CN101033546A - Composite preparation method of vacuum sputtering coating and chemical coating for electromagnetic wave screen fabric and production thereof - Google Patents
Composite preparation method of vacuum sputtering coating and chemical coating for electromagnetic wave screen fabric and production thereof Download PDFInfo
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- CN101033546A CN101033546A CN 200710039226 CN200710039226A CN101033546A CN 101033546 A CN101033546 A CN 101033546A CN 200710039226 CN200710039226 CN 200710039226 CN 200710039226 A CN200710039226 A CN 200710039226A CN 101033546 A CN101033546 A CN 101033546A
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Abstract
This invention relates to a complex manufacturing method and its product for vacuum sputter and chemical film-platings on industrial and household electromagnetic wave screen fabrics including one of the two methods: a, a fabric backing->plating a metal film by vacuum sputter->plating a metal film chemically->washing->exerting a protection layer->drying, b, factric backing->catalyzing->washing->activating->washing->plating metal film chemically->washing->drying->plating a metal film by vacuum sputter->enforcing a protection layer, in which, the fabrics can be processed with low temperature plasma before vacuum sputtering metal film characterizing in including a layer of tatted cloth or non-woven cloth , a layer of metal film deposited by a sputter film-plating method, an another metal film and a protection layer.
Description
Technical field
The present invention relates in the caused by spinning industrial production textile materials be carried out vacuum splashing and plating and the method for electroless plating composite manufacturing making electromagnetic wave screen fabric and the high-performance electromagnetic wave shielding fabric that makes in this way, product can be widely used in industrial fields such as military project, scientific research, workers and peasants doctor, and the shielding and the protection of the household electrical appliance unwanted electromagnetic wave of common people family.
Background technology
The textile materials that electromagnetic wave shielding is used has wire cloth, wire and textile yarn interweave or the embedding woven fabric, the blended fabric of steel fiber or carbon fiber and conventional textile fibres, plated metal film fabric, the chemical plating metal film fabric, vacuum metallization film fabric etc.In above-mentioned numerous electromagnetic wave shielding textile materials, wire cloth and wire interweave or the embedding woven fabric emerges the earliest.Wire mainly adopts copper wire, nickel wire or Stainless Steel Wire, and its fabric shield effectiveness is better, in 0.15MHz～20GHz scope, can reach 〉=60dB, but fabric is thick and heavy, firmly, not folding.As a radar operation soldier's the protective clothing 9kg that just weighs.Steel fiber and conventional textile fibres BLENDED FABRIC are metal (mainly being nickel or stainless steel) to be pumped into fibrous, are made into cloth with 5%～20% left and right sides ratio after with textile fibres blending resultant yarn.This class textile materials is lighter, and wear behavior makes moderate progress, and feel is soft, and chromatogram is also more.But because steel fiber is than great, cohesive force is little, is difficult to the spinning high grade cotton yarn, and effectiveness of shielding only reaches 15～30dB in 0.15～3GHz scope, far inferior to the wire cloth and the embedding woven fabric that interweaves thereof.Plated metal fabric cost is lower, but the compactness of metallic membrane, the too late vacuum plating of homogeneity and electroless plating fabric, feel is also poor, and fabric is harder, not folding.Owing to electroplate is that the mat electric current makes the reduction of solution metal ion being formed metallic membrane by the plating substrate surface, so be used for metallizing and plastics morely, seldom is used to plate the very big fabric of surface-area.And electroplating technology produces a large amount of waste water, and is seriously polluted.The chemical plating metal fabric has good shield effectiveness, and is soft, good permeability, and waste water is less, but chemical plating technology is more complicated.The stability of chemical plating fluid is difficult to control, especially electroless copper.The electroless plating of textiles is based on copper facing, nickel plating and silver-plated at present.The effectiveness of shielding of electroless copper, silver coating fabric can reach 〉=60dB in 0.15MHz～20GHz scope, and the effectiveness of shielding of chemical nickel plating fabric can reach 40～60dB in 0.15MHz～20GHz scope.The vacuum splashing and plating metal fabric also has a good protection effect with chemical metal-coated fabric is the same, and the gained metallic membrane is finer and close evenly, and ventilation property might as well.Nearly all metal all can be used for sputter, and technology is simple, and whole technological process does not have the three wastes and produces.But the sputter rete is very thin, and it is very uneconomical to reach the above effectiveness of shielding of 60dB, and cost is high, and applying of vacuum splashing and plating fabric is very limited.ZL97106422.7 is the manufacture method that Chinese patent has proposed a kind of radiation-proof fabric, it is characterized in that base material is the synthetic fibre mixed fabric that polyblends of elemental substances such as general fibre and carbon containing, barium, its material is activated, sensitization handles that the back is silver-plated with chemical plating method, copper, nickel etc., do cylinder or PLATE SCREAM PRINTING processing with the acrylate thickener seal slurry of multiple elemental substances such as siliceous, carbon, sodium, niobium, lithium, iron more subsequently, this fabric has good absorptive character to hertzian wave, and 40～60dB decays in 30～1000MHz scope.
Above-mentioned all kinds of electromagnetic wave screen fabric all can't integrate flexibility, environmental protection, economy, high-effect, and none method can obtain the electromagnetic shielding effectiveness of flexible fabric more than wideband segment limit 90dB.
Summary of the invention
Be the deficiency of avoiding above-mentioned electromagnetic wave screen fabric to exist, obtain the above high effectiveness of shielding of 90dB in the wideband segment limit, the flexible high-performance electromagnetic wave shielding fabric that the invention provides a kind of vacuum sputtering coating and plated film compound manufacture method and make by rationally the inlaying of this compounding technology, cooperation, synergy.
The vacuum sputtering coating and the plated film composite manufacturing method of the electromagnetic wave screen fabric that the present invention proposes are characterised in that:
The technical process of being adopted is one of following two kinds:
A. fabric substrate → vacuum sputtering metal-coated membrane → chemical plating metal film → wash → apply protective layer → oven dry;
B. fabric substrate → catalysis → washing → activation → washing → chemical plating metal film → washing → oven dry → vacuum sputtering metal-coated membrane → apply protective layer;
Before above-mentioned vacuum sputtering metal-coated membrane operation, fabric is made Low Temperature Plasma Treating;
Described fabric substrate is Woven Fabrics and non-woven, and described washing is the room temperature washing, and time 0.5～5min, described chemical plating metal film are the existing method in the background technology, and described catalysis, activation are the necessary pre-treatment processes of existing chemical plating metal membrane method;
Described Low Temperature Plasma Treating is to carry out on existing dielectric barrier discharge low-temperature plasma machine, and processing condition are:
Low Temperature Plasma Treating time: 0.5～5min,
Gas temperature: 200～350K,
Air pressure: normal atmospheric is pressed;
Described vacuum sputtering metal-coated membrane carries out on existing magnetron sputtering coater, and sputtering target material is various metals, and processing condition are:
Energizing gas: argon gas,
Sputter coating time: 2～70min,
Working vacuum degree: 1～133 * 10
-3Pa;
The described technology that applies protective layer of above-mentioned flow process a is for flooding the 0.5%～2%PVA aqueous solution that contains 0.05～2g/L antioxidant, and processing condition are:
Dipping time: 1～10min,
Dipping temperature: room temperature;
The described protective layer that applies of flow process b carries out on existing magnetron sputtering coater, and processing condition are:
Energizing gas: argon gas,
Time: 0.5～5min,
Working vacuum degree: 1～10
-3Pa,
Apply material for protective layer: nickel or iron, cobalt, nickelalloy.
Be characterised in that with the vacuum sputtering coating of this electromagnetic wave screen fabric and the prepared product of plated film composite manufacturing method and comprise one deck Woven Fabrics or non-woven base material; form and sedimentary layer of metal film with sputtering film coating method; form and sedimentary another layer metallic membrane with chemical plating method, and layer protective layer.
When adopting base material to be polyester piece good, the existing technology during the base material of flow process b should be produced with weaving is made the alkali decrement treatment earlier, and flow process a base material needn't be made the alkali decrement treatment.
Advantage of the present invention is that the electromagnetic wave screen fabric that adopts vacuum sputtering coating and plated film composite manufacturing method to make can obtain the above electromagnetic shielding effectiveness of wideband segment limit 90dB, textile substrate is done the plasma body pre-treatment can make vacuum sputtering metal-plated rete densification, stable, firm, fabric sofetening is environmental protection, economical technology.
Embodiment
The principle of vacuum splashing and plating is a metal targets of utilizing the energetic particle hits shielding electromagnetic wave to use, do energy exchange after, sputter atom or molecule deposition from target material surface and form metallic film to the textile substrate substrate.Primary process is such: utilize discharge to make the gas that feeds vacuum chamber excite the generation plasma body, contain the electronics and the ion that are ionized out in this plasma body, they are in higher-energy state.Positive ion is driven target out of under effect of electric field.After doing energy exchange, the state of target with atom or molecule sputtered out, fly to the textile substrate substrate, and be deposited on the film that substrate forms shielding electromagnetic wave with the atom of target material surface or molecule.The result of mass spectroscopy shows that most sputtering particles are the monatomic of target material, though there is the part sputtering particle can be in the discharge space ionization, ratio be very little, generally only accounts for about 1%.So their electromagnetic shielding effectiveness is directly based on atoms metals such as copper, silver.Because sputtering coating target does not have phase transformation, the compound composition is difficult for changing, and alloy also is difficult for taking place fractionation, and therefore the plated film that uses is very extensive with material.And sputtering sedimentation is 50 times that evaporation coating produces particle energy to the particle energy on the substrate, so the electromagnetic shielded film that is formed by sputtering particle can adhere on fabric very securely.
Chemical plating principle is to adopt reductive agent to make the metal ion reduce deposition form metallic membrane, must be before the fabric plated film through abundant pre-treatment, remove impurity such as grease, dirt, polyester piece good need be made the alkali decrement treatment, to improve the attachment fastness of coating and base material.The present invention adopts the conventional chemical coating process, generally comprises catalysis, activation, three primary processes of plated film.
Can directly enter plated film behind the fabric vacuum splashing and plating film and bathe, can save the preceding necessary catalysis of former plated film and two processes of activation.Also technology can be adjusted into first plated film vacuum sputtering coating again, can save like this and go up this process of protective layer after the electroless plating, but can not save catalysis and activation before the plated film.
Embodiment 1:
The compounding technology of vacuum sputtering copper facing and electroless copper prepares electromagnetic wave shielding terylene woven
(1) technical process
Terylene woven → Low Temperature Plasma Treating → sputter copper facing → electroless copper → wash → apply protective layer → oven dry → electromagnetic wave shielding polyester piece good
(2) processing condition
1. 210T terylene woven base material, technology is made the alkali decrement treatment routinely in advance.
2. Low Temperature Plasma Treating technology
Fabric travelling speed: 1m/min;
Gas temperature: 300K;
Air pressure: normal pressure.
3. vacuum sputtering copper-plating technique
Energizing gas: argon gas;
The sputter copper facing time: 10min;
Working vacuum degree: 1.2 * 10
-2Pa.
4. chemical-copper-plating process
Electroplate liquid formulation:
Copper sulfate 25g/L,
Methyl alcohol 13mL/L,
Seignette salt 70g/L,
Dipyridyl 0.3mL/L,
Polyacrylamide 4mL/L,
Single nickel salt 1.5g/L,
Formaldehyde 16mL/L;
Bath pH value: 12～13,
Bath temperature: 35～38 ℃,
The immersion plating time: 30min.
5. apply protective layer technology
Protective layer liquid formula: the 2%PVA aqueous solution+0.2g/L benzodiazepine azoles;
The immersion plating time: 2min
Immersion plating temperature: room temperature.
Embodiment 2
The compounding technology of vacuum sputtering copper facing and electroless copper prepares the terylene spun-bonded non-woven of electromagnetic wave shielding.
(1) technical process
Non-woven → Low Temperature Plasma Treating → sputter copper facing → electroless copper → wash → apply protective layer → oven dry → electromagnetic wave shielding non-woven.
(2) processing condition
1. base cloth is 60g/m
2Terylene non-weaving cloth.
2. Low Temperature Plasma Treating:
Fabric travelling speed: 1.5m/min;
Gas temperature: 300K;
Air pressure: normal pressure.
3. vacuum sputtering copper-plating technique
Energizing gas: argon gas;
The sputter coating time: 10min;
Working vacuum degree: 1.2 * 10
-2Pa.
4. chemical-copper-plating process
Electroplate liquid formulation:
Copper sulfate 28g/L,
Methyl alcohol 15mL/L,
Seignette salt 80g/L,
Dipyridyl 0.5mL/L,
Polyacrylamide 4mL/L,
Single nickel salt 1.5g/L,
Formaldehyde 16mL/L;
Bath pH value: 12～13,
Bath temperature: 35～38 ℃,
The immersion plating time: 45min.
5. apply protective layer technology
Protective layer liquid formula: the 1%PVA aqueous solution+0.2g/L benzotriazole;
The immersion plating time: 2min;
Immersion plating temperature: room temperature.
Embodiment 3
The silver-plated compounding technology of electroless copper and vacuum sputtering prepares electromagnetic wave shielding terylene woven.
(1) technical process
Alkali decrement terylene woven → catalysis → washing → activation → washing → electroless copper → washing → oven dry → Low Temperature Plasma Treating → vacuum sputtering is silver-plated → apply protective layer.
(2) processing condition
1. base cloth is a 260T alkali decrement terylene woven.
2. catalysis
The catalytic liquid prescription:
Tin protochloride (SnCl
2) 20g/L,
Hydrochloric acid (HCl) 40mL/L;
Catalysis working temperature: 25 ℃;
The catalysis time: 10min.
3. activation
The activation solution prescription:
Palladous chloride (PdCl
2) 0.5g/L,
Hydrochloric acid (HCl) 5mL/L;
Activation working temperature: 25 ℃;
Soak time: 5min.
4. electroless copper
Electroplate liquid formulation:
Copper sulfate 29g/L,
Methyl alcohol 16mL/L,
Seignette salt 80g/L,
Dipyridyl 0.5mL/L,
Polyacrylamide 5mL/L,
Single nickel salt 2g/L,
Formaldehyde 18mL/L;
Bath pH value: 12～13,
Bath temperature: 35～38 ℃,
The immersion plating time: 45min.
5. Low Temperature Plasma Treating technology
Fabric travelling speed: 1m/min;
Gas temperature: 350K;
Air pressure: normal pressure.
6. vacuum sputtering silver plating process
Energizing gas: argon gas;
The silver-plated time of sputter: 5min;
Working vacuum degree: 1.2 * 10
-2Pa.
7. apply protective layer technology
Energizing gas: argon gas;
The sputter time: 1min;
Working vacuum plating: 1.2 * 10
-2Pa;
Apply material: iron, cobalt, nickelalloy.
Embodiment 4
The copper-plated compounding technology of electroless copper and vacuum sputtering prepares the terylene spun-bonded non-woven of electromagnetic wave shielding.
(1) technical process
Non-woven → catalysis → washing → activation → washing → electroless copper → washing → oven dry → Low Temperature Plasma Treating → vacuum sputtering copper facing → apply protective layer.
(2) processing condition
1. base cloth 100g/m
2Terylene spun-bonded non-woven.
2. catalysis
The catalytic liquid prescription:
Tin protochloride (SnCl
2) 22g/L,
Hydrochloric acid (HCl) 44mL/L;
Catalysis working temperature: 25 ℃;
The catalysis time: 20min.
3. activation
The activation solution prescription:
Palladous chloride (PdCl
2) 0.6g/L,
Hydrochloric acid (HCl) 6mL/L;
Activation working temperature: 25 ℃;
Soak time: 5min.
4. electroless copper
Electroplate liquid formulation:
Copper sulfate 30g/L,
Methyl alcohol 16mL/L,
Seignette salt 90g/L,
Dipyridyl 0.6mL/L,
Polyacrylamide 6mL/L,
Single nickel salt 2.2g/L,
Formaldehyde 20mL/L;
Bath pH value: 12～13,
Bath temperature: 35～38 ℃,
Change plating time: 45min.
5. Low Temperature Plasma Treating technology
Fabric travelling speed: 1.5m/min;
Gas temperature: 350K;
Air pressure: normal pressure.
6. vacuum sputtering copper-plating technique
Energizing gas: argon gas;
The sputter coating time: 10min;
Working vacuum degree: 1.2 * 10
-2Pa.
7. apply protective layer technology
Energizing gas: argon gas;
The sputter time: 2min;
Working vacuum degree: 1.2 * 10
-2Pa;
Apply material: nickel.
Claims (4)
1. the vacuum sputtering coating of electromagnetic wave screen fabric and plated film composite manufacturing method is characterized in that the technical process of being adopted is one of following two kinds:
A. fabric substrate → vacuum sputtering metal-coated membrane → chemical plating metal film → wash → apply protective layer → oven dry;
B. fabric substrate → catalysis → washing → activation → washing → chemical plating metal film → washing → oven dry → vacuum sputtering metal-coated membrane → apply protective layer;
Described fabric substrate is Woven Fabrics or non-woven, described washing is the room temperature washing, washing time 0.5～5min, described chemical plating metal film are the existing method in the background technology, and described catalysis, activation are the necessary pre-treatment processes of existing chemical plating metal membrane method;
Described vacuum sputtering metal-coated membrane carries out on existing magnetron sputtering coater, and sputtering target material is various metals, and processing condition are:
Energizing gas: argon gas,
Sputter coating time: 2～70min,
Working vacuum degree: 1～133 * 10
-3Pa;
The technology that above-mentioned flow process a is described to apply protective layer contains 0.5%～2% the PVA aqueous solution of 0.05～2g/L antioxidant for dipping, and processing condition are:
Dipping time: 1～10min,
Dipping temperature: room temperature;
The described protective layer that applies of above-mentioned flow process b carries out on existing magnetron sputtering coater, and processing condition are:
Energizing gas: argon gas,
Time: 0.5～5min,
Working vacuum degree: 1～10
-3Pa,
Apply material for protective layer: nickel or iron, cobalt, nickelalloy.
2. the vacuum sputtering coating of electromagnetic wave screen fabric and the prepared product of plated film composite manufacturing method according to claim 1; it is characterized in that comprising one deck Woven Fabrics or non-woven base material; form and sedimentary layer of metal film with sputtering film coating method; form and sedimentary another layer metallic membrane with chemical plating method, and layer protective layer.
3. the vacuum sputtering coating of electromagnetic wave screen fabric and plated film composite manufacturing method according to claim 1 is characterized in that before the vacuum sputtering metal-coated membrane of described flow process fabric being made Low Temperature Plasma Treating, and processing condition are:
The Low Temperature Plasma Treating time: 0.5～5min;
Gas temperature: 200～350K;
Air pressure: normal atmospheric is pressed.
4. as the vacuum sputtering coating and the plated film composite manufacturing method of electromagnetic wave screen fabric as described in claim 1 or 3, when it is characterized in that base material is polyester piece good, the existing technology during the base material of flow process b is produced with weaving is made the alkali decrement treatment earlier.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100392262A CN100507081C (en) | 2007-04-06 | 2007-04-06 | Composite preparation method of vacuum sputtering coating and chemical coating for electromagnetic wave screen fabric and product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100392262A CN100507081C (en) | 2007-04-06 | 2007-04-06 | Composite preparation method of vacuum sputtering coating and chemical coating for electromagnetic wave screen fabric and product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101033546A true CN101033546A (en) | 2007-09-12 |
| CN100507081C CN100507081C (en) | 2009-07-01 |
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ID=38730281
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| CN102505463A (en) * | 2011-11-09 | 2012-06-20 | 天诺光电材料股份有限公司 | Method for preparing silver-plated fiber fabric |
| CN103543054A (en) * | 2013-10-25 | 2014-01-29 | 国家电网公司 | Sample preparation method of metallographic sample with or without oxide layer |
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| CN102505463A (en) * | 2011-11-09 | 2012-06-20 | 天诺光电材料股份有限公司 | Method for preparing silver-plated fiber fabric |
| CN103543054A (en) * | 2013-10-25 | 2014-01-29 | 国家电网公司 | Sample preparation method of metallographic sample with or without oxide layer |
| CN104553137A (en) * | 2014-12-31 | 2015-04-29 | 河北科技大学 | Flexible wave absorbing fabric and application thereof |
| CN105538815A (en) * | 2016-01-12 | 2016-05-04 | 襄阳精鑫电子设备制造有限公司 | Preparing method for carbon-fiber-based shell fabric with electromagnetic protection function |
| CN105538815B (en) * | 2016-01-12 | 2017-09-29 | 襄阳精鑫电子设备制造有限公司 | Carbon fiber-based fabric preparation method with electromagnetic protection function |
| CN105575451A (en) * | 2016-03-11 | 2016-05-11 | 金陵科技学院 | Maternity electromagnetic protection dress |
| RU2659852C2 (en) * | 2016-11-29 | 2018-07-04 | Борис Львович Горберг | Radar absorbing material |
| WO2018170899A1 (en) * | 2017-03-20 | 2018-09-27 | 香港纺织及成衣研发中心有限公司 | Functional curtain fabric with anhydrous coating layer and method for manufacturing same |
| US11788184B2 (en) | 2017-03-20 | 2023-10-17 | The Hong Kong Research Institute Of Textiles And Apparel Limited | Functional curtain fabric with anhydrous coating layer and method for manufacturing same |
| CN108978179A (en) * | 2018-07-10 | 2018-12-11 | 安徽玉然经编科技有限公司 | A kind of plasma of dacron-chitosan base load silver-nano-titanium oxide antibacterial hydrophilic finiss technique |
| CN109306460A (en) * | 2018-09-25 | 2019-02-05 | 广州小楠科技有限公司 | A kind of Electromagnetically shielding fabrics and preparation method thereof |
| CN110106474A (en) * | 2019-06-10 | 2019-08-09 | 北京星网宇达科技股份有限公司 | Conductive fabric, preparation method and application |
| CN110438499A (en) * | 2019-07-30 | 2019-11-12 | 广东硕成科技有限公司 | A kind of non-metal material surface metalized article and its method for metallising |
| CN112687421A (en) * | 2019-10-18 | 2021-04-20 | 福懋兴业股份有限公司 | Conductive cloth and preparation method and application thereof |
| CN112267211A (en) * | 2020-10-15 | 2021-01-26 | 青岛大学 | High-performance electromagnetic shielding fabric based on elastic base cloth and preparation method thereof |
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