, by those skilled in the art, the nominal gas sensing that the existence of halogen used and survey device and detect； And halogen can not contained, i.e. aerofluxus comprises halogen that is undetectable or that measure and exists.This poly-silica carbon protective coating is also It is nontoxic, and toxicity or dangerous gas will not be produced during being exposed to fire or high temperature.Therefore, it is arranged for avirulence Gas coating.Additionally, it will not produce the catabolite of any harmful or toxicity.Substantially, when being exposed to flame, poly-silicon Described coating, through pyrolytic reaction, is changed into pottery by oxygen carbon coating.Poly-silica carbon protective coating or reactive-type flame retardant or Person's activity extinguishing chemical.For reactive-type flame retardant, it means when exposed to flame, described coating experience go from environment deoxygenation, Heat and both reactions.
The most poly-silica carbon coating be preferably capable by the one in such as following fire-retardant mechanism, two kinds or All to base material offer flameproof protection: the endothermic reaction；Heat shielding；And quenching (such as, removing the oxygen as Combustion Source).
Furthermore it is preferred that described coating is solidified to optimize active flame-proof mechanism firmly；And also reduce any hydrogen discharge Produce.(embodiment of the other embodiments that these general mechanism and benefit are applicable in this specification, and except this Other embodiment beyond the embodiment of embodiment and other preparation and component).
Poly-silica carbon coating or additive can also give or the heat-proof quality of reinforcing material.
Steel or the xoncrete structure of this type of coating such as can have the fire resistance shown in Table I, or they are more excellent Selection of land can exceed these performances.
Table I
Embodiment 43
The building structure parts being prepared embodiment 42 by the poly-silica carbon preparation with the MHF of the 41% and TV of 59% are fire-resistant Coating.
Embodiment 44
The building structure parts being prepared embodiment 42 by the poly-silica carbon preparation with the MHF of the 41% and MVF of 59% are resistance to Fire coating.
Embodiment 45
Poly-silica carbon system by the MVF of the MVF to about 55% of the MHF and about 60% of the MHF to about 55% with about 40% The building structure parts fireproof coating of embodiment 40 is prepared in agent.
Embodiment 46
By poly-silica carbon preparation flame-spraying or thermal jet are applied to Application Example 42-45 on building structure parts Building structure parts fireproof coating.In this process, the most poly-silica carbon preparation is cured and is in the form of fine powder, then Its thermal jet is applied on building structural element.
Embodiment 47
Ceramic bead or particulate (and the most poly-silicon-oxygen-carbon ceramic pearl or particulate) are added the poly-silicon to embodiment 42-45 In oxygen carbon preparation.
Embodiment 48
In such an embodiment, by fire-retardant or resistance to combustion outsourcing thing or the outer cover of poly-silica carbon preparation dipping routine. Then the material of dipping is solidified, the most firmly solidify, and be fixed on building structural element, as generally being entered As row.Additionally, in order to existing structure is increased extra fire resistance, can be existing (such as, with poly-silica carbon preparation dipping It is currently installed in building) fire prevention outsourcing thing or covering and solidify.
Embodiment 49
By the poly-silica carbon preparation flame-retardant additive acting on plastic of solidification.Poly-silica carbon preparation can be hard Solidification, this is preferred, and condition is that hard curing materials fully carries out moulding with preparation in plastic, extrusion or forming process Material products.
Described plastics it may be that such as, thermosetting plastics, thermoplastic, polyolefin, polyamide, engineering plastics, weaving Adhesive coating (TAC), plastic foam, styrene alloy, acrylonitrile butadiene styrene (ABS), polyurethane, polystyrene, third Olefin(e) acid resin, Merlon (PC), epoxy resin, polyester, nylon, polyethylene, high density polyethylene (HDPE) (HDPE), extremely-low density are poly- Ethylene (VLDPE), Low Density Polyethylene (LDPE), polypropylene (PP), polrvinyl chloride (PVC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethers ethyl ketone (PEEK), polyether sulfone (PES), BMI and fiber Glue (cellulose acetate).
Poly-silica carbonaceous additive is preferably the form of powder, pearl or bead, and it is chosen to be prone to mate plastics and initiates material Material (such as, resin), so that preferably can process with existing manufacture equipment with process in plastics poly-silica carbonaceous additive, And the plastic (such as, part or parts) needed for being Xing Chenged, it can include, such as, automobile component, airborne vehicle portion Part, ship components, consumer goods parts (such as, hay mover, electronic product, electrical equipment, (such as, window is repaiied for furniture, at home articles for use Jewelry and carpet)).
The plastic with poly-silica carbon flame-retardant additive most preferably will have the ability by the V0 tested by UL-94 (on vertical sample, burning stopped in 10 seconds；As long as they are the redest as fire, it is allowed to granule drops).By UL-94 test program and The entire content of standard is incorporated herein by.
In addition to other testing scheme, according to their application with use requirement, these goods can have by by The following ability of UL-94 test: the HB smoulder on horizon sample；For thickness, < 3mm, < 76mm/min is also for burn rate And burning stops before 100mm, (on vertical sample, burning stopped in 30 seconds V2；Allow dropping of burning particles), V1 (on vertical sample, burning stopped in 30 seconds；As long as they are the redest as fire, it is allowed to dropping of granule), 5VB is (at vertical sample On, burning stopped in 60 seconds；Do not allow to drop；Plate (plaque) sample can form hole), 5VA is (at vertical sample On, burning stopped in 60 seconds；Do not allow to drop；Plate sample cannot form hole).
In addition to other testing scheme, for foam, these plastics adding poly-silica carbon can have and pass through (burning stopped in 2 seconds the following ability tested by UL-94: HF-1；Twilight sunset is less than 30s；Burning is not allowed to drop), burning Stopped in 3 seconds；Twilight sunset is less than 30s；Permission burning is dropped.
Can be used for poly-silica carbon flame-retardant additive replacing existing fire retardant (such as, ATH based on (aluminum trihydrate), Based on bromine, based on phosphorus, based on chlorine, tripolycyanamide based on antimony) and other fire retardant well known by persons skilled in the art.These are existing Some fire retardants have many shortcomings, including there is halogen, producing that be harmful to or the catabolite of danger, dangerous initial material Expect, produce the refuse of danger, high cost etc. during manufacture.Poly-silica carbon fire retardant avoid (such as, they do not have) this Any one in a little shortcomings.
