CN109312496A - 制造柔性陶瓷纤维和聚合物复合材料的方法 - Google Patents

制造柔性陶瓷纤维和聚合物复合材料的方法 Download PDF

Info

Publication number
CN109312496A
CN109312496A CN201780037100.3A CN201780037100A CN109312496A CN 109312496 A CN109312496 A CN 109312496A CN 201780037100 A CN201780037100 A CN 201780037100A CN 109312496 A CN109312496 A CN 109312496A
Authority
CN
China
Prior art keywords
polymer
ceramic
flexible
composite
composite material
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
CN201780037100.3A
Other languages
English (en)
Inventor
G·卡达法尔克加斯奎兹
R·B·埃斯皮诺萨
J·E·T·埃尔肖夫
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.)
Youruijit Holdings Co Ltd
Original Assignee
Youruijit Holdings 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 Youruijit Holdings Co Ltd filed Critical Youruijit Holdings Co Ltd
Publication of CN109312496A publication Critical patent/CN109312496A/zh
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/22—Component parts, details or accessories; Auxiliary operations
    • B29C39/38—Heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
    • C04B35/62236—Fibres based on aluminium oxide
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
    • C04B35/6224—Fibres based on silica
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
    • C04B35/6225—Fibres based on zirconium oxide, e.g. zirconates such as PZT
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
    • C04B35/62259—Fibres based on titanium oxide
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
    • C04B35/62231—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on oxide ceramics
    • C04B35/62263—Fibres based on magnesium oxide
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/6269—Curing of mixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62844—Coating fibres
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63408—Polyalkenes
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63444—Nitrogen-containing polymers, e.g. polyacrylamides, polyacrylonitriles, polyvinylpyrrolidone [PVP], polyethylenimine [PEI]
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63452—Polyepoxides
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63456—Polyurethanes; Polyisocyanates
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/6346—Polyesters
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63468—Polyamides
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63472—Condensation polymers of aldehydes or ketones
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63472—Condensation polymers of aldehydes or ketones
    • C04B35/63484—Urea-formaldehyde condensation polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/638—Removal thereof
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/248—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using pre-treated fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/10—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material by decomposition of organic substances
    • 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
    • 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
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0393—Flexible materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
    • B29K2105/122—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles microfibres or nanofibers
    • B29K2105/124—Nanofibers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2309/00—Use of inorganic materials not provided for in groups B29K2303/00 - B29K2307/00, as reinforcement
    • B29K2309/02—Ceramics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • 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
    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • 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
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C04B2235/3246—Stabilised zirconias, e.g. YSZ or cerium stabilised zirconia
    • 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
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
    • 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
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/5252—Fibers having a specific pre-form
    • C04B2235/5256—Two-dimensional, e.g. woven structures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/526—Fibers characterised by the length of the fibers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/5264—Fibers characterised by the diameter of the fibers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
    • C04B2235/781—Nanograined materials, i.e. having grain sizes below 100 nm
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/963—Surface properties, e.g. surface roughness
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/02—Inorganic fibres based on oxides or oxide ceramics, e.g. silicates
    • D10B2101/08—Ceramic

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Composite Materials (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Nonwoven Fabrics (AREA)
  • Inorganic Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本申请公开并要求保护制造柔性陶瓷纤维(FlexiramicsTM)和聚合物复合材料的方法。当与FlexiramicsTM和单独的纳米纤维分别对比时所得的复合材料具有改进的机械强度(拉伸)。此外复合材料比单独的聚合物具有更好的性质，例如更低的阻燃性、更高的热传导率和更低的热膨胀。可使用若干不同的聚合物(热固性材料和热塑性材料两种)。FlexiramicsTM具有独特的物理特性并且可将复合材料用于许多工业和实验室应用。

