CN101505955A - 含有碳纤维的叠层成型体及其制造方法 - Google Patents

含有碳纤维的叠层成型体及其制造方法 Download PDF

Info

Publication number
CN101505955A
CN101505955A CNA2007800307342A CN200780030734A CN101505955A CN 101505955 A CN101505955 A CN 101505955A CN A2007800307342 A CNA2007800307342 A CN A2007800307342A CN 200780030734 A CN200780030734 A CN 200780030734A CN 101505955 A CN101505955 A CN 101505955A
Authority
CN
China
Prior art keywords
carbon fiber
spun yarn
forms
molded article
base 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.)
Granted
Application number
CNA2007800307342A
Other languages
English (en)
Other versions
CN101505955B (zh
Inventor
冈田康
小林辰男
园部直弘
龟山贵
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.)
Kureha Corp
Original Assignee
Kureha Corp
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 Kureha Corp filed Critical Kureha Corp
Publication of CN101505955A publication Critical patent/CN101505955A/zh
Application granted granted Critical
Publication of CN101505955B publication Critical patent/CN101505955B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered 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
    • B32B5/02Layered 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 structural features of a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered 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
    • B32B5/22Layered 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
    • B32B5/24Layered 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
    • B32B5/28Layered 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 impregnated with or embedded in a plastic substance
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06Fibrous reinforcements only
    • B29C70/10Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06Fibrous reinforcements only
    • B29C70/10Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/22Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in at least two directions forming a two dimensional structure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered 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
    • B32B5/02Layered 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 structural features of a fibrous or filamentary layer
    • B32B5/022Non-woven fabric
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered 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
    • B32B5/02Layered 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 structural features of a fibrous or filamentary layer
    • B32B5/024Woven fabric
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered 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
    • B32B5/02Layered 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 structural features of a fibrous or filamentary layer
    • B32B5/08Layered 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 structural features of a fibrous or filamentary layer the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered 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
    • B32B5/22Layered 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
    • B32B5/24Layered 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
    • B32B5/26Layered 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 another layer next to it also being fibrous or filamentary
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/522Graphite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628Coating the powders or the macroscopic reinforcing agents
    • C04B35/62844Coating fibres
    • C04B35/62857Coating fibres with non-oxide ceramics
    • C04B35/62873Carbon
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628Coating the powders or the macroscopic reinforcing agents
    • C04B35/62892Coating the powders or the macroscopic reinforcing agents with a coating layer consisting of particles
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71Ceramic products containing macroscopic reinforcing agents
    • C04B35/78Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80Fibres, filaments, whiskers, platelets, or the like
    • C04B35/83Carbon fibres in a carbon matrix
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/008Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of an organic adhesive, e.g. phenol resin or pitch
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/16Yarns or threads made from mineral substances
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/242Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads inorganic, e.g. basalt
    • D03D15/275Carbon fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2707/00Use of elements other than metals for preformed parts, e.g. for inserts
    • B29K2707/04Carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING 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
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0012Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
    • B29K2995/0017Heat stable
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29LINDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00Other particular articles
    • B29L2031/726Fabrics
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/20All layers being fibrous or filamentary
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/02Coating on the layer surface on fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/26Polymeric coating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02Composition of the impregnated, bonded or embedded layer
    • B32B2260/021Fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04Impregnation, embedding, or binder material
    • B32B2260/046Synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10Inorganic fibres
    • B32B2262/106Carbon fibres, e.g. graphite fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/12Conjugate fibres, e.g. core/sheath or side-by-side
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/304Insulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54Yield strength; Tensile strength
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546Flexural strength; Flexion stiffness
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/706Anisotropic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/708Isotropic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/718Weight, e.g. weight per square meter
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/72Density
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/732Dimensional properties
    • B32B2307/734Dimensional stability
    • B32B2307/736Shrinkable
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5208Fibers
    • C04B2235/5252Fibers having a specific pre-form
    • C04B2235/5256Two-dimensional, e.g. woven structures
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5208Fibers
    • C04B2235/5264Fibers characterised by the diameter of the fibers
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5208Fibers
    • C04B2235/5272Fibers of the same material with different length or diameter
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32Ceramic
    • C04B2237/38Fiber or whisker reinforced
    • C04B2237/385Carbon or carbon composite
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00Inorganic fibres
    • D10B2101/10Inorganic fibres based on non-oxides other than metals
    • D10B2101/12Carbon; Pitch
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3065Including strand which is of specific structural definition
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3065Including strand which is of specific structural definition
    • Y10T442/3073Strand material is core-spun [not sheath-core bicomponent strand]

Abstract

本发明提供兼有充分的强度和耐剥离性的成型体,特别是高温炉用绝热材料。含有碳纤维的叠层成型体1含有:将第1碳纤维集结在一起而成的基材10;以及,位于基材10的至少一面上、由含有纤维平均直径12μm以下的第2碳纤维22和纤维平均直径超过12μm的第3碳纤维23的碳纤维细纱21形成的织物层20。