In particular it is preferred to ground, poly-silica carbon flame-retardant additive is halogen-free, and such as, it does not comprise any halogen.Cause This, it can be substantially free of halogen, i.e. the amount of halogen is the lowest so that it is can that its level exposes for people in any aerofluxus That accept or admissible；Halogen can be substantially free of, i.e. the amount of halogen is the lowest so that making them in any aerofluxus Existence can not test, by those skilled in the art, the nominal gas sensing that the existence of halogen used and survey device and detect； And halogen can not contained, i.e. aerofluxus comprises halogen that is undetectable or that measure and exists.This poly-silica carbon flame-retardant additive is also It is nontoxic, and toxicity or dangerous gas will not be produced during being exposed to fire high temperature.Therefore, it adds for avirulence aerofluxus Add agent.Additionally, it is highly preferred that to a certain extent, for any catabolite produced by poly-silica carbonaceous additive, they It is nontoxic.
Embodiment 50
The poly-silica carbon preparation of embodiment 49 has the MHF of 70%, the VT of the TV of 20% and 10%.By described poly-silica carbon Firmly solidified, ground and screened to less than the particle diameter of 10 μm and the proportion of below about 1.4.Plastics are loaded with below about 20% The poly-silica carbon fire retardant of hard solidification.Described plastics can be PP, PET-PBT alloy and PC-ABS alloy.
Embodiment 51
The poly-silica carbon preparation of embodiment 49 has the MHF of the 95% and TV of 5%.
Embodiment 52
The poly-silica carbon preparation of embodiment 49 has the MHF of the 41% and TV of 59%.
Embodiment 53
The particle diameter of the additive that the poly-silica carbon of embodiment 49 solidifies firmly be less than about 75 microns, greater than about 0.05 micron, about 0.1 micron to about 50 microns, preferably from about 3 microns to about 10 microns, and proportion is about 0.5 to about 2.0, preferably from about 1 to about 1.5 's.Described plastic has the fire retardant of the poly-silica carbon fire retardant to about 100% of about 0.05%, and preferably from about 30% to about 50%.
Embodiment 54
The poly-silica carbon flame-retardant additive of embodiment 49-53 also comprises pottery, and the most ceramic poly-silica carbon is fire-retardant Additive.Ceramic additive can be about the 1% to about 100% of total additive.
Embodiment 55
The poly-silica carbon flame-retardant additive of embodiment 49-54 and conventional flame retardants combine and in plastic.Poly- Silica carbon flame-retardant additive can be about the 1% to about 99% of the total flame-retardant additive used.
Embodiment 56
Poly-silica carbon preparation is applied to base material, in liquid form to form coating.Then coating is solidified, strengthen Described base material is the ability of resistance to burning when experiencing fire.Described preparation can be catalysis or uncatalyzed.Described coating is permissible It is a painting of poly-silica carbon preparation, two paintings, three painting or more overbrushings (such as, layer).Preferably, described coating at ambient conditions with Time less than 2 days is cured to firmly solidify.However, it is possible to be used for external heat source solidifying described coating.Described base material can be Existing goods, such as, house or the inwall of building, the wooden of the building before wall, floor, roof, plate face is being installed Framework, the outside (such as, house, office or granary) of structure, ground or brush (such as, to form fire wall), and And they can be building supply material, such as, at dry wall, plywood and the 2 × 4s of coating before building.
Preferably, described coating provides for wood substrates under ASTM E84 and meets or more than the ability of A level material.
Embodiment 57
The refractory coating of embodiment 56 is prepared by the poly-silica carbon preparation with the MHF of the 41% and TV of 59%.
Embodiment 57
The refractory coating of embodiment 56 is prepared by the poly-silica carbon preparation with the MHF of the 41% and MVF of 59%.
Embodiment 58
Poly-silica carbon system by the MVF of the MVF to about 55% of the MHF and about 60% of the MHF to about 55% with about 40% The refractory coating of the building structure parts of embodiment 56 is prepared in agent.
Embodiment 59
Plastic components is prepared by the poly-silica carbon preparation solidified.These structure members have burning time maintain its structure complete The ability of whole property.When described component combust, they will more or less be pyrolyzed into pottery, therefore maintain their intensity and structure Integrity, it is highly preferred that those features may be increased.These parts can be used for example as the luggage carrier on the crown of aircraft or Person's internal part.They can be the plastic member of other structure.
Additionally, plastic components need not be made up of poly-silica carbon preparation completely.But, poly-silica carbon preparation can be distributed in pre- Within modeling type, on described parts or around so that when being exposed to that in fire, poly-silica carbon is changed into pottery, can obtain Obtain intensity to increase.
Embodiment 60
Poly-silica carbon preparation is configured to the fiber of solidification, is then pyrolyzed.If desired or expectation, ceramic poly-silica Carbon fiber can carry out extra infiltrating again, solidify and pyrolysis step (step to five steps or more multistep) is to provide pottery, or Person they can carry out extra infiltration again and curing schedule (step to three steps or more multistep) to provide plastics-pottery.Excellent Selection of land, uses phenyl triethoxysilane (Figure 45), phenyl methyl diethoxy silane (Figure 38), methyldiethoxysilane (Figure 39) and vinyl methyl diethoxy silane (Figure 40) and dimethyldiethoxysilane and MTES Prepare poly-silica carbon preparation.Phenyl triethoxysilane and phenyl methyl diethoxy silane (or dimethyl diethoxy silicon Alkane and MTES) mass percent may be 10% to 80%, preferably from about 40-60% (any one or Both persons are altogether).
Fiber can be prepared by the poly-silica carbon preparation of embodiment 61 and 62.
For the formation of flame-retardant textile, poly-silica carbon fiber can be solidified, the most firmly solidify, but not necessarily Pyrolysis.
Embodiment 61
Use response type technique, use formula as below to prepare precursor formulation.The temperature of reaction is remained 21 little at 61 DEG C Time.
Embodiment 62
Use response type technique, use formula as below to prepare precursor formulation.The temperature of reaction is remained 21 little at 61 DEG C Time.
Embodiment 63
The poly-silica carbon fiber of embodiment 60-62 has the coloring agent adding extremely poly-silica carbon preparation.Obtain by this way The poly-silicon-oxygen-carbon ceramic fiber that must colour.Preferably, coloring agent extends to whole fiber, it is highly preferred that be evenly distributed in fibre In the whole volume of dimension, such as, whole fiber, and it is not only surface coloring.Color can be substantially any color, example As, red, blue, green, orange, yellow, purple etc..Coloring agent can also have non-visible wavelength, but it passes through machine Device is visible, therefore, it can have the such as application in machine vision control system or process.