Description

制造柔性陶瓷纤维和聚合物复合材料的方法
相关申请的交叉引用：无
关于联邦政府资助的研究与开发的声明：不适用
联合研究协议缔约方的名称：不适用
在光盘上提交的材料通过引用并入：不适用
发明背景
发明领域
本发明总体上涉及复合材料。更特别地，本发明属于柔性陶瓷纤维尤其是纳米纤维，和它们形成复合材料的用途及其制造方法。甚至更具体地，本发明涉及使用电纺丝、压纺(forcespinning)和吹纺(blowspinning)方法制造包含柔性陶瓷微米和纳米纤维和聚合物的复合材料。
包括在37 CFR 1.97和37 CFR 1.98下所公开信息的相关技术的描述
与本发明相关技术的以下描述涉及多个出版物和引用文献。本文给出对这样的出版物的讨论以提供与本发明相关原理的更完整的背景，并且不应被解释为承认这样的出版物必然是用于专利性确定目的的现有技术。
复合材料是由两种或更多种成分材料制成的材料，所述成分材料具有显著不同的物理或化学性质，在组合时产生具有与所述成分材料不同特性的所得的“复合的”材料。制造复合材料的目标通常是获得当与成分材料对比时具有某种增强性质或特性的材料。
现有技术揭示了陶瓷和聚合物复合材料的多个实例，其包括不同组合比率的陶瓷和聚合物。在那些复合材料实例中使用的陶瓷材料包括但不限于：氧化铝、二氧化硅、氧化锆、钇稳定的氧化锆、二氧化钛、和碳化钛。在那些复合材料实例中使用的聚合物材料包括但不限于聚乙烯醇、聚甲基丙烯酸甲酯和聚二甲基硅氧烷。
电纺丝工艺由以下组成：通过高电场驱动聚合物溶液喷射流，使中尺度流体喷射流成为纳米尺度纤维。电纺丝工艺作为制造“细”纤维的方法追溯至Morton(美国专利号705,691)和Cooley(美国专利号692,631)20世纪初的工作。目前的技术限制破坏了Morton和Cooley的专利(其在1939年由Formhals(美国专利号2,158,416)改善)。因此，由Morton、Cooley和Fromhals开发的方法没有教导制造纳米纤维的方式。
在1995年，Soshi和Reneker通过使用当时可用的扫描电子显微镜(“SEM”)技术从而导致制备了纳米纤维再次提出了电纺丝工艺(如今天我们所知的)。此外，Soshi和Reneker在如结构、纺织、膜和生物医学工程等众多领域中确定了电纺纳米纤维的众多应用。(参见Sakar等，Materials Today，第13卷，第11号，2010年)。
几十年前第一次报道了用电纺丝制造的聚合物微米和纳米纤维。然而，在相对最近的2003年制备了由电纺丝制造的第一个陶瓷纳米纤维。但是，那些纳米纤维不是柔性的。甚至更最近地大约从2006年开始先前报道了包含电纺纳米纤维的柔性陶瓷材料(参见Reneker等的美国专利公开号2006/034948)。
更最近地，已经开发了从广泛的材料制造纳米纤维的方法。该方法已知为压纺。压纺使用离心力而不是静电力来纺丝纳米纤维、纳米线或纳米棒。使用压纺制备纤维(更具体地纳米纤维)的实例公开于JPS 6 125 807 B2中。压纺作为电纺丝的更快且更便宜的替代出现。可使用压纺制造陶瓷纳米纤维。制造聚合物和陶瓷的微米和纳米纤维的另一个方法是Medeiros的美国专利号8,641,960中公开且要求保护的吹纺。吹纺使用压缩空气来将溶液纺成纳米纤维。然而，申请人没有找到使用压纺或吹纺制造柔性陶瓷的现有技术实例。
尽管如此，存在通过使用非常薄的沉积物或陶瓷材料的生长制造其他小厚度柔性陶瓷的现有技术实例(参见http://www.enrg-inc.com和http://www.camnano.com)。自从2014年已知“通过溶液吹出工艺制造ZrO2陶瓷纤维垫”(由Bowen Chlang等出版的CeramicsInternational 40(2014))。
本申请中所实现发明的主要目的之一是使用电纺丝、吹纺或压纺提供独立的柔性且连续的陶瓷膜(还被称作样品)。为本申请主题的材料将在下文中被称作FlexiramicsTM，即陶瓷纳米纤维和柔性垫或膜，或通常使用这些陶瓷纳米纤维的柔性样品。一般地，陶瓷的电纺丝产生陶瓷微米和纳米纤维的刚性非织造垫。那些垫不是连续的和片状的。另外，需要充当机械支撑的基材。本发明克服了现有技术的所有那些缺点。
发明概述
因为它的物理和化学性质，独立的柔性且连续的表面陶瓷膜和使用本申请中所实现发明的膜的复合材料满足或超过对于许多实际的工业和商业用途而言的要求。
例如本文所述和要求保护的材料可用于：(1)代替目前使用的柔性印刷电路板基材，其通常使用聚酰亚胺(PI)制成；和(2)代替用于线缆绝缘的一些聚合物保护层(具有氢氧化铝填料的聚乙烯)。
正常地，申请人研究采用0％至50％，尤其是12％氧化钇稳定的氧化锆。即，前体溶液含有比率为88:12(二氧化锆重量：钇重量)的作为金属性离子的二氧化锆(Zr4+)和钇(y3 +)作为其组分中的至少两种。然而，申请人发现了若干金属氧化物(包括但不限于氧化铝、二氧化硅和二氧化钛、氧化锌、氧化镁和钙钛矿)的薄层还可形成基底以制备柔性非织造独立的陶瓷纤维垫。
膜复合材料或通常由陶瓷纳米纤维制成的本发明的样品可弯曲至如图6D中所示接近0°的弯曲半径。实验数据显示本发明的材料可经历疲劳测试，其中可在如图2中所示的3-点弯曲测试中将其弯曲45°并返回至扁平。此外，本发明的材料可经受超过2000次疲劳循环，由此该材料退化但其未断裂。
发明一般描述
本发明描述与原始材料对比具有增强性质的复合材料的制造。所述复合材料由陶瓷微米和纳米纤维(以下简称为陶瓷纳米纤维)和聚合物组成。聚合物/陶瓷比率范围为从>0％至<100％。本发明涉及制备根据权利要求1的柔性陶瓷纳米纤维以及使用该柔性陶瓷纳米纤维的复合材料或膜或通常地样品。在后一种情况下，柔性陶瓷纳米纤维形成如在权利要求5ff中所述的柔性陶瓷复合材料。
为了制备陶瓷纳米纤维，通过准备根据权利要求1中a的前体溶液开始制造工艺。该溶液包含所溶解金属的前体和提高该溶液黏度的聚合物。为了溶解金属，例如甲苯或己烷的溶剂由于在室温下它们的挥发性特性是适合的。前体溶液(溶剂加金属加聚合物)中固体含量(聚合物和前体)必须大于5重量％以便得到细的沉积物。溶液(聚合物加金属的前体/金属加溶剂)的(动力学)黏度在0.01s-1至1s-1的剪切速率下、优选地在0.1s-1的剪切速率下必须保持在0.01和5000帕斯卡-秒(Pa·s)之间，以便能够纺丝合适的纤维(对比权利要求1中的c)。例如采用公开于US 8 881 577 B1中的方法和系统测量黏度和剪切速率。
纺成纤维的直径取决于前体和聚合物含量。即，可通过提高溶液中聚合物和/或金属的前体含量来提高纤维直径。
根据权利要求1所施加工序的第二阶段是纺丝工艺，其可优选为压纺或电纺丝。吹纺也是可能的。纺丝工艺的参数例如所用针头的直径、距多孔收集器的距离和溶液的注射速率(对比已经提到的出版物“制造ZrO2陶瓷纤维垫…”)对纺成纤维的柔性没有大的影响。因此设定它们以得到根据权利要求1中d的连续的膜或垫或通常聚合物纤维的连续样品(纤维离开用于注射溶液的电纺丝针头)。
最后的步骤是根据权利要求1中e、f、g和h的退火。这一阶段是必要的因为离开根据权利要求1中d的纺丝工艺的纤维还不是陶瓷纤维。由退火时的热处理所致，烧光了聚合物纤维的所有有机组分。此外温度处理使金属离子氧化以形成陶瓷。如图3中所示温度分布随时间优选是梯形形状。随着高至几百℃固定值的提高的温度，退火的第一阶段工作。退火温度需要大于金属离子的结晶点以形成陶瓷。保持退火温度恒定持续直至若干小时(根据权利要求1中h的停留时间)。此后使纤维冷却。根据图4从1℃/min直至5℃/min并最终直至热冲击，即通过热对流(热对流烘箱)或在微波炉(MW)中从室温(RT)至退火温度(RTA)变化加热和冷却速率。由于如图3中所示在退火过程中优化的梯形形状温度分布，可通过如图4中所示实例的方式设定晶体尺寸为10nm直至25nm。
值得注意的是梯形形状温度分布仅是一种优选可能性。因为加热和冷却速率可含有一些平台。例如可以以5℃/min加热直至达到150℃。然后保持该温度15min。此后，以1℃/min的加热速率将温度提高至250℃，保持1h并然后以5℃/min提高直至达到最终温度。
陶瓷纳米纤维的光滑度取决于如图7中所示退火参数，其导致在实例中0.3nm直至0.8nm的值。光滑度对应于均方根粗糙度Rq并且其取决于加热/冷却速率以及方法(对流/微波)。如所期待的，晶体尺寸随提高的加热/冷却速率而降低，并因此光滑度相应地降低。
根据本发明的第二方法使用纺成(非织造)陶瓷纳米纤维作为柔性陶瓷填料或通常地由根据独立权利要求5和6的纳米纤维制成的陶瓷样品(膜或垫)。该样品即所得非织造垫示于图5中。由根据权利要求5中a至e和权利要求7中a至c的聚合物溶液浸透陶瓷样品，导致由样品和聚合物制成的复合材料，其中用聚合物单独涂覆陶瓷纳米纤维。权利要求6描述了制造对应的致密复合材料的方法。因此权利要求6中步骤a至c描述复合材料的热固化。形成膜的复合物或复合材料可弯曲至接近0°的弯曲半径，即如图6A至6D中所示膜的相对端可一起弯曲，其中所述端相互靠近。
以下详细描述主要集中在权利要求5ff和对应的实例。在这些权利要求中详细地描述了由具有聚合物的陶瓷纳米纤维制备的样品制成的复合材料。可使用陶瓷纳米纤维和通常地热塑性材料作为聚合物来制备复合材料。如果热塑性材料是熔融的，可实现致密的复合材料。然而，可通过用溶剂稀释聚合物来实现致密的或单个纳米纤维涂覆的复合材料。还可由热固性材料制成复合材料，其需要固化温度。取决于添加至热固性材料的溶剂的量，也可获得致密的或单个纤维涂覆的复合材料。
发明详细描述
将结合附图在接下来的详细描述中部分地阐述本发明的目的、优点和新颖特征以及进一步的适用范围。本发明的目的、优点和新颖特征以及进一步的适用范围对在研究以下内容后的本领域技术人员将是显而易见的，或者可通过本发明的实践了解本发明的目的、优点和新颖特征以及进一步的适用范围。可通过所附权利要求中特别指出的手段和组合实现和获得本发明的目的和优点。
本申请中所实施的发明的主要目的是制造FlexiramicsTM用于通过添加陶瓷纳米纤维制备具有若干聚合物以提高聚合物性质的复合材料。除此之外，复合材料具有比FlexiramicsTM更高的机械强度(拉伸强度)。聚合物可为热固性材料(需要固化温度来产生完全的聚合物交联，其通常在20℃和300℃之间)或热塑性材料(需要熔融温度来使聚合物软化并成为流体，其通常在100℃和400℃之间)。热塑性材料也可像热固性材料一样溶解。因此不仅需要熔融温度。
具体地，申请人已经使用了聚二甲基硅氧烷(PDMS)作为聚合物来制造复合材料。申请人制备了PDMS/陶瓷纳米纤维复合材料，其中陶瓷/最终产物的总重量的重量比率范围为0.1至99.9％。申请人通过使用稀释的PDMS前体溶液实现了高的比率。溶液中稀释百分数通常范围为从70％至90％。即最终溶液含有10％至30％体积百分数的聚合物和70％至90％体积百分数的溶剂。用于稀释PDMS前体的优选溶剂是甲苯和己烷。所得稀释溶液的黏度通常在80至200毫帕斯卡每秒(mPa·s)之间。
通常，为了实现该期望的黏度范围，需要在60℃下预交联。由溶液的低黏度所致，可通过优选在如权利要求5所述在平且刚性的表面上延伸的样品(即陶瓷纳米纤维)上方施加溶液从而容易浸透陶瓷纳米纤维。这可使用流延刀(casting knife)或喷涂枪来实现。由毛细作用和重力所致，陶瓷纳米纤维被溶液完全浸透。
接下来，通过将样品(即用PDMS前体溶液浸透的陶瓷纳米纤维)放置在60℃和90℃之间温度下的烘箱中使聚合物热固化。可在低至20℃的温度下实现固化步骤，其唯一的影响是更长的固化时间。由于申请人在每个单独的陶瓷纳米纤维上施加PDMS作为薄涂层的事实，所得复合材料(用聚合物浸透的陶瓷纳米纤维样品)维持期望的纤维结构。在本发明的优选实施方案中，该涂层在几十至几百纳米的范围内。
申请人通过将陶瓷纤维嵌入未稀释的PDMS前体溶液中实现了期望的低陶瓷纳米纤维/总重量比率。未稀释的PDMS前体溶液优选黏度范围在1000至150000(mPa·s)之间、优选地1500和15000(mPa·s)之间。申请人然后将未稀释的溶液流延在平且刚性的表面上，采用如权利要求6中所述在0.1至5.0毫米(mm)之间的优选厚度。
接下来，在流延的溶液上面沉积陶瓷纳米纤维，如此通过毛细作用力使溶液渗透整个样品(即整个陶瓷纳米纤维)。
接下来，通过将样品放置在60℃和90℃之间温度下的烘箱中使样品热固化。固化时间与固化温度成反比。例如，在60℃下固化时间为一个(1)小时。
固化的样品包含在一侧上的厚的PDMS层(在0.1至5.0mm之间)和在另一侧上的几微米的薄的PDMS层，其通常为从1μm至5mm。固化的复合材料还可包含在一侧或两侧的典型厚度为1μm至5mm的PDMS层。如果流延厚度正好含有渗入陶瓷纳米纤维的PDMS的精确量，没有一侧包含PDMS层也是可能的。
在本发明的替代实施方案中，申请人通过在已有的PDMS层上面流延额外的PDMS前体溶液层制备了在复合材料的两侧上具有较厚的PDMS层的复合材料。申请人可通过改变PDMS前体溶液的黏度来容易地控制该层的厚度。为了提高PDMS前体溶液的黏度，可在适中的温度下(在30℃至60℃之间)进行短的热处理。或者，申请人可通过将少量的甲苯或己烷(1％至99体积％)与PDMS前体溶液混合来降低PDMS的黏度。
在本发明的又一个替代实施方案中，使用聚乙烯(PE)来制备具有陶瓷纳米纤维的复合材料。在该实施方案中，在大于其135℃熔点的温度下使PE熔融。然后将熔融的PE施加在陶瓷纳米纤维上面，施加对于PE完整的嵌入至陶瓷纳米纤维上而言充分的压力(通常在1至10千牛顿之间)。这是使用热压熔融设备完成的，其导致施加充分的压力。然后使复合材料冷却降至室温，导致在复合材料表面上不同的PE厚度(范围从0.1至5.0mm)。之前校准PE的量导致能够控制PE层的厚度。因此，可实现大范围的PE/陶瓷纳米纤维/总重量比率。
可通过在沉积第一PE层之后双侧涂覆来实现本发明的另一个实施方案。可通过调节喷枪设备的狭缝模头的开口并通过提高或降低用于使聚合物熔融的温度操纵熔融PE的黏度从而控制新的PE层的厚度。这些控制步骤导致可取决于应用而预测性改变的大范围的PE/陶瓷纳米纤维比率。
本发明的另一个实施方案包括使用聚氨酯(PUR)用于制造复合材料。在该实施方案中，在大于200℃温度下熔融PUR前体。然后使用具有狭缝模头的喷枪设备将熔融的PUR前体施加在陶瓷纳米纤维上面(或底部)。接下来，在大约100℃下的烘箱内热固化所得的PUR前体/陶瓷纳米纤维样品。所得的复合材料实施方案具有厚度范围通常从1μm至几个mm、优选从0.1mm至5.0mm。
可通过使用聚酰亚胺(PI)作为聚合物材料用于制造具有陶瓷纳米纤维的复合材料来获得本发明的另一个实施方案。为了获得本发明的该实施方案，申请人在N-甲基-2-吡咯烷酮(NMP)中溶解聚酰胺酸，产生具有1000至10000mPa·s的典型黏度的PI前体溶液。为了获得前体溶液的替代实施方案，申请人使用例如NMP和γ-丁内酯的溶剂。然后将溶液流延在平且固体平面上并在上面沉积陶瓷纳米纤维，如此通过毛细作用力使溶液渗透整个样品(即陶瓷纳米纤维)。接下来，通常在80℃下干燥样品(即用PI前体溶液浸透的陶瓷纳米纤维)1h并然后通过使用热板或炉施加通常最高至300℃的热通常持续30分钟从而将其热干燥。在使复合材料冷却时，在陶瓷纳米纤维的两侧上存在聚酰亚胺膜，通常范围从1至100μm。可通过流延较薄或较厚的PI前体溶液膜改变或抑制该厚度。
可使用具有狭缝模头的喷枪以及其他技术例如刮板或流延刀执行本发明的方法。所得的复合材料是致密的但是可通过用较高量溶剂稀释聚酰胺酸对应的PI从而维持陶瓷纳米纤维的纤维结构以便使黏度降低至例如50至300mPa·s的范围。然后，可用如对于PDMS而言上述薄的聚酰亚胺涂层单独涂覆陶瓷纳米纤维。
还可用不同的聚合物(热塑性材料或热固性材料)例如权利要求3中提及的聚丙烯(PP)、聚醚醚酮(PEEK)、聚乙烯亚胺(PEI)、氰酸酯、环氧树脂、聚酯、乙烯基酯、脲甲醛、烯丙基类、聚邻苯二甲酰胺(PPA)、聚苯硫醚(PPS)和聚四氟乙烯(PTFE)和聚苯并咪唑(PBI)制备这些复合材料。所应用的技术将与之前的一样，即喷涂、具有狭缝模头的喷枪、刮板、流延刀和热压熔融。
这种复合材料保持它们的柔性并且可弯曲至非常低的弯曲半径而没有断裂或损坏，即使当最终产物中聚合物含量甚至没有超过5％(依照重量)。此外，这些复合材料与聚合物本身对比呈现出热性质的大幅增强。例如，当暴露于甲烷火焰时用PDMS制成的复合材料比独立的PDMS箔(具有相同厚度)着火慢两倍。用PE制成的复合材料可甚至比具有相同厚度的独立的PE阻止火焰大至少两倍且最高至一个数量级。此外，当复合材料燃烧时，没有任何部分滴下，其防止火蔓延。相反，形成了保护壳。说明用聚酰亚胺制备的复合材料的优异热性质的另一个实例是当最终产物中陶瓷含量通常为25％(依据重量)时其可抵抗住暴露在高达500℃的温度下而没有失去柔性和平整性。相反，具有相同厚度的独立的聚酰亚胺膜在大约300℃或更高的温度下开始收缩，因为超过了聚酰亚胺的玻璃化转变。大体上，可使用陶瓷纳米纤维来产生具有较高热耐久性和较好阻燃性质的可弯曲的复合材料。陶瓷/最终产物总重量的比率的范围可从非常低(其为具有非常低陶瓷纤维含量的致密聚合物膜)至非常高(其为具有用聚合物单独涂覆的陶瓷纤维的多孔膜(非织造))。
本发明的陶瓷纳米纤维在宏观尺度(作为垫)且在单个纤维尺度是柔性的。本发明材料的机械性质可归于以下若干因素：
·包含范围在20-10000nm之间的纤维直径的细长形状，如此允许可弯曲性；
·纤维长度可测量多达4cm，然而，假设它们是更长的；
·较小晶粒具有的范围从1至100nm的小晶体尺寸，允许提高的延性；
·范围在0.05和5nm均方根粗糙度(Rq)之间的纤维光滑度；和
·在本发明材料的非织造垫形式中纤维彼此没有物理连接，其使纤维自由移动并在宏观尺度具有更可弯曲的材料。
包含非织造陶瓷微米和纳米纤维(FlexiramicsTM)和聚酰亚胺的本发明的复合材料呈现优化的热稳定性。在暴露在高达400℃至500℃的温度下时，即暴露若干分钟，复合材料没有收缩或损失柔性，并因此提高其可使用的温度界限。此外，该材料轻并具有低密度(10-40g/m3)。
包含Flexiramic和聚乙烯的本发明的复合材料呈现优化的阻燃性质。申请人发现了与用于类似目的的现有技术的材料对比时，材料开始着火至少需要两倍的时间。此外，一旦本发明的材料开始燃烧，因为形成了所煅烧材料的壳并保持在纤维上，所以没有部分滴下并且火可被包含。该壳还防止火焰通过材料传播。
本发明优选实施方案的描述
本发明优选实施方案描述了陶瓷纳米纤维的制备。方法包括以下步骤：
1.制备前体溶液，该前体溶液包含将形成最终金属氧化物(陶瓷)的无机聚合物(溶胶)或金属性离子，以及提高黏度的聚合物。
a.可使用溶胶-凝胶参数以提高溶液的黏度，但是溶胶-凝胶不是完全必要的，因为还可通过使用添加剂改变黏度。
b.可通过提高聚合物含量和/或前体含量实现较大的纤维直径。这必须调整以实现期望的纤维直径。
c.材料的黏度必须在优选0.1s-1的剪切速率下保持在0.01和1000帕斯卡秒(Pa-s)之间以便纺丝可用的纤维。
d.固体含量(聚合物加前体)必须大于5％(依据重量)以便获得需要的沉积物。
e.必须仔细选择所利用的溶剂以便提供足够高的蒸发速率。这可通过但不限于将水与酒精混合(因为酒精提高蒸发速率)来完成。
2.通过使用压纺或电纺丝或吹纺纺丝前体溶液。
a.纺丝参数对所得聚合物纤维的柔性具有很小影响或没有影响。
b.相反，可调整纺丝参数使得纺丝步骤可导致连续的膜或聚合物纤维。这必须适应于每种不同的溶液。
3.退火从纺丝工艺获得的纤维，其在纺丝之后不是陶瓷。相反，纺成纤维是包含离子金属或无机聚合物的聚合物纤维。
a.退火纤维直至烧光所有的有机内容物并且金属离子氧化以形成陶瓷。
b.如图3中所示产生典型的热分布，其中优选的梯形形状热分布表现出包含加热/冷却速率、退火温度和停留时间的退火工艺参数。必须注意必要的调整该分布以获得以上呈现的期望的结晶度。
c.退火工艺的参数对每种材料组成不同。例如，低至0.5℃/min、优选低至1℃/min，并和热冲击一样高(从室温至退火温度)的加热/冷却速率。
d.退火温度不得不大于结晶点，因此允许陶瓷材料的形成。
e.停留时间范围从0至5小时并甚至更高。
附图简要描述
结合至说明书中并形成说明书一部分的附图说明了本发明的实施方案，并且与描述一起用于解释本发明的原理。附图仅用于说明本发明的优选实施方案的目的，并且不应被解释为限制本发明。本发明的范围仅受限于所附权利要求中含有的具体限制。
简单草图使不必然熟悉本申请所属技术领域的技术人员获得对本发明的可视化理解。
图1：嵌入聚酰亚胺的Flexiramic的照片图，具有在一侧上的厚层(顶部)和在另一侧上的薄层(底部)。
图2：显示测量力与时间关系的陶瓷纳米纤维3点弯曲疲劳测试的图表。
图3：典型热分布，表现出包含加热/冷却速率、退火温度和停留时间的退火工艺参数。
图4：说明在退火步骤中YSZ(12％氧化钇稳定的氧化锆)纳米纤维的晶体尺寸依赖性的图表图。退火从对流烘箱变化至微波(MW)。加热和冷却速率范围从1℃/min至热冲击(RTA)。
图5：所形成的柔性YSZ非织造纤维垫的显微镜图片。
图6A至6D：所得柔性陶瓷YSZ材料(FlexiramicsTM)的照片图，清楚地显示材料的可弯曲性及其不可燃的纯陶瓷属性。
图7：说明YSZ纳米纤维的粗糙度对退火步骤依赖性的图表图。退火从对流烘箱变化至微波(MW)。加热和冷却速率范围从1℃/min至热冲击(RTA)。

Claims (13)

1.制造包含柔性陶瓷纳米纤维和聚合物的柔性复合材料的方法，该制造柔性陶瓷纳米纤维的方法包括以下步骤：
a.制备陶瓷纤维前体溶液，该前体溶液包含(i)选自金属性离子和含金属聚合物的用于陶瓷的溶解金属前体，其中该金属优选选自Si4+、Zr4+、Ti4+、Y3+、Al3+、Zn2+、Mg2+、Pb4+、Ni2+、Sr2+、Ca2+、La3+；(ii)提高该前体溶液的黏度的聚合物，其中该前体溶液的固体含量(聚合物加前体)为大于5重量％、优选15重量％，以便获得所需的沉积物，和(iii)溶剂，该溶剂能够提供产生足够高蒸发速率的前体溶液；
b.使该用于陶瓷的溶解金属前体形成还已知为陶瓷的最终金属氧化物；
c.在0.01至1s-1、优选地0.1s-1的剪切速率下维持该前体溶液的黏度在0.01和1000帕斯卡-秒(Pa·s)之间，优选在0.01和5000帕斯卡-秒(Pa·s)之间以便纺丝可用的纤维；
d.通过使用选自例如压纺、电纺丝和吹纺的纺丝工艺纺丝该前体溶液，其中纺丝参数是可调的使得纺丝步骤可导致聚合物纤维并且纺丝参数可适应于每种前体溶液；
e.退火由纺丝工艺获得的聚合物纤维，该聚合物纤维包含该用于陶瓷的金属前体，直至烧光所有的有机内容物并且金属性离子氧化以形成陶瓷；
f.调整和校准退火参数，该退火参数包含加热和冷却速率、退火温度和停留时间，其优选地与梯形形状的热分布一致，因此获得了所得的20至10000nm厚纤维的包括1至100nm的晶体尺寸的结晶度和0.05至5nm的Rq的光滑度，该退火参数对于每种材料组成是不同的和特定的；
g.设定该退火温度大于陶瓷纤维的结晶点，导致陶瓷材料的形成；和
h.设定停留时间为从0至5小时或甚至更多。
2.权利要求1的制造柔性复合材料的方法，其中该柔性陶瓷纳米纤维的组成优选选自以下：氧化钇稳定的氧化锆(具有钇重量：氧化锆重量高于0:100且低于50:100的重量比率)、氧化锆、二氧化钛、氧化铝、氧化锌、二氧化硅、氧化镁和钙钛矿例如锆钛酸铅(PZT)。
3.权利要求1至2的制造柔性复合材料的方法，其中该聚合物(热塑性或热固性)选自以下：聚二甲基硅氧烷(PDMS)、聚酰亚胺、聚丙烯(PP)、聚乙烯(PE)、聚醚醚酮(PEEK)、聚乙烯亚胺(PEI)、聚氨酯(PUR)、氰酸酯、环氧树脂、聚酯、乙烯基酯、脲甲醛、烯丙基类、聚邻苯二甲酰胺(PPA)和聚苯硫醚(PPS)、聚四氟乙烯(PTFE)、聚苯并咪唑(PBI)，且其中陶瓷含量在0.1至99.9％的陶瓷/总重量之间，导致复合材料保持接近0°弯曲半径的柔性。
4.权利要求1至3的制造柔性复合材料的方法，其中所得的柔性陶瓷纳米纤维包含范围在20和10000纳米之间的纤维直径，如此允许陶瓷纳米纤维的可弯曲性，可测量的多达至少4厘米的纤维长度，范围从1至100纳米的晶体尺寸，范围从0.05至5纳米Rq(均方根粗糙度)的纤维光滑度和以非织造垫形式设置的纤维，其中该纤维彼此没有物理连接，如此使纤维自由移动并在宏观尺度是极度可弯曲的。
5.权利要求1至4的制造包含柔性陶瓷纳米纤维和聚合物的柔性复合材料的方法，还包括以下步骤：
a.通过如下浸透柔性陶瓷纳米纤维样品：优选在平且刚性的表面上先前已经延伸的样品上面施加聚合物溶液；
b.通过毛细作用和重力使该陶瓷纳米纤维样品被聚合物溶液完全浸透；
c.通过将样品放置在范围在20℃和优选地60℃直至300℃之间温度下的烘箱中使陶瓷纳米纤维样品上方铺开的聚合物溶液热固化，注意到可在低至20℃的温度下实现该固化步骤，而唯一的影响是更长的固化时间；
d.通过在每个单独的陶瓷纳米纤维上施加聚合物作为薄涂层从而所得的固化样品能够维持期望的纤维结构，而该涂层在几十至几百纳米的优选范围内；
e.通过调整用于嵌入陶瓷纳米纤维的聚合物溶液的黏度来实现期望的聚合物/陶瓷纳米纤维比率。
6.权利要求1至5的制造柔性复合材料的方法，还包括：
a.将未稀释的或极少稀释的聚合物溶液在平且刚性的表面上流延在陶瓷纳米纤维上，具有在0.1至5.0毫米之间的优选厚度；
b.优选地在流延的溶液上面沉积陶瓷纳米纤维，如此通过毛细作用力使溶液渗透整个样品；和
c.通过将样品放置在20℃和300℃之间、优选地在20℃和60℃之间的温度下的烘箱中热固化所得的溶液渗透样品持续预定的固化时间，并且固化的样品包含具有范围从1μm至5mm典型厚度的在复合材料的一侧或两侧上的聚合物层；
d.实现没有孔隙的致密复合材料。
7.根据权利要求5或6的方法，对于单独涂覆的纳米纤维具有以下步骤：
a.在溶剂中溶解热塑性材料(塑料的少量稀释也可导致致密复合材料)；
b.浸透该柔性陶瓷纳米纤维和
c.提高温度以蒸发该溶剂，留下该聚合物作为陶瓷纳米纤维的薄涂层。
或对于致密复合材料具有以下步骤：
d.在陶瓷纳米纤维上面或底部使聚合物熔融；
e.优选地施加一些压力和/或温度用于聚合物更好地浸润在陶瓷纳米纤维基体中和
f.降低温度以使聚合物硬化。
8.权利要求5至7的制造柔性复合材料的方法，其中所得的复合材料包含大于0％且小于100％的陶瓷/总重量，其通过用具有在50至150000mPas之间黏度的聚合物溶液嵌入柔性陶瓷纳米纤维来实现，其中涂覆步骤选自通过毛细作用和/或重力浸透从而在平的基材上方流延聚合物溶液。
9.权利要求5至7的制造柔性复合材料的方法，其中所得的复合材料包含大于0％且小于100％的陶瓷/总重量，其通过可商购得到的流延装置在柔性陶瓷填料上面流延聚合物溶液从而允许通过毛细作用浸透来实现，所述可商购得到的流延装置选自配备有狭缝模头的喷枪、流延刀、喷涂枪和刮板。
10.权利要求5至9的制造柔性复合材料的方法，其中所得的复合材料包含大于0％且小于100％的陶瓷/总重量，其通过在热压熔融中采用范围在1和10千牛顿之间的典型压力压制和加热固体聚合物和陶瓷填料来实现。
11.权利要求5至10的制造柔性复合材料的方法，其中所得的复合材料包含大于0％且小于100％的陶瓷/总重量，其通过使用需要范围从20至300℃和优选地最高至500℃的固化温度的热固性材料和需要最高至700℃、优选地最高至400℃的熔融温度的热塑性材料来实现。
12.权利要求5至11的制造柔性复合材料的方法，其中可使用所得的复合材料来代替经常使用聚酰亚胺或具有低陶瓷填料的聚酰亚胺制成的目前使用的柔性印刷电路板基材。
13.权利要求5至12的制造柔性复合材料的方法，其中可使用所得的复合材料来代替用于线缆绝缘的聚合物保护层，例如聚乙烯。
CN201780037100.3A 2016-06-16 2017-06-16 制造柔性陶瓷纤维和聚合物复合材料的方法 Pending CN109312496A (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US15/184,905 US20170362740A1 (en) 2016-06-16 2016-06-16 Flexible ceramic fibers and polymer composite and method of making the same
US15/184,905 2016-06-16
PCT/EP2017/064819 WO2017216367A1 (en) 2016-06-16 2017-06-16 Method of making flexible ceramic fibers and polymer composite