Description

含有碳纤维的叠层成型体及其制造方法
技术领域
本发明涉及兼有充分的抗拉强度、抗弯强度(以下将两方面统称为“强度”)和耐剥离性,特别是作为高温炉用绝热材料有用的含有碳纤维的叠层成型体及其制造方法。
背景技术
碳纤维叠层体在各种用途中使用,特别作为高温绝热材料等使用。作为高温绝热材料的必须特性是绝热性能优异、较轻、具有适度的强度。碳纤维叠层体是充分满足这些必须特性的材料,但要求抑制起灰、进一步提高表面硬度。
作为对该要求的对策,到目前为止提出了贴合石墨片、碳纤维布(机织布、织物)而形成的成型体(专利文献1),但在提案中,尚存在生产效率性与性能不平衡等问题、不能得到理想的效果等问题。
专利文献1:日本专利第3029534号公报
专利文献2:特开平3-248838号公报
专利文献3:特开平2-208264号公报
专利文献4:实开昭63-97797号公报
专利文献5:实开昭61-138998号公报
专利文献6:特开2005-133032号公报
发明内容
本发明的目的是消除现有技术的问题,提供兼有充分的强度和耐剥离性的成型体,特别是高温炉用绝热材料。
本发明者们为了解决上述问题而进行了深入研究,结果发现,由仅由纤维平均直径超过12μm的碳纤维构成的细纱得到的织物,织物本身的抗拉强度弱,含有基材和织物层的成型体的表面保护效果小,另外,由仅由纤维平均直径12μm以下的碳纤维构成的细纱得到的织物不仅成本高,而且基材与织物层的粘结性弱,容易剥离。基于该发现进行了进一步研究,结果发现,可以通过使用含有由纤维平均直径不同的碳纤维形成的碳纤维细纱的织物来实现上述目的,从而完成了本发明。
即,本发明提供一种含有碳纤维的叠层成型体,其特征在于,含有:将第1碳纤维集结在一起而成的基材,以及位于该基材的至少一面上、由含有纤维平均直径12μm以下的第2碳纤维和纤维平均直径超过12μm的第3碳纤维的碳纤维细纱形成的织物层。
本发明所使用的基材是将第1碳纤维集结在一起而成的。具体地说,优选使用在由第1碳纤维形成的毡叠层物中浸渍热固性树脂而得的叠层体,或在由第1碳纤维形成的毡叠层物中浸渍热固性树脂,然后煅烧而得的碳纤维叠层体。由于在由第1碳纤维形成的毡叠层物中浸渍热固性树脂,然后煅烧而得的碳纤维叠层体尺寸稳定性优异,故而更优选。
作为第1碳纤维,优选纤维平均直径为5~20μm。更优选使用纤维平均直径为8~18μm的纤维。因为如果不足5μm则有时生产效率降低,如果超过20μm则有时绝热性降低,所以优选为上述范围。另外,第1碳纤维的纤维长优选为30~500mm的范围,更优选为50~250mm的范围。因为如果不足30mm则有时基材的抗曲强度弱,如果超过500mm则有时纤维难以均匀分散、难以制作均匀的毡,所以优选为上述范围。作为第1碳纤维,优选列举沥青系各向同性碳纤维、聚丙烯腈系(PAN系)碳纤维、人造丝系碳纤维、基诺尔(Kynol)碳纤维等。
基材是将1种或2种以上第1碳纤维形成毡而成的。毡可以按照常规方法形成,也可以将单独1种毡或2种以上毡叠层而构成基材。
基材的厚度根据用途不同而不同,在将本发明的成型体作为高温炉用绝热材料使用的情况下,通常优选为10~500mm的范围,更优选为10~300mm的范围。如果基材的厚度过厚则生产性降低,如果过薄则绝热性降低。
基材的堆密度优选为0.05~0.50g/cm3的范围,更优选为0.10~0.30g/cm3的范围。因为如果不足0.05g/cm3,则有时生产性降低,如果超过0.50g/cm3,则有时导热性升高而绝热性降低,所以优选为上述范围。
本发明所使用的织物层位于上述基材的至少一面上,考虑到作为对来自外部的冲击和应力的防破损用保护层的效果、以及基材上的起毛不与制品接触的效果,优选位于基材的两面。
织物层含有将下述碳纤维细纱进行织造而成的织物,所述碳纤维细纱含有纤维平均直径12μm以下、优选为5~12μm的第2碳纤维和纤维平均直径超过12μm、优选为超过12μm且为20μm以下的第3碳纤维。如果第2碳纤维的纤维平均直径不足5μm则生产效率降低。另外,如果第3碳纤维的纤维平均直径超过20μm,则抗拉强度降低、加捻时容易发生断丝。
本发明所使用的碳纤维细纱,优选是第2碳纤维为各向异性碳纤维、第3碳纤维为各向同性碳纤维的细纱。通过第2碳纤维可以实现高抗拉强度和高弹性模量,通过第3碳纤维可以用粘结剂实现与热处理物的良好粘结性。这里所谓“各向异性碳纤维”是指碳纤维的抗拉强度为1000MPa以上或抗拉弹性模量为100GPa以上,且具有(002)碳层面在纤维轴方向选择性地排列的组织的纤维。例如,在非氧化性气氛中,在2000℃进行热处理之后,可在碳纤维剖面用扫描型电子显微镜(SEM)观察到高次元结构的碳纤维,可用偏光显微镜观察到由(002)碳层面排列产生的光学各向异性的碳纤维,或者由用侧角仪测定排列函数而得到的半值宽为50度以下的碳纤维等都是各向异性碳纤维。作为例子,优选列举聚丙烯腈系(PAN系)碳纤维、沥青系各向异性碳纤维、人造丝系碳纤维等。另一方面,所谓“各向同性碳纤维”是指碳纤维的抗拉强度为不足1000MPa或抗拉弹性模量为不足100GPa,且具有(002)碳层面未排列的组织的纤维。例如,在非氧化性气氛中,在2000℃进行热处理之后,可在碳纤维剖面用扫描型电子显微镜(SEM)观察到各向相同结构的碳纤维、可用偏光显微镜观察到(002)碳层面排列产生的光学各向同性的碳纤维、或者由用侧角仪测定排列函数得到的半值宽超过50度的碳纤维等都是各向同性碳纤维。作为例子,优选可以列举沥青系各向同性碳纤维等。
第2碳纤维在成型体中通常最长纤维长为20m以下。作为构成第2碳纤维的原材料纤维,通常优选平均纤维长为500mm以上,更优选为1000mm以上,进而优选为3m以上。对构成第2碳纤维的原材料纤维的平均纤维长的上限不特别限制,可以自能够获得的纤维长中根据用途适当选择,通常可工业获得5000m以下的连续长纤维。因为在细纱中,所使用的纤维长越长则纤维之间的接合点越少,所以可以提高细纱的强度。另外,对构成第3碳纤维的原材料纤维的平均纤维长,通常可工业获得的不足500mm,优选为300mm以下,更优选为200mm以下。进而特别优选含有3~30质量%、优选为5~20质量%的平均纤维长为150mm以上且不足500mm的碳纤维,并含有97~70质量%、优选为95~80质量%的平均纤维长不足150mm的碳纤维。如果平均纤维长150mm以上的碳纤维过少则碳纤维细纱的抗拉强度降低,如果过多则在纺纱工序中容易发生断丝而产生纤度不均匀,且容易生成被称为疙瘩(スラブ)、尘绵(フライ)的块状部分,故而品质降低。
第2碳纤维的密度优选为1.65~2.30g/cm3的范围,更优选为1.70~2.00g/cm3的范围,特别优选为1.70~1.90g/cm3的范围。如果第2碳纤维的密度过小则碳化不充分,如果过大则结晶化过度进行,任何一种情况下强度均降低,难以实现强化织物的强度等作为第2碳纤维的功能。另外,第3碳纤维的密度优选为1.50~1.80g/cm3的范围,更优选为1.50~1.70g/cm3的范围,特别优选为1.55~1.70g/cm3的范围。如果第3碳纤维的密度过小则碳化不充分而碳纤维的强度降低,如果过大则与树脂(粘结剂)的润湿性变差,难以实现将织物与基材粘结等作为第3碳纤维的功能。
由第2碳纤维和第3碳纤维构成的碳纤维细纱每1000m的质量(纤度)优选为30~1000特(特克斯,tex),更优选为30~750特,更优选为60~400特。因为如果小于上述范围则要花费细纱的制造成本,如果过多则有时难以进行织造,所以优选为上述范围。
细纱的抗拉强度直接影响织物的抗拉强度,其起决定作用的是作为第2碳纤维的细径、长的碳纤维。第2碳纤维的抗拉强度(此外,碳纤维的抗拉强度依据JIS R 7601-1986)优选为1000MPa以上,特别优选为1600MPa~6000MPa的范围。第3碳纤维的抗拉强度优选为不足1000MPa,特别优选为300~900MPa的范围。第3碳纤维因为是粗径、短的碳纤维且绒毛较多,所以被认为发挥锚固效果,或通过与粘结剂的高粘结性而发挥将与基材的粘附性维持在充分高的状态的功能。
但是,织物层的强度不仅受细纱的抗拉强度影响,还受织法、细纱的捻数等影响。例如,如果一定程度加捻则抗拉强度增加,但如果过度加捻则由于扭曲、拉伸应力而抗拉强度反而下降。碳纤维细纱的捻数(用于使细纱集结在一起、赋予细纱抗拉强度)优选为50~400次/米的范围,更优选为100~200次/米的范围。因为如果加捻过多则细纱可能被破坏,如果加捻过少则细纱有抗拉强度降低的倾向,所以优选为上述范围。整个织物的抗拉强度为0.2kN以上较好,优选为0.2~2.0kN的范围。可以通过第2碳纤维、第2碳纤维与第3碳纤维的配合比、细纱的捻数、织物层的厚度、单位面积重量的选择来实现。
优选成型体的抗曲强度为1.5MPa以上且不足5.0MPa,优选为1.8MPa以上且不足5.0MPa。该抗曲强度也可以通过调节第2碳纤维与第3碳纤维的配合比来实现。为了得到本发明的成型体,优选的第2碳纤维具体地说,从纤维平均直径为5μm~12μm、成型体中的最长纤维长为20m以下、密度为1.65~2.30g/cm3的范围、抗拉强度为1000MPa~6000MPa的由沥青系各向异性碳纤维(长纤维)、聚丙烯腈系(PAN系)碳纤维和人造丝系碳纤维形成的高强度、细径、长的碳纤维之中选择,第3碳纤维具体地说,优选从纤维平均直径超过12μm且为20μm以下、密度为1.50~1.80g/cm3的范围、抗拉强度不足1000MPa的由沥青系各向同性碳纤维(短纤维)形成的低强度、粗径、短的碳纤维之中选择。第3碳纤维优选是含有3~30质量%的平均纤维长不足500mm的原材料纤维和97~70质量%的平均纤维长不足150mm的原材料纤维的细纱。
更优选碳纤维细纱为下述的细纱:以第2碳纤维为芯材、以第3碳纤维为壳材的芯壳结构细纱;由上述第2碳纤维形成的细纱与由上述第3碳纤维形成的细纱的合捻细纱;以第2碳纤维为芯材、以第3碳纤维为壳材的芯壳结构细纱的合捻细纱;以及它们的组合。这些细纱的织法可以采用斜纹组织、平纹组织、缎纹组织、方平组织等公知的方法。
第2碳纤维与第3碳纤维的配合比例,优选第2碳纤维的配合量为10质量%~90质量%,更优选为20质量%~80质量%,进而优选为30质量%~70质量%。如果第2碳纤维的配合量不足10质量%,则有时细纱的强度不足,如果超过90质量%,则有时细纱与基材的粘结性降低而不能确保成型体的(抗弯)强度。此外,在不妨碍本发明的理想效果的范围内,该织物层可以含有其它由碳纤维形成的细纱,例如仅由第2碳纤维形成的细纱、仅由第3碳纤维形成的细纱。
对碳纤维细纱的制造方法不特别限制,例如,在使用图3所示的精纺机100,将第3碳纤维的束32进行拉伸、加捻时,可以自中辊37投入第2碳纤维的丝束36进行混纺。在图3所示的精纺机100中,第3碳纤维的丝束32自制品箱31经由卷辊33而被导入后辊34中,另一方面,通过碳纤维线轴35自中辊37投入第2碳纤维的丝束36。第2和第3碳纤维的丝束在托辊38、底辊39和前辊40之间进行传送期间,第3碳纤维的丝束32通过前辊40与后辊34之间的圆周速度比而被拉伸,同时与第2碳纤维束36合并。接着,合并到一起的第2和第3碳纤维的丝束经由蜗形导杆41,通过具有环42和制动踏板43的锭子44进行加捻,用卷取线轴45进行卷取,从而得到碳纤维细纱。
将这样得到的碳纤维细纱进行织造而成的织物层的单位面积重量(FAW)优选为50~1200g/m2,更优选为200~800g/m2。当然单位面积重量越大的,细纱的根数越多,故而强度增加,但因为产生厚度而成型性降低(难以估计厚度份额),所以优选上述范围。织物层的厚度优选为0.1~2.0mm,更优选为0.6~1.1mm。
在本发明的成型体中,优选上述基材与上述织物层之间介由粘结剂而进行粘结。作为这时可以使用的粘结剂,可以使用含有短纤维长炭纤维的粘结剂、含有石墨粉末的粘结剂。
作为粘结剂,可以使用将60~100质量份热固性预聚物、20~60质量份热固性树脂;5~20质量份短纤维长碳纤维、炭黑、碳粉末或石墨粉末;5~20质量份溶剂和5~20质量份水均匀混合分散而成的粘结剂组合物。作为热固性预聚物,优选可以列举尿素树脂预聚物;蜜胺树脂预聚物,尿素改性蜜胺树脂预聚物;胍胺树脂预聚物;胍胺改性蜜胺树脂预聚物;呋喃树脂预聚物;醇酸树脂预聚物;酚树脂预聚物,例如酚醛清漆型酚树脂预聚物,可熔酚醛清漆型酚树脂预聚物,酚醛清漆型烷基酚树脂预聚物,可熔酚醛清漆型烷基酚树脂预聚物和它们的二甲苯/甲醛缩合物、甲苯/甲醛缩合物或通过蜜胺树脂、胍胺树脂或尿素树脂改性的改性树脂预聚物;环氧树脂预聚物,例如双酚A二缩水甘油醚、脂环式二醇的二缩水甘油醚、双酚A二(α-甲基缩水甘油醚)、脂环式二醇的二(α-甲基缩水甘油醚)等。根据需要,可以混合固化剂、固化催化剂等。其中,优选碳化收率较高的树脂预聚物,特别优选可以使用酚醛清漆型酚树脂预聚物、可熔酚醛清漆型酚树脂预聚物、酚醛清漆型烷基酚树脂预聚物、可熔酚醛清漆型烷基酚树脂预聚物。作为热固性树脂,优选可以列举尿素树脂;蜜胺树脂;尿素改性蜜胺树脂;胍胺树脂;胍胺改性蜜胺树脂;醇酸树脂;呋喃树脂;不饱和聚酯树脂;酚树脂,例如酚醛清漆型酚树脂,可熔酚醛清漆型酚树脂,酚醛清漆型烷基酚树脂,可熔酚醛清漆型烷基酚树脂;环氧树脂,例如双酚A二缩水甘油醚、脂环式二醇的二缩水甘油醚、双酚A二(α-甲基缩水甘油醚)、脂环式二醇的二(α-甲基缩水甘油醚)等。其中,优选碳化收率较高的树脂,特别优选可以使用酚醛清漆型酚树脂、可熔酚醛清漆型酚树脂、酚醛清漆型烷基酚树脂、可熔酚醛清漆型烷基酚树脂。作为溶剂,可以优选使用丙酮、甲乙酮、甲基异丁基酮、甲醇、乙醇、2-呋喃甲醇、甲苯、二甲苯或二甲亚砜等。粘结剂的使用量相对于基材优选为300~1000g/m2,更优选为400~800g/m2。另外,相对于1片织物优选为500~3000g/m2,更优选为1000~2500g/m2
作为本发明的成型体的具体例,可以列举加工成平板状、圆筒状、圆盘状、四方形状等的成型绝热材料,特别是在高温炉的内部作为衬里而使用的高温炉用绝热材料等。
本发明的成型体可以通过进行以下各工序等来制造。
[基材制造工序]
可以在碳纤维毡中浸渍热固性树脂浸渍液等来得到基材。或者,可以在碳纤维毡中浸渍热固性树脂浸渍液等,使数片得到的热固性树脂浸渍的碳纤维毡叠层,加压加热到使热固性树脂固化的规定压力和温度从而进行压缩成型,然后,进一步进行高温处理而得到基材。此外,通过在叠层形成的叠层体周围配置规定厚度的垫片,然后进行压缩成型,从而可以调节厚度,由此可以控制毡叠层体的堆密度。
作为热固性树脂,可以优选使用尿素树脂、蜜胺树脂、酚树脂、环氧树脂、不饱和聚酯树脂、醇酸树脂、聚氨酯树脂、呋喃树脂等。其中,优选酚树脂。
[织物制造工序]
可以使用规定的碳纤维细纱,按照常规方法制成织物。例如,使用通常织造碳纤维时可以使用的织机,例如梭织机、剑杆织机,从而制成平纹组织、斜纹组织、缎纹组织、方平组织等的织物。
[粘结工序]
将规定的成分进行配合并均匀混合而调制粘结剂组合物,将得到的粘结剂以规定量涂布在基材和织物两者上,使二者贴合。此外,作为将粘结剂涂布在织物上的方法,可以用刮刀、毛刷或辊等涂布规定量的粘结剂,或者可以在减压槽中使织物浸渍在粘结剂中,并通过真空脱泡使粘结剂充分浸渍到构成织物的细纱的芯部,然后将织物从减压槽取出,用刮刀、毛刷或辊等去除织物上过多附着的粘结剂直至其为规定的涂布量。
[煅烧工序]
将基材与织物贴合之后,加热加压到规定压力和温度而进行压缩成型,进一步在非氧化性气氛中、在3000℃以下进行热处理。
本发明的含有碳纤维的叠层成型体绝热性能优异,并兼具充分的强度和耐剥离性。
附图说明
图1是显示本发明的含有碳纤维的叠层成型体的一种实施方式的剖面图。
图2是显示图1所示的实施方式中所使用的碳纤维细纱的一种实施方式的剖面图。
图3是显示本发明所使用的碳纤维细纱的制造工序的示意图。
图4是显示实施例1所得的成型体的放大剖面(×25)的SEM照片。
图5是显示实施例1所使用的芯壳结构的碳纤维细纱的放大剖面(×150)的SEM照片。
图6是显示将图5的一部分进行放大显示的SEM照片(×400)。
图7是将图5的第2碳纤维和第3碳纤维部分进行放大显示的SEM照片(×4300)。
符号说明
1  含有碳纤维的叠层成型体
10 基材
20  织物层
30  粘结剂
21  碳纤维细纱
22  芯部
23  壳部
100 精纺机
具体实施方式
以下,参考附图来更详细地说明本发明,但本发明不受它们限制。
图1是显示本发明的含有碳纤维的叠层成型体的一种实施方式的剖面图,图2是显示图1所示的实施方式中所使用的碳纤维细纱的一种实施方式的剖面图。
图1所示方式的含有碳纤维的叠层成型体1含有:由碳纤维毡叠层体形成的基材10、由将碳纤维细纱21进行斜纹组织而成的织物形成的织物层20、和将基材10与织物层20进行粘结的粘结剂30。
而且,如图2所示,在本实施方式中用于形成织物20的碳纤维细纱21,由芯部22和被覆芯部22的外周的壳部23构成。芯部22是由纤维平均直径较细(优选为5μm~12μm)的第2碳纤维形成的,壳部23是由纤维平均直径较粗(优选超过12μm)的第3碳纤维形成的。
此外,本发明不受上述实施方式任何限制,可以在不脱离本发明的宗旨的范围内进行各种变化。
例如,形成织物层20的碳纤维细纱可以不是芯壳结构,而是合股线结构。
实施例
以下,通过实施例具体地说明本发明,但本发明不受这些实施例限制。实施例中所进行的评价如下所示。
[碳纤维的密度]
在烧杯中称量规定量的氧化锌和1%盐酸,然后进行混合而制成混合液,将混合液移入500ml的量筒中,浸渍在20±1.0℃的低温恒温水槽中使得温度为20±1.0℃,然后悬浮比重计来测定比重。适当改变氧化锌与1%盐酸的相对量,从而调制10种比重液。
将各2ml的这10种比重液按照比重高低的顺序分别沿管壁缓缓注入20ml的量筒中,从而制作密度梯度管。另一方面,使约0.1g的用研钵碾碎并通过网眼150μm的标准筛而得的碳纤维样品在少量的乙醇中分散从而得到样品分散液。将密度梯度管浸入20±1.0℃的低温恒温水槽中,在经过30分钟之后,将样品分散液缓缓注入密度梯度管并静置12小时以上,然后读取样品在密度梯度管中的位置,使用密度换算表求得样品的密度。
[碳纤维的抗拉强度]
碳纤维的抗拉强度是根据JIS R 7601-1986来测定单纤维的抗拉强度而得的。
[细纱织物的抗拉强度]
使用テンシロン(TENSILON)万能拉力试验机((株)オリエンテツク制造,“RTC-1310型”),在测力传感器额定值10kN、样品长150mm、样品宽50mm、拉伸速度200mm/分钟的条件下,将拉伸时的断裂强度换算成相当于每厘米样品宽的值,将该值作为该细纱织物的抗拉强度。
[细纱织物的厚度]
在距细纱织物的边缘30mm以上的内侧位置,切出100mm×100mm见方的样品,用测微计((株)ミツトヨ制造,U字型测微计“PUM 150-2”)测定其中央部,将测得的值作为细纱织物的厚度。
[抗曲强度]
将得到的含有碳纤维的叠层成型体进行切削加工,切割成5个尺寸为宽10mm、厚13~15mm、长100mm的样品。使用自动绘图仪(岛津制作所制造,“岛津オ—トグラフAGS-H5kN”),在支点间距80mm、十字头速度1.0mm/分钟、塑料用支点和冲孔半径r=5mm的条件下,将样品通过中央集中负荷来实施弯曲试验,基于最大破坏负荷来求出抗曲强度。
实施例1
[基材制造工序]
在各100质量份的2种堆密度0.08g/cm3的沥青系各向同性碳纤维毡((株)クレハ制造“クレカフエルトF-105”和“クレカフエルトF-110”)中,浸渍44质量份市售的酚系树脂浸渍液(昭和高分子(株)制造“シヨウノ—ルBRS-3897”),然后叠层各1片从而形成叠层体,在所形成的叠层体的周围配置用于将基材的厚度调整为10mm的垫片,然后在温度175℃、压力0.5MPa的条件下,进行压缩成型35分钟,从而制成平板状。将压缩成型后的叠层体在真空中、在2000℃进行石墨化处理1小时,从而得到基材,该基材为厚10mm、宽200mm、长250mm、堆密度0.16g/cm3的平板状碳纤维叠层体。
[织物制造工序]
使用图3所示的精纺机,使用聚丙烯腈系(PAN系)碳纤维(将东邦テナツクス(株)制造的“ベスフアイトHTA-3K”拆分成80特的丝束、纤维平均直径7μm、密度1.77g/cm3)作为第2碳纤维,使用沥青系各向同性碳纤维((株)クレハ制造“クレカスライバ—”,320特、纤维平均直径14.5μm、密度1.63g/cm3)作为第3碳纤维,从而调制由20质量%的由第2碳纤维形成的芯部和80质量%的由第3碳纤维形成的壳部构成的芯壳结构的碳纤维细纱。以该碳纤维细纱作为经线和纬线进行斜纹组织,从而制成细纱织物(斜纹组织,FAW580g/m2、纬密19.0根/英寸、抗拉强度0.32kN、厚度0.88mm)。将该细纱织物切割成4片宽220mm、长270mm的织物,从而得到用于形成织物层的织物。
[粘结工序]
作为使基材与细纱织物粘结的粘结剂,使80质量份酚系树脂浸渍液(昭和高分子(株)制造“シヨウノ—ルBRS-3897”)、40质量份粉末酚树脂(カシユ—(株)制造“カシユ—No.05”)、13质量份碳短纤维((株)クレハ制造“クレカチヨツプM-107T”,平均纤维长0.4mm、
Figure A200780030734D0016155223QIETU
、密度1.63g/cm3)、13质量份2-呋喃甲醇(纯正化学(株)制造,纯正1级)、11质量份水均匀混合分散,从而调制由粘结剂组合物形成的粘结剂。分别在织物的一面上用毛刷以2000g/m2的坪量涂布粘结剂,并在基材的两面的整个面上用刮刀以400g/m2的坪量涂布粘结剂。将织物涂布了粘结剂的一面朝向基材侧,在基材的各面各叠层2片织物使之粘结,使用压缩成型机((株)神藤金属工业所制造“F-37”)在温度175℃、压力0.1MPa以下的条件下,进行压缩成型60分钟。
[煅烧工序]
进而在真空中在2000℃进行石墨化处理1小时,从而得到在基材的两面各叠层了2片细纱织物层的平板状的含有碳纤维的叠层成型体。所得的成型体上未观察到细纱织物剥离、膨胀。
将显示得到的成型体的剖面的照片示于图4。另外,将使用的碳纤维细纱的剖面放大照片示于图5~图7。
将使用的碳纤维细纱的组成示于表1,将对得到的成型体的评价结果示于表2。
实施例2
使用聚丙烯腈系(PAN系)碳纤维(东邦テナツクス(株)制造的“ベスフアイトHTA-3K”,200特、纤维平均直径7μm、密度1.77g/cm3)作为芯部,使用沥青系各向同性碳纤维((株)クレハ制造“クレカスライバ—”,200特、纤维平均直径14.5μm、密度1.63g/cm3)作为壳部,使用两者的配合比分别为50质量%的细纱来形成织物(斜纹组织,FAW580g/m2、纬密19.0根/英寸、抗拉强度0.52kN、厚度0.88mm),除了使用该织物之外,与实施例1同样地得到成型体。在得到的成型体中未观察到细纱织物剥离、膨胀。
将使用的碳纤维细纱的组成示于表1,将对于得到的成型体的评价结果示于表2。
实施例3
使用聚丙烯腈系(PAN系)碳纤维(将东邦テナツクス(株)制造的“ベスフアイトHTA-6K”拆分成320特的丝束、纤维平均直径7μm、密度1.77g/cm3)作为芯部,使用沥青系各向同性碳纤维((株)クレハ制造“クレカスライバ—”,80特、纤维平均直径14.5μm、密度1.63g/cm3)作为壳部,使用两者的配比为80质量%:20质量%的细纱来形成织物(斜纹组织,FAW580g/m2、纬密19.0根/英寸、抗拉强度0.70kN、厚度0.88mm),除了使用该织物之外,与实施例2同样地得到成型体。在得到的成型体中未观察到细纱织物剥离、膨胀。
将使用的碳纤维细纱的组成示于表1,将对得到的成型体的评价结果示于表2。
实施例4
织物的叠层片数为在基材的两面各1片,除此之外,与实施例2同样地得到成型体。在得到的成型体中未观察到细纱织物剥离、膨胀。
将使用的碳纤维细纱的组成示于表1,将对得到的成型体的评价结果示于表2。
实施例5
用煅烧工序代替石墨化处理,在常压、氮气气氛中,在1200℃进行碳化处理1小时,除此之外,与实施例4同样地得到成型体。在得到的成型体中未观察到细纱织物剥离、膨胀。
将使用的碳纤维细纱的组成示于表1,将对得到的成型体的评价结果示于表2。
实施例6
使用沥青系各向异性碳纤维(将三菱化学产资(株)制造“ダイアリ—ドK32112”拆分得到的200特的丝束、纤维平均直径10μm、密度1.93g/cm3)作为芯部,使用沥青系各向同性碳纤维((株)クレハ制造“クレカスライバ—”,200特、纤维平均直径14.5μm、密度1.63g/cm3)作为壳部,使用两者的配比分别为50质量%的细纱来形成织物(斜纹组织,FAW 580g/m2、纬密19.0根/英寸、抗拉强度0.28kN、厚度0.88mm),除了使用该织物之外,与实施例2同样地得到成型体。在得到的成型体中未观察到细纱织物剥离、膨胀。
将使用的碳纤维细纱的组成示于表1,将对得到的成型体的评价结果示于表2。
实施例7
使用将实施例2所调制的碳纤维细纱进行平纹组织而得的织物(平纹组织,FAW 530g/m2、纬密19.0根/英寸、抗拉强度0.64kN、厚度0.78mm),除此之外,与实施例2同样地得到成型体。在得到的成型体中未观察到细纱织物剥离、膨胀。
将使用的碳纤维细纱的组成示于表1,将对得到的成型体的评价结果示于表2。
实施例8
使用实施例2所调制的碳纤维细纱,改变织造条件(FAW和纬密)而得到织物(斜纹组织,FAW 310g/m2、纬密10.0根/英寸、抗拉强度0.26kN、厚度0.62mm),除了使用该织物之外,与实施例2同样地得到成型体。在得到的成型体中未观察到细纱织物剥离、膨胀。
将使用的碳纤维细纱的组成示于表1,将对得到的成型体的评价结果示于表2。
实施例9
使用实施例2所调制的碳纤维细纱,改变织造条件(FAW和纬密)而得到织物(斜纹组织,FAW670g/m2、纬密22.0根/英寸、抗拉强度0.60kN、厚度1.08mm),除了使用该织物之外,与实施例2同样地得到成型体。在得到的成型体中未观察到细纱织物剥离、膨胀。
将使用的碳纤维细纱的组成示于表1,将对得到的成型体的评价结果示于表2。
实施例10
将1片堆密度0.08g/m3的沥青系各向同性碳纤维毡(株)クレハ制造的“クレカフエルトF-110”,在温度175℃、压力0.5MPa的条件下进行压缩成型25分钟,从而制成平板状的叠层体,使用将该叠层体调整成厚10mm、宽200mm、长250mm、堆密度0.10g/cm3的叠层体作为基材,除此之外,与实施例2同样地得到成型体。在得到的成型体中未观察到细纱织物剥离、膨胀。
将使用的碳纤维细纱的组成示于表1,将对于得到的成型体的评价结果示于表2。
实施例11
将3片堆密度0.08g/m3的沥青系各向同性碳纤维毡(株)クレハ制造的“クレカフエルトF-110”,在温度175℃、压力0.6MPa的条件下进行压缩成型80分钟,从而制成平板状的叠层体,使用将该叠层体调整成厚10mm、宽200mm、长250mm、堆密度0.30g/cm3的叠层体作为基材,除此之外,与实施例2同样地得到成型体。在得到的成型体中未观察到细纱织物剥离、膨胀。
将使用的碳纤维细纱的组成示于表1,将对于得到的成型体的评价结果示于表2。
实施例12
用含有碳纤维的叠层体的煅烧工序代替石墨化处理,在常压、氮气气氛中,在1200℃进行碳化处理1小时,除此之外,与实施例2同样地得到成型体。在得到的成型体中未观察到细纱织物剥离、膨胀。
将使用的碳纤维细纱的组成示于表1,将对得到的成型体的评价结果示于表2。
实施例13
作为粘结剂,使用用13质量份石墨粉末(日本黑铅工业(株)制造“HAG-15”)代替13质量份碳短纤维((株)クレハ制造“クレカチヨツプM-107T”,平均纤维长0.4mm、
Figure A200780030734D0020155327QIETU
、密度1.63g/cm3)的粘结剂,除此之外,与实施例4同样地得到成型体。在得到的成型体中未观察到细纱织物剥离、膨胀。
将使用的碳纤维细纱的组成示于表1,将对得到的成型体的评价结果示于表2。
实施例14
作为粘结剂,使用用13质量份石墨粉末(日本黑铅工业(株)制造“HAG-15”)代替13质量份碳短纤维((株)クレハ制造“クレカチヨツプM-107T”,平均纤维长0.4mm、
Figure A200780030734D0020155327QIETU
、密度1.63g/cm3)的粘结剂,除此之外,与实施例2同样地得到成型体。在得到的成型体中未观察到细纱织物剥离、膨胀。
将使用的碳纤维细纱的组成示于表1,将对于得到的成型体的评价结果示于表2。
实施例15
在各100质量份的2种堆密度0.08g/m3的沥青系各向同性碳纤维毡(株)クレハ制造的“クレカフエルトF-105”和“クレカフエルトF-110”中,浸渍44质量份市售的酚系树脂浸渍液(昭和高分子(株)制造“シヨウノ—ルBRS-3897”),然后将各1片叠层而形成叠层体,将得到的叠层体作为基材,除此之外,与实施例2同样地得到成型体。在得到的成型体中未观察到细纱织物剥离、膨胀。
比较例1
仅制成实施例1中作为基材使用的平板状碳纤维叠层体(10mm、宽200mm、长250mm、堆密度0.16g/cm3)而得到成型体。将对得到的成型体的评价结果示于表2。
比较例2
作为织物,使用仅由沥青系各向同性碳纤维((株)クレハ制造“クレカスライバ—SY-652”,纤维平均直径14.5μm、密度1.63g/cm3)构成的细纱来形成织物(斜纹组织,FAW 215g/m2、纬密19.0根/英寸、抗拉强度0.14kN、厚度0.38mm),将该织物裁剪成2片来使用,并且分别在其一面上用毛刷以1000g/m2的量涂布粘结剂,在基材的两面各叠层1片,除此之外,与实施例1同样地得到成型体。在得到的成型体中未观察到细纱织物剥离、膨胀。
将使用的碳纤维细纱的组成示于表1,将对得到的成型体的评价结果示于表2。
比较例3
在平板状碳纤维叠层体的两面各叠层2片细纱织物,以代替比较例2的在平板状碳纤维叠层体的两面各叠层1片细纱织物的条件,除此之外,与比较例2同样地得到成型体。在得到的成型体中未观察到细纱织物剥离、膨胀。
将使用的碳纤维细纱的组成示于表1,将对得到的成型体的评价结果示于表2。
比较例4
作为织物,在100质量份聚丙烯腈系(PAN系)碳纤维织物(由东邦テナツクス(株)制造的ベスフアイト织物“W-3161”)中浸渍40质量份酚树脂,准备4片经浸渍处理的织物,在基材的两面各叠层2片,同时,使粉末酚树脂(カシユ—(株)制造“カシユ—No.05”)与碳短纤维((株)クレハ制造“クレカチヨツプM-107T”,平均纤维长0.4mm、
Figure A200780030734D0020155327QIETU
、密度1.63g/cm3)以1:1(质量比)均匀混合分散,使该混合物介于碳纤维织物之间、以及碳纤维织物与碳纤维叠层体之间作为粘结剂,除此之外,与实施例1在相同条件下进行压缩成型、石墨化处理,从而得到平板状成型体。在得到的成型体中,观察到基材与织物层的界面剥离。
将使用的碳纤维细纱的组成示于表1,将对得到的成型体的评价结果示于表2。
比较例5
使用实施例1所记载的粘结剂,代替比较例4的介于碳纤维织物与碳纤维叠层体之间的粉末酚树脂与碳短纤维的混合物,除此之外,与比较例4同样地进行从而得到平板状成型体。在得到的成型体中,观察到碳纤维叠层体的毡彼此界面剥离。
将使用的碳纤维细纱的组成示于表1,将对得到的成型体的评价结果示于表2。
表1
Figure A200780030734D00231
表2
Figure A200780030734D00241

Claims (19)

1.一种含有碳纤维的叠层成型体,其特征在于,含有:
由第1碳纤维集结在一起而成的基材;以及,
位于该基材的至少一面上、将含有纤维平均直径12μm以下的第2碳纤维和纤维平均直径超过12μm的第3碳纤维的碳纤维细纱进行织造而成的织物层。
2.根据权利要求1所述的含有碳纤维的叠层成型体,所述基材是在由第1碳纤维形成的毡叠层物中浸渍热固性树脂而得的叠层体,或在由第1碳纤维形成的毡叠层物中浸渍热固性树脂,然后煅烧而得的碳纤维叠层体。
3.根据权利要求1所述的含有碳纤维的叠层成型体,所述第2碳纤维是各向异性碳纤维,所述第3碳纤维是各向同性碳纤维。
4.根据权利要求1所述的含有碳纤维的叠层成型体,所述碳纤维细纱选自:以所述第2碳纤维为芯材、以所述第3碳纤维为壳材的芯壳结构细纱;由所述第2碳纤维形成的细纱与由所述第3碳纤维形成的细纱的合捻细纱;以所述第2碳纤维为芯材、以所述第3碳纤维为壳材的芯壳结构细纱的合捻细纱;以及它们的组合。
5.根据权利要求4所述的含有碳纤维的叠层成型体,所述第2碳纤维是各向异性碳纤维,所述第3碳纤维是各向同性碳纤维。
6.根据权利要求1所述的含有碳纤维的叠层成型体,构成所述织物层的细纱织物的抗拉强度为0.2kN以上。
7.根据权利要求1所述的含有碳纤维的叠层成型体,抗弯强度为1.5MPa以上且不足5.0MPa。
8.一种含有碳纤维的叠层成型体,其特征在于,含有:
在由第1碳纤维形成的毡叠层物中浸渍热固性树脂而得的叠层体,或在由第1碳纤维形成的毡叠层物中浸渍热固性树脂,然后煅烧而得的碳纤维叠层体;以及,
位于在该碳纤维叠层体的至少一面上的织物层,该织物层是将下述细纱进行织造而成的织物层,所述细纱选自以纤维平均直径12μm以下的第2碳纤维为芯材、以纤维平均直径超过12μm的第3碳纤维为壳材的芯壳结构细纱;由上述第2碳纤维形成的细纱与由上述第3碳纤维形成的细纱的合捻细纱;以上述第2碳纤维为芯材、以上述第3碳纤维为壳材的芯壳结构细纱的合捻细纱;以及它们的组合。
9.根据权利要求8所述的含有碳纤维的叠层成型体,所述第2碳纤维是各向异性碳纤维,所述第3碳纤维是各向同性碳纤维。
10.根据权利要求8所述的含有碳纤维的叠层成型体,构成所述织物层的细纱织物的抗拉强度为0.2kN以上。
11.根据权利要求8所述的含有碳纤维的叠层成型体,抗弯强度为1.5MPa以上且不足5.0MPa。
12.一种绝热材料,由权利要求1~7的任一项所述的含有碳纤维的叠层成型体形成。
13.一种绝热材料,由权利要求8~11的任一项所述的含有碳纤维的叠层成型体形成。
14.一种含有碳纤维的叠层成型体的制造方法,包括下述工序:
通过聚集第1碳纤维来调制基材的基材调制工序;
将纤维平均直径12μm以下的第2碳纤维与纤维平均直径超过12μm的第3碳纤维进行纺纱,从而调制碳纤维细纱,然后由得到的碳纤维细纱形成织物的织物形成工序;
使用粘结剂在该基材的至少一面上贴合至少1片该织物,从而形成具有基材和织物层的含有碳纤维的叠层体的粘结工序;以及,
将该含有碳纤维的叠层体进行压缩成型,接着进行热处理的煅烧工序。
15.根据权利要求14所述的制造方法,所述基材调制工序包括在由第1碳纤维形成的毡叠层物中浸渍热固性树脂从而形成叠层体。
16.根据权利要求14所述的制造方法,所述基材调制工序包括在由第1碳纤维形成的毡叠层物中浸溃热固性树脂,然后进行煅烧。
17.根据权利要求14所述的制造方法,所述第2碳纤维是各向异性碳纤维,所述第3碳纤维是各向同性碳纤维。
18.根据权利要求14所述的制造方法,所述碳纤维细纱选自:以所述第2碳纤维为芯材、以所述第3碳纤维为壳材的芯壳结构细纱;由所述第2碳纤维形成的细纱与由所述第3碳纤维形成的细纱的合捻细纱;以所述第2碳纤维为芯材、以所述第3碳纤维为壳材的芯壳结构细纱的合捻细纱;以及它们的组合。
19.根据权利要求18所述的制造方法,所述第2碳纤维是各向异性碳纤维,所述第3碳纤维是各向同性碳纤维。
CN2007800307342A 2006-08-22 2007-08-17 含有碳纤维的叠层成型体及其制造方法 Active CN101505955B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP225833/2006 2006-08-22
JP2006225833 2006-08-22
PCT/JP2007/066401 WO2008023777A1 (fr) 2006-08-22 2007-08-17 Article moulé stratifié contenant une fibre de carbone et son procédé de fabrication

Publications (2)

Publication Number Publication Date
CN101505955A true CN101505955A (zh) 2009-08-12
CN101505955B CN101505955B (zh) 2012-04-11

Family

ID=39106860

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2007800307342A Active CN101505955B (zh) 2006-08-22 2007-08-17 含有碳纤维的叠层成型体及其制造方法

Country Status (6)

Country Link
US (1) US8962500B2 (zh)
EP (1) EP2065109B1 (zh)
JP (1) JP4889741B2 (zh)
KR (1) KR101299777B1 (zh)
CN (1) CN101505955B (zh)
WO (1) WO2008023777A1 (zh)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102543324A (zh) * 2010-12-21 2012-07-04 哈米尔顿森德斯特兰德公司 空气循环机复合绝缘板
CN105339721A (zh) * 2013-06-04 2016-02-17 霓佳斯株式会社 绝热材料和绝热材料的制造方法
CN106715995A (zh) * 2014-09-11 2017-05-24 霓佳斯株式会社 隔热材料及其制造方法
CN107091392A (zh) * 2016-02-18 2017-08-25 松下知识产权经营株式会社 绝热件及其制造方法
CN109049762A (zh) * 2018-08-01 2018-12-21 南京新核复合材料有限公司 一种小孔控胶装置
CN112778706A (zh) * 2021-01-05 2021-05-11 中国电子科技集团公司第三十三研究所 一种拉挤碳纤维电磁屏蔽复合材料型材及其制作方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201139151A (en) * 2010-01-22 2011-11-16 Kureha Corp Carbon fiber-laminated product and method of preparing the same
KR101356893B1 (ko) * 2012-09-05 2014-01-29 엘지전자 주식회사 탄소/탄소 복합 섬유의 제조 방법, 이를 이용하여 제조되는 탄소 히터 및 조리 기기
JP2017197854A (ja) * 2016-04-25 2017-11-02 ▲翼▼程科技股▲分▼有限公司 炭素繊維スペーサー及びその結合方法
EP3463871B1 (de) * 2016-06-03 2023-08-30 Schunk Kohlenstofftechnik GmbH Verfahren zur herstellung einer trägerplatte und trägerplatte

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS634956Y2 (zh) 1985-02-19 1988-02-09
JPS6397797U (zh) 1986-12-15 1988-06-24
JP3003935B2 (ja) 1989-02-04 2000-01-31 大阪瓦斯株式会社 成形断熱材とその製造方法
JPH03248838A (ja) * 1990-02-27 1991-11-06 Osaka Gas Co Ltd 断熱材
JPH03294541A (ja) * 1990-03-23 1991-12-25 Tonen Corp ハイブリッドプリプレグ及びその製造方法
EP0459916B1 (fr) * 1990-05-10 1995-04-12 Le Carbone Lorraine Eléments de friction en matériau composite carbone-carbone à texture différentielle, procédés et dispositifs pour les fabriquer
EP0543147B1 (en) * 1991-10-18 1997-06-25 PETOCA Ltd. Carbon fiber felt and process for its production
US5380477A (en) * 1993-05-25 1995-01-10 Basf Corporation Process of making fiber reinforced laminates
JP3029534B2 (ja) 1994-04-08 2000-04-04 日本カーボン株式会社 高温炉用断熱材
FR2734581B1 (fr) * 1995-05-24 1997-08-14 Europ Propulsion Fil hybride pour la fabrication de preformes fibreuses de pieces en materiau composite et procede pour sa preparation
JP2960038B2 (ja) * 1997-07-02 1999-10-06 サンキョン・インダストリーズ・カンパニー・リミテッド 建築構造物補強用の一方向繊維シート及びその製造方法
CN1101231C (zh) * 2000-04-28 2003-02-12 刘学锋 防火隔热卷帘用耐火纤维复合卷帘及其应用
US6555211B2 (en) * 2001-01-10 2003-04-29 Albany International Techniweave, Inc. Carbon composites with silicon based resin to inhibit oxidation
JPWO2003068707A1 (ja) * 2002-02-14 2005-06-02 東洋炭素株式会社 耐酸化性炭素繊維強化炭素複合材料及びその製造方法
JP4582685B2 (ja) 2003-10-31 2010-11-17 株式会社クレハ 断熱材用接着剤及びそれを用いた断熱材用炭素化積層体
JP4446721B2 (ja) * 2003-12-01 2010-04-07 株式会社クレハ 炭素繊維紡績糸およびその織物
WO2005090664A1 (ja) * 2004-03-22 2005-09-29 Otas Company, Limited 等方性ピッチ系炭素繊維紡績糸、それを用いた複合糸及び織物、並びにそれらの製造方法
US8171711B2 (en) * 2005-02-22 2012-05-08 Kureha Corporation Hybrid carbon fiber spun yarn and hybrid carbon fiber spun yarn fabric using the same
CN101935919B (zh) * 2005-04-18 2011-09-14 帝人株式会社 沥青类碳纤维、毡以及含有它们的树脂成型体
KR200420515Y1 (ko) * 2006-02-10 2006-07-04 김원기 탄소섬유를 다방향으로 배치하여 제조한 다방향 탄소판

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102543324A (zh) * 2010-12-21 2012-07-04 哈米尔顿森德斯特兰德公司 空气循环机复合绝缘板
CN105339721A (zh) * 2013-06-04 2016-02-17 霓佳斯株式会社 绝热材料和绝热材料的制造方法
CN106715995A (zh) * 2014-09-11 2017-05-24 霓佳斯株式会社 隔热材料及其制造方法
CN106715995B (zh) * 2014-09-11 2019-12-17 霓佳斯株式会社 隔热材料及其制造方法
CN107091392A (zh) * 2016-02-18 2017-08-25 松下知识产权经营株式会社 绝热件及其制造方法
CN109049762A (zh) * 2018-08-01 2018-12-21 南京新核复合材料有限公司 一种小孔控胶装置
CN112778706A (zh) * 2021-01-05 2021-05-11 中国电子科技集团公司第三十三研究所 一种拉挤碳纤维电磁屏蔽复合材料型材及其制作方法

Also Published As

Publication number Publication date
WO2008023777A1 (fr) 2008-02-28
JPWO2008023777A1 (ja) 2010-01-14
US20100330858A1 (en) 2010-12-30
EP2065109A4 (en) 2015-11-04
CN101505955B (zh) 2012-04-11
KR20090041415A (ko) 2009-04-28
US8962500B2 (en) 2015-02-24
JP4889741B2 (ja) 2012-03-07
KR101299777B1 (ko) 2013-08-23
EP2065109A2 (en) 2009-06-03
EP2065109B1 (en) 2018-12-05

Similar Documents

Publication Publication Date Title
CN101505955B (zh) 含有碳纤维的叠层成型体及其制造方法
Fernández et al. Role of flax cell wall components on the microstructure and transverse mechanical behaviour of flax fabrics reinforced epoxy biocomposites
Ray et al. Microstructural characterization of bamboo
US8171711B2 (en) Hybrid carbon fiber spun yarn and hybrid carbon fiber spun yarn fabric using the same
MXPA02009445A (es) Produccion de esteras, no tejidas, de filamentos cortados.
Liu et al. Micromechanical properties of the interphase in cellulose nanofiber-reinforced phenol formaldehyde bondlines
Hamdan et al. The effect of customized woven and stacked layer orientation on tensile and flexural properties of woven kenaf fibre reinforced epoxy composites
Yu et al. Twisting in improving processing of waste-derived yarn into high-performance reinforced composite
CN102712168A (zh) 碳纤维层压成形体及其制备方法
JP7007630B2 (ja) セルロースナノファイバーを配合した炭素繊維強化プラスチック
Bar et al. Effect of interface on composites made from DREF spun hybrid yarn with low twisted core flax yarn
JP6175936B2 (ja) サイジング剤塗布炭素繊維およびその製造方法、炭素繊維強化複合材料
Hasan et al. Improved mechanical performances of unidirectional jute fibre composites developed with new fibre architectures
Tong et al. Influence of alkali treatment on physico-chemical properties of Malaysian bamboo fiber: A preliminary study
Guan et al. Shape memory polyurethane‐based electrospun yarns for thermo‐responsive actuation
CN113715452B (zh) 一种自润滑衬垫复合材料及其制备方法和应用
JP2015157740A (ja) ガラスクロス及びガラス繊維強化複合樹脂材
Yue et al. Surface treatments of solvated mesophase pitch-based carbon fibers
Song et al. Mechanical properties of sisal natural fiber composites according to strain rate and absorption ratio
Kers et al. Preliminary investigation into tensile characteristics of long flax fibre reinforced composite material.
Wu et al. Fabrication and mechanical properties of self‐reinforced polyester composites by double covered uncommingled yarn
CN202543476U (zh) 用于抗疲劳加固的纤维布
JPH032224A (ja) ハイブリッドプリプレグ
Bin Saiman et al. The effect of alkali treatment on impact strength of woven kenaf reinforced unsaturated polyester composite using vacuum infusion process
EP3650592B1 (en) Method for producing combined filament yarn, mixed filament yarn, and method for producing woven fabric or knitted fabric

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant