CN103060740B - Airglow-discharge low-temperature plasma coating technique - Google Patents

Airglow-discharge low-temperature plasma coating technique Download PDF

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Publication number
CN103060740B
CN103060740B CN201310033588.6A CN201310033588A CN103060740B CN 103060740 B CN103060740 B CN 103060740B CN 201310033588 A CN201310033588 A CN 201310033588A CN 103060740 B CN103060740 B CN 103060740B
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low
temperature plasma
temperature
coating technique
powder
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CN103060740A (en
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向勇
闫宗楷
朱焱麟
常小幻
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Ningbo Xinghe Material Technology Co Ltd
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University of Electronic Science and Technology of China
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Abstract

The invention provides an airglow-discharge low-temperature plasma coating technique, belonging to the field of plasma coating. The technique can effectively solve the problems of the overhigh coating temperature can damage the substrate and the preparation technique is complex in the field of coating. The technique comprises the following steps: a. low-temperature plasma breakdown by electrifying a discharge tube: gas introduced from a gas source reaches breakdown voltage under the action of a power source with an excitation source, and discharge is initiated to excite and generate low-temperature plasma; b. introduction of a powder material: the fed powder material is locally heated to be molten under the action of the low-temperature plasma and is accelerated; and c. injection and coating of low-temperature plasma: the powder material and the low-temperature plasma are injected together and deposited on the substrate surface to implement coating. The invention can be widely used for preparing metal materials, semiconductor materials, compound materials, polymers and other materials in the fields of printing electronics, 3D printing and the like.

Description

A kind of atmospheric glow discharge low-temperature plasma coating technique
Technical field
The present invention relates to plasma coating field, specifically refer to a kind of atmospheric glow discharge low-temperature plasma coating technique.
Background technology
Current vacuum coating technique especially plasma vacuum coating technique plays extremely important effect in fields such as field of electronic components manufacturing, electric circuit electronics technical field, solar cells.It compares antivacuum technology of preparing, although have film growth densification, preparation speed fast, be easy to control the advantages such as thin film composition, simultaneously because equipment is complicated, usual material preparation cost is higher, complicated operation, is unfavorable for reducing material cost.And the antivacuum plasma coating technology of current widespread use is owing to adopting thermal plasma, temperature is higher, high to thin film deposition substrate requirements