CN108189518B - Graphene electromagnetic shield cloth and its manufacturing method - Google Patents
Graphene electromagnetic shield cloth and its manufacturing method Download PDFInfo
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- CN108189518B CN108189518B CN201711480538.7A CN201711480538A CN108189518B CN 108189518 B CN108189518 B CN 108189518B CN 201711480538 A CN201711480538 A CN 201711480538A CN 108189518 B CN108189518 B CN 108189518B
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- 239000004744 fabric Substances 0.000 title claims abstract description 174
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 115
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000002313 adhesive film Substances 0.000 claims abstract description 70
- 239000002131 composite material Substances 0.000 claims abstract description 59
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052802 copper Inorganic materials 0.000 claims abstract description 40
- 239000010949 copper Substances 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 26
- 239000005751 Copper oxide Substances 0.000 claims abstract description 20
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 20
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000005488 sandblasting Methods 0.000 claims abstract description 4
- 230000003746 surface roughness Effects 0.000 claims abstract description 4
- 239000000853 adhesive Substances 0.000 claims description 40
- 230000001070 adhesive effect Effects 0.000 claims description 40
- 229920000642 polymer Polymers 0.000 claims description 34
- 238000007731 hot pressing Methods 0.000 claims description 22
- 230000005298 paramagnetic effect Effects 0.000 claims description 18
- 239000002105 nanoparticle Substances 0.000 claims description 17
- 239000003292 glue Substances 0.000 claims description 14
- 239000013528 metallic particle Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000010451 perlite Substances 0.000 claims description 10
- 235000019362 perlite Nutrition 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 5
- 238000005422 blasting Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000004026 adhesive bonding Methods 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- -1 graphite Alkene Chemical class 0.000 claims 1
- 239000002585 base Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
- 229920000914 Metallic fiber Polymers 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/067—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of fibres or filaments
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- 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
- B32B3/02—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 features of form at particular places, e.g. in edge regions
- B32B3/08—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 features of form at particular places, e.g. in edge regions characterised by added members at particular parts
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
- B32B37/1018—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure using only vacuum
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- 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
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- 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
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/087—Oxides of copper or solid solutions thereof
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- B32B2307/212—Electromagnetic interference shielding
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Laminated Bodies (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
The invention discloses a kind of graphene electromagnetic shield cloth and its manufacturing methods, the electromagnetic shield cloth from bottom to top successively includes preventing puncturing layer, base cloth layer, copper oxide, layers of copper, first adhesive film, first graphene composite material layer of cloth, second adhesive film and the second graphene composite material layer of cloth, base cloth layer is blended cloth, first adhesive film and the second adhesive film include graphene powder, the resistance value of first graphene composite material layer of cloth is greater than the resistance value of the second graphene composite material layer of cloth, the resistance value of first adhesive film is greater than the resistance value of second adhesive film, the resistance value of first graphene composite material layer of cloth and the resistance value of the first adhesive film are essentially identical, the resistance value of second graphene composite material layer of cloth and the resistance value of the second adhesive film are essentially identical, layers of copper passes through surface sand-blasting process, its surface roughness is greater than Ra 0.05.Graphene electromagnetic shield cloth shield effectiveness of the invention is good, durability is good, while excellent in mechanical performance, use scope are wide.
Description
Technical field
The present invention relates to a kind of electromagnetic shield cloth and its manufacturing method, in particular to a kind of graphene electromagnetic shield cloth and its
Manufacturing method.
Background technique
Electromagnetic shield cloth is actually a kind of product of comparative maturity, and the popular electromagnetic shield cloth of existing market is divided into
Metallic fiber and two kinds of silver fiber, wherein cloth used by metallic fiber electromagnetic shield cloth be about 0.008 millimeter by diameter
Metallic fiber (metallic fiber that every wires contain 8 or so) and cotton etc. is blended is made into, can be to 100-3000MHz
Electromagnetic wave within (civilian common frequency) is effectively shielded, and shielding rate is at 30 decibels or so.This cloth not only has good
Good gas permeability, but also can wash, it is current most practical domestic electromagnetic shielding cloth fabric.It is exactly also silver fiber,
This cloth, which uses silver-plated technology, makes silver fiber well and the fusion of other fibers (cotton, terylene etc.), not only has metal fibre
The advantages of tieing up cloth, and quality is more soft.But there is also very big defect, both shielding cloth power for these two types of shielding cloths
Learn that performance is poor, not acid and alkali-resistance, non-refractory, so, when using these two types shielding cloth, shielding cloth cannot be folded, cannot be approached
Chemical reagent, need far from acid or alkali environment, will be far from high temperature source.So this very harsh use condition determines this screen
It covers cloth and is only used for civil field, in industrial circle and military field, this shielding cloth is no any use.
