CN105951301A - Preparation method of antioxidant carbon fiber heat insulation felt - Google Patents

Preparation method of antioxidant carbon fiber heat insulation felt Download PDF

Info

Publication number
CN105951301A
CN105951301A CN201610514672.3A CN201610514672A CN105951301A CN 105951301 A CN105951301 A CN 105951301A CN 201610514672 A CN201610514672 A CN 201610514672A CN 105951301 A CN105951301 A CN 105951301A
Authority
CN
China
Prior art keywords
carbon fiber
carbon
chlorosilane
oxidation resistant
vinyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610514672.3A
Other languages
Chinese (zh)
Inventor
唐波
吴新锋
彭熙瑜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
New Material Technology (shanghai) Co Ltd
Original Assignee
New Material Technology (shanghai) Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by New Material Technology (shanghai) Co Ltd filed Critical New Material Technology (shanghai) Co Ltd
Priority to CN201610514672.3A priority Critical patent/CN105951301A/en
Publication of CN105951301A publication Critical patent/CN105951301A/en
Pending legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/44—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
    • D04H1/46—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • D04H1/4242—Carbon fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • D06M13/5135—Unsaturated compounds containing silicon atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • D06M13/517—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond containing silicon-halogen bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Inorganic Fibers (AREA)

Abstract

The invention relates to a preparation method of an antioxidant carbon fiber heat insulation felt. An antioxidant carbon fiber heat insulation felt adopts chopped carbon fibers as a matrix, and the carbon fiber matrix is made into the antioxidant carbon fiber heat insulation felt by virtue of steps such as surface hydroxylation, vinylation, chloro-silylation, polysilane grafting, needling and felt formation, high-temperature sintering and the like. The surface of the carbon fiber is coated with a silicon carbide coating, the silicon carbide coating and the carbon fiber matrix are combined by virtue of a chemical bond, so that the silicon carbide coating and the carbon fiber matrix are tightly combined and are uneasy to separate and durable to use, and the antioxidant property of the carbon fiber heat insulation material is improved. The service life of the antioxidant heat insulation felt material can be increased from one year to more than two years, the antioxidant heat insulation felt material is uneasy to separate, the application performance is not influenced, and the purity of a final product is not influenced.

Description

A kind of preparation method of oxidation resistant carbon Fibrous insulation
Technical field
The invention belongs to carbon fiber heat insulation field of material technology, be specifically related to the preparation of a kind of oxidation resistant carbon Fibrous insulation Method, is to be used directly in the high temperature furnace of vacuum and inert gas shielding, can stable at a temperature of 1000-2500 DEG C use, It is especially more than requisite heat-barrier material in 1500 DEG C of high temperature furnaces using temperature requirement.The invention belongs to high-temperature energy-conservation neck Territory.
Background technology
Carbon fiber heat insulation felt material is the high temperature resistant carbon requisite raw material of carbon composite heat-insulated material, and itself is also simultaneously Thermostable heat-isolating material, the features such as, processability high temperature resistant with it is good, be widely used in Aero-Space, communication optical fiber, New forms of energy, high-performance ceramic manufacture, field of crystal growth, and along with the development of new forms of energy photovoltaic industry, current polycrystalline ingot furnace And the heat-barrier material of thermal field of single crystal furnace is the most concerned and becomes a focus.
Carbon carbon composite heat-insulated material and the many field of carbon fiber heat insulation material present stage Application comparison are polycrystalline-silicon furnace fields And monocrystaline silicon stove field.High temperature furnace use during in order to improve its application efficiency, often the most higher at 400 DEG C Temperature blow-on, after blow-on, air enters, and is very easy to cause the oxidation of heat-barrier material, ultimately results in the service life of insulation material Reducing, sometimes will change once half a year, add cost also can affect production efficiency simultaneously.Carbon fiber heat insulation material exists simultaneously In the environment of applied at elevated temperature, it is frequently subjected to washing away and impacting of silicon vapor, it is easy to suffer erosion and cause perforated phenomenon, to peace Full production threatens.Therefore antioxygenic property and the anti-steam performance of flushing of carbon carbon composite heat-insulated material becomes carbon carbon and is combined One very important performance indications of heat-barrier material.
Although present stage can temporarily can be solved by the method adding carbon cloth or graphite paper on heat-barrier material surface Gas oxidation and the problem washed away, but carbon cloth or graphite paper can be affected by aoxidizing equally, additionally carbon cloth or graphite paper After being destroyed, steam enters internal oxidation and the erosion damage that can accelerate heat-barrier material equally.By at carbon carbon compound heat-insulation Material surface one layer of fire-resistant oxidation resistant coating of coating is relatively effective method, but the research of present stage this respect is also compared Few；And it is not that each high-temperaure coating is suitable in crystal silicon stove using, because high-temperaure coating sometimes can overflow Enter in silicon wafer material, and then affect the generating efficiency of silicon wafer material.Present stage is in carbon carbon composite heat-insulated material surface-coated one Layer carbofrax material is to improve the very effective method of its antioxygenic property, but this method does not ensures that each carbon fibre Dimension can be carbonized silicon materials and is coated with, and therefore preparing a kind of the coat of silicon carbide of carbon coated fibrous material completely can become one Individual very important research field.
Layer protecting film can be formed at carbon fiber surface by the method for coating, but owing to carbon fiber and carborundum are coated with Not having chemical bond to be attached between Ceng, i.e. coat of silicon carbide is because combining and loosely falling off, and cast is fallen in product The purity of product can be affected thus affect performance and the qualification rate of product.
Because of carborundum 3.2 g/cm3Proportion and high sublimation temperature (about 2700 DEG C), carborundum is well suited as high temperature Stove raw material.But under any pressure that can reach, carborundum is all without fusing, and has at a fairly low chemism.Cause This carries out the most difficult realization of method of carbon coated fiber with carborundum powder.Use in carbon fiber surface grafting herein, be polymerized poly-carbon The method of silane then high temperature sintering makes carbon fiber surface form one layer of carborundum protective coating, and carborundum and carbon fiber are originally It is combined by chemical bond between body, is tightly combined, difficult drop-off, use persistently, thus the surface of a kind of carbon fiber is provided Anti-oxidation treatment method, and then the preparation method of a kind of oxidation resistant carbon Fibrous insulation is provided.
