CN106922112A - A kind of electromagnetic shielding composite material and its manufacture method - Google Patents
A kind of electromagnetic shielding composite material and its manufacture method Download PDFInfo
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- CN106922112A CN106922112A CN201510990343.1A CN201510990343A CN106922112A CN 106922112 A CN106922112 A CN 106922112A CN 201510990343 A CN201510990343 A CN 201510990343A CN 106922112 A CN106922112 A CN 106922112A
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- electromagnetic shielding
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- 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
Abstract
The present invention provides a kind of electromagnetic shielding composite material and its manufacture method.The electromagnetic shielding composite material is in layer structure, including：Amorphous, nanocrystalline basalis；One layer or two-layer above metal film layer, on amorphous, the surface of nanocrystalline basalis, the interlayer of the electromagnetic shielding composite material is that electric conductivity and soft magnetism are alternate to lamination.Its gross thickness of electromagnetic shielding composite material is 10 110 μm, and the thickness of the metal level lamination is at 0.02 70 μm.The metal deposition layer is that one or more method in the method by electro-deposition or chemical deposition or sputtering sedimentation is formed.Electromagnetic shielding composite material of the invention can simultaneously take into account the influence of low frequency and frequency electromagnetic waves, all have good shield effectiveness to the electromagnetic wave of wide-band.
Description
Technical field
The present invention relates to field of magnetic material, more particularly to a kind of electromagnetic shielding composite material and its manufacture method.
Background technology
With the development of economic society, increasing electronic product is appeared in our daily life, to our life
Unlimited convenient and enjoyment is brought, but just while we enjoy these high-tech products, we will also bear electronics
Life of the electromagnetic wave of the worry that equipment is brought to us, various frequency ranges and intensity to us brings very big negative effect,
Can not only be influenced each other between electronic equipment, while can also influence our health.So in the world to each electronic equipment
Dispatch from the factory and carried out strict Electro Magnetic Compatibility control and require.So carrying out shielding electromagnetic waves using electromagnetic shielding material turns into
The essential material of electronic equipment producer.
The theory of electromagnetic shielding is reflection and absorption of the shielding material to electromagnetic wave.Reflection is the high conductivity for utilizing material, right
There is preferable shield effectiveness in electric field and high frequency magnetic field.Absorption is the magnetic conductivity using material, for low frequency magnetic field have compared with
Good shield effectiveness.
However, traditional electromagnetic shielding material is typically all have preferable shield effectiveness to the electromagnetic wave of a certain frequency range, for example
Generally common soft magnetic material can be used in low frequency field, and common high conductivity material can be used in high frequency field, but
It is difficult on a material while taking into account low-and high-frequency.
It is preferable in order to all have in the EMI of electronic equipment compatibilities, magnetic control plate technique, and the wireless charging technology for developing
Effect, be badly in need of a kind of electromagnetic shielding composite material of brand-new wide-band of exploitation.
The content of the invention
The present invention is directed to above-mentioned technical problem, and the present invention proposes a kind of electromagnetic shielding composite material and its manufacture method, can be with
All there is good shield effectiveness to the electromagnetic wave of wide-band.
A kind of electromagnetic shielding composite material of the invention, the composite is in layer structure, including：Amorphous, nanocrystalline base
Bottom；
One layer or two-layer above metal film layer, lamination is on amorphous, the surface of nanocrystalline basalis, and the electromagnetic shielding is multiple
The interlayer of condensation material is that electric conductivity and soft magnetism are alternate.
Preferably, the gross thickness of electromagnetic shielding composite material is 10-110 μm, and the thickness of the metal level lamination is in 0.02-70
μm。
Preferably, the metal level lamination include metallic copper, aluminium, zinc, iron, cobalt, nickel, chromium, tin, silver, palladium, gold,
Platinum, rhodium, ruthenium, iridium, nickel zinc alloy, nickel tungsten, nickel-molybdenum alloy, Ni-Pd alloy, dilval, nickel cobalt (alloy), iron
One kind or several in cobalt alloy, gold cobalt alloy, iron-cobalt-nickel ternary alloy three-partalloy, ormolu, signal bronze and Jackson's alloy
Kind.