Embodiment 64
The poly-silica carbon fiber of the coloring of embodiment 60-63 has color that is predetermined and that mate with composite.With The pottery poly-silica carbon fiber that this mode colours is the enhancing to composite.The color of fiber and the color of composite Joining, the particularly final color with the matrix material in composite is mated.Therefore, when worn composite or aging time, Its color will not change, and the exposure of reinforcing fiber will substantially become undetectable, because they are and matrix material phase Same color.
Embodiment 65
The poly-silica carbon fiber of the some different colorings of embodiment 60-63 respectively has predetermined and different color.Ground floor And generally outermost layer has or the color of coupling identical with composite.Internal fiber can have different colors to carry For abrasion or aging visually indicating, such as, it is changed into yellow fibers, is then changed into red fiber, to indicate composite component The final utilization life-span or recommended lifetime.Alternatively, the fiber of different colours can be new with instruction at the outside area of composite Composite, the colored fiber then mated can under this outside area, with instruction use occur, such as, outer surface On the loss of white fiber mean that these parts have been used, or mean initial period (such as, these parts rupture period) It is complete.Poly-for the pottery of coloring silica carbon fiber can be used for aesthetic feeling and the offer of reinforcing member simultaneously by this way Instruction about the use of these parts.Additionally, in some applications, have as the coloured fiber with matrix material different colours It it is gratifying or pleasant aesthetically.
Embodiment 66
Use response type technique, use formula as below to prepare MVF precursor formulation.The temperature of reaction is maintained 21 at 72 DEG C Hour.
Embodiment 67
Use response type technique, use formula as below to prepare MVF precursor formulation.The temperature of reaction is maintained 21 at 61 DEG C Hour.
Embodiment 68
Use response type technique, use formula as below to prepare MVF precursor formulation.The temperature of reaction is maintained 21 at 61 DEG C Hour.
Embodiment 69
Use response type technique, use formula as below to prepare precursor formulation.The temperature of reaction is remained 21 little at 72 DEG C Time.
Embodiment 70
Use response type technique, use formula as below to prepare precursor formulation.The temperature of reaction is remained 21 little at 61 DEG C Time.
Embodiment 71
The proppant for fracturing is prepared by the preparation of embodiment 22,60 and 61.
Embodiment 72
The poly-silica carbon preparation with the VT of the MHF of 80%, the TV of 15% and 5% is prepared as propping up for fracturing Support agent.
Embodiment 73
The poly-silica carbon preparation with the MHF of the 95% and TV of 5% is prepared as the proppant for fracturing.
Embodiment 74
The poly-silica carbon preparation with the VT of the MHF of 90%, the TV of 5% and 5% is prepared as propping up for fracturing Support agent.
Embodiment 75
One or more layers poly-silica carbon preparation is used to form explosion-proof and impact-resistant barrier.By poly-silica carbon ghe layer at base material Top on firmly solidify.Strengthen described layer and can be realized by the various Weaving patterns between layer.Composite bed is tied Structure provides for blast, projectile and blow out protection.This protective barrier can ratio conventional safety barrier and armor lighter in weight, simultaneously There is provided equal or preferably protect.
Embodiment 76
Use 12 layers of 1200g/m2Glass fibre, 20 layers of unidirectional carbon fiber (in 5 parts with 0,45 ,-45, 90 orientation, to prepare 20 layers) and 1 layer of 0.032 steel as panel to prepare shellproof composite construction.Use poly-silica carbon batch of material and Under the pressure of 150-160 DEG C and minimum 500psi, glass fibre is bonded together to form glass fibre by temperature and pressure for 1-2 hour Plate.It is bonded together under the same conditions to form carbon fiber board by 20 layers of carbon fibre fabric.Then poly-silica carbon batch of material is used As the binding agent between steel and carbon fiber board and between carbon fiber board and glass mat, a step is by glass mat, carbon Fibre board and steel disc bonding.In the case of projectile impact steel plate, composite has and uses thicker glass fiber sheets support Carbon fiber board bonding steel facing.Poly-silica carbon batch of material can be the batch of material illustrating 76A, 76B, 76C and 15.
In addition to steel plate or replace steel plate, it is possible to use layered ceramic plate (such as, SiC, aluminium oxide, boron nitride).Also The ceramic composite prepared by our polymer and pottery or carbon fiber can be used.
Embodiment 76A
Use response type technique, use formula as below to prepare poly-silica carbon precursor formulation.By the temperature of reaction at 72 DEG C Maintain 21 hours.
Embodiment 76B
Use response type technique, use formula as below to prepare poly-silica carbon precursor formulation.By the temperature of reaction at 61 DEG C Maintain 21 hours.
Embodiment 76C
Use response type technique, use formula as below to prepare poly-silica carbon precursor formulation.By the temperature of reaction at 61 DEG C Maintain 21 hours.
Embodiment 76D
The ballistic composite of embodiment 76 keep out live 22Mag, 45,22 rifle, 280,9mm, 22 pistons (piston) With 223 shooting.
Embodiment 77
Poly-silica carbon preparation is pyrolyzed with the form of volume structure.The volume structure that the poly-silica carbon of pottery derives shows Reflection and the optical property of refraction, such as opalescence, light, flash and glitter.When described structure is that black (such as, does not has Toner adds to described preparation) time, there is these optical properties；Or (such as, non-black is any when being colored such as fruit structure Color, such as, white, yellow, redness etc.).
Embodiment 78
The volume structure of embodiment 77 is working surface, for example, such as desktop, work top, plug-in unit or kitchen Counter top.
Embodiment 79
The volume structure of embodiment 78 has other coloring agent or additive and simulates granitoid outward appearance to provide.
Embodiment 80
The volume structure of embodiment 77 is black and the globule showing flicker, opalescence or light.By these pearls Mix in paint formulations.This patent preparation is such as applied to automobile or electrical equipment.Its provide such as update BMW and The upper popular plane of Mercede or delustring processing, but delustring processing is increased internal glittering or gloss.Therefore, based on poly- The paint formulations of silica carbon provides the delustring processing glittered to automobile, electrical equipment or other goods.
Embodiment 81
By the poly-silica carbon pearl of the pyrolysis of a size of about 100 microns to about 1000 microns with the load of about 1% to about 40% Amount is added to paint formulations.
Embodiment 82
The paint (wherein paint formulations) of embodiment 81 be automotive paints and color be blueness, and described pearl and paint Blue color identical and there is size and the load capacity of about 25% of 350 microns (+/-5%).
Embodiment 83
The paint of embodiment 81, wherein said pearl does not colours, i.e. they are black, and has about 300-500 micron Size, described paint is black, although not necessarily identical with described pearl black.