Summary of the invention
Present invention aim at providing a kind of can the coat of silicon carbide of carbon coated fiber completely, this coat of silicon carbide and carbon It is combined by chemical bond between fibrous matrix, is tightly combined, difficult drop-off, use persistently, improve carbon fiber heat insulation material Antioxygenic property, the preparation method of a kind of oxidation resistant carbon Fibrous insulation is i.e. provided.
A kind of oxidation resistant carbon Fibrous insulation is with chopped carbon fiber as matrix, carbon fiber substrate through surface hydroxylation, The steps such as vinylated, chlorosilane, grafting polysilane, needle felting, high temperature sintering prepare oxidation resistant carbon Fibrous insulation.
The preparation method of a kind of oxidation resistant carbon Fibrous insulation, the preparation method of oxidation resistant carbon Fibrous insulation specifically includes Following steps:
(1) hydroxylating of carbon fiber: select T300 carbon fiber as matrix carbon fiber, chopped carbon fiber tow is immersed dioxygen In water, reflow treatment 8 hours at 100 DEG C, obtain the carbon fiber of surface hydroxylation, the wherein length of chopped carbon fiber tow For 50mm-150mm, tow k number is 12 k-48 k；
(2) carbon fiber is vinylated: hydroxylated carbon fiber is put into backflow 2 in vinyl silicane coupling agent ethanol solution Hour obtain vinylated carbon fiber, the wherein concentration of vinyl silicane coupling agent ethanol solution medium vinyl silane coupler For 5%-20%, vinylsiloxane selects VTES A-151；
(3) chlorosilane of carbon fiber: by methylvinyl-chlorosilanes CH2=CH-Si(CH3)Cl2Put in xylene solvent, Concentration is 5-20%；Then vinyl carbon fiber is put in mixed solution, the quality of vinyl carbon fiber and the quality in solution Ratio is 1:1；By above-mentioned three mixed liquor put in polyethylene plastic packaging bag, rush nitrogen and catch up with except the oxygen in solution for 5 minutes, mould Envelope, is put in electron accelerator underdrive irradiation, cools down with fan simultaneously, and irradiation dose is 5-30kGy, and beam energy is 2MeV, 10mA, in irradiation process, the vinyl in carbon fiber carries out cross-linking reaction with the vinyl in methylvinyl-chlorosilanes, I.e. can get the carbon fiber of chlorosilane；Sample after irradiation is through filtering, and dimethylbenzene washs, and filters, and is dried and i.e. can get chlorine silicon The carbon fiber of alkanisation；
(4) carbon fiber grafting polysilane: by methylvinyl-chlorosilanes CH2=CH-Si(CH3)Cl2Put in xylene solvent, Concentration is 5%-20%；Then the carbon fiber of the chlorosilane obtained in (3) is put in mixed solution, the carbon fiber of chlorosilane The mass ratio of quality and solution be 1:1；Being subsequently adding metallic sodium, 100-110 DEG C of reaction, metallic sodium is excessive, until metal Till sodium no longer reacts；In course of reaction, the chlorosilane graft in the carbon fiber of chlorosilane will be with methylvinyl-chlorosilanes Carrying out polyreaction, chlorine is removed；
(5) carbon fiber needle felting: the carbon fiber obtained in above-mentioned (4) step is grafted polysilane product at needle felting machine On carry out needle felting, wherein needling density is 1/50-1/250, i.e. its fiber orientation anisotropy X-Y plane and Z-direction fiber Portion rate is 50-250:1, and the thickness of Nomex is 10 mm ± 1mm, and the surface density of Nomex is 400 g/m2-900 g/m2；
(6) high temperature sintering: be sintered in high temperature furnace by the Nomex obtained in above-mentioned (5) step, carbon fiber surface is grafted Polycarbosilane graft become carbofrax material be coated on carbon fiber surface formed one layer of oxidation resistant protective layer: at 10- Under 1000Pa pressure, to heat up 40-70 DEG C to 400 DEG C per hour, intensification the most per hour 20-40 DEG C to 700 DEG C, 700 DEG C of guarantors Temperature 2-3 hour, intensification the most per hour 20-40 DEG C to 1000 DEG C, it is incubated 1-2 hour, intensification per hour 20-40 DEG C to 1200 DEG C, it is incubated 1-2 hour, comes out of the stove after Temperature fall to room temperature.
Persursor material in above-mentioned steps (1) selects polyacrylonitrile-based carbon fibre as chopped carbon fiber matrix, model For T300 type, chopped strand length range is 50mm-150mm, selects large-tow carbon fiber as far as possible, if tow k number is 12 k-48 k。
Coupling agent in above-mentioned steps (2) selects vinyl silicane coupling agent, and the vinyl groups of introducing is conducive to and second The functional group of thiazolinyl carries out irradiation grafting reaction such as next step vinyl chlorosilane, and the vinyl silanes of introducing can be vinyl Triethoxysilane A-151, reaction solution elects the ethanol solution of 5%-20% as, higher than theoretical usage amount.
Chlorosilane in above-mentioned steps (3) selects vinyl chlorosilane, and vinyl can enter with the vinyl in step (2) Row graft reaction, the present invention selects methylvinyl-chlorosilanes as graft；By methylvinyl-chlorosilanes CH2=CH-Si (CH3)Cl2Putting in xylene solvent, concentration is 5-20%；Then vinyl carbon fiber is put in mixed solution, vinyl carbon The quality of fiber and the mass ratio of solution are 1:1；By above-mentioned three mixed liquor put in polyethylene plastic packaging bag, rush nitrogen 5 Minute catch up with except the oxygen in solution, thoroughly remove the oxygen interference for graft reaction；Additionally irradiation sample must be placed on poly- In ethylene plastic packaging bag, preventing the infiltration of oxygen in irradiation process, transmission irradiation ensures heat radiation in time simultaneously, and irradiation dose also to be controlled Making, irradiation dose elects 5-30kGy as, controls irradiation grafting degree.
Chlorosilane in above-mentioned steps (4) selects the methylvinyl-chlorosilanes CH containing vinyl equally2=CH-Si (CH3)Cl2Putting in xylene solvent, concentration is 5%-20%；Then the carbon fiber of the chlorosilane obtained in (3) is put into mixed Closing in solution, the quality of the carbon fiber of chlorosilane and the mass ratio of solution are 1:1；It is subsequently adding metallic sodium, at 100-110 DEG C reaction, metallic sodium excess, till metallic sodium no longer reacts；Chlorosilane in the carbon fiber of chlorosilane in course of reaction Graft will carry out polyreaction with methylvinyl-chlorosilanes, and chlorine is removed.
Needling density in above-mentioned steps (5) controls at 1/50-1/250, i.e. its fiber orientation anisotropy X-Y plane with Z-direction fiber portion rate is 50-250:1, and the THICKNESS CONTROL of Nomex is at 10 mm ± 1mm, and the surface density of Nomex is 400 g/ m2-900 g/m2。
High temperature sintering condition in above-mentioned steps (6) is: under 10-1000Pa pressure, arrives to heat up per hour 40-70 DEG C 400 DEG C, intensification the most per hour 20-40 DEG C to 700 DEG C, 700 DEG C are incubated 2-3 hour, and intensification the most per hour 20-40 DEG C is arrived 1000 DEG C, it is incubated 1-2 hour, intensification per hour 20-40 DEG C to 1200 DEG C, it is incubated 1-2 hour, goes out after Temperature fall to room temperature Stove.
Accompanying drawing explanation
Fig. 1 is the structural representation of the oxidation resistant carbon Fibrous insulation described in patent of the present invention, and described oxidation resistant carbon is fine Dimension heat insulation felt include X to carbon fiber 001, Y-direction carbon fiber 002, Z-direction carbon fiber 003, wherein every carbon fiber is all carbonized silicon institute Cladding, carbon fiber structural includes carbon fiber substrate 004, carborundum clad 005.
Detailed description of the invention
Below by embodiment, the present invention is described in further detail, but the present invention is not limited only to the following example.
Embodiment 1
A kind of preparation method of oxidation resistant carbon Fibrous insulation, the preparation process of its oxidation resistant carbon Fibrous insulation is as follows:
(1) hydroxylating of carbon fiber: select T300 carbon fiber as matrix carbon fiber, chopped carbon fiber tow is immersed dioxygen In water, reflow treatment 8 hours at 100 DEG C, obtain the carbon fiber of surface hydroxylation, the wherein length of chopped carbon fiber tow For 50mm 150mm, tow k number is 12 k 18K；
(2) carbon fiber is vinylated: hydroxylated carbon fiber is put into backflow 2 in vinyl silicane coupling agent ethanol solution Hour obtain vinylated carbon fiber, the wherein concentration of vinyl silicane coupling agent ethanol solution medium vinyl silane coupler Being 10%, vinylsiloxane selects VTES A-151；
(3) chlorosilane of carbon fiber: by methylvinyl-chlorosilanes CH2=CH-Si(CH3)Cl2Put in xylene solvent, Concentration is 10%；Then vinyl carbon fiber is put in mixed solution, the quality of vinyl carbon fiber and the mass ratio in solution For 1:1；By above-mentioned three mixed liquor put in polyethylene plastic packaging bag, rush nitrogen and catch up with except the oxygen in solution for 5 minutes, mould Envelope, is put in electron accelerator underdrive irradiation, cools down with fan simultaneously, and irradiation dose is 10kGy, and beam energy is 2MeV, 10mA, in irradiation process, the vinyl in carbon fiber carries out cross-linking reaction with the vinyl in methylvinyl-chlorosilanes, I.e. can get the carbon fiber of chlorosilane；Sample after irradiation is through filtering, and dimethylbenzene washs, and filters, and is dried and i.e. can get chlorine silicon The carbon fiber of alkanisation；
(4) carbon fiber grafting polysilane: by methylvinyl-chlorosilanes CH2=CH-Si(CH3)Cl2Put in xylene solvent, Concentration is 10%；Then the carbon fiber of the chlorosilane obtained in (3) is put in mixed solution, the carbon fiber of chlorosilane Quality is 1:1 with the mass ratio of solution；Being subsequently adding metallic sodium, 100-110 DEG C of reaction, metallic sodium is excessive, until metallic sodium No longer till reaction；In course of reaction, the chlorosilane graft in the carbon fiber of chlorosilane will enter with methylvinyl-chlorosilanes Row polyreaction, chlorine is removed；
(5) carbon fiber needle felting: the carbon fiber obtained in above-mentioned (4) step is grafted polysilane product at needle felting machine On carry out needle felting, wherein needling density is 1/100, i.e. its fiber orientation anisotropy X-Y plane and Z-direction fiber number Ratio is 100:1, and the thickness of Nomex is 10 mm ± 1mm, and the surface density of Nomex is 600 g/m2；
(6) high temperature sintering: be sintered in high temperature furnace by the Nomex obtained in above-mentioned (5) step, carbon fiber surface is grafted Polycarbosilane graft become carbofrax material be coated on carbon fiber surface formed one layer of oxidation resistant protective layer: 100Pa press Under power, to heat up 50 DEG C to 400 DEG C per hour, heating up 40 DEG C to 700 DEG C the most per hour, 700 DEG C are incubated 2 hours, the most often Hour heat up 25 DEG C to 1000 DEG C, be incubated 1 hour, per hour intensification 25 DEG C to 1200 DEG C, be incubated 1 hour, Temperature fall is to room Come out of the stove after temperature.
Embodiment 2
A kind of preparation method of oxidation resistant carbon Fibrous insulation, the preparation process of its oxidation resistant carbon Fibrous insulation is as follows:
(1) hydroxylating of carbon fiber: select T300 carbon fiber as matrix carbon fiber, chopped carbon fiber tow is immersed dioxygen In water, reflow treatment 8 hours at 100 DEG C, obtain the carbon fiber of surface hydroxylation, the wherein length of chopped carbon fiber tow For 50mm-150mm, tow k number is 48 k；
(2) carbon fiber is vinylated: hydroxylated carbon fiber is put into backflow 2 in vinyl silicane coupling agent ethanol solution Hour obtain vinylated carbon fiber, the wherein concentration of vinyl silicane coupling agent ethanol solution medium vinyl silane coupler Being 15%, vinylsiloxane selects VTES A-151；
(3) chlorosilane of carbon fiber: by methylvinyl-chlorosilanes CH2=CH-Si(CH3)Cl2Put in xylene solvent, Concentration is 15%；Then putting in mixed solution by vinyl carbon fiber, the quality of vinyl carbon fiber with the mass ratio of solution is 1:1；By above-mentioned three mixed liquor put in polyethylene plastic packaging bag, rush nitrogen and within 5 minutes, catch up with except the oxygen in solution, plastic packaging, Being put in electron accelerator underdrive irradiation, cool down with fan simultaneously, irradiation dose is 15kGy, and beam energy is 2MeV, 10mA, in irradiation process, the vinyl in carbon fiber carries out cross-linking reaction with the vinyl in methylvinyl-chlorosilanes, Obtain the carbon fiber of chlorosilane；Sample after irradiation is through filtering, and dimethylbenzene washs, and filters, and is dried and i.e. can get chlorosilane Carbon fiber；
(4) carbon fiber grafting polysilane: by methylvinyl-chlorosilanes CH2=CH-Si(CH3)Cl2Put in xylene solvent, Concentration is 15%；Then the carbon fiber of the chlorosilane obtained in (3) is put in mixed solution, the carbon fiber of chlorosilane Quality is 1:1 with the mass ratio of solution；Being subsequently adding metallic sodium, 100-110 DEG C of reaction, metallic sodium is excessive, until metallic sodium No longer till reaction；In course of reaction, the chlorosilane graft in the carbon fiber of chlorosilane will enter with methylvinyl-chlorosilanes Row polyreaction, chlorine is removed；
(5) carbon fiber needle felting: the carbon fiber obtained in above-mentioned (4) step is grafted polysilane product at needle felting machine On carry out needle felting, wherein needling density is 1/120, i.e. its fiber orientation anisotropy X-Y plane and Z-direction fiber number Ratio is 120:1, and the thickness of Nomex is 10 mm ± 1mm, and the surface density of Nomex is 800 g/m2；
(6) high temperature sintering: be sintered in high temperature furnace by the Nomex obtained in above-mentioned (5) step, carbon fiber surface is grafted Polycarbosilane graft become carbofrax material be coated on carbon fiber surface formed one layer of oxidation resistant protective layer: 100Pa press Under power, to heat up 50 DEG C to 400 DEG C per hour, heating up 40 DEG C to 700 DEG C the most per hour, 700 DEG C are incubated 2.5 hours, then Heating up 20 DEG C to 1000 DEG C per hour, be incubated 1 hour, heat up 20 DEG C to 1200 DEG C per hour, be incubated 1 hour, Temperature fall arrives Come out of the stove after room temperature.
During high temperature sintering, polysilane is converted into carbofrax material and is coated on carbon fiber surface, due to carbon fiber and Polysilane by chemical bond grafting link together, so the carbofrax material after Shao Jie also can be chemically bound together, This results in carborundum clad and is closely linked with carbon fiber, it is not easy to come off from carbon fiber surface, plays antioxidation Effect, above anti-oxidation method can be greatly improved the antioxygenic property of material, the service life of material can from 1 year improve By more than 2 years, and it is not easy to come off, does not affect serviceability, do not affect the degree of purity of final products.

Claims (10)

1. an oxidation resistant carbon Fibrous insulation is with chopped carbon fiber as matrix, and carbon fiber substrate is through surface hydroxylation, second The step such as alkenyl, chlorosilane, grafting polysilane, needle felting, high temperature sintering prepares oxidation resistant carbon Fibrous insulation.
2. oxidation resistant carbon Fibrous insulation is to be coated with one layer of coat of silicon carbide, coat of silicon carbide and carbon at carbon fiber surface It is combined by chemical bond between fibrous matrix, is tightly combined, difficult drop-off, use persistently, improve carbon fiber heat insulation material Antioxygenic property;Described oxidation resistant carbon Fibrous insulation includes that X is to carbon fiber 001, Y-direction carbon fiber 002, Z-direction carbon fiber 003, wherein every carbon fiber is all carbonized silicon and is coated with, and carbon fiber structural includes carbon fiber substrate 004, carborundum clad 005。
3. its fiber orientation anisotropy X-Y plane of oxidation resistant carbon Fibrous insulation is 50-250 with Z-direction fiber portion rate: 1, the THICKNESS CONTROL of Nomex is at 10 mm ± 1mm, and the surface density of Nomex is 400 g/m2-900 g/m2。
4. a preparation method for oxidation resistant carbon Fibrous insulation, the preparation method of oxidation resistant carbon Fibrous insulation specifically include as Lower step:
(1) hydroxylating of carbon fiber: select T300 carbon fiber as matrix carbon fiber, chopped carbon fiber tow is immersed dioxygen In water, reflow treatment 8 hours at 100 DEG C, obtain the carbon fiber of surface hydroxylation, the wherein length of chopped carbon fiber tow For 50mm-150mm, tow k number is 12 k-48 k；
(2) carbon fiber is vinylated: hydroxylated carbon fiber is put into backflow 2 in vinyl silicane coupling agent ethanol solution Hour obtain vinylated carbon fiber, the wherein concentration of vinyl silicane coupling agent ethanol solution medium vinyl silane coupler For 5%-20%, vinylsiloxane selects VTES A-151；
(3) chlorosilane of carbon fiber: by methylvinyl-chlorosilanes CH2=CH-Si(CH3)Cl2Put in xylene solvent, Concentration is 5-20%；Then vinyl carbon fiber is put in mixed solution, the quality of vinyl carbon fiber and the mass ratio of solution For 1:1；By above-mentioned three mixed liquor put in polyethylene plastic packaging bag, rush nitrogen and within 5 minutes, catch up with the oxygen except solution, plastic packaging, Being put in electron accelerator underdrive irradiation, cool down with fan simultaneously, irradiation dose is 5-30kGy, and beam energy is 2MeV, 10mA, in irradiation process, the vinyl in carbon fiber carries out cross-linking reaction with the vinyl in methylvinyl-chlorosilanes, I.e. can get the carbon fiber of chlorosilane；Sample after irradiation is through filtering, and dimethylbenzene washs, and filters, and is dried and i.e. can get chlorine silicon The carbon fiber of alkanisation；
(4) carbon fiber grafting polysilane: by methylvinyl-chlorosilanes CH2=CH-Si(CH3)Cl2Put in xylene solvent, Concentration is 5%-20%；Then the carbon fiber of the chlorosilane obtained in (3) is put in mixed solution, the carbon fiber of chlorosilane The mass ratio of quality and solution be 1:1；Being subsequently adding metallic sodium, 100-110 DEG C of reaction, metallic sodium is excessive, until metal Till sodium no longer reacts；In course of reaction, the chlorosilane graft in the carbon fiber of chlorosilane will be with methylvinyl-chlorosilanes Carrying out polyreaction, chlorine is removed；
(5) carbon fiber needle felting: the carbon fiber obtained in above-mentioned (4) step is grafted polysilane product at needle felting machine On carry out needle felting, wherein needling density is 1/50-1/250, i.e. its fiber orientation anisotropy X-Y plane and Z-direction fiber Portion rate is 50-250:1, and the thickness of Nomex is 10 mm ± 1mm, and the surface density of Nomex is 400 g/m2-900 g/m2；
(6) high temperature sintering: be sintered in high temperature furnace by the Nomex obtained in above-mentioned (5) step, carbon fiber surface is grafted Polycarbosilane graft become carbofrax material be coated on carbon fiber surface formed one layer of oxidation resistant protective layer: at 10- Under 1000Pa pressure, to heat up 40-70 DEG C to 400 DEG C per hour, intensification the most per hour 20-40 DEG C to 700 DEG C, 700 DEG C of guarantors Temperature 2-3 hour, intensification the most per hour 20-40 DEG C to 1000 DEG C, it is incubated 1-2 hour, intensification per hour 20-40 DEG C to 1200 DEG C, it is incubated 1-2 hour, comes out of the stove after Temperature fall to room temperature.
The preparation method of a kind of oxidation resistant carbon Fibrous insulation the most as claimed in claim 4, step 4(1 described in its feature) In persursor material select polyacrylonitrile-based carbon fibre as chopped carbon fiber matrix, model is T300 type, and chopped strand is long Degree scope is 50mm-150mm, and tow k number is 12 k-48 k.
The preparation method of a kind of oxidation resistant carbon Fibrous insulation the most as claimed in claim 4, step 4(2 described in its feature) In coupling agent be VTES A-151, reaction solution elects the ethanol solution of 5%-20% as.
The preparation method of a kind of oxidation resistant carbon Fibrous insulation the most as claimed in claim 4, step 4(3 described in its feature) In chlorosilane select vinyl chlorosilane, as graft；By methylvinyl-chlorosilanes CH2=CH-Si(CH3)Cl2 Putting in xylene solvent, concentration is 5-20%；Then vinyl carbon fiber is put in mixed solution, vinyl carbon fiber Quality is 1:1 with the mass ratio of solution；By above-mentioned three mixed liquor put in polyethylene plastic packaging bag, rush nitrogen and catch up with for 5 minutes Except the oxygen in solution；Irradiation sample must be placed in polyethylene plastic packaging bag, prevents the infiltration of oxygen in irradiation process, simultaneously Transmission irradiation ensures heat radiation in time, and irradiation dose also to be controlled well, and irradiation dose elects 5-30kGy as, controls irradiation grafting degree.
The preparation method of a kind of oxidation resistant carbon Fibrous insulation the most as claimed in claim 4, step 4(4 described in its feature) In chlorosilane select the methylvinyl-chlorosilanes CH containing vinyl equally2=CH-Si(CH3)Cl2Put into xylene solvent In, concentration is 5%-20%；Then the carbon fiber of the chlorosilane obtained in 4 (3) is put in mixed solution, the carbon of chlorosilane The quality of fiber and the mass ratio of solution are 1:1；Being subsequently adding metallic sodium, 100-110 DEG C of reaction, metallic sodium is excessive, until Till metallic sodium no longer reacts；During course of reaction, the chlorosilane graft in the carbon fiber of chlorosilane will be with ethylene methacrylic Base chlorosilane carries out polyreaction, and chlorine is removed.
The preparation method of a kind of oxidation resistant carbon Fibrous insulation the most as claimed in claim 4, its step 4 (5) described in feature In needling density control at 1/50-1/250, i.e. its fiber orientation anisotropy X-Y plane and Z-direction fiber portion rate is 50- 250:1, the THICKNESS CONTROL of Nomex is at 10 mm ± 1mm, and the surface density of Nomex is 400 g/m2-900 g/m2。
The preparation method of a kind of oxidation resistant carbon Fibrous insulation the most as claimed in claim 4, its step 4 (6) described in feature In high temperature sintering condition be: under 10-1000Pa pressure, with heat up per hour 40-70 DEG C to 400 DEG C, rise the most per hour Temperature 20-40 DEG C to 700 DEG C, 700 DEG C are incubated 2-3 hour, and intensification the most per hour 20-40 DEG C to 1000 DEG C is incubated 1-2 hour, Intensification per hour 20-40 DEG C to 1200 DEG C, is incubated 1-2 hour, and coming out of the stove after Temperature fall to room temperature, it is fine to obtain oxidation resistant carbon Dimension heat insulation felt.
CN201610514672.3A 2016-07-04 2016-07-04 Preparation method of antioxidant carbon fiber heat insulation felt Pending CN105951301A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610514672.3A CN105951301A (en) 2016-07-04 2016-07-04 Preparation method of antioxidant carbon fiber heat insulation felt

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610514672.3A CN105951301A (en) 2016-07-04 2016-07-04 Preparation method of antioxidant carbon fiber heat insulation felt

Publications (1)

Publication Number Publication Date
CN105951301A true CN105951301A (en) 2016-09-21

Family

ID=56903266

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610514672.3A Pending CN105951301A (en) 2016-07-04 2016-07-04 Preparation method of antioxidant carbon fiber heat insulation felt

Country Status (1)

Country Link
CN (1) CN105951301A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110820323A (en) * 2019-10-31 2020-02-21 哈尔滨工业大学 Preparation method of Si-C-O ceramic antioxidant coating on surface of carbon fiber
CN110944963A (en) * 2017-06-13 2020-03-31 赛峰集团陶瓷 Method for manufacturing composite part
CN111925206A (en) * 2020-07-01 2020-11-13 安徽锦华氧化锌有限公司 Preparation method of lightning arrester zinc oxide pressure-sensitive valve plate ceramic precursor
CN113121775A (en) * 2021-04-13 2021-07-16 陈小龙 High-temperature-resistant light high-strength heat-insulating material and preparation method thereof
CN113149716A (en) * 2021-03-25 2021-07-23 哈尔滨工业大学 Integral modification treatment method for high-porosity carbon fiber framework connecting material
CN115976880A (en) * 2022-12-23 2023-04-18 航天特种材料及工艺技术研究所 High-temperature-resistant antioxidant electromagnetic film and preparation method thereof
CN116178873A (en) * 2023-03-06 2023-05-30 国网四川省电力公司电力科学研究院 Silane crosslinked flame-retardant insulating material for overhead insulated conductor, production process and application

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101899748A (en) * 2010-05-28 2010-12-01 上海麦戈士科贸有限公司 High-temperature resistant carbon fiber heat insulation felt
JP2013144859A (en) * 2012-01-16 2013-07-25 Osaka Gas Chem Kk Method for producing carbon fiber felt
CN103266470A (en) * 2013-05-17 2013-08-28 东南大学 Carbon fiber antioxidation coating and preparation method thereof
CN103774435A (en) * 2012-10-18 2014-05-07 甘肃郝氏炭纤维有限公司 Preparation and application methods of carbon fiber mat surface antioxidation coating
JP2014167173A (en) * 2013-02-28 2014-09-11 Toray Ind Inc Method for manufacturing carbon fiber nonwoven fabric and nonwoven fabric
CN104230368A (en) * 2014-09-26 2014-12-24 辽宁奥亿达新材料有限公司 Pitch-based carbon fiber nonwoven felt insulation board and manufacturing method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101899748A (en) * 2010-05-28 2010-12-01 上海麦戈士科贸有限公司 High-temperature resistant carbon fiber heat insulation felt
JP2013144859A (en) * 2012-01-16 2013-07-25 Osaka Gas Chem Kk Method for producing carbon fiber felt
CN103774435A (en) * 2012-10-18 2014-05-07 甘肃郝氏炭纤维有限公司 Preparation and application methods of carbon fiber mat surface antioxidation coating
JP2014167173A (en) * 2013-02-28 2014-09-11 Toray Ind Inc Method for manufacturing carbon fiber nonwoven fabric and nonwoven fabric
CN103266470A (en) * 2013-05-17 2013-08-28 东南大学 Carbon fiber antioxidation coating and preparation method thereof
CN104230368A (en) * 2014-09-26 2014-12-24 辽宁奥亿达新材料有限公司 Pitch-based carbon fiber nonwoven felt insulation board and manufacturing method thereof

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7068352B2 (en) 2017-06-13 2022-05-16 サフラン・セラミックス Methods for manufacturing composite parts
CN110944963A (en) * 2017-06-13 2020-03-31 赛峰集团陶瓷 Method for manufacturing composite part
JP2020523275A (en) * 2017-06-13 2020-08-06 サフラン・セラミックス Method for manufacturing composite parts
US10882795B2 (en) 2017-06-13 2021-01-05 Safran Ceramics Process for manufacturing a composite part
CN110944963B (en) * 2017-06-13 2021-04-13 赛峰集团陶瓷 Method for manufacturing composite part
EP3638640B1 (en) * 2017-06-13 2021-05-19 Safran Ceramics Process for manufacturing a composite part
CN110820323A (en) * 2019-10-31 2020-02-21 哈尔滨工业大学 Preparation method of Si-C-O ceramic antioxidant coating on surface of carbon fiber
CN110820323B (en) * 2019-10-31 2022-08-09 哈尔滨工业大学 Preparation method of Si-C-O ceramic antioxidant coating on surface of carbon fiber
CN111925206A (en) * 2020-07-01 2020-11-13 安徽锦华氧化锌有限公司 Preparation method of lightning arrester zinc oxide pressure-sensitive valve plate ceramic precursor
CN111925206B (en) * 2020-07-01 2022-05-03 安徽锦华氧化锌有限公司 Preparation method of lightning arrester zinc oxide pressure-sensitive valve plate ceramic precursor
CN113149716A (en) * 2021-03-25 2021-07-23 哈尔滨工业大学 Integral modification treatment method for high-porosity carbon fiber framework connecting material
CN113121775A (en) * 2021-04-13 2021-07-16 陈小龙 High-temperature-resistant light high-strength heat-insulating material and preparation method thereof
CN113121775B (en) * 2021-04-13 2022-12-16 浙江鹏飞绝热安装有限公司 High-temperature-resistant light high-strength heat-insulating material and preparation method thereof
CN115976880A (en) * 2022-12-23 2023-04-18 航天特种材料及工艺技术研究所 High-temperature-resistant antioxidant electromagnetic film and preparation method thereof
CN116178873A (en) * 2023-03-06 2023-05-30 国网四川省电力公司电力科学研究院 Silane crosslinked flame-retardant insulating material for overhead insulated conductor, production process and application

Similar Documents

Publication Publication Date Title
CN105951301A (en) Preparation method of antioxidant carbon fiber heat insulation felt
KR101810238B1 (en) A method for coating oxidation protective layer for carbon/carbon composite, a carbon heater, and cooker
CN109053207A (en) A kind of modified silicon carbide fiber reinforced silicon carbide composite material and preparation method of yttrium silicate
CN103724042B (en) A kind of lamination mixes the preparation method of solar heat protection sandwich
CN104671815B (en) ZrC-TiC modified C/C-SiC composite material and preparation method thereof
CN106083114A (en) A kind of C/C ZrC SiC ceramic based composites brake disc and preparation method thereof
CN106116626A (en) A kind of preparation method of oxidation resistant carbon carbon composite heat-insulated material
CN112374917B (en) High-temperature ceramic coating and preparation method thereof
CN102795871A (en) Method for quickly preparing C/SiC ceramic matrix composite material
CN108264352B (en) Method for preparing Si-C-O ceramic fiber by organic silicon resin conversion
CN103046166A (en) Chemical gas-phase crosslinking method of polycarbosilane fibers
CN102659442A (en) Preparation method for oxide fiber toughened silicon dioxide ceramic-based composite material gap interface
CN112028657A (en) Preparation method of carbon/carbon composite material crucible
CN108129156A (en) A kind of carbon ceramic composite material and its precursor impregnation preparation method
CN103614858A (en) Micron silicon-carbide fibrofelt and production method thereof
CN106192078A (en) A kind of air curing is used to carry out method prepared by low oxygen content continuous SiC fiber
CN109402786A (en) Preparation method of near-stoichiometric SiC fibers
KR101266074B1 (en) Manufacturing method of preform for silicon carbide fiber composite
EP0448236B1 (en) Curing preceramic polymers by exposure to nitrogen dioxide
CN110105070A (en) Continuous silicon carbide fiber with controllable electrical property and wide range and preparation method thereof
JP2017071535A (en) METHOD FOR PRODUCING SiC/SiC COMPOSITE MATERIAL
Chang et al. Synthesis and Characterization of Carbon Fiber‐Reinforced Silicon Carbide Composites with an Interlayer of Amorphous Carbon Thin Film Prepared by Precursor Infiltration and Pyrolysis Processes
CN106478120B (en) A kind of preparation method of the modified C/C composite material of binary ceramic
CN108996924A (en) A kind of kiln high temperature resistant fire door curtain fiber
Xia et al. Rapid Densification of Carbon/Carbon Composites Plate by Pressure‐Gradient Chemical Vapor Infiltration

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20160921