Publications (1)

Publication Number Publication Date
CN109312496A true CN109312496A (zh) 2019-02-05

Family

ID=59067681

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201780037100.3A Pending CN109312496A (zh) 2016-06-16 2017-06-16 制造柔性陶瓷纤维和聚合物复合材料的方法

Country Status (6)

Country Link
US (2) US20170362740A1 (zh)
EP (1) EP3472377A1 (zh)
JP (1) JP6899895B2 (zh)
KR (1) KR102284001B1 (zh)
CN (1) CN109312496A (zh)
WO (1) WO2017216367A1 (zh)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110016723A (zh) * 2019-04-08 2019-07-16 深圳先进技术研究院 一种介电复合材料、其制备方法及平板型电容器
CN110042564A (zh) * 2019-04-18 2019-07-23 东华大学 一种辐射制冷纤维膜及其制备方法和应用
CN110359103B (zh) * 2019-07-10 2020-09-08 西安交通大学 一种基于步进拉伸法制备聚合物微纳米纤维的方法
CN112210848A (zh) * 2020-10-12 2021-01-12 中国人民解放军国防科技大学 一种多相SiZrOC微纳隔热纤维的制备方法
CN113737395A (zh) * 2021-08-06 2021-12-03 华南理工大学 一种柔性二氧化钛纳米纤维膜及其制备方法和应用
CN114334238A (zh) * 2021-12-31 2022-04-12 福建成田科技有限公司 双层共挤绝缘型b1级阻燃电缆
CN115474345A (zh) * 2022-09-14 2022-12-13 东华大学 基于丝网印刷和化学沉积的陶瓷织物电路制作方法

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11127664B2 (en) * 2011-10-31 2021-09-21 Unimicron Technology Corp. Circuit board and manufacturing method thereof
CN109251535A (zh) * 2018-09-19 2019-01-22 铜陵市铜都特种线缆有限公司 一种防水抗冻电缆护套
CN109385743A (zh) * 2018-09-21 2019-02-26 华中科技大学 一种无机纳米纤维网络的柔性化复合结构及制备方法
CN109888346A (zh) * 2019-02-18 2019-06-14 山东星火科学技术研究院 利用静电纺丝技术负载催化剂于膜纤维表面的燃料电池质子交换膜的制备方法
US10759697B1 (en) 2019-06-11 2020-09-01 MSB Global, Inc. Curable formulations for structural and non-structural applications
CN113493959B (zh) * 2020-04-05 2023-02-28 北京化工大学 一种表面包覆二氧化硅的聚酰亚胺纳米纤维膜
US20220228295A1 (en) * 2020-09-30 2022-07-21 National Technology & Engineering Solutions Of Sandia, Llc Synthesis of Refractory Transition Metal-Carbide Fibers
CN112295315A (zh) * 2020-10-27 2021-02-02 安徽中电环保材料股份有限公司 一种抗形变pps过滤材料、制备工艺及过滤袋
CN113502597B (zh) * 2021-06-28 2022-09-16 南通大学 一种柔性高红外反射率锰酸钇纳米纤维膜及其制备方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0205704A2 (en) * 1985-06-18 1986-12-30 Isolite Babcock Refractories Company Limited Method of treating a blanket of ceramic fibres
CN101213330A (zh) * 2005-05-31 2008-07-02 帝人株式会社 陶瓷纤维及其制造方法
CN101257977A (zh) * 2005-09-07 2008-09-03 阿克伦大学 柔性陶瓷纤维及其制造方法
CN102218271A (zh) * 2010-04-19 2011-10-19 韩国科学技术研究院 以金属氧化物超细纤维为基本成分的耐热性复合分离膜以及利用其制备的蓄电池
US20110281034A1 (en) * 2010-05-12 2011-11-17 Lee James L Layer-by-layer fabrication method of sprayed nanopaper
CN102695824A (zh) * 2009-11-04 2012-09-26 巴斯夫欧洲公司 生产纳米纤维的方法
CN103975100A (zh) * 2011-08-30 2014-08-06 康奈尔大学 金属和陶瓷纳米纤维
WO2015038735A1 (en) * 2013-09-11 2015-03-19 Candace Chan Nanowire-based solid electrolytes and lithium-ion batteries including the same
WO2015084951A1 (en) * 2013-12-04 2015-06-11 Cornell University Ceramic-polymer hybrid nanostructures, methods for producing and applications thereof

Family Cites Families (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US692631A (en) 1899-10-06 1902-02-04 Charles S Farquhar Apparatus for electrically dispersing fluids.
US705691A (en) 1900-02-20 1902-07-29 William James Morton Method of dispersing fluids.
US2158416A (en) 1937-07-28 1939-05-16 Richard Schrelber Gastell Method and apparatus for the production of artificial fibers
DK121919B (da) * 1965-03-30 1971-12-20 Monsanto Co Fremgangsmåde til fremstilling af filamenter direkte fra smelter med lav viskositet.
US3574811A (en) * 1969-10-08 1971-04-13 Celanese Corp Polyamide wet-spinning and stretching process
US5223197A (en) * 1986-01-30 1993-06-29 E. I. Du Pont De Nemours And Company Process of making mixed filament yarn
US5087401A (en) * 1988-11-24 1992-02-11 Toray Industries, Inc. Process for preparing polyester filamentary material
US5827797A (en) * 1989-08-28 1998-10-27 Cass; Richard B. Method for producing refractory filaments
US7270693B2 (en) * 2000-09-05 2007-09-18 Donaldson Company, Inc. Polymer, polymer microfiber, polymer nanofiber and applications including filter structures
US6743273B2 (en) * 2000-09-05 2004-06-01 Donaldson Company, Inc. Polymer, polymer microfiber, polymer nanofiber and applications including filter structures
JP4730495B2 (ja) * 2001-05-25 2011-07-20 イビデン株式会社 触媒コンバータ用保持シール材及びその製造方法、触媒コンバータ
RU2300543C2 (ru) * 2001-05-31 2007-06-10 Дональдсон Компани, Инк. Составы тонкого волокна, способы их получения, способ изготовления тонковолокнистого материала
AU2003300023A1 (en) 2002-10-10 2004-05-04 Larry D. Rogers Method for treating an environment that may be or is contaminated with an undesirable bacteria, virus and/or spore
US7134857B2 (en) * 2004-04-08 2006-11-14 Research Triangle Institute Electrospinning of fibers using a rotatable spray head
US7762801B2 (en) * 2004-04-08 2010-07-27 Research Triangle Institute Electrospray/electrospinning apparatus and method
WO2006137893A2 (en) * 2004-10-01 2006-12-28 Board Of Regents Of The University Of Texas System Polymer-free carbon nanotube assemblies (fibers, ropes, ribbons, films)
KR101536669B1 (ko) * 2004-11-09 2015-07-15 더 보드 오브 리전츠 오브 더 유니버시티 오브 텍사스 시스템 나노섬유 리본과 시트 및 트위스팅 및 논-트위스팅 나노섬유 방적사의 제조 및 애플리케이션
WO2008028194A2 (en) * 2006-09-01 2008-03-06 Cornell Research Foundation, Inc. Calcium phosphate nanofibers
CA2664837A1 (en) * 2006-09-29 2008-09-18 University Of Akron Metal oxide fibers and nanofibers, method for making same, and uses thereof
US20080230773A1 (en) * 2007-03-20 2008-09-25 Nano Terra Inc. Polymer Composition for Preparing Electronic Devices by Microcontact Printing Processes and Products Prepared by the Processes
ES2326455B2 (es) * 2007-11-27 2010-02-26 Universidad De Sevilla Procedimiento para la fabricacion a temperatura ambiente de micro y nanofibras de lignina y otros compuestos resinosos.
KR101420680B1 (ko) * 2008-09-22 2014-07-17 삼성전자주식회사 저항가열을 이용한 탄소섬유의 표면처리 장치 및 표면처리 방법
JP5300987B2 (ja) * 2009-01-16 2013-09-25 ゼウス インダストリアル プロダクツ， インコーポレイテッド 高粘度材料を含むｐｔｆｅのエレクトロスピニング
US9217210B2 (en) * 2009-03-24 2015-12-22 North Carolina State University Process of making composite inorganic/polymer nanofibers
US20100330419A1 (en) * 2009-06-02 2010-12-30 Yi Cui Electrospinning to fabricate battery electrodes
US8641960B1 (en) 2009-09-29 2014-02-04 The United States Of America, As Represented By The Secretary Of Agriculture Solution blow spinning
WO2011075619A1 (en) * 2009-12-17 2011-06-23 3M Innovative Properties Company Dimensionally stable nonwoven fibrous webs, melt blown fine fibers, and methods of making and using the same
KR20120076997A (ko) * 2010-12-30 2012-07-10 한국에너지기술연구원 섬유 형태의 고분자/에어로겔을 포함하는 시트 및 그 제조방법
US9555392B2 (en) * 2011-06-24 2017-01-31 University Of South Florida Electrospun cactus mucilage nanofibers
US8881577B1 (en) 2012-04-02 2014-11-11 Agar Corporation, Ltd. Method and system for analysis of rheological properties and composition of multi-component fluids
US9816206B2 (en) * 2012-09-17 2017-11-14 Cornell University Carbonaceous metal/ceramic nanofibers
KR20160002754A (ko) * 2013-03-12 2016-01-08 니혼바이린 가부시기가이샤 무기 나노 섬유 및 그 제조 방법
KR20150101039A (ko) * 2014-02-25 2015-09-03 코오롱패션머티리얼 (주) 다공성 지지체, 이의 제조방법, 및 이를 포함하는 강화막
WO2016014654A1 (en) * 2014-07-22 2016-01-28 Xerion Advanced Battery Corp. Monolithic porous open-cell structures