There is also other types of shielding cloths, such as existing technical literature CN106567178A to disclose one in the prior art
Kind Multifunctional electromagnetic shielding cloth, this shielding cloth uses stainless steel fibre instead of silver fiber, but actually this electromagnetic screen
Cover cloth still based on the shielding cloth of metallic fiber, so this shielding cloth is not still resistant to bending, and its electromagnetic shielding performance compared with
Difference is not able to satisfy the needs of certain special dimensions.For another example existing technical literature CN205522734U discloses a kind of electromagnetic shielding
Cloth, this electromagnetic shield cloth have been abandoned by metallic fiber and the blended preparation method of other organic fibers, in electromagnetic shield cloth
Be individually added into one layer of metallic fibrous layer, even if but carried out this transformation, the metallic fibrous layer still not bend resistance, and by
It is non-conductive in the surface of this shielding cloth, so shield effectiveness is poor.For another example existing technical literature CN2720576Y discloses one
Kind electromagnetic shield cloth, this electromagnetic shield cloth do not use metallic fiber, are changed to using electrodeposition of metals, so overcoming metal fibre
Defect not resistant to bending is tieed up, but the prior art is the plating metal multilayer film directly in base fabric, so metal film and base fabric
Between binding force it is poor, due to the difference of lattice structure between metal film, there is also the defects of binding force difference, and base fabric belongs to
How rough surface guarantees that plating is uniformly still insoluble problem.So this shielding cloth due to coating not
Uniformly, cause shield effectiveness poor, and due between film layer binding force it is poor, so durability is poor.
The information disclosed in the background technology section is intended only to increase the understanding to general background of the invention, without answering
When being considered as recognizing or imply that the information constitutes the prior art already known to those of ordinary skill in the art in any form.
Summary of the invention
The purpose of the present invention is to provide a kind of graphene electromagnetic shield cloths, thus the shortcomings that overcoming the prior art.
To achieve the above object, the present invention provides a kind of graphene electromagnetic shield cloth, electromagnetic shield cloth from bottom to top according to
Secondary includes preventing puncturing layer, base cloth layer, copper oxide, layers of copper, the first adhesive film, the first graphene composite material layer of cloth, the second glue
Film layer and the second graphene composite material layer of cloth, base cloth layer are blended cloths, and the first adhesive film and the second adhesive film include stone
Black alkene powder, the resistance value of the first graphene composite material layer of cloth are greater than the resistance value of the second graphene composite material layer of cloth, the
The resistance value of one adhesive film is greater than the resistance value of the second adhesive film, the resistance value and the first glue of the first graphene composite material layer of cloth
The resistance value of film layer is essentially identical, the resistance value and the basic phase of resistance value of the second adhesive film of the second graphene composite material layer of cloth
Together, layers of copper passes through surface sand-blasting process, and the surface roughness of layers of copper is greater than Ra0.05.
Preferably, in above-mentioned technical proposal, base cloth layer is the blended cloth of aramid fiber and Fypro.
Preferably, in above-mentioned technical proposal, the anti-layer that punctures is glass fabric, glass fabric with a thickness of 1-5mm.
Preferably, in above-mentioned technical proposal, by weight, the first adhesive film and the second adhesive film respectively include graphite
1-10 parts of alkene powder, 1-10 parts of perlite powder, 40-60 parts of solvent, 20-80 parts of thermoplastic polymer adhesive, amorphous
1-10 parts of state paramagnetic nanoparticles metallic particles, the first adhesive film is different from the ingredient of the second adhesive film.
Preferably, in above-mentioned technical proposal, the first graphene composite material layer of cloth is the first graphene polymer glue of dipping
The glass fabric of glutinous agent, by weight, the first graphene polymer adhesive includes 1-10 parts of graphene powder, solvent
40-60 parts, 20-80 parts of polymer adhesive, 1-10 parts of amorphous state paramagnetic nanoparticles metallic particles.
Preferably, in above-mentioned technical proposal, the second graphene composite material layer of cloth is the second graphene polymer glue of dipping
The glass fabric of glutinous agent, by weight, the second graphene polymer adhesive includes 1-10 parts of graphene powder, solvent
40-60 parts, 20-80 parts of polymer adhesive, 1-10 parts of amorphous state paramagnetic nanoparticles metallic particles, wherein the second graphene is poly-
The ingredient for closing object adhesive is different from the ingredient of the first graphene polymer adhesive.
Preferably, in above-mentioned technical proposal, copper oxide with a thickness of 20-50nm.
The present invention also provides a kind of manufacturing method of graphene electromagnetic shield cloth, which includes: to prepare anti-puncture
Layer and base cloth layer；Non-conductive adhesive is coated on layer in anti-puncture, and then base cloth layer is layed in and prevents puncturing on layer, with laggard
Row hot-pressing processing obtains first layer stack；Using magnetically controlled sputter method in first layer stack deposited oxide layers of copper；Utilize magnetic control
Sputtering method copper layer on copper oxide, and blasting treatment is carried out to the layers of copper, obtain the second laminated body；Prepare first
Graphene composite material layer of cloth and the second graphene composite material layer of cloth: various raw materials are put into instead first, in accordance with material rate
Answer in kettle, be then stirred, it is to be mixed uniformly after, graphene polymer adhesive is obtained, then by graphene polymer glue
Glutinous agent is poured into dipping tank, and glass fibre is arranged in dipping tank and is impregnated；Prepare the first adhesive film and the second adhesive film；By suitable
It is multiple that sequence stacks the second laminated body, the first adhesive film, the first graphene composite material layer of cloth, the second adhesive film and the second graphene
Condensation material layer of cloth obtains stacked body, and then stacked body is put into vacuum hotpressing machine and carries out hot pressing, which includes four ranks
Section, wherein first stage temperature is 100-150 DEG C, pressure 5-10MPa, duration 10-30s, and second stage temperature is
200-300 DEG C, pressure 10-20MPa, duration 10-20min, phase III temperature is 100-200 DEG C, pressure 10-
20MPa, duration 3-5min, fourth stage temperature are 50-70 DEG C, pressure 5-10MPa, duration 3-5min,
Obtain graphene electromagnetic shield cloth.
Preferably, in above-mentioned technical proposal, copper oxide with a thickness of 20-50nm.
Preferably, in above-mentioned technical proposal, layers of copper with a thickness of 100-200nm.
Compared with prior art, the invention has the following beneficial effects:
1, the present invention deposits one layer of copper oxide on base cloth layer, and inventor has found that the binding force of copper oxide and base cloth layer is big
In the binding force of layers of copper and base cloth layer, and the lattice structure similarity of copper oxide and copper is higher, so boundary between the two
Face residual stress is smaller, thus solves the defect of metal layer and base cloth layer binding force difference in the prior art；2, inventors have found that
When wave frequency is higher, the vortex that shielding cloth generates concentrates on shielding cloth outer layer, sets smaller value for outer layer resistance value,
Outer layer eddy-current loss can be made larger, enhance effectiveness.By the resistance value of middle layer graphene composite material layer of cloth
Be designed as it is lower can stop vortex pass through material interface, to prevent effectiveness to be deteriorated, simultaneously because middle layer stone
The resistance value of black alkene composite material layer of cloth can be lower, so middle layer graphene composite material layer of cloth may include more non-
Conductive particles, so that the mechanical property of middle layer graphene composite material layer of cloth is stronger；3, in the first adhesive film, the first graphene
Amorphous state paramagnetic nanoparticles metal is added in composite material layer of cloth, the second adhesive film and the second graphene composite material layer of cloth
Grain, can be effectively reduced the resistance value of above layers, simultaneously because the specific surface area of amorphous nano particle is larger, it can be effective
Increase the interface gross area in adhesive, so that the mechanical property of glue film and layer of cloth is greatly improved, and due to metal
Particle is paramagnetic, so will not magnetize under the action of alternating electromagnetism wave, so will not be because of addition metallic particles
And shield effectiveness is caused to deteriorate；4, four stage hot pressings are proposed for special layers structure of the invention, so that product mechanics
Better performances.
Detailed description of the invention
Fig. 1 is the schematic diagram of graphene electromagnetic shield cloth according to the present invention.
Main appended drawing reference explanation:
11- is anti-to puncture layer, 12- base cloth layer, 13- copper oxide, 14- layers of copper, the first adhesive film of 15-, the first graphene of 16-
Composite material layer of cloth, the second adhesive film of 17-, 18- the second graphene composite material layer of cloth.
Specific embodiment
With reference to the accompanying drawing, specific embodiments of the present invention will be described in detail, it is to be understood that guarantor of the invention
Shield range is not limited by the specific implementation.
Unless otherwise explicitly stated, otherwise in entire disclosure and claims, term " includes " or its change
Changing such as "comprising" or " including " etc. will be understood to comprise stated element or component, and not exclude other members
Part or other component parts.
Present invention does not require the source of chemical reagent, all chemical reagent that the present invention uses all are can be from chemical industry shop
Or the chemicals of Online Shopping, the glass fabric and blended fabric that the present invention uses can be bought from network, it can also be with
It is manufactured based on method well known in the art.The so-called "upper" of the present invention refers on the outside of shielding cloth namely external environment, institute of the present invention
The "lower" of title refers on the inside of shielding cloth namely internal environment.For example, if the shielding cloth using the application makes military account
Paulin is "lower" alleged by the present invention within tent then being "upper" alleged by the present invention except tent.It is real carrying out shield effectiveness
When testing, the comparative example 1 that the present invention uses is the shielding cloth that embodiment 1 is introduced in CN106567178A, and comparative example 2 is
Shielding cloth disclosed in CN2720576Y embodiment 2.
Embodiment 1
Electromagnetic shield cloth from bottom to top successively includes anti-puncturing layer, base cloth layer, copper oxide, layers of copper, the first adhesive film, the
One graphene composite material layer of cloth, the second adhesive film and the second graphene composite material layer of cloth, base cloth layer are blended cloths, first
Adhesive film and the second adhesive film include graphene powder, and the resistance value of the first graphene composite material layer of cloth is greater than the second graphite
The resistance value of alkene composite material layer of cloth, the resistance value of the first adhesive film are greater than the resistance value of the second adhesive film, and the first graphene is multiple
The resistance value of condensation material layer of cloth and the resistance value of the first adhesive film are essentially identical, the resistance value of the second graphene composite material layer of cloth
Essentially identical with the resistance value of the second adhesive film, layers of copper passes through surface sand-blasting process, and the surface roughness of layers of copper is greater than Ra0.05.
In parts by weight, the first adhesive film includes 1 part of graphene powder, 10 parts of perlite powder, 40 parts of solvent, thermoplasticity polymerization
80 parts of object adhesive, 1 part of amorphous state paramagnetic nanoparticles metallic particles, the second adhesive film include 10 parts of graphene powder, expansion treasure
Pearl rock powder last 1 part, 60 parts of solvent, 80 parts of thermoplastic polymer adhesive, 10 parts of amorphous state paramagnetic nanoparticles metallic particles.First
Graphene composite material layer of cloth is the glass fabric for impregnating the first graphene polymer adhesive, by weight, the first stone
Black alkene polymer adhesive includes 1 part of graphene powder, 60 parts of solvent, 80 parts of polymer adhesive, amorphous state paramagnetic nanoparticles
1 part of metallic particles.Second graphene composite material layer of cloth is the glass fabric for impregnating the second graphene polymer adhesive, is pressed
Parts by weight meter, the second graphene polymer adhesive include 10 parts of graphene powder, 60 parts of solvent, 20 parts of polymer adhesive,
10 parts of amorphous state paramagnetic nanoparticles metallic particles.Copper oxide with a thickness of 20-50nm.Preparation method specifically: prepare anti-stab
Broken layer and base cloth layer；Non-conductive adhesive is coated on layer in anti-puncture, and then base cloth layer is layed in and prevents puncturing on layer, then
Hot-pressing processing is carried out, first layer stack is obtained；Using magnetically controlled sputter method in first layer stack deposited oxide layers of copper；Utilize magnetic
Sputtering method copper layer on copper oxide is controlled, and blasting treatment is carried out to the layers of copper, obtains the second laminated body；Prepare the
One graphene composite material layer of cloth and the second graphene composite material layer of cloth: various raw materials are put into first, in accordance with material rate
In reaction kettle, be then stirred, it is to be mixed uniformly after, graphene polymer adhesive is obtained, then by graphene polymer
Adhesive pours into dipping tank, and glass fibre is arranged in dipping tank and is impregnated；Prepare the first adhesive film and the second adhesive film；It presses
Sequence stacks the second laminated body, the first adhesive film, the first graphene composite material layer of cloth, the second adhesive film and the second graphene
Composite material layer of cloth obtains stacked body, and then stacked body is put into vacuum hotpressing machine and carries out hot pressing, which includes four ranks
Section, wherein first stage temperature is 100 DEG C, pressure 10MPa, duration 30s, and second stage temperature is 200 DEG C, pressure
Power is 20MPa, duration 20min, and phase III temperature is 100 DEG C, pressure 20MPa, duration 5min, the 4th
Phase temperature is 50 DEG C, pressure 10MPa, duration 5min and obtains graphene electromagnetic shield cloth.Layers of copper with a thickness of
100-200nm。
Embodiment 2
Electromagnetic shield cloth from bottom to top successively includes preventing puncturing layer, base cloth layer, layers of copper, the first adhesive film, the first graphene
Composite material layer of cloth, the second adhesive film and the second graphene composite material layer of cloth, it is corresponding in manufacturing method to reduce deposited oxide
The step of copper, remaining parameter, condition, manufacturing method are same as Example 1.
Embodiment 3
Electromagnetic shield cloth from bottom to top successively include it is anti-puncture layer, base cloth layer, copper oxide, layers of copper, the second adhesive film with
And the second graphene composite material layer of cloth, in manufacturing method it is corresponding reduce prepare and the first adhesive film of stacking and the first graphene it is multiple
The step of condensation material layer of cloth, remaining parameter, condition, manufacturing method are same as Example 1.
Embodiment 4
Copper oxide is adjusted with a thickness of 50nm.Remaining parameter, condition, manufacturing method are same as Example 1.
Embodiment 5
Copper oxide is adjusted with a thickness of 35nm.Remaining parameter, condition, manufacturing method are same as Example 1.
Embodiment 6
Copper oxide is adjusted with a thickness of 10nm.Remaining parameter, condition, manufacturing method are same as Example 1.
Embodiment 7
Copper oxide is adjusted with a thickness of 70nm.Remaining parameter, condition, manufacturing method are same as Example 1.
Embodiment 8
Adjust layers of copper with a thickness of 200nm.Remaining parameter, condition, manufacturing method are same as Example 1.
Embodiment 9
Adjust layers of copper with a thickness of 300nm.Remaining parameter, condition, manufacturing method are same as Example 1.
To the product test shield effectiveness and durability of embodiment 1-9 preparation.The wherein test frequency range of shield effectiveness
It is 0.1MHz-40GHz, test method is method well known in the art, and details are not described herein again, it should be pointed out that the present invention is closed
The heart is overall performance of the shielding cloth in test spectral range, so only marking the shielding within the scope of test frequency in result
Efficiency minimum.Durability test is as follows: the shielding cloth being prepared being folded 100 times, is then toasted in 80 DEG C of baking ovens
10h is rinsed shielding cloth 20 times using the diluted acid that pH value is 1 or so followed by, is then again folded shielding cloth 100 times, then will
Shielding cloth is cleaned up and is dried, the remaining percentage of the shield effectiveness for the shielding cloth that then test processes are crossed.For example, false
If the shield effectiveness of untreated shielding cloth is 60dB, the shield effectiveness of processed shielding cloth is 30dB, then according to the invention
Definition, durability 50%.Table 1 is listed in the test result of embodiment 1-9.
Table 1
| Shield effectiveness | Durability | |
| Embodiment 1 | Greater than 60dB | About 90% |
| Embodiment 2 | Greater than 45dB | About 50% |
| Embodiment 3 | Greater than 50dB | About 85% |
| Embodiment 4 | Greater than 60dB | About 90% |
| Embodiment 5 | Greater than 60dB | About 90% |
| Embodiment 6 | Greater than 40dB | About 50% |
| Embodiment 7 | Greater than 40dB | About 50% |
| Embodiment 8 | Greater than 60dB | About 90% |
| Embodiment 9 | Greater than 55dB | About 60% |
| Comparative example 1 | Greater than 30dB | About 30% |
| Comparative example 2 | Greater than 60dB | About 40% |
By 1 result of table as it can be seen that the prior art can be much higher than according to the shield effectiveness of shielding cloth obtained according to the present invention
In existing shielding cloth (such as comparative example 1 is visible with comparative example 1) or shielding cloth produced by the present invention at least have far
Higher than the durability (such as comparative example 1 is visible with comparative example 2) of prior art shielding cloth.Simultaneously as embodiment 2 is not wrapped
Cuprous oxide layer is included, the copper layer directly in base fabric, so layers of copper is uneven, there are microcosmic discontinuous, although leading to layers of copper
Macroscopical conductivity it is still very low, but the conductivity difference of microcosmic upper layers of copper everywhere is very big, certain position resistance values of layers of copper
It is very high, it is especially poor in shortwave frequency range effectiveness.And since there is no cuprous oxide layer, so layers of copper and base fabric knot
It closes loosely, the two is easy delamination, so shield effectiveness reduces more after multiple bending.The performance of embodiment 6,7
Similar explanation can be done.For embodiment 3, due to lacking the first graphene composite material layer of cloth and the first adhesive film, so
Shield effectiveness is poor, and the concrete reason for generating this phenomenon is not clear, but actually embodiment 3 is only in high frequency section
The shield effectiveness of (25GHz or more) is poor, so it may be multiple due to lacking the first graphene of high resistance that inventor, which speculates,
Condensation material layer of cloth and the first adhesive film, so vortex is constantly permeated to layers of copper, but due to from the second graphene composite material
Layer of cloth endosmosis needs to cause the electron transport on microcosmic to be hindered across several interfaces to layers of copper, so while implementing
The macroscopic resistance value of example 3 is close with embodiment 1, but shield effectiveness is poor.
Embodiment 10
Adjusting the first adhesive film includes 10 parts of graphene powder, 10 parts of perlite powder, 60 parts of solvent, thermoplastic poly
80 parts of object adhesive, 1 part of amorphous state paramagnetic nanoparticles metallic particles are closed, the second adhesive film includes 10 parts of graphene powder, expansion
10 parts of perlite powder, 60 parts of solvent, 20 parts of thermoplastic polymer adhesive, 10 parts of amorphous state paramagnetic nanoparticles metallic particles,
Remaining parameter, condition, manufacturing method are same as Example 1.
Embodiment 11
It adjusts the first adhesive film and the second adhesive film is all free of amorphous state paramagnetic nanoparticles metallic particles, remaining parameter,
Condition, manufacturing method are same as Example 1.
Embodiment 12
Adjusting the first adhesive film includes 20 parts of perlite powder, and the second adhesive film includes perlite powder 20
Part, remaining parameter, condition, manufacturing method are same as Example 1.
Embodiment 13
The first adhesive film and the second adhesive film are adjusted without expanded perlite, remaining parameter, condition, manufacturing method with
Embodiment 1 is identical.
Embodiment 14
Adjusting the first graphene composite material layer of cloth is the glass fabric for impregnating the first graphene polymer adhesive, is pressed
Parts by weight meter, the first graphene polymer adhesive include 10 parts of graphene powder, 40 parts of solvent, 80 parts of polymer adhesive,
1 part of amorphous state paramagnetic nanoparticles metallic particles.Second graphene composite material layer of cloth is the second graphene polymer gluing of dipping
The glass fabric of agent, by weight, the second graphene polymer adhesive includes 10 parts of graphene powder, 40 parts of solvent,
20 parts of polymer adhesive, 10 parts of amorphous state paramagnetic nanoparticles metallic particles.Remaining parameter, condition, manufacturing method with implementation
Example 1 is identical.
Embodiment 15
It adjusts the first graphene polymer adhesive and the second graphene polymer adhesive is all free of amorphous state paramagnetic
Property nano-metal particle, remaining parameter, condition, manufacturing method are same as Example 1.
To the product test shield effectiveness and durability of embodiment 10-15 preparation.Test condition and related description can join
See the narration before specification.Test result is listed in table 2.
Table 2
From 2 result of table as it can be seen that becoming insulator if excessive expanded perlite is added in adhesive film and will lead to glue film, from
And being electrically connected between the first graphene composite material layer of cloth, the second graphene composite material layer of cloth and layers of copper is obstructed, cause to shield
Cover effect variation.But the humidification excellent due to expanded perlite, it is significantly mentioned so that the durability of shielding cloth has
It rises.
Embodiment 16
It is 150 DEG C that adjustment hot compression parameters, which are first stage temperature, pressure 5MPa, duration 10s, second stage temperature
Degree is 300 DEG C, pressure 10MPa, duration 10min, and phase III temperature is 200 DEG C, pressure 10MPa, when continuing
Between be 3min, fourth stage temperature be 70 DEG C, pressure 10MPa, duration 3min, remaining parameter, condition, manufacturing method
It is same as Example 1.
Embodiment 17
Adjusting the hot pressing of four stages is the hot pressing of three stages, and three stages were respectively that first stage temperature is 100 DEG C, and pressure is
10MPa, duration 30s, second stage temperature are 200 DEG C, pressure 20MPa, duration 20min, the phase III
Temperature is 50 DEG C, pressure 10MPa, duration 5min, remaining parameter, condition, manufacturing method are same as Example 1.
Embodiment 18
Adjusting the hot pressing of four stages is the hot pressing of three stages, and three stages were respectively that first stage temperature is 200 DEG C, and pressure is
20MPa, duration 20min, second stage temperature are 100 DEG C, pressure 20MPa, duration 5min, the phase III
Temperature is 50 DEG C, pressure 10MPa, duration 5min, remaining parameter, condition, manufacturing method are same as Example 1.
Embodiment 19
Adjusting the hot pressing of four stages is the hot pressing of three stages, and three stages were respectively that first stage temperature is 100 DEG C, and pressure is
10MPa, duration 30s, second stage temperature are 200 DEG C, pressure 20MPa, duration 20min, the phase III
Temperature is 100 DEG C, pressure 20MPa, duration 5min, remaining parameter, condition, manufacturing method are same as Example 1.
To the product test shield effectiveness and durability of embodiment 16-19 preparation.Test condition and related description can join
See the narration before specification.Test result is listed in table 3.
Table 3
| Shield effectiveness | Durability | |
| Embodiment 1 | Greater than 60dB | About 90% |
| Embodiment 16 | Greater than 60dB | About 90% |
| Embodiment 17 | Greater than 40dB | About 60% |
| Embodiment 18 | Greater than 45dB | About 75% |
| Embodiment 19 | Greater than 45dB | About 65% |
By 3 result of table as it can be seen that the hot pressing of four stages is vital, concrete reason possibility for product of the invention
Be: first stage hot pressing can actually exclude the water in stacked body, and under high pressure, high temperature and vacuum state, water can be with
Rapid evaporation comes out, so that there is no microdefects in glue film and composite material cloth.Second stage hot pressing is actually tradition
The hot pressing that softens of the thermoplastic resin made in glue film, in this stage, thermoplastic resin flow is best, can fill
The glue film two sides higher position of irregularity degree.In phase III hot pressing, thermoplastic resin flow is deteriorated, and resin surface can become
Height, in this stage, resin will not be flowed out from the higher position of glue film two sides irregularity degree, and can fill glue film two sides irregularity degree
Lower position.In fourth stage hot pressing, the small-molecule substance of first three stage hot pressing generation can be promoted by low temperature and pressure
It excludes, reduces the microscopic bubble in composite material.
The aforementioned description to specific exemplary embodiment of the invention is in order to illustrate and illustration purpose.These descriptions
It is not wishing to limit the invention to disclosed precise forms, and it will be apparent that according to the above instruction, can much be changed
And variation.The purpose of selecting and describing the exemplary embodiment is that explaining specific principle of the invention and its actually answering
With so that those skilled in the art can be realized and utilize a variety of different exemplary implementation schemes of the invention and
Various chooses and changes.The scope of the present invention is intended to be limited by claims and its equivalents.
Claims (1)
1. a kind of graphene electromagnetic shield cloth, it is characterised in that: the electromagnetic shield cloth from bottom to top successively include it is anti-puncture layer,
Base cloth layer, copper oxide, layers of copper, the first adhesive film, the first graphene composite material layer of cloth, the second adhesive film and the second graphite
Alkene composite material layer of cloth, the base cloth layer are blended cloths, and first adhesive film and the second adhesive film include graphene powder,
The resistance value of the first graphene composite material layer of cloth is greater than the resistance value of the second graphene composite material layer of cloth, described
The resistance value of first adhesive film be greater than second adhesive film resistance value, the resistance value of the first graphene composite material layer of cloth with
The resistance value of first adhesive film is essentially identical, the resistance value of the second graphene composite material layer of cloth and second glue
The resistance value of film layer is essentially identical, and the layers of copper passes through surface sand-blasting process, and the surface roughness of the layers of copper is greater than Ra0.05,
The base cloth layer is the blended cloth of aramid fiber and Fypro, described to prevent that puncturing layer is glass fabric, the glass fibers
Tie up cloth with a thickness of 1-5mm, first adhesive film and second adhesive film respectively include 1-10 parts of graphene powder, swollen
Swollen perlite powder 1-10 parts, 40-60 parts of solvent, 20-80 parts of thermoplastic polymer adhesive, amorphous state paramagnetic nanoparticles metal
1-10 parts of particle, first adhesive film is different from the ingredient of second adhesive film, the first graphene composite material cloth
Layer is the glass fabric for impregnating the first graphene polymer adhesive, by weight, the first graphene polymer glue
Glutinous agent includes 1-10 parts of graphene powder, 40-60 parts of solvent, 20-80 parts of polymer adhesive, amorphous state paramagnetic nanoparticles metal
1-10 parts of particle, the second graphene composite material layer of cloth is the glass fibre for impregnating the second graphene polymer adhesive
Cloth, by weight, the second graphene polymer adhesive include 1-10 parts of graphene powder, 40-60 parts of solvent, polymerization
20-80 parts of object adhesive, 1-10 parts of amorphous state paramagnetic nanoparticles metallic particles, wherein the second graphene polymer gluing
The ingredient of agent is different from the ingredient of the first graphene polymer adhesive, the manufacturing method of the graphene electromagnetic shield cloth
Include:
Prepare to prevent puncturing layer and base cloth layer；
Non-conductive adhesive is coated on layer in anti-puncture, then by the base cloth layer be layed in it is described it is anti-puncture on layer, with
After carry out hot-pressing processing, obtain first layer stack；
Using magnetically controlled sputter method in the first layer stack deposited oxide layers of copper；
It deposits the layers of copper on copper oxide using magnetically controlled sputter method, and blasting treatment is carried out to the layers of copper, obtain the
Two laminated bodies；
Prepare the first graphene composite material layer of cloth and the second graphene composite material layer of cloth: will be each first, in accordance with material rate
Kind of raw material is put into reaction kettle, is then stirred, it is to be mixed uniformly after, graphene polymer adhesive is obtained, then by institute
It states graphene polymer adhesive to pour into dipping tank, glass fibre is arranged in the dipping tank and is impregnated；
Prepare the first adhesive film and the second adhesive film；
Second laminated body, first adhesive film, the first graphene composite material layer of cloth, described are stacked in order
Two adhesive films and the second graphene composite material layer of cloth, obtain stacked body, the stacked body are then put into Vacuum Heat
Hot pressing being carried out in press, which includes four-stage, wherein first stage temperature is 100-150 DEG C, pressure 5-10MPa,
Duration is 10-30s, and second stage temperature is 200-300 DEG C, pressure 10-20MPa, duration 10-20min, the
Three phase temperatures are 100-200 DEG C, pressure 10-20MPa, duration 3-5min, and fourth stage temperature is 50-70 DEG C,
Pressure is 5-10MPa, duration 3-5min, obtains the graphene electromagnetic shield cloth, the copper oxide with a thickness of
20-50nm, the layers of copper with a thickness of 100-200nm.
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