Embodiment 84
Adding the latex paint preparation with the poly-silica carbon dust of pyrolysis to described preparation, described powder has about The size of 0.5-100 micron, and described powder has the load capacity of about 15%.
Embodiment 85
The paint formulations of embodiment 83 is enamel paint.
Embodiment 86
Poly-silicon-oxygen-carbon ceramic pigment can be prepared from the pyrolysis of any poly-silica carbon batch of material that can be pyrolyzed.Can be by Poly-silica carbon paint material is provided as, such as, and pearl, powder, thin slice, particulate or can be scattered in or be suspended in paint formulations In other form (such as, small pieces, spheroid, lunute, angular shape, bulk, irregularity or amorphous shape). Pearl can have about 100 microns of sizes to about 1000 micron diameters.Powder can have about 0.5 micron to about 100 microns directly The particle diameter in footpath.Any subset range in the range of these can produce desired effect or color.Bigger and less Size desired effect can also be provided in other preparation.Such as: the pearl of 300-500 micron；350 (+/-5%) micron Pearl；The powder of 5-15 micron.The particle size range of specific poly-silicon-oxygen-carbon ceramic pigment is preferably and closely becomes in +/-10% Change, it is highly preferred that +/-5%.Described scope in some applications can also be wider, such as, is 100-1000 for pearl, and It is such as 0.5-100 for powder.The condition that can pass through used precursor formulation and solidification and pyrolysis changes, controls Density and hardness with predetermined poly-silicon-oxygen-carbon ceramic pigment.Poly-silicon-oxygen-carbon ceramic pigment can provide the resistance to of enhancing to paint formulations Corrosivity, anti scuffing and color (UV) stability.In addition to alternate manner, can mix by using different gas and gas The condition of compound and other solidification and pyrolysis controls optical property or the effect of poly-silicon-oxygen-carbon ceramic pigment.Poly-silica carbon Ceramic paint load can be with 1% to 40% for Anywhere, in order to realizes desired effect.Additionally, poly-silica carbon pottery The use of porcelain pigment can provide the fire-retardant benefit of enhancing.Poly-silicon-oxygen-carbon ceramic pigment has the further advantage that: lacks dirt and is prone to Be mixed into any kind of paint formulations (such as, latex, enamel paint, polyurethane, automotive OEM and mending paint, alkyd resin, aqueous, Acrylic acid and polyhydric alcohol coating formulation).Poly-silicon-oxygen-carbon ceramic pigment can also be used as excellent in ink and graphic arts preparation Coloring agent.
Embodiment 87
Poly-silica carbon preparation is configured to the shape of the tubular structure of larger interior diameter (about 5 inches to about 36 inches, or bigger) Shape.This tubular structure is strengthened to provide hoop intensity (such as, explode and crush) and axial strength with the reinforcing material of arrangement Both (such as, bend, extend and compress).The thickness of described tube wall depends on final use requirement, reinforcing material, Yi Jishi No described material is plastics, pottery or plastics-pottery.Such as, described thickness can be about less than 1/4 inch to 5 inch or Person is bigger.Then these poly-silica carbon tubular structures are solidified, the most finally solidify.They can also be pyrolyzed into Pottery, what it can be carried out infiltrate again, solidify and pyrolysis step (step to five steps or more multistep) is to provide pottery, or it Can carry out extra infiltration again and curing schedule (step to three steps or more multistep) to provide plastics-pottery.Once this Sample is formed, and described tubular structure can be carried out: being processed further, such as, machining is to specification；It is incorporated to final assembly such as, The edge of a wing, connector, joint, adapter；Be incorporated to branch line (outside, internal and both), such as, data wire, choke flow line, Kill line, hydraulic line, electric lines of force etc.；They can have at the second pipe formed about, or may be inserted into the second pipe In or be inserted on the second pipe, formed tube-in-tube structure (such as, double-walled pipeline)；And add to sensor and monitoring device (most Pipe is it should be noted that, tubular structure can be incorporated to during shaping by the Safety check-up device of the form of such as line or optical fiber In wall).These tubular structures provide many features, including the intensity increased and the ratio of weight (such as, higher and lighter, Intensity is identical and lighter, higher and weight is identical).
Embodiment 88
The poly-silica carbon tubular structure of embodiment 87 is for offshore hydrocarbon prospecting and the marine riser of production activity.Each riser Part is about 75 feet long, and described riser part can be assembled into deep-sea and promote, and it can extend downward from surface The degree of depth is more than 5000ft, 10000ft, 15000ft, 20000ft or deeper seabed.Described riser is substantially than conventional steel Riser densities processed is low.Therefore, riser wall can have below about 5g/cm3, below about 3g/cm3Density, it is the lowest Density (about 7.8g/cm in steel3).The density of the reduction of poly-silica carbon riser decreases the amount of required water wings, therefore drops Total external diameter of the low riser disposed.Less external diameter provides the advantage of the amount reducing the surface area suffering trend, Therefore, the stress put on described riser is reduced.
Embodiment 89
Poly-silica carbon preparation is coated on the surface of pipe and carries out softcure.Poly-silica carbon preparation can be pure , or its poly-silicon-oxygen-carbon ceramic particulate that can be such as pyrolyzed is full (according to the mode of embodiment).Repeat this process straight Coating layer thickness needed for acquisition.Obtain required coating layer thickness, the layer of softcure has finally been solidified.Along The coating of the outside of pipe can be that pipe provides heat insulation and corrosion resistance.The undercoating of described pipe can also carry for the material in pipe Supply heat insulation and corrosion resistance is provided.The corrosion resistance provided by the poly-silica carbon coated inside solidified allows to use lower price Metal replace more expensive rustless steel and other high price alloy.
Embodiment 90
Add poly-silica carbon preparation as layer, parts or whole outer covering, such as, the insulator of electric wire.By poly-silicon Oxygen carbon preparation firmly solidifies and provides mechanical strength and fire resistance to described line covering.
Embodiment 91
By solidifying poly-silica carbon preparation, described preparation is ground to about 0.1 μm to about 10mm to prepare highly purified α The SiC of SiC, β SiC and α and β.Then be pyrolyzed the granule of this solidification, and control to shrink during being pyrolyzed, can make a reservation for and Control the final size of the granule of pyrolysis.Preferably, SiC particulate is less than 1 μm.Can be by poly-silica carbon preparation and pyrolytical condition Control contraction rate.More than 1400 DEG C (and more preferably at about 1600 DEG C) under vacuo in inert atmosphere or decompression It is pyrolyzed under inert atmosphere.β SiC will be mainly produced at about 1650 DEG C.At a temperature of higher than 2200 DEG C to about 2400 DEG C To mainly produce α SiC.
Embodiment 92
Poly-silica carbon preparation is cured to form firmly the aggregation of poly-silica carbon solidification.Described aggregation is added extremely Concrete.
Embodiment 93
Poly-silica carbon preparation is configured to the ceramic structure carrier for use as catalyst of porous.The poly-silica carbon pottery of porous Ceramic carrier can be pearl, bead, the shape of honeycomb and be used as catalyst carrier or other shape any of system or structure. Porous poly-silicon-oxygen-carbon ceramic carrier can be the catalytic converter of vehicle.In addition to the carrier of catalyst, outside catalytic unit Structure, shell, parts and assembly can also be prepared by poly-silica carbon plastics, pottery or plastics-pottery.
Embodiment 94
Poly-silica carbon preparation is contoured for the ceramic air-exhaust device of vehicle (such as, automobile, truck and motorcycle).
Embodiment 95
Poly-silica carbon preparation is coated on materials for wall and solidifies.Described coating provides vapor barrier, minimizing And it is preferably prevented from the abnormal smells from the patient smelling in the body of wall of damage by fire the most in a room.
Embodiment 96
With silane, antistatic additive and these combination to thermal depolymerization silicone compositions (such as, proppant and other volume Shape) process there is the ability of intensity of the material increasing and dramatically increasing pyrolysis.
Therefore, treatment compositions can optionally comprise conventional additives such as, rheology modifier, filler, such as second two The coalescent (to contribute to the bin stability of proppant) of alcohol and glycol ether, such as Drew L-139 (available commercially from The branch company Drew Industries of Ashland Chemical) defoamer, such as Emerstat 6660A (available commercially from Or the antistatic additive of Katex 6760 (from Pulcra Chemicals), dust inhibitor and/or other is conventional Cognis) Additive.Additive can be with about 5.0 weights of the most total compositions of trace (such as, < about 0.1 weight % of total compositions) Amount % is present in coating composition.
Preferably process solution and comprise silane, from the Silquest A1100 of Momentive, and there is following chemistry Formula, H2NCH2CH2CH2Si(OCH2CH3)3。
In order to process proppant, it is possible to use following procedure.Proppant (current program) is washed thin to remove in water Grain, to proppant washing 5min (at 25 DEG C) in silane/antistatic additive aqueous solution.Take out proppant and preserve the most Remaining silane/antistatic agent solution is used for being used for multiple times.By proppant at 105-110 DEG C be dried 30min-1h (preferably, its Should be completely dried).
Such as, use procedure above to process 40 mesh proppants of the crushing strength with 13200psi, and show excess of export Cross 17600psi and bigger crushing strength.The particulate percent of the proppant of these silane treatment be less than 1.7% and Lower.
Embodiment 97
By having the Si of 41%, (carbon with 27.5% is Si-C Bonding Type to the C of the O of 31% and 27%, and remains Carbon be free carbon type) the derivative pottery of polymer for structure member, component, abrasive material, device and above reality Execute the ceramic application described in the embodiment of example and accompanying drawing.
By having the Si of 45%, (carbon with 34.4% is Si-C Bonding Type to the C of the O of 22% and 33%, and remains Carbon be free carbon type) the derivative pottery of polymer for structure member, component, abrasive material, device and above reality Execute the ceramic application described in the embodiment of example and accompanying drawing.
Embodiment 99
By having the Si of 44%, (carbon with 27.3% is Si-C Bonding Type to the C of the O of 31% and 25%, and remains Carbon be free carbon type) the derivative ceramic black pigment of polymer for structure member, component, abrasive material, device with And the application of the pottery described in the embodiment of above example and accompanying drawing.
Embodiment 100
By having the Si of 50%, (carbon with 25% is Si-C Bonding Type to the C of the O of 20% and 30%, and remaining Carbon is free carbon type) the derivative ceramic black pigment of polymer for structure member, component, abrasive material, device and The application of the pottery described in the embodiment of above example and accompanying drawing.
Embodiment 101
By have 75% MH, the TV of 15%, catalyst (10ppm platinum and the 0.5%Luperox of the VT of 10% and 1% 231 peroxide) poly-silica carbon batch of material solidify and be pyrolyzed, using formed be applicable to include existing as black ceramic pigment The pottery of interior some application.
Embodiment 102
By have 70% MH, the TV of 20%, catalyst (10ppm platinum and the 0.5%Luperox of the VT of 10% and 1% 231 peroxide) poly-silica carbon batch of material solidify and be pyrolyzed, using formed be applicable to include existing as black ceramic pigment The pottery of interior some application.
Embodiment 103
The poly-silica carbon batch of material with the carbon black of 50 volume % is added to the MH with 70%, the TV of 20%, 10% The poly-silica carbon batch of material of the catalyst (10ppm platinum and 0.5%Luperox 231 peroxide) of VT and 1% carries out solidifying also And pyrolysis, it is applicable to include the pottery as the some application including black ceramic filler pigment using formation.
Embodiment 104
Ceramic poly-silica carbon proppant is placed in the down-hole of deep hydrocarbon producing well, by described proppant is placed in reservoir also And it being used in combination the heat of formation, described proppant plays " cracking " instrumentality with cracking in position as lighter hydrocarbons in forming hydrocarbon.? Support agent can also have the ability mixing catalyst therein to strengthen cracking hydrocarbons.
Embodiment 105
Poly-silica carbon preparation is configured to fiberglass type materials, the insulator class material of blowing, cellosilk and similar The insulator of type and insulation system and structure.
Embodiment 106
Sand or any material with porosity (including micro-porosity) have the poly-silica of this material of vacuum immersion Carbon preparation.Can carry out solidifying and being pyrolyzed by the material of vacuum immersion.This step can repeat.This with poly-silica carbon preparation is true Empty impregnation process produces predetermined reinforcing material.
Embodiment 107
Carry out poly-silica carbon preparation being pyrolyzed to form the black pigment that can be used in sintering process.
Embodiment 108
Poly-silicon-oxygen-carbon ceramic is configured to pearl.It is used for described pearl filling vehicle panel, door, vest, other structure etc. Space.Described pearl is lightweight and gives bulletproof ability for panel.Described pearl can also be described panel, vehicle and structure Fire resistance is provided.
Embodiment 109
Poly-silicon-oxygen-carbon ceramic can be configured to fireplace case, grill, baking box, fire-fighting instrument, rifle cabinet, condom, refuse appearance Device and ball bearing.
Embodiment 110
Poly-silicon-oxygen-carbon ceramic can be configured to powder be used for adding to cosmetics and being used in cosmetics.
Embodiment 111
Can using the poly-silica carbon preparation of the pearl as solidification, pyrolysis and solidification and pyrolysis together with aggregation or Person adds to cement, concrete or other flowable curing building material as the replacement of aggregation.Described pottery has More much bigger intensity than bead and lighter than most of aggregations is many.Although it is flowable, but can be added To construction material.
It should be noted that, it is not necessary to provide or propose to think embodiment of the present invention theme or with the reality of the present invention Theory based on novel and initiative method, material, performance or other beneficial aspects that scheme of executing is relevant and performance. But, provide various theory in this manual to improve the technology in this field further.Unless otherwise explicitly indicated, originally These theories proposed in the bright book of book are in no way intended to limit, retrain or reduce the protection domain that invention required for protection provides.Make Can need not or put into practice these by the present invention theoretical.It is also understood that the present invention can produce new and the most not The theory known is to explain the functional character of the embodiment of the method for the present invention, goods, material, device and system；And hereafter The theory of development should not limit the protection domain that the present invention provides.
Can by the preparation described in this specification, plastics, goods, parts, part, purposes, application, method, activity and The various embodiments of operation are for other fields various and for various other movable, purposes and embodiments.Additionally, this A little embodiments may be used for: such as, existing system, goods, parts, operation or activity；May be used for following developable System, goods, parts, operation or activity；And for carrying out modifying in teaching based on this specification, separate This type of system, goods, parts, operation or activity.Furthermore, it is possible to by the various embodiments in this specification and embodiment with In whole or in part and use mutually with various combination and various combination.It is therefoie, for example, can be by the various realities of this specification The configuration that executing provides in scheme and embodiment uses mutually；And the protection domain that the present invention provides should not limit particular implementation side The configuration described in embodiment in case, embodiment, or particular, embodiment or certain figures or layout.
In the case of without departing substantially from the purport of the present invention or substitutive characteristics, can by the present invention with except institute herein public especially Other form beyond those opened is implemented.Described embodiment in all respects in be considered only as being exemplary rather than Restrictive.

Claims (71)

  1. Enhancing multiple grinding component that the most poly-silica carbon is derivative or cutting element；Described component comprises: body phase and cutting material；Its Described in body derive autohemagglutination silica carbon preparation mutually.
  2. 2. multiple grinding component as claimed in claim 1 or cutting element, wherein said poly-silica carbon preparation is response type system Agent.
  3. 3. multiple grinding component as claimed in claim 1 or cutting element, wherein said poly-silica carbon preparation is response type system Agent, wherein said preparation comprises at least one selected from following precursor: phenyl triethoxysilane, phenyl methyl diethoxy silicon Alkane, methyldiethoxysilane, vinyl methyl diethoxy silane, trimethylethoxysilane, triethoxysilane and TES 40。
  4. 4. multiple grinding component as claimed in claim 1 or cutting element, wherein said poly-silica carbon preparation is response type system Agent, the most described preparation comprises at least two selected from following precursor: phenyl triethoxysilane, phenyl methyl diethoxy silicon Alkane, methyldiethoxysilane, vinyl methyl diethoxy silane, trimethylethoxysilane, triethoxysilane and TES 40 precursors.
  5. 5. multiple grinding component as claimed in claim 1 or cutting element, wherein said cutting material is selected from polycrystalline diamond Composite sheet, SiC, aluminium oxide and diamond.
  6. 6. multiple grinding component as claimed in claim 2 or cutting element, wherein said cutting material is selected from polycrystalline diamond Composite sheet, SiC, aluminium oxide and diamond.
  7. 7. multiple grinding component as claimed in claim 1 or cutting element, wherein said cutting material is evenly distributed on whole In described component.
  8. 8. multiple grinding component as claimed in claim 2 or cutting element, wherein said cutting material is evenly distributed on whole In described component.
  9. 9. multiple grinding component as claimed in claim 1 or cutting element, wherein said cutting material is evenly distributed on described In most of outer volume of component, wherein said outer volume limits at least about the 50% of the cumulative volume of described component.
  10. 10. Grinding structural unit as claimed in claim 1 or cutting element, wherein said poly-silica carbon preparation is slurriable combination.
  11. 11. Grinding structural unit as claimed in claim 1 or cutting elements, wherein said poly-silica carbon preparation is slurriable combination, Wherein said preparation comprises at least one selected from following precursor: the vinyl polysiloxane of methyl blocking, ethenyl blocking The vinyl polysiloxane of vinyl polysiloxane, hydride end-blocking, the dimethyl polysiloxane of ethenyl blocking, hydroxy-end capped Dimethyl polysiloxane, phenyl end capped dimethyl polysiloxane, the phenethyl polysiloxanes of methyl blocking and tetravinyl Cyclosiloxane.
  12. 12. Grinding structural unit as claimed in claim 10 or cutting elements, wherein said poly-silica carbon preparation is substantially free of solvent.
  13. 13. multiple grinding component as claimed in claim 12 or cutting elements, wherein said cutting material is selected from glomerocryst Buddha's warrior attendant Stone composite sheet, SiC, aluminium oxide and diamond.
  14. 14. multiple grinding component as claimed in claim 13 or cutting elements, wherein said cutting material is evenly distributed on institute Stating in most of outer volume of component, wherein said outer volume limits at least about the 50% of the cumulative volume of described component.
  15. 15. structural building element, it comprises the poly-silica carbon preparation of solidification.
  16. 16. structural building element as claimed in claim 15, it comprises the polysiloxanes preparation of structure member and solidification.
  17. 17. structural building element as claimed in claim 16, wherein said structure member is selected from dry wall, slabby rocks, Gypsum Fibrosum Plate, MDF plate, plywood, plastics and flakeboard.
  18. 18. structural building element as claimed in claim 15, it comprises selected from paint, glue and the second component of plastics；And And wherein said second component comprises the polysiloxanes preparation of solidification.
  19. 19. structural building element as claimed in claim 15, the polysiloxanes preparation of wherein said solidification is volume profiles.
  20. 20. structural building element as claimed in claim 15, wherein said poly-silica carbon preparation is response type preparation.
  21. 21. structural building element as claimed in claim 15, wherein said poly-silica carbon preparation is response type preparation.
  22. 22. structural building element as claimed in claim 15, wherein said poly-silica carbon preparation is response type preparation, Qi Zhongsuo State preparation and comprise at least one selected from following precursor: phenyl triethoxysilane, phenyl methyl diethoxy silane, methyl two Ethoxysilane, vinyl methyl diethoxy silane, trimethylethoxysilane, triethoxysilane and TES 40.
  23. 23. composite construction building elements as claimed in claim 15, wherein said poly-silica carbon preparation is response type preparation, by This described preparation comprises at least two selected from following precursor: phenyl triethoxysilane, phenyl methyl diethoxy silane, first Base diethoxy silane, vinyl methyl diethoxy silane, trimethylethoxysilane, triethoxysilane and TES 40.
  24. 24. composite construction building elements as claimed in claim 15, wherein said poly-silica carbon preparation is slurriable combination.
  25. 25. composite construction building elements as claimed in claim 15, wherein said poly-silica carbon preparation is slurriable combination, its Described in preparation comprise at least one selected from following precursor: the vinyl polysiloxane of methyl blocking, the second of ethenyl blocking The vinyl polysiloxane of thiazolinyl polysiloxanes, hydride end-blocking, the dimethyl polysiloxane of ethenyl blocking, hydroxy-end capped Dimethyl polysiloxane, phenyl end capped dimethyl polysiloxane, the phenethyl polysiloxanes of methyl blocking and tetravinyl ring Siloxanes.
  26. 26. composite construction building elements as claimed in claim 15, wherein said poly-silica carbon preparation is substantially free of solvent.
  27. 27. composite construction building elements as claimed in claim 25, wherein said poly-silica carbon preparation is substantially free of solvent.
  28. The structural building element of the 28. poly-silicon-oxygen-carbon ceramics comprising pyrolysis, described pottery comprises about 30 weight % to about 60 weights The amount silicon of %, the oxygen of about 5 weight % to about 40 weight % and the carbon of about 3 weight % to about 35 weight %, and wherein 20 weight Measure the carbon that carbon is silicon bonding of % to 80 weight % and the carbon of 80 weight % to about 20 weight % is free carbon.
  29. 29. structural building element as claimed in claim 28, wherein said ceramic material comprises about 40 weight % to about 50 weights The silicon of amount %, and the carbon that the carbon of the most about 25 weight % to about 40 weight % is silicon bonding.
  30. 30. structural building element as claimed in claim 28, wherein said ceramic material comprises about 40 weight % to about 50 weights Measure the silicon of %, and the carbon of the most about 55 weight % to about 75 weight % is free carbon.
  31. 31. structural building element as claimed in claim 28, wherein said ceramic material comprises about 20 weight % to about 30 weights The oxygen of amount %, and the carbon that the carbon of the most about 25 weight % to about 40 weight % is silicon bonding.
  32. 32. structural building element as claimed in claim 28, wherein said ceramic material comprises about 20 weight % to about 30 weights Measure the oxygen of %, and the carbon of the most about 55 weight % to about 75 weight % is free carbon.
  33. 33. structural building element as claimed in claim 28, wherein said ceramic material comprises about 20 weight % to about 30 weights The carbon of amount %, and the carbon that the carbon of the most about 25 weight % to about 40 weight % is silicon bonding.
  34. 34. structural building element as claimed in claim 28, wherein said ceramic material comprises about 20 weight % to about 30 weights Measure the carbon of %, and the carbon of the most about 55 weight % to about 75 weight % is free carbon.
  35. 35. structural building element as claimed in claim 28, it comprises the polysiloxanes preparation of structure member and solidification.
  36. 36. structural building element as claimed in claim 28, wherein said structure member is selected from dry wall, slabby rocks, Gypsum Fibrosum Plate, MDF plate, plywood, plastics and flakeboard.
  37. 37. structural building element as claimed in claim 28, it comprises selected from paint, glue and the second component of plastics；And And wherein said second component comprises the polysiloxanes preparation of solidification.
  38. The method that 38. pairs of construction packages provide anti-flaming protection, described method includes selecting polysiloxanes preparation to be used to process Construction package；By described polysiloxanes formulation application in described construction package；Described polysiloxanes preparation can exist at 75f Time response less than two days is to hard solidification；Solidify described polysiloxanes preparation；Thus there is the polysiloxanes of described hard solidification The described construction package of application has the standard refractory test of at least about 1/2-h under ASTM E-119.
  39. 39. methods as claimed in claim 38, thus have the described construction package of the polysiloxanes application of described hard solidification There is under ASTM E-119 the standard refractory test of at least about 2-h.
  40. 40. methods as claimed in claim 38, thus have the described construction package of the polysiloxanes application of described hard solidification There is under ASTM E-119 the standard refractory test of at least about 4-h.
  41. 41. methods as claimed in claim 38, wherein said construction package selected from load bearing wall, masonry units, for building The composite component of structural material, non-load bearing wall, partition thing, post, longeron, crossbeam, flat board, composite plate and for floor and room The beam assembly on top.
  42. 42. construction packages of resistance to combustion, it comprises: construction package and the polysiloxanes preparation of hard solidification；Described polysiloxanes preparation is extremely Few substantially free of halogen；The wherein said construction package of resistance to combustion exceedes the standard refractory of at least about 1/2-h under ASTM E-119 and surveys Examination.
  43. 43. construction packages of resistance to combustion as claimed in claim 42, wherein said construction package is selected from load bearing wall, masonry units, use In the composite component of structural material, non-load bearing wall, partition thing, post, longeron, crossbeam, flat board, the composite plate of building and be used for Floor and the beam assembly on roof.
  44. 44. construction packages of resistance to combustion as claimed in claim 43, wherein said poly-silica carbon preparation is response type preparation.
  45. 45. for the resistance to combustion outsourcing things of construction package, and it comprises: for the resistance to combustion outsourcing thing of construction package with immerse described outsourcing The polysiloxanes preparation of the hard solidification in thing；Described polysiloxanes preparation is the most halogen-free.
  46. 46. plastic refractories comprising the first plastics and halogen-free flame-retardant, described fire retardant comprises the polysiloxanes system of hard solidification Agent；Described plastics can meet at least V0 grade under UL-94.
  47. 47. final products comprising poly-silica carbon preparation, described final products are selected from fiber, proppant, the support of silane cladding Agent, silane and the proppant of antistatic additive cladding, explosion-proof barriers, ballistic composite, structural elements, trailer, movable building, fortune Defeated container, friction member, lapping device, armored vehicle, flak jackets, insulator, paint, fireproof coating, table top, gas extraction system, Tubular structure, line insulators, conduit insulators, conduit lining, concrete and vapour barrier.
  48. 48. final products as claimed in claim 47, wherein said poly-silica carbon preparation comprises the pottery of pyrolysis, described pottery Comprise the silicon of about 30 weight % to about 60 weight %, the oxygen of about 5 weight % to about 40 weight % and about 3 weight % to about 35 weights The carbon of amount %, and carbon that the carbon of wherein 20 weight % to 80 weight % is silicon bonding and 80 weight % are to about 20 weight % Carbon is free carbon.
  49. 49. final products as claimed in claim 47, wherein said ceramic material comprises about 40 weight % to about 50 weight % Silicon, and the carbon of the most about 25 weight % to about 40 weight % be silicon bonding carbon.
  50. 50. final products as claimed in claim 47, wherein said ceramic material comprises about 40 weight % to about 50 weight % Silicon, and the carbon of the most about 55 weight % to about 75 weight % is free carbon.
  51. 51. final products as claimed in claim 47, wherein said ceramic material comprises about 20 weight % to about 30 weight % Oxygen, and the carbon of the most about 25 weight % to about 40 weight % be silicon bonding carbon.
  52. 52. final products as claimed in claim 47, wherein said ceramic material comprises about 20 weight % to about 30 weight % Oxygen, and the carbon of the most about 55 weight % to about 75 weight % is free carbon.
  53. 53. final products as claimed in claim 47, wherein said ceramic material comprises about 20 weight % to about 30 weight % Carbon, and the carbon of the most about 25 weight % to about 40 weight % be silicon bonding carbon.
  54. 54. final products as claimed in claim 47, wherein said ceramic material comprises about 20 weight % to about 30 weight % Carbon, and the carbon of the most about 55 weight % to about 75 weight % is free carbon.
  55. 55. methods preparing goods, wherein said goods are selected from fiber, proppant, the proppant of silane cladding, silane and resist quiet The proppant of electricity agent cladding, explosion-proof barriers, ballistic composite, structural elements, trailer, movable building, transport container, friction structure Part, lapping device, armored vehicle, flak jackets, insulator, paint, fireproof coating, table top, gas extraction system, tubular structure, circuit Insulator, conduit insulators, conduit lining, concrete and vapour barrier；Described method includes selecting poly-silica carbon preparation, preparation Described poly-silica carbon preparation, makes to 100% as at least the 0.05% of described goods by processing described poly-silica carbon preparation Standby described goods.
  56. 56. methods as claimed in claim 55, comprise the pottery being pyrolyzed described poly-silica carbon preparation to form pyrolysis, described pottery Porcelain comprises the silicon of about 30 weight % to about 60 weight %, the oxygen of about 5 weight % to about 40 weight % and about 3 weight % to about 35 weights The carbon of amount %, and carbon that the carbon of wherein 20 weight % to 80 weight % is silicon bonding and 80 weight % are to about 20 weight % Carbon is free carbon.
  57. The goods of the 57. poly-silicon-oxygen-carbon ceramics comprising pyrolysis, described pottery comprises the silicon, about of about 30 weight % to about 60 weight % The oxygen of 5 weight % to about 40 weight % and the carbon of about 3 weight % to about 35 weight %, and wherein 20 weight % to 80 weight % The carbon that carbon is silicon bonding and the carbon of 80 weight % to about 20 weight % be free carbon.
  58. 58. goods as claimed in claim 57, wherein said goods are vehicle.
  59. 59. vehicles as claimed in claim 57, it includes the panel containing described pottery.
  60. 60. goods as claimed in claim 57, wherein said goods are ball bearing.
  61. 61. goods as claimed in claim 57, wherein said goods are wallboard.
  62. 62. goods as claimed in claim 57, wherein said goods are rope.
  63. 63. goods as claimed in claim 62, wherein said rope comprises the fiber containing described pottery.
  64. 64. goods as claimed in claim 57, wherein said goods comprise cement.
  65. 65. goods as claimed in claim 57, wherein said goods comprise concrete.
  66. 66. goods as claimed in claim 57, wherein said goods are selected from fiber, coated sand, explosion-proof barriers, shellproof composite wood Material, structural elements, trailer, transport container, friction member, lapping device, armored vehicle, flak jackets, insulator, gas extraction system, Tubular structure, line insulators, conduit insulators, conduit lining, concrete and vapour barrier.
  67. 67. goods as claimed in claim 57, wherein said goods are selected from fiber, proppant, coated sand, explosion-proof barriers, prevent Elastic composite material, structural elements, trailer, movable building, transport container, friction member, flak jackets, insulator, paint, fire-resistant painting Material, table top, gas extraction system, conduit insulators, conduit lining, concrete, cement and vapour barrier.
  68. 68. goods as claimed in claim 57, wherein said goods are selected from the proppant of cladding, coated sand, priming by vacuum Sand, the material of priming by vacuum, explosion-proof barriers, ballistic composite, structural elements, trailer, movable building, transport container, friction Component, lapping device, abrasive material, abrasion device, armored vehicle, flak jackets, insulator, paint, fireproof coating, table top, lead Pipelining, concrete, cement and vapour barrier.
  69. 69. goods as claimed in claim 57, wherein said goods are selected from fiber, proppant, the proppant of silane cladding, silicon Alkane and the proppant of antistatic additive cladding, coated sand, trailer, movable building, transport container, friction member, lapping device, plate armour Vehicle, flak jackets, insulator, cement and vapour barrier.
  70. 70. goods as claimed in claim 57, wherein said goods are selected from trailer, movable building, transport container, friction structure Part, lapping device, armored vehicle, flak jackets, insulator, paint, table top, gas extraction system, tubular structure, line insulators, water Mud and vapour barrier.
  71. 71. goods as claimed in claim 57, wherein said goods are selected from fiber, proppant, the proppant of silane cladding, silicon Alkane and antistatic additive cladding proppant, coated sand, explosion-proof barriers, ballistic composite, structural elements, trailer, movable building, Transport container, friction member, lapping device, armored vehicle, flak jackets, insulator, paint, fireproof coating, table top, exhaust system System, tubular structure, line insulators, conduit insulators, conduit lining, concrete, cement and vapour barrier.
CN201580021474.7A 2014-02-28 2015-02-28 Poly-silica material with carbon element, method and purposes Pending CN106232748A (en)

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US201461946598P 2014-02-28 2014-02-28
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US14/212,896 US9815952B2 (en) 2013-03-15 2014-03-14 Solvent free solid material
US14/212,896 2014-03-14
US14/268,150 2014-05-02
US14/268,150 US9815943B2 (en) 2013-03-15 2014-05-02 Polysilocarb materials and methods
US201562106094P 2015-01-21 2015-01-21
US62/106,094 2015-01-21
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