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0205704A2 (en) * 1985-06-18 1986-12-30 Isolite Babcock Refractories Company Limited Method of treating a blanket of ceramic fibres
CN101213330A (zh) * 2005-05-31 2008-07-02 帝人株式会社 陶瓷纤维及其制造方法
CN101257977A (zh) * 2005-09-07 2008-09-03 阿克伦大学 柔性陶瓷纤维及其制造方法
CN102695824A (zh) * 2009-11-04 2012-09-26 巴斯夫欧洲公司 生产纳米纤维的方法
CN102218271A (zh) * 2010-04-19 2011-10-19 韩国科学技术研究院 以金属氧化物超细纤维为基本成分的耐热性复合分离膜以及利用其制备的蓄电池
US20110281034A1 (en) * 2010-05-12 2011-11-17 Lee James L Layer-by-layer fabrication method of sprayed nanopaper
CN103975100A (zh) * 2011-08-30 2014-08-06 康奈尔大学 金属和陶瓷纳米纤维
WO2015038735A1 (en) * 2013-09-11 2015-03-19 Candace Chan Nanowire-based solid electrolytes and lithium-ion batteries including the same
WO2015084951A1 (en) * 2013-12-04 2015-06-11 Cornell University Ceramic-polymer hybrid nanostructures, methods for producing and applications thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
张大省: "《超细纤维生产技术及应用》", 31 January 2007, 中国纺织出版社 *
齐宝森等: "《机械工程材料》", 30 April 2009, 哈尔滨工业大学出版社 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110016723A (zh) * 2019-04-08 2019-07-16 深圳先进技术研究院 一种介电复合材料、其制备方法及平板型电容器
CN110042564A (zh) * 2019-04-18 2019-07-23 东华大学 一种辐射制冷纤维膜及其制备方法和应用
CN110359103B (zh) * 2019-07-10 2020-09-08 西安交通大学 一种基于步进拉伸法制备聚合物微纳米纤维的方法
CN112210848A (zh) * 2020-10-12 2021-01-12 中国人民解放军国防科技大学 一种多相SiZrOC微纳隔热纤维的制备方法
CN112210848B (zh) * 2020-10-12 2023-04-28 中国人民解放军国防科技大学 一种多相SiZrOC微纳隔热纤维的制备方法
CN113737395A (zh) * 2021-08-06 2021-12-03 华南理工大学 一种柔性二氧化钛纳米纤维膜及其制备方法和应用
CN114334238A (zh) * 2021-12-31 2022-04-12 福建成田科技有限公司 双层共挤绝缘型b1级阻燃电缆
CN114334238B (zh) * 2021-12-31 2024-01-19 福建成田科技有限公司 双层共挤绝缘型b1级阻燃电缆
CN115474345A (zh) * 2022-09-14 2022-12-13 东华大学 基于丝网印刷和化学沉积的陶瓷织物电路制作方法

Also Published As

Publication number Publication date
KR102284001B1 (ko) 2021-08-02
KR20190020671A (ko) 2019-03-04
JP6899895B2 (ja) 2021-07-07
WO2017216367A1 (en) 2017-12-21
EP3472377A1 (en) 2019-04-24
US11802351B2 (en) 2023-10-31
JP2019519696A (ja) 2019-07-11
US20170362740A1 (en) 2017-12-21
US20200318257A1 (en) 2020-10-08

Similar Documents

Publication Publication Date Title
CN109312496A (zh) 制造柔性陶瓷纤维和聚合物复合材料的方法
Tokarev et al. Touch-and brush-spinning of nanofibers
JP2019519696A5 (zh)
JP2010534579A (ja) ファイバー構造体およびその製造方法
Gao et al. Thermally triggered mechanically destructive electronics based on electrospun poly (ε-caprolactone) nanofibrous polymer films
US20080211121A1 (en) Device for manufacturing fabrils and method thereof
Chen et al. Effect of thermal annealing on the surface properties of electrospun polymer fibers
US20050048274A1 (en) Production of nanowebs by an electrostatic spinning apparatus and method
Middleton et al. Near‐Field Electrospinning Patterning Polycaprolactone and Polycaprolactone/Collagen Interconnected Fiber Membrane
Liang et al. Coaxial nozzle-assisted electrohydrodynamic printing for microscale 3D cell-laden constructs
Fathona et al. A simple one-step fabrication of short polymer nanofibers via electrospinning
JP2015140492A (ja) 繊維材料およびその製造方法
Yang et al. Printed flexible transparent electrodes for harsh environments
JP2007083467A (ja) 複合シート
KR100746643B1 (ko) 폴리스티렌 초발수성 멤브레인의 제조 방법 및 그에 의하여제조된 초발수성 멤브레인
Choi et al. Fabrication of capacitive yarn torsion sensors based on an electrospinning coating method
US8683798B2 (en) Stimuli-responsive product
Sarkar et al. Electrodeposition as a facile way for the preparation of piezoelectric ultrathin silk film–based flexible nanogenerators
Dong et al. Unveiling the mechanism of the in situ formation of 3D Fiber macroassemblies with controlled properties
Jain et al. Synthetic adhesive attachment discs inspired by spider's pyriform silk architecture
Kumar et al. Shape memory effect of four-dimensional printed polylactic acid-based scaffold with nature-inspired structure
JP7169868B2 (ja) ナノ物質含有樹脂複合体の製造方法、ナノ物質含有樹脂複合体の製造装置および透明導電性膜を有する装置の製造方法
JPH0544146A (ja) 高強力シート状物およびその製造法
Haag et al. Melt electrowriting to produce microfiber fragments
Lombard et al. Thermal treatment of electrospun polystyrene fibers: microstructural evolution and mechanical behavior

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination