CN112437723B - 具有优异电磁屏蔽性能和导热率的多层石墨片及其制备方法 - Google Patents

具有优异电磁屏蔽性能和导热率的多层石墨片及其制备方法 Download PDF

Info

Publication number
CN112437723B
CN112437723B CN201980044044.5A CN201980044044A CN112437723B CN 112437723 B CN112437723 B CN 112437723B CN 201980044044 A CN201980044044 A CN 201980044044A CN 112437723 B CN112437723 B CN 112437723B
Authority
CN
China
Prior art keywords
graphite
graphite sheet
layered
layer
sheet
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.)
Active
Application number
CN201980044044.5A
Other languages
English (en)
Other versions
CN112437723A (zh
Inventor
徐正斗
金熏
金政圭
白种甲
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.)
SKC Co Ltd
Original Assignee
SKC 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 SKC Co Ltd filed Critical SKC Co Ltd
Publication of CN112437723A publication Critical patent/CN112437723A/zh
Application granted granted Critical
Publication of CN112437723B publication Critical patent/CN112437723B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B32B5/26—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 another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/263—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer having non-uniform thickness
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/28—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer comprising a deformed thin sheet, i.e. the layer having its entire thickness deformed out of the plane, e.g. corrugated, crumpled
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0036—Heat treatment
    • B32B38/004—Heat treatment by physically contacting the layers, e.g. by the use of heated platens or rollers
    • 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
    • B32B5/02—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 structural features of a fibrous or filamentary layer
    • 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
    • B32B5/02—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 structural features of a fibrous or filamentary layer
    • B32B5/024—Woven fabric
    • 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
    • B32B7/00—Layered 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/047—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material made of fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/522—Graphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
    • 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
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • 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
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/0088—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a plurality of shielding layers; combining different shielding material structure
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/20—All layers being fibrous or filamentary
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/06—Vegetal fibres
    • B32B2262/062—Cellulose fibres, e.g. cotton
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/10—Fibres of continuous length
    • B32B2305/18—Fabrics, textiles
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/10—Fibres of continuous length
    • B32B2305/18—Fabrics, textiles
    • B32B2305/188—Woven fabrics
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/10—Fibres of continuous length
    • B32B2305/20—Fibres of continuous length in the form of a non-woven mat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/212—Electromagnetic interference shielding
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/302—Conductive
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/72—Density
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08—Dimensions, e.g. volume
    • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105—Thickness
    • 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
    • B32B2313/00—Elements other than metals
    • B32B2313/04—Carbon
    • 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
    • B32B2509/00—Household appliances
    • 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
    • B32B2605/00—Vehicles
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • 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
    • B32B5/02—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 structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • 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
    • B32B7/00—Layered 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • 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
    • B32B7/00—Layered 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • 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
    • B32B7/00—Layered 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • 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
    • H05K7/00—Constructional details common to different types of electric apparatus
    • H05K7/20—Modifications to facilitate cooling, ventilating, or heating
    • H05K7/2039—Modifications to facilitate cooling, ventilating, or heating characterised by the heat transfer by conduction from the heat generating element to a dissipating body
    • 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
    • H05K7/00—Constructional details common to different types of electric apparatus
    • H05K7/20—Modifications to facilitate cooling, ventilating, or heating
    • H05K7/2039—Modifications to facilitate cooling, ventilating, or heating characterised by the heat transfer by conduction from the heat generating element to a dissipating body
    • H05K7/20436—Inner thermal coupling elements in heat dissipating housings, e.g. protrusions or depressions integrally formed in the housing
    • H05K7/20445—Inner thermal coupling elements in heat dissipating housings, e.g. protrusions or depressions integrally formed in the housing the coupling element being an additional piece, e.g. thermal standoff
    • H05K7/20472—Sheet interfaces
    • H05K7/20481—Sheet interfaces characterised by the material composition exhibiting specific thermal properties
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified
    • Y10T428/24975—No layer or component greater than 5 mils thick
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/24992—Density or compression of components
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3854—Woven fabric with a preformed polymeric film or sheet

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Geology (AREA)
  • Electromagnetism (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Thermal Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Textile Engineering (AREA)
  • Laminated Bodies (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)

Abstract

实施方案涉及具有优异的电磁屏蔽能力和导热率的多层石墨片及其制造方法，所述多层石墨片具有五层以上的多层结构，并且能被制造成厚度为70μm以上以达到显著提高电磁屏蔽能力的目的。此外，所述多层石墨片通过将混合了非均质材料的混合型层压板石墨化而制成的，使得以较低的成本同时实现导热率和电磁屏蔽能力，从而可用作厚膜片，广泛应用于例如家用电器和电动汽车等领域。

Description

具有优异电磁屏蔽性能和导热率的多层石墨片及其制备方法
技术领域
本实施方案涉及一种具有优异电磁屏蔽性能和导热率的多层石墨片及其制备方法。
背景技术
石墨片可采用天然石墨通过石墨膨胀法来制备。具体来说，在石墨膨胀法中，将天然石墨浸入浓硫酸和醋酸的混合液中，并快速加热，通过一系列洗涤工艺除去酸，并利用高压压力机将其形成薄膜形状。但是，通过该方法制备的石墨片具有强度弱并且在导热率方面散热性差的缺点。该方法还有一个缺点，即洗涤过程中的残酸可能会造成缺陷。
为了解决上述问题，开发了一种聚合物石墨化方法，即将聚合物薄膜进行热处理后以使其碳化和石墨化来制备石墨片。该方法使用的聚合物薄膜包括，例如聚噁二唑薄膜、聚酰亚胺薄膜、聚对亚苯基亚乙烯薄膜、聚苯并咪唑薄膜、聚苯并噁唑薄膜、聚噻唑薄膜和聚酰胺薄膜。
与传统的石墨膨胀法相比，聚合物石墨化方法非常简单。其还有一个优点在于该方法不涉及杂质例如酸的掺入。此外，通过聚合物石墨化方法制备的石墨片具有接近于单晶石墨的优异的导热率和导电性能(参见日本特开昭60-181129，平7-109171和昭61-275116)。
同时，近年来，需要一种可以安装在移动设备如手机、平板电脑和笔记本电脑上的片材，该片材不仅要表现出散热功能，还要表现出电磁屏蔽功能。
发明内容
技术问题
尽管常规的聚合物石墨化方法具有诸多优点，但仍然存在以下问题：作为原料的聚合物薄膜例如聚酰亚胺薄膜通常很昂贵，并且由于材料的限制，难以制备70μm以上的石墨片。然而，厚度小于70μm的石墨片不能很好地实现电磁屏蔽能力。因此，采用常规的方法很难同时获得高导热率和电磁屏蔽能力。
因此，本实施方案旨在通过混合相对便宜的材料以获得混合型层压板并将其进行碳化和石墨化来提供具有优异的电磁屏蔽能力和导热率的多层石墨片及其制备方法。
解决方案
根据一实施方案，提供了一种多层石墨片，其包括一层压板，所述层压板至少一层第一石墨层和至少一层第二石墨层交替层叠成共5层以上，其中第一石墨层比第二石墨层致密。
此外，根据一实施方案，提供了一种多层石墨片的制备方法，所述制备方法包括：将树脂组合物涂覆在纤维基材的一侧或两侧以形成涂层；制备层压板，其中至少一层纤维基材和至少一层涂层交替层叠成共5层以上；将层压板进行热处理以固化涂层作为第一热处理；然后对进行了第一热处理的层压板进行第二热处理，以碳化和石墨化纤维基材和涂层。
本发明的有益效果
由于上述实施方案中的多层石墨片具有共5层以上的多层结构，因此即使在轧制后也可以将其制备成70μm以上的厚度，从而可以显著提高电磁屏蔽能力。
此外，多层石墨片可以通过轧制增加其密度并进一步加强所述层状结构而具有优异的导热率。
特别地，多层石墨片是通过对包含不同材料的混合型层压板进行石墨化来制备的。因此，可以以较低的成本同时实现导热率和电磁屏蔽能力。
因此，多层石墨片作为一种厚的片材，可以广泛应用于例如家用电器和电动汽车等各种领域。
附图说明
图1为一实施方案中多层石墨片(共5层)的制备方法。
图2为一实施方案中多层石墨片(共7层)的横截面的扫描电子显微镜(SEM)图像。
图3为示意性地示出了一实施方案的多层石墨片(共5层)的横截面。
[附图编号]
11：涂层                        12：纤维基材
100'：层压板(碳化和石墨化之前)
100：多层石墨片                 200：热处理
T1,T1'：最大厚度                T2,T2'：最小厚度
d：多层石墨片的厚度
发明的最佳实施方式
下面将详细描述本实施方案。
根据一实施方案，提供了一种多层石墨片，其包括一层压板，所述层压板中至少一层第一石墨层和至少一层第二石墨层交替层叠成共5层以上，其中第一石墨层比第二石墨层致密。
所述多层石墨片包括层压板，所述层压板中所述第一石墨层和所述第二石墨层交替层叠。
所述第一石墨层比所述第二石墨层致密。
即，所述第一石墨层中的组分可以比所述第二石墨层中的组分更紧密地相互接触。
因此，所述第一石墨层的密度可高于所述第二石墨层。例如，所述第一石墨层的密度可为所述第二石墨层密度的1.1倍以上，1.5倍以上，或者2倍以上。具体地，所述第一石墨层的密度可为所述第二石墨层的密度的1.1～10倍，1.1～5倍，1.1～3倍或1.1～2倍。
所述层压板的总层数可为5层以上，例如：8层以上，或者10层以上。具体地，层压板的总层数可为5～30层，5～20层，5～15层，5～11层或10～20层。
在一实施方案中，所述多层石墨片可为轧制片。
即，所述多层石墨片在制备过程中可以通过轧制获得。因此，所述多层石墨片可具有更高的密度，并且由于这种高密度和层状结构，可增强在水平方向上的热导性能。
此外，由图1可知，由于所述多层石墨片(100)是多层结构，即使在轧制时也可至少达到一定水平的厚度(d)。
例如，所述多层石墨片的总厚度可为70μm以上。进一步地，所述多层石墨片的总厚度可以是100μm以上，120μm以上，或150μm以上。具体地，所述多层石墨片的总厚度可以是70μm～1000μm，例如100μm～1000μm，例如100μm～600μm，例如100μm～400μm，例如100μm～250μm，例如100μm～200μm。
同时，由于材料的特性，通过对常规的聚酰亚胺类薄膜或类似的薄膜进行碳化和石墨化以制备合成的石墨片很难达到70μm以上的厚度。另一方面，由于多层石墨片比常规的石墨片具有更大的厚度，它可以具有显著增强电磁屏蔽能力和增加热容量的优点。
在另一实施方案中，多层石墨片可以是未轧制的片材。在这种情况下，多层石墨片可以具有更大的厚度。
例如，多层石墨片的总厚度可以是200μm以上，或者300μm以上。具体地，多层石墨片的总厚度可以为200～1,000μm，例如250～600μm，例如300～450μm。
在30～1500MHz范围内，多层石墨片可以具有100dB以上的电磁屏蔽能力，例如110dB以上，例如130dB以上。
具体地，在30～1500MHz范围内，多层石墨片可以具有100～200dB的电磁屏蔽能力，例如110～200dB，例如130～200dB，例如100～150dB，例如110～150dB，例如130～150dB。
在水平方向上，多层石墨片可以具有600W/m·K以上的导热率，例如700W/m·K以上，例如700W/m·K～1,300W/m·K，例如850W/m·K～1,100W/m·K。
此外，在垂直方向上，多层石墨片可以具有1W/m·K以上的导热率，例如5W/m·K以上，例如5W/m·K～10W/m·K。
在一实施方案中，所述多层石墨片可以同时具有在30～1500MHz范围内的100dB以上的电磁屏蔽能力和在水平方向上700W/m·K～1,300W/m·K的导热率。
此外，所述多层石墨片的密度可为1.3g/cm3～1.8g/cm3，例如1.5g/cm3～1.8g/cm3。上述密度可为表观密度。在此，所述表观密度的值可通过多层石墨片的质量除以其体积计算得到。即，所述多层石墨片包括第一石墨层和第二石墨层，并且它们之间具有不同的密度，且由于包括它们的整个多层结构而具有在上述范围的表观密度。由于借助于包括第一石墨层和第二石墨层的整个多层结构，其表观密度在上述范围内，因此所述多层石墨片可以在导热率和热容量方面产生优异的效果。
层压板可以具有第一石墨层作为两侧的表面层。
即层压板两侧的表面层可以是第一石墨层，并且第二石墨层和第一石墨层可以交替层叠作为内层。因此，层压板中第一石墨层的数量可比第二石墨层的数量多一个。
例如，层压板可以包括3～6层的第一石墨层和2～5层的第二石墨层。
具体地，所述层压板可以是具有第一石墨层/第二石墨层/第一石墨层/第二石墨层/第一石墨层的五层结构。或者，其可以是第一石墨层/第二石墨层/…/第二石墨层/第一石墨层的五层以上的层叠结构。
第一石墨层的厚度可为10μm～50μm，第二石墨层的厚度可为5μm～60μm。具体地，第一石墨层的厚度可为15μm～45μm，第二石墨层的厚度可为20μm～50μm。
第二石墨层的厚度变化可大于第一石墨层。此处，所述厚度变化是指当测量一个层的多个点处的厚度时最大厚度和最小厚度之间的差值。例如，如图3所示，当测量第一石墨层(110)的多个点处的厚度时，第一石墨层的厚度变化可计算为最大厚度(T1)和最小厚度(T2)之间的差值(T1-T2)。此外，当测量第二石墨层(120)的多个点处的厚度时，第二石墨层的厚度变化可计算为最大厚度(T1')和最小厚度(T2')之间的差值(T1'-T2')。
作为示例，第一石墨层的厚度变化可小于40μm，第二石墨层的厚度变化可为40μm以上。具体地，第一石墨层的厚度变化可为5μm～20μm，第二石墨层的厚度变化可为40μm～60μm。
此外，在多层石墨片的厚度方向上，第一石墨层与第二石墨层在横截面上的界面可为弯曲形状。例如，第一石墨层和第二石墨层之间的界面可为弯曲形状，例如波浪形图案。
如图2所示为一实施方案中多层石墨片的横截面的扫描电子显微镜(SEM)图像。
具体地，如图2所示的多层石墨片具有七层结构(即第一石墨层/第二石墨层/第一石墨层/第二石墨层/第一石墨层/第二石墨层/第一石墨层)，并且可以看出第一石墨层和第二石墨层之间的界面呈现出波浪形图案的曲线形状。此外，可以看出第二石墨层的厚度变化较大，而第一石墨层的厚度几乎不变。
第一石墨层和第二石墨层可以包含不同的石墨化材料。
作为示例，第一石墨层可包含固化树脂的石墨化材料，第二石墨层可包含纤维基材的石墨化材料。
所述固化树脂没有特别限定，只要是可固化聚合物树脂的固化材料即可。例如，所述固化树脂是选自聚酰胺酸、聚氯乙烯、聚酯、聚氨酯、聚乙烯、聚氟乙烯、聚乙烯醇、丙烯酸和聚丙烯中的一种或多种的树脂的固化材料，或者所述固化树脂是包含树脂的组合物的固化材料。
作为优选的例子，所述固化树脂可包括含有聚酰胺酸的组合物的固化材料。在这种情况下，包含聚酰胺酸的组合物的固化材料可为聚酰亚胺组合物。
所述纤维基材没有特别限定，只要它是包含纤维或纤维材料的基材即可。例如，所述纤维基材可包括机织物、无纺布或纸。
此外，所述纤维基材可包括天然纤维或合成纤维。具体地，纤维基材可以是机织物、无纺布或纸，其包括至少一种选自以下的纤维：包括棉花、大麻、羊毛和丝的天然纤维；包括人造丝、醋酸纤维和三醋酸纤维的纤维素类纤维；包括尼龙、聚酯、聚氨酯、聚乙烯、聚氯乙烯、聚氟乙烯、聚乙烯醇、丙烯酸和聚丙烯的合成纤维。
作为具体的例子，多层石墨片可以通过对层压板以热处理方式进行固化、碳化和石墨化获得，所述层压板中，纤维基材和由聚酰胺酸(即，聚酰亚胺前体)制成的涂层交替层叠成五层以上。
图1为一实施方案中多层石墨片的制备方法。
在一实施方案中，如图1所示，提供了一种多层石墨片(100)的制备方法，其包括在纤维基材(12)的一侧或两侧涂覆上树脂组合物以形成涂层(11)；制备层压板(100')，其中至少一种纤维基材(12)和至少一种涂层(11)交替层叠成5层以上；对层压板进行热处理(200)，将涂层固化作为第一热处理；然后对进行了第一热处理的层压板进行第二热处理，以碳化和石墨化纤维基材和涂层。
首先，将树脂组合物涂覆在纤维基材的一侧或两侧。
此处使用的纤维基材的具体类型如上所示。
此外，所述树脂组合物可为液态树脂组合物。例如，其可包含聚合物树脂、溶剂、催化剂和脱水剂。在这种情况下，所述树脂组合物中聚合物树脂的含量可为1％～85％，例如5％～50％，例如10％～30％，以重量计。此外，树脂组合物中催化剂的含量可为1％～5％，以重量计，树脂组合物中脱水剂的重量百分数可为10％～20％，以重量计。
聚合物树脂是可固化的聚合物树脂，其具体类型如上所述。例如，聚合物树脂可为聚酰胺酸。因此，树脂组合物可包含聚酰胺酸、溶剂、催化剂和脱水剂。
聚酰胺酸的重均分子量可为100,000～400,000g/mole或者200,000～300,000g/mol。
涂层的方法没有特别限定，只要是用于形成涂层的常规方法即可。
例如，可以通过模具涂布、凹版涂布、微凹版涂布、逗号涂布、辊涂、浸涂、喷涂、棒涂和浸涂等方法进行涂布以形成层状结构。
涂层可进行一次或多次，以形成具有适当厚度的涂层。例如，基于一层聚酰胺酸涂层，其厚度可以形成5μm～60μm，或者20μm～50μm。
接着，制备层压板，其中至少一层纤维基材和至少一层涂层交替层叠成共5层以上。
例如，可以层叠在先前步骤中涂覆的两个以上的纤维基材以制备层压板。具体地，在层叠两个涂覆的纤维基材的情况下，可以按照涂层/基材/涂层/基材/涂层的顺序制备五层层压板。
在这种情况下，可以根据需要或多或少地调节层叠层的层数，并且可以根据层叠层的层数制备具有不同厚度的多层片材。
同时，进行交替层叠以使涂层处于最外层。因此，层压板的两个表面层均可以形成涂层。
层压板的总厚度可为200μm以上，或者300μm以上。具体的，层压板的总厚度可为200μm～1,000μm，例如250μm～600μm，例如300μm～450μm。在上述范围内，经过后续的热处理步骤和其他加工步骤例如轧制，可以获得具有适当厚度的多层石墨片。
此后，在第一热处理中对层压板进行热处理以固化涂层。该步骤中的热处理条件没有特别限定，只要是可用于固化常规可固化的聚合物的工艺条件即可。具体地，热处理可以在用于聚酰胺酸亚胺化的工艺条件下进行。
例如，所述第一热处理包括：在100～150℃下进行10分钟至15分钟的第一阶段热处理；在230～250℃下进行5分钟至7分钟的第二阶段热处理；在400～420℃下进行5分钟至7分钟的第三阶段热处理。
接着，在第二热处理中，对层压板做进一步热处理以碳化和石墨化纤维基材和涂层。
该步骤中的热处理条件没有特别限定，只要是可用于常规碳化和石墨化聚合物和/或纤维的工艺条件即可。
例如，所述第二热处理可包括：在700℃～1800℃下进行1小时至20小时的第一阶段热处理；在2000℃～3200℃下进行1小时至20小时的第二阶段热处理。
具体的，第二热处理可包括：在1,000℃～1,500℃下进行1小时至3小时的第一阶段热处理；在2,000℃～3,000℃下进行5小时至10小时的第二阶段热处理。
制备多层石墨片的方法可进一步包括对已经过第二热处理的层压板进行轧制。所述轧制可以提高多层石墨片的密度，使其层状结构和碳的排列整齐，从而进一步提高导热率。
此外，所述轧制可以调整多层石墨片的厚度。为了提高电磁屏蔽能力，优选将多层石墨片轧制到最终厚度为70μm以上。
所述轧制可以通过辊压机或类似的方式进行。具体的，所述轧制可采用陶瓷辊、金属辊(例如铜或不锈钢)、聚氨酯辊和橡胶辊进行。但是对轧制没有特别限定，只要是能被用来调节片材厚度的常规方法即可。
所述轧制的压力可为20N/cm2～80N/cm2，例如30N/cm2～50N/cm2。
由于上述实施方案的多层石墨片具有5层以上的多层结构，因此，即使经过轧制，也可以制备70μm以上的厚度，从而显著增强电磁屏蔽能力。
此外，多层石墨片可通过轧制增加其密度以及进一步强化层状结构从而具有优异的导热率。
特别地，多层石墨片是通过对包含不同材料的混合型层压板进行石墨化来制备的。因此，可以以较低的成本同时实现导热率和电磁屏蔽能力。
因此，多层石墨片作为一种厚的片材，可以广泛应用于例如家用电器和电动汽车等各种领域。
具体实施方式
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。
实施例1
采用中国制造的平纹棉织物(100m/g)作为基材。使用辊涂机将液态树脂组合物(聚酰胺酸的固体含量为18％)涂布在基材的两侧。将两种涂覆的基材进行层叠以获得共5层的层压板(涂层/基材层/涂层/基材层/涂层)。通过采用热空气干燥对层压板进行酰亚胺化，热空气干燥分为在150℃下干燥10分钟、在250℃下干燥5分钟和在420℃下干燥5分钟三个步骤。将酰亚胺化后的片材在1200℃下热处理2小时使其碳化，然后在2700℃下热处理7小时对其进行石墨化。对石墨化片在50N/m2的压力下进行轧制，以制备总厚度约为100μm的石墨片。
实施例2
重复实施例1的步骤，不同之处在于，将5个涂覆有聚酰胺酸的基材层叠以获得共11层的层压板(涂层/基材层/.../基底层/涂层)，并进行酰亚胺化、碳化、石墨化和轧制以制备总厚度为200μm的石墨片。
对比例1
在市售的厚度为40μm的聚酰亚胺薄膜的两侧涂覆上丙烯酸粘合剂。将2层薄膜层叠成共5层层压板(粘合剂层/薄膜层/粘合剂层/薄膜层/粘合剂层)。对其进行与实施例1相同的碳化、石墨化和轧制以制备总厚度为100μm的石墨片。
对比例2
重复实施例1的步骤，不同之处在于，对涂覆有聚酰胺酸(涂层/基材层/涂层)的基材进行酰亚胺化、碳化、石墨化和轧制以制备总厚度为40μm的石墨片。
对比例3
重复对比例2的步骤，不同之处在于，调节轧制压力以制备总厚度约为25μm的石墨片。
测试实施例1：比热的测量
在实施例和对比例中制备的石墨片的比热用LFA装置(LFA 447型，NETZSCH)测量。
测试实施例2：密度的测量
在实施例和对比例中制备的石墨片的密度用阿基米德密度计(SD-200L，AlfaMirage)测量。
测试实施例3：热扩散率的测量
在实施例和对比例中制备的石墨片的热扩散率用LFA装置(LFA 447型，NETZSCH)测量。
测试实施例4：热导率的测量
根据测试实施例1至3中测量的比热、密度和热扩散率，计算实施例和对比例中制备的石墨片的热导率。
测试实施例5：电磁屏蔽能力
通过测试实施例和对比例中制备的石墨片在30MHz～1500MHz范围内的电磁衰减(dB)来评价其电磁屏蔽能力。
[表1]
Figure BDA0002868124240000111
Figure BDA0002868124240000121
如上表1所示，相比于具有相同厚度的对比例1，厚度分别为100μm和200μm的实施例1和实施例2的多层石墨片具有优异的热导率。此外，实施例1和2的多层石墨片在电磁屏蔽能力方面明显优于对比例1～3的石墨片。
同时，由于材料的特性，未能通过碳化和石墨化单层聚酰亚胺薄膜来制备厚度为70μm以上的石墨片。

Claims (17)

1.一种多层石墨片，其包括一层压板，所述层压板中至少一层第一石墨层和至少一层第二石墨层交替层叠成共5层以上，其中第一石墨层比第二石墨层致密；
其中，所述第一石墨层包括固化树脂的石墨化材料，和所述第二石墨层包括纤维基材的石墨化材料；
其中，多层石墨片的总厚度为70μm至1000μm；
其中，所述第一石墨层的厚度为10μm至50μm，和所述第二石墨层的厚度为5μm至60μm。
2.如权利要求1所述多层石墨片，其中，所述多层石墨片为轧制片。
3.如权利要求2所述多层石墨片，其中，其在30MHz～1,500MHz范围内具有110dB以上的电磁屏蔽能力，在水平方向上的热导率为700W/m·K～1,300W/m·K。
4.如权利要求2所述多层石墨片，其中，其表观密度为1.3～1.8g/cm3。
5.如权利要求1所述多层石墨片，其中，所述层压板的两侧具有第一石墨层作为表面层。
6.如权利要求1所述多层石墨片，其中，所述第一石墨层的厚度变化小于40μm，和所述第二石墨层的厚度变化为40μm以上。
7.如权利要求1所述多层石墨片，其中，所述第一石墨层和所述第二石墨层之间的界面为波浪形图案的曲线形状。
8.如权利要求1所述多层石墨片，其中，所述层压板包括3～6层第一石墨层和2～5层第二石墨层。
9.如权利要求1所述多层石墨片，其中，所述固化树脂包括含有聚酰胺酸的组合物的固化材料。
10.如权利要求1所述多层石墨片，其中，所述纤维基材为机织物、无纺布或纸，其包括至少一种选自以下的纤维：包括棉花、大麻、羊毛和丝的天然纤维；包括人造丝、醋酸纤维和三醋酸纤维的纤维素类纤维；包括尼龙、聚酯、聚氨酯、聚乙烯、聚氯乙烯、聚氟乙烯、聚乙烯醇、聚丙烯酸和聚丙烯的合成纤维。
11.一种如权利要求1所述的多层石墨片的制备方法，其包括：
在纤维基材的一侧或两侧涂覆上树脂组合物以形成涂层；
制备层压板，所述层压板中至少一层纤维基材和至少一层涂层交替层叠成共5层以上；
热处理所述层压板以固化涂层作为第一热处理；和
对进行了第一热处理的层压板进行第二热处理以碳化和石墨化纤维基材和涂层。
12.如权利要求11所述的多层石墨片的制备方法，其中，所述层压板的两侧表面层均为涂层。
13.如权利要求11所述的多层石墨片的制备方法，其中，第一热处理包括：
在100～150℃下进行10分钟至15分钟的第一阶段热处理；
在230～250℃下进行5分钟至7分钟的第二阶段热处理；和
在400～420℃下进行5分钟至7分钟的第三阶段热处理。
14.如权利要求11所述的多层石墨片的制备方法，其中，第二热处理包括：
在1,000℃～1,500℃下进行1小时至3小时的第一阶段热处理；和
在2,000℃～3,000℃下进行5小时至10小时的第二阶段热处理。
15.如权利要求11所述的多层石墨片的制备方法，其中，所述树脂组合物包括聚酰胺酸、溶剂、催化剂和脱水剂。
16.如权利要求11所述的多层石墨片的制备方法，其中，所述制备方法进一步包括对已经过第二热处理的层压板进行轧制。
17.如权利要求16所述的多层石墨片的制备方法，其中，所述轧制为使得所述多层石墨片的最终厚度为70μm以上。
CN201980044044.5A 2018-05-03 2019-05-03 具有优异电磁屏蔽性能和导热率的多层石墨片及其制备方法 Active CN112437723B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR10-2018-0051022 2018-05-03
KR1020180051022A KR102094925B1 (ko) 2018-05-03 2018-05-03 전자파 차폐능 및 열전도도가 우수한 다층 그라파이트 시트 및 이의 제조방법
PCT/KR2019/005323 WO2019212284A1 (ko) 2018-05-03 2019-05-03 전자파 차폐능 및 열전도도가 우수한 다층 그라파이트 시트 및 이의 제조방법

Publications (2)

Publication Number Publication Date
CN112437723A CN112437723A (zh) 2021-03-02
CN112437723B true CN112437723B (zh) 2023-05-16

Family

ID=68386897

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201980044044.5A Active CN112437723B (zh) 2018-05-03 2019-05-03 具有优异电磁屏蔽性能和导热率的多层石墨片及其制备方法

Country Status (4)

Country Link
US (1) US11745463B2 (zh)
KR (1) KR102094925B1 (zh)
CN (1) CN112437723B (zh)
WO (1) WO2019212284A1 (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112888149A (zh) * 2021-01-12 2021-06-01 深圳市鑫诺诚科技有限公司 一种导电、屏蔽、散热复合材料
CN113292341A (zh) * 2021-05-21 2021-08-24 北京中石伟业科技无锡有限公司 一种散热石墨膜的制备方法
CN217217226U (zh) * 2021-08-11 2022-08-16 荣耀终端有限公司 均热板及电子设备
CN114771040A (zh) * 2022-03-17 2022-07-22 株洲时代华昇新材料技术有限公司 一种石墨叠层复合材料及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102575400A (zh) * 2009-10-06 2012-07-11 西格里碳素欧洲公司 包含碳纤维软毡和碳纤维硬毡的复合材料
WO2018074889A2 (ko) * 2016-10-21 2018-04-26 에스케이씨 주식회사 그라파이트 시트의 제조방법

Family Cites Families (73)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3174895A (en) * 1960-09-07 1965-03-23 Union Carbide Corp Graphite cloth laminates
JPS5941239B2 (ja) * 1976-06-25 1984-10-05 オムロン株式会社 交通標識制御装置
JPS56157478A (en) * 1980-05-07 1981-12-04 Hitachi Chem Co Ltd Combined graphite sheet laminated gasket
DE3307090A1 (de) * 1983-03-01 1984-09-06 Sigri Elektrographit Gmbh, 8901 Meitingen Verfahren zum herstellen eines schichtstoffes aus kohlenstoff
JPS60181129A (ja) 1984-02-28 1985-09-14 Agency Of Ind Science & Technol 高導電性ポリイミド熱処理物及びその組成物の製造法
DE3435043A1 (de) * 1984-09-24 1986-04-03 C. Conradty Nürnberg GmbH & Co KG, 8505 Röthenbach Polygranularer kohlenstoffkoerper und verfahren zu seiner herstellung
DE3435044A1 (de) * 1984-09-24 1986-04-03 C. Conradty Nürnberg GmbH & Co KG, 8505 Röthenbach Selbsttragender, formbestaendiger kohlenstoffverbundkoerper und verfahren zu seiner herstellung
JPS61155260A (ja) * 1984-12-27 1986-07-14 呉羽化学工業株式会社 炭素材同士を接合した炭素製品の製造方法
JPS61367A (ja) * 1985-05-24 1986-01-06 株式会社日立製作所 ケーブル火災消化装置
JPS61275116A (ja) 1985-05-30 1986-12-05 Res Dev Corp Of Japan グラフアイトフイルムおよび繊維の製造方法
DE3603305C1 (de) * 1986-02-04 1987-07-23 Sigri Gmbh Verfahren zum Herstellen eines aus mehreren Schichten bestehenden,zwischen den Schichten Graphitfolie enthaltenden fuer Fluide undurchlaessigen Kohlenstoff- oder Graphitkoerpers und dessen Verwendung
DE3608063A1 (de) * 1986-03-11 1987-09-17 Conradty Nuernberg Kohlenstoffkoerper hoher porositaet und verfahren zu seiner herstellung
JPH0265299A (ja) * 1988-08-31 1990-03-05 Matsushita Electric Ind Co Ltd 電磁波遮蔽材料
CA2045409C (en) * 1989-02-15 1995-07-11 Zoran Dordevic Textile fabric shielding electromagnetic radiation, and clothing made thereof
DE8914883U1 (zh) * 1989-12-20 1990-03-15 Sigri Gmbh, 8901 Meitingen, De
JPH03279207A (ja) * 1990-03-29 1991-12-10 Matsushita Electric Ind Co Ltd グラファイトの製造方法
GB9202486D0 (en) * 1992-02-06 1992-03-25 Dunlop Ltd Carbon-carbon composite material
JPH05301781A (ja) * 1992-04-27 1993-11-16 Dainippon Ink & Chem Inc 炭素材用シート状接着材及び炭素材の接着方法
JPH06100367A (ja) * 1992-09-16 1994-04-12 Osaka Gas Co Ltd 異方性炭素−炭素複合材料およびその製造方法
JP3345986B2 (ja) 1993-10-15 2002-11-18 松下電器産業株式会社 グラファイト熱伝導体およびそれを用いたコールドプレート
JPH1045474A (ja) * 1996-08-01 1998-02-17 Toyo Tanso Kk 熱分解炭素被覆黒鉛材の製造方法
JP3267194B2 (ja) * 1997-06-24 2002-03-18 松下電器産業株式会社 電磁波シールド材の製造方法及び電磁波シールド材並びにそのシールド材を用いた電磁波発生源
WO1999010598A1 (fr) * 1997-08-26 1999-03-04 Toyo Tanso Kabushiki Kaisya Tole de graphite deploye pour blindage contre les ondes electromagnetiques et son procede de fabrication
JP2000178016A (ja) * 1998-12-11 2000-06-27 Matsushita Electric Ind Co Ltd グラファイトシートの製造方法及びグラファイトシートを用いた熱伝導体
JP4338844B2 (ja) * 1999-07-19 2009-10-07 東洋炭素株式会社 成形断熱材及びヒートシールド
CA2393697A1 (en) * 1999-12-10 2001-06-14 Graftech Inc. Thermal insulating device
JP3480459B2 (ja) * 2001-09-19 2003-12-22 松下電器産業株式会社 グラファイトシート
JP2008120680A (ja) * 2002-06-18 2008-05-29 Toyo Tanso Kk 可撓性を有する高純度膨張黒鉛シート
RU2234176C2 (ru) * 2002-08-07 2004-08-10 Общество с ограниченной ответственностью Научно-техническое внедренческое предприятие "Гироконт" Защитный экран от воздействия электромагнитного излучения и способ его изготовления
US20040076810A1 (en) * 2002-10-17 2004-04-22 Ucar Carbon Company Inc. Composite high temperature insulator
FR2849651B1 (fr) * 2003-01-08 2008-02-15 Carbone Lorraine Composants Structures isolante comprenant des couches en particules de graphite expanse comprimees a des densites differentes, elements isolants thermiques realises a partir de ces structures
JP3691836B1 (ja) * 2004-08-27 2005-09-07 東洋炭素株式会社 膨張黒鉛シート
JP5438882B2 (ja) * 2006-09-15 2014-03-12 株式会社カネカ 折り曲げ特性に優れたグラファイトフィルム
WO2009060818A1 (ja) * 2007-11-06 2009-05-14 Kaneka Corporation グラファイトフィルムの製造方法
JP5295631B2 (ja) * 2008-01-18 2013-09-18 株式会社カネカ 多層グラファイトフィルムおよびその製造方法、電子機器、ディスプレイならびにバックライト
WO2009147771A1 (ja) * 2008-06-02 2009-12-10 パナソニック株式会社 グラファイト複合体及びその製造方法
JP5329135B2 (ja) * 2008-06-20 2013-10-30 株式会社カネカ グラファイト複合フィルム
JP5322587B2 (ja) * 2008-08-12 2013-10-23 株式会社カネカ グラファイトフィルムの製造方法
JP5107191B2 (ja) * 2008-09-11 2012-12-26 株式会社カネカ グラファイト複合フィルム
JP5343478B2 (ja) * 2008-09-18 2013-11-13 パナソニック株式会社 グラファイト複合体
JP5343477B2 (ja) * 2008-09-18 2013-11-13 パナソニック株式会社 グラファイト複合シートおよびその製造方法
RU2427530C1 (ru) * 2010-02-10 2011-08-27 Институт новых углеродных материалов и технологий (Закрытое акционерное общество), (ИНУМиТ (ЗАО)) Способ получения многослойного углеродного теплоизоляционного материала и многослойный материал
RU95592U1 (ru) * 2010-03-15 2010-07-10 Институт новых углеродных материалов и технологий (Закрытое акционерное общество) (ИНУМиТ (ЗАО)) Многослойный теплоизоляционный материал
CN203415567U (zh) * 2010-09-21 2014-01-29 格拉弗技术国际控股有限公司 复合散热器
JP2012076958A (ja) * 2010-09-30 2012-04-19 Sekisui Chem Co Ltd グラフェン複合材料及びグラフェン複合シートの製造方法
JP5887494B2 (ja) * 2012-03-22 2016-03-16 パナソニックＩｐマネジメント株式会社 グラファイトシートの製造方法
CN102795617B (zh) * 2012-07-24 2014-10-29 清华大学深圳研究生院 一种石墨块材料及其制备方法
JP6172732B2 (ja) * 2012-10-25 2017-08-02 リグナイト株式会社 黒鉛シート複合材及びその製造方法
CN104310379A (zh) * 2012-12-28 2015-01-28 苏州斯迪克新材料科技股份有限公司 高模量石墨散热片
CN103450857A (zh) * 2013-09-05 2013-12-18 中国科学院青岛生物能源与过程研究所 一种导热率可控的复合石墨导热膜材料及其制备工艺
CN105579393B (zh) * 2013-09-26 2018-12-11 株式会社钟化 石墨片、其制造方法、配线用层叠板、石墨配线材料和配线板的制造方法
TWI641552B (zh) 2013-11-28 2018-11-21 鐘化股份有限公司 石墨膜之製造方法
CN103770415B (zh) * 2014-01-26 2015-07-22 斯迪克新型材料（江苏）有限公司 导热石墨片及其制造方法
JP2015174807A (ja) * 2014-03-17 2015-10-05 大阪ガスケミカル株式会社 炭素繊維系断熱材及びその製造方法
US9359208B2 (en) * 2014-03-20 2016-06-07 Nanotek Instruments, Inc. Production process for highly conductive graphitic films
US20170110385A1 (en) * 2014-04-08 2017-04-20 Panasonic Intellectual Property Management Co., Ltd. Heat-conductive sheet and production method therefor
CN103922324A (zh) * 2014-04-11 2014-07-16 江苏悦达新材料科技有限公司 一种高导热石墨膜的制备方法
JP6435507B2 (ja) * 2014-07-18 2018-12-12 パナソニックＩｐマネジメント株式会社 複合シートとその製造方法および複合シートを用いた電子機器
CN104445174A (zh) * 2014-12-12 2015-03-25 碳元科技股份有限公司 一种超薄高导热石墨膜及其制备方法
JP6594639B2 (ja) * 2015-02-12 2019-10-23 株式会社カネカ 高熱伝導性放熱基板、及びその製造方法
EP3257811B1 (en) * 2015-02-12 2022-03-30 Kaneka Corporation Smooth-surfaced graphite membrane and method for producing same
KR101669204B1 (ko) * 2015-04-30 2016-10-25 에스케이씨 주식회사 그라파이트 시트 및 이의 제조방법
CN105113088A (zh) * 2015-06-08 2015-12-02 江西先材纳米纤维科技有限公司 一种聚酰亚胺基高导热石墨纳米纤维膜材料及其制备方法
KR101705222B1 (ko) * 2015-07-20 2017-02-09 에스케이씨 주식회사 공압출을 이용한 열전도 이방성 필름의 제조 방법
KR101729006B1 (ko) * 2015-07-23 2017-05-02 주식회사 뉴파워 프라즈마 탄소섬유가 포함된 방열시트 ,이의 제조방법 및 제조장치
US20170089650A1 (en) * 2015-09-24 2017-03-30 Jones Tech (USA), Inc. Flexible heat transfer structure
JP6574667B2 (ja) * 2015-10-05 2019-09-11 積水化学工業株式会社 熱伝導シート、熱伝導シート積層体及び熱伝導シート成形体
KR101855281B1 (ko) * 2015-12-17 2018-05-08 에스케이씨 주식회사 방열 시트 및 이의 제조방법
EP3392369B1 (en) * 2015-12-18 2023-07-19 Nippon Piston Ring Co., Ltd. Coating film, manufacturing method therefor, and pvd apparatus
WO2017131205A1 (ja) * 2016-01-29 2017-08-03 株式会社カネカ 黒鉛膜及び黒鉛テープ
CN105752959A (zh) * 2016-03-04 2016-07-13 深圳丹邦科技股份有限公司 热塑性聚酰亚胺薄膜碳化复合膜及其制备方法
CN109311282B (zh) * 2016-06-03 2021-11-02 申克碳化技术股份有限公司 制造承载板的方法及承载板
DE102016219214A1 (de) * 2016-10-04 2018-04-05 Schunk Kohlenstofftechnik Gmbh Verfahren zur Herstellung eines Bauelements und Bauelement

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102575400A (zh) * 2009-10-06 2012-07-11 西格里碳素欧洲公司 包含碳纤维软毡和碳纤维硬毡的复合材料
WO2018074889A2 (ko) * 2016-10-21 2018-04-26 에스케이씨 주식회사 그라파이트 시트의 제조방법

Also Published As

Publication number Publication date
US11745463B2 (en) 2023-09-05
US20210086474A1 (en) 2021-03-25
KR102094925B1 (ko) 2020-03-30
CN112437723A (zh) 2021-03-02
WO2019212284A1 (ko) 2019-11-07
KR20190127005A (ko) 2019-11-13

Similar Documents

Publication Publication Date Title
CN112437723B (zh) 具有优异电磁屏蔽性能和导热率的多层石墨片及其制备方法
EP1502992B1 (en) Carbon fiber paper and porous carbon electrode substrate for fuel cell therefrom
JP4377867B2 (ja) 銅張積層板、プリント配線板及び多層プリント配線板並びにこれらの製造方法
CN107108227B (zh) 石墨片及其制备方法
CA2234317C (en) Composite film comprising low-dielectric resin and para-oriented aromatic polyamide
CN109923091B (zh) 制备石墨片的方法
WO2015069382A2 (en) Flexible composites containing graphite and fillers
TW202120775A (zh) 石墨片的製造方法
WO1996015306A1 (fr) Materiau en feuille pour stratifie de circuit imprime et stratifie pour circuit imprime
JPS63242395A (ja) 黒鉛・繊維複合材料
EP0428991A2 (en) Composite material of carbon fibers and method for producing the same
CN113292341A (zh) 一种散热石墨膜的制备方法
TWI477386B (zh) 熱壓機用之緩衝材及其應用
CN114538422A (zh) 一种多孔-微气囊结构的石墨烯交替薄膜、制备方法及应用
JP2003151568A (ja) 固体高分子型燃料電池用の電極基材とその製造方法
TW202124155A (zh) 熱壓用緩衝材
CN111331951A (zh) 一种含硅芳炔树脂复合材料及其制备方法
KR102212191B1 (ko) 다공성의 그래파이트 나노섬유 웹, 상기 웹 구조를 포함하는 멤브레인, 상기 멤브레인을 포함하는 방열시트 및 상기 나노섬유 웹의 제조방법
JP4154666B2 (ja) 機能性シートまたは機能性シート複合体の製造方法
CN115991013B (zh) 石墨烯复合导热膜及制备方法
CN112724445A (zh) 一种pi/氧化石墨烯/石墨烯复合膜及其制备方法和应用
TW202319215A (zh) 複合片材之製造方法及複合片材
KR910008864B1 (ko) 금속-피복 적층판의 연속적 제조방법
JP2003251774A (ja) 複合シートおよびその製造方法
JPH04161450A (ja) 複合材料成形体の成形方法

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
GR01 Patent grant
GR01 Patent grant