Preferably, the metal deposition layer is one or more side in the method by electro-deposition or chemical deposition or sputtering sedimentation
Method is formed.
Preferably, the combination between layers of layered structure includes that metallic bond is combined, solid solution is combined and physical mechanical
With reference to.
Present invention also offers a kind of manufacture method of electromagnetic shielding composite material, in amorphous, the substrate of nanometer crystal alloy band
One or more layers metal is deposited by one or more method in the method for electro-deposition or chemical deposition or sputtering sedimentation on layer
Film layer, the interlayer of the electromagnetic shielding composite material is that electric conductivity and soft magnetism are alternate.
Beneficial effects of the present invention：
1st, electromagnetic shielding composite material of the invention can simultaneously take into account the influence of low frequency and frequency electromagnetic waves, to the electricity of wide-band
Magnetic wave all has good shield effectiveness.
2nd, in the case of there is excellent electromagnetic shield effectiveness in wide frequency range, it is also possible that electromagnetic shielding piece is thinner, root
Can suitably be adjusted according to different application bands, minimum thickness can accomplish 10 μm.
3) preparation technology of electromagnetic shielding composite material of the invention flexibly, made of soft, easy to use, and low cost,
Performance is good.
Brief description of the drawings
Fig. 1 is the structure chart of the electromagnetic shielding composite material of embodiments of the invention.
Specific embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail.Following examples are not limitation of the present invention.Do not carrying on the back
Under the spirit and scope of inventive concept, those skilled in the art it is conceivable that change and advantage be all included in the present invention
In.
Fig. 1 is the structure chart of the electromagnetic shielding composite material of embodiments of the invention.As shown in figure 1, electromagnetic shielding of the invention
Composite includes：Amorphous, nanocrystalline basalis 1；And lamination is in one layer on amorphous, the surface of nanocrystalline basalis
Or two-layer above metal film layer 2.The interlayer of the electromagnetic shielding composite material is that electric conductivity and soft magnetism are alternate.Here, institute
The interlayer electric conductivity and soft magnetism stated are alternate to be referred to for electromagnetic shielding composite material generally, is electric conductivity and soft magnetism
Property is alternate.For example, meet material in the case of 2 layers in electromagnetic shielding, because basalis is amorphous, nanocrystalline
Material (soft magnetic materials), then lamination metal level thereon should be conductive material.Meet material for 3 layers in electromagnetic shielding
In the case of, can be that basalis and the first metal layer thereon are soft magnetic material, lamination is on the first metal layer
Two metal levels are conductive material, also meet electric conductivity and soft magnetism is alternate.
The gross thickness of electromagnetic shielding composite material of the invention is 10-110 μm, and the thickness of the metal level lamination is in 0.02-70
μm。
In electromagnetic shielding composite material of the invention, the metal level lamination include metallic copper, aluminium, zinc, iron, cobalt, nickel,
Chromium, tin, silver, palladium, gold, platinum, rhodium, ruthenium, iridium, nickel zinc alloy, nickel tungsten, nickel-molybdenum alloy, Ni-Pd alloy, nickel
Ferroalloy, nickel cobalt (alloy), ferrocobalt, gold cobalt alloy, iron-cobalt-nickel ternary alloy three-partalloy, ormolu, signal bronze and copper
One or more in Zinc-tin alloy.
The metal deposition layer is that one or more method in the method by electro-deposition or chemical deposition or sputtering sedimentation is formed.
The combination between layers of the layer structure of the electromagnetic shielding composite material includes that metallic bond is combined, solid solution is combined and physics
Mechanical bond.
The manufacture method of electromagnetic shielding composite material of the invention is described below.The method of the present invention is directly in amorphous, nanometer
Sunk by one or more method in the method for electro-deposition or chemical deposition or sputtering sedimentation on the basalis of peritectic alloy band
Long-pending one or more layers metal film layer, the interlayer of the electromagnetic shielding composite material is that electric conductivity and soft magnetism are alternate.The present invention
In the method for accumulated metal film layer used be existing method.
Electro-deposition and chemical deposition are carried out in aqueous, and sputtering sedimentation can be carried out directly on material.Before sputtering sedimentation
The pre-treatment of ultrasonic wave cleaning, plasma cleaning etc. must be carried out to material；It is necessary before electro-deposition or chemical deposition first layer metal
To base material amorphous or nanocrystalline carry out pre-treatment；The technique that each of which method is met during various method compound uses
It is required that.Using the water phase deposition solution containing the metal when needing chemical deposition or certain metal film layer of electro-deposition, deposition every time
After layer of metal film layer, material need to be cleaned, be further continued for depositing next layer of metal film layer after cleaning, deposited
Metal needs to be cleaned after finishing, and blots drying after cleaning again.
Sputtering sedimentation is only introduced below is applied to specific steps of the invention.
1) certain metal or alloy film layer of deposition according to needed for prepares the sputtered target material of identical component, and is installed solid
It is scheduled on cathodic sputtering target position；
2) prepare amorphous or nanocrystalline material, ultrasonic wave cleaning is carried out to the material；
3) feeding-vacuumize-argon ion bombardment-ion gun bombardment (electric arc bombardment)-sputter coating-vacuumize-be filled with
Nitrogen cooling-deflation-blanking terminates；
4) after the completion of sputtering layer of metal layer, if also needing to splash-proofing sputtering metal layer, aforesaid operations are repeated；Can also be changed to
Electric layer is accumulated or chemical lamination carries out next layer of metal deposit.
Those skilled in the art can be according to actual conditions and needing to select suitable lamination method.
The electromagnetic shielding composite material obtained by the inventive method, is had the advantages that：
1) generally common soft magnetic material can be used in low frequency field, and common high conductivity material can be used in high frequency field, difficult
To take into account low-and high-frequency, electromagnetic shielding composite material of the invention, because its compound architectural feature can simultaneously in height simultaneously
Frequency field uses, such that it is able to reach the effect of wide-band shielding；
2) limitation that sputtering sedimentation, chemical deposition, electro-deposition method can be greatly on quantum jump material thicknesses, can be prepared into 1um
Following thin-film material, material integral thickness can decline, and can be manufactured using one or more above-mentioned method, system
Making mode diversification material can be thinned；
3) shield effectiveness that can be reached as needed selects the compound number of plies of composite electromagnetic shield materials, and selectivity is wide；
4) each layer can be controlled to constitute the thickness of layer by adjusting technological parameter, is controlled during manufacture easy；
5) composite electromagnetic screen film material itself for preparing can not receive sole mass, shield shape with wideband shielding range of application
Limitation, has a wide range of application；
6) the composite electromagnetic screen film for preparing is the material of light flexible；
7) the composite shielding material thin-film material diversification for preparing, available property is big.
Embodiment 1
A kind of novel electromagnetic shielding composite material of double-layer structure is prepared according to manufacture method of the present invention, i.e., in amorphous base
One layer of conductive metal layer of Direct Electroplating on bottom, conducting metal selection metallic copper, in the material of preparation not only amorphous containing soft magnetic materials but also
Copper containing conductive material.
The non-crystalline material thickness 20um for using, is the common amorphous in market.
The electroplate liquid component of the electro-coppering for using：CuSO4.5H2O—210g/l；H2SO4—65g/l；Cl---60ppm；HSR
Photo etching -2ml/l；HSR leveling agents --- 7ml/l.
Plating solution using 3 grades of filterings, that is, first passes around filter screen filtration using electroplating bath solution, is then 10 μm by aperture
The filter element filtering of cotton material, eventually passes active carbon filter core filtering；Plating solution is stirred using the sealing and circulating type of flow.
Plating solution is configured, has been heated up and controlled at 35 DEG C；Base material amorphous as negative electrode, soluble copper ball be anode simultaneously
It is mounted in titanium basket；Anode and cathode area compares 1：3, negative and positive die opening 20mm；Carried out before amorphous enters groove alkaline degreasing and
Acid deoiling, and clear water cleaned standby seam；By anode and cathode by area than being fixed on the specified location of aqueduct with spacing；Connect direct current
Power supply, passes to required electric current, is electroplated according to electroplating time.
Copper plating process parameter：35 DEG C of copper facing temperature；Current density 3.5Amp/dm2；Electroplating deposition time 3min；Plating solution
Stirred using the sealing and circulating type of flow.Plating uses cold water hot water cleaning product until cleaning after terminating, and then first blots,
Dry again, that is, obtain novel electromagnetic shielding composite material of the present invention.
Under above-mentioned process conditions, prepared bilayer meets electromagnetic shielding composite material, soft magnetic material amorphous 20um,
Conductive material layers of copper 2.2um, its coercivity is 3.2A/m；Saturation induction density is 1.53T, and maximum permeability is
45100, average shield effectiveness reaches 68dB.
Embodiment 2
A kind of novel electromagnetic shielding composite material of three-decker is prepared according to manufacture method of the present invention, i.e., in amorphous base
First electroplated conductive metal layer one layer of soft magnetism coating of chemical plating on conductive metal layer, electroplated conductive metal selection metal again on bottom
Copper, changes plating selection metallic nickel.
The non-crystalline material thickness 20um for using, is the common amorphous in market.
The electroplate liquid component of the electro-coppering for using：CuSO4。5H2O—210g/l；H2SO4—65g/l；Cl---60ppm；HSR
Photo etching -2ml/l；HSR leveling agents --- 7ml/l.
Use chemical nickel-plating plating solution component：Nickel oxalate 30g/L, ethylenediamine 100ml/L, NaOH 46g/L, sodium borohydride
0.8g/l, thiocarbamide 0.5mg/l, saccharin sodium 2g/l
Plating copper electrolyte using 3 grades of filterings, that is, first passes around filter screen filtration using electroplating bath solution, is then 10 by aperture
μm cotton material filter element filtering, eventually pass active carbon filter core filtering；Plating solution is stirred using the sealing and circulating type of flow.
Change nickel plating bath during electroless deposition using 2 grades of filterings, that is, filter screen filtration is first passed around, then by aperture
It is the filter element filtering of 10 μm of PP materials；Plating solution is stirred using the sealing and circulating type of flow.
Configure and electroplate copper electrolyte, heated up and controlled at 35 DEG C；Base material amorphous as negative electrode, soluble copper ball
For anode and it is mounted in titanium basket；Anode and cathode area compares 1：3, negative and positive die opening 25mm；Alkali is carried out before amorphous enters groove
Property oil removing and acid deoiling, and clear water cleaned standby seam；By anode and cathode by area than being fixed on the specified location of aqueduct with spacing；
Dc source is connected, required electric current is passed to, electroplated according to electroplating time.
Copper plating process parameter：35 DEG C of copper facing temperature；Current density 3.5Amp/dm2；Electroplating deposition time 15min；Plating solution
Stirred using the sealing and circulating type of flow.Plating uses cold water hot water cleaning product until cleaning after terminating, then carrying out nickel
Treatment
The good chemistry nickel plating bath of configuration, is heated up and is controlled at 87 DEG C；Base material amorphous and copper plate are used as overall material
Material changes nickel plating in layers of copper, changes and need to presoak and activate before plating, and must assure that tank liquor useful load reaches 1.0dm2/L (dresses when changing plating
Carrying capacity adds auxiliary material when not enough), then plated according to change plating Zeitigung.
Chemical nickel technological parameter：Change nickel temperature：83—88℃；PH value：>13；Useful load：1.0dm2/L, when changing plating
Between：15min.Change and use cold water hot water cleaning product until cleaning after plating terminates, then first blot, then dry, that is, obtain
Novel electromagnetic shielding composite material of the present invention
Under above-mentioned process conditions, three layers of prepared electromagnetic shielding composite material, soft magnetic material amorphous 20um leads
Electric material layers of copper 10um, soft magnetic material nickel 2um, its coercivity are 3.1A/m；Saturation induction density is 1.38T,
Maximum permeability is 54000, and average shield effectiveness reaches 72dB.
Embodiment 3
A kind of novel electromagnetic shielding composite material of three-decker is prepared according to manufacture method of the present invention, i.e., in nanocrystalline base
One layer of conductive metal layer is first sputtered on bottom, then one layer of soft magnetism coating is electroplated on conductive metal layer, sputtering conducting metal selection
Metallic aluminium, plating soft magnetism plating plating selection metallic nickel.
The nanocrystalline material thickness 10um for using.
Sputtering selection magnetron sputtering, target selects metallic aluminium, and aluminium sheet is fixed on into target position.Nanocrystalline material is carried out into ultrasonic wave
Cleaning, starts feeding-vacuumize-argon ion bombardment-ion gun bombardment (electric arc bombardment)-sputter coating-take out after the completion of cleaning
Vacuum-be filled with nitrogen cooling-deflation-blanking terminates.
Major parameter during sputtering：Accelerating potential：300-800V；Magnetic field is about：50-300G；Air pressure：1-10mTorr；
Current density：4-60mA/cm；Power density：1-40W/cm；Its thickness is controlled by sputtering time, 30min is sputtered.
The electroplate liquid component of the electronickelling for using：Nickel sulfamic acid 380g/L, nickelous bromide 50g/L, boric acid 30g/L, saccharin sodium
1g/L, dodecyl sodium sulfate 15gml/L.
Plating nickel plating bath using 3 grades of filterings, that is, first passes around filter screen filtration using electroplating bath solution, is then 10 by aperture
μm cotton material filter element filtering, eventually pass active carbon filter core filtering；Plating solution is stirred using the sealing and circulating type of flow.
Configure and electroplate nickel plating bath, heated up and controlled at 40 DEG C；Using the layers of copper (amorphous containing base material) that has sputtered as
Negative electrode, soluble nickel cake is anode and is mounted in titanium basket；Anode and cathode area compares 1：4, negative and positive die opening 20mm；,
Material nickel plating preamble carries out pre-preg, and clear water cleaned standby seam to material；Anode and cathode is fixed on and is crossed by area ratio and spacing
The specified location of groove；Dc source is connected, required electric current is passed to, electroplated according to electroplating time.
Electro-nickel process parameter：40 DEG C of nickel plating temperature；PH value 4.0；Current density 2.5Amp/dm2；The electroplating deposition time
5min；Plating solution uses cold water hot water cleaning product until cleaning, so after terminating using the stirring plating of the sealing and circulating type of flow
First blot afterwards, then dry, that is, obtain novel electromagnetic shielding composite material of the present invention.
Under above-mentioned process conditions, prepared three layers meet electromagnetic shielding composite material, the nanocrystalline 10um of soft magnetic material,
Conductive material aluminium lamination 2um, soft magnetic material nickel 2um, its coercivity are 2.6A/m；Saturation induction density is 1.13T,
Maximum permeability is 68000, and average shield effectiveness reaches 70dB.
It is only in sum presently preferred embodiments of the present invention, not for limiting practical range of the invention.It is i.e. all according to the present invention
The equivalence changes that the content of claim is made and modification, should all belong to technology category of the invention.
Claims (8)
1. a kind of electromagnetic shielding composite material, it is characterised in that the composite is in layer structure, including：
Amorphous, nanocrystalline basalis；
One layer or two-layer above metal film layer, lamination on amorphous, the surface of nanocrystalline basalis,
The interlayer of the electromagnetic shielding composite material is that electric conductivity and soft magnetism are alternate.
2. electromagnetic shielding composite material according to claim 1, it is characterised in that its gross thickness is 10-110 μm, institute
The thickness of metal level lamination is stated at 0.02-70 μm.
3. electromagnetic shielding composite material according to claim 1, it is characterised in that the metal level lamination includes metal
Copper, aluminium, zinc, iron, cobalt, nickel, chromium, tin, silver, palladium, gold, platinum, rhodium, ruthenium, iridium, nickel zinc alloy, nickel tungsten,
Nickel-molybdenum alloy, Ni-Pd alloy, dilval, nickel cobalt (alloy), ferrocobalt, gold cobalt alloy, iron-cobalt-nickel ternary alloy three-partalloy, copper
One or more in kirsite, signal bronze and Jackson's alloy.
4. electromagnetic shielding composite material according to claim 1, it is characterised in that the metal deposition layer is heavy by electricity
One or more method in the method for product or chemical deposition or sputtering sedimentation is formed.
5. according to claim 1 electromagnetic shielding composite material, it is characterised in that layered structure is between layers
Combination include metallic bond combine, solid solution combine and physical mechanical combine.
6. the manufacture method of the electromagnetic shielding composite material described in a kind of Claims 1 to 5, it is characterised in that in amorphous, receive
By one or more method in the method for electro-deposition or chemical deposition or sputtering sedimentation on the basalis of rice peritectic alloy band
One or more layers metal film layer is deposited, the interlayer of the electromagnetic shielding composite material is that electric conductivity and soft magnetism are alternate.
7. manufacture method according to claim 6, it is characterised in that the gross thickness of the electromagnetic shielding composite material is
10-110 μm, the thickness of the metal level lamination is at 0.02-70 μm.
8. manufacture method according to claim 7, it is characterised in that the metal level lamination include metallic copper, aluminium,
Zinc, iron, cobalt, nickel, chromium, tin, silver, palladium, gold, platinum, rhodium, ruthenium, iridium, nickel zinc alloy, nickel tungsten, nickel molybdenum are closed
Gold, Ni-Pd alloy, dilval, nickel cobalt (alloy), ferrocobalt, gold cobalt alloy, iron-cobalt-nickel ternary alloy three-partalloy, ormolu,
One or more in signal bronze and Jackson's alloy.
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| CN108746331A (en) * | 2018-05-29 | 2018-11-06 | 江西省科学院应用物理研究所 | Non-crystaline amorphous metal braid over braid and its preparation method and application |
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| CN110853861A (en) * | 2019-11-29 | 2020-02-28 | 横店集团东磁股份有限公司 | Magnetic separation sheet for wireless charging receiving end and preparation method thereof |
| CN110853861B (en) * | 2019-11-29 | 2021-11-09 | 横店集团东磁股份有限公司 | Magnetic separation sheet for wireless charging receiving end and preparation method thereof |
| CN111050535A (en) * | 2019-12-24 | 2020-04-21 | 苏州威斯东山电子技术有限公司 | Broadband high-efficiency electromagnetic shielding material with soft magnetic material and metal composite lamination |
| CN111031774A (en) * | 2019-12-24 | 2020-04-17 | 苏州威斯东山电子技术有限公司 | Electromagnetic shielding material of ferrite and metal composite lamination |
| CN111321408A (en) * | 2020-03-02 | 2020-06-23 | 中国科学院宁波材料技术与工程研究所 | Multi-interface amorphous nanocrystalline electromagnetic shielding composite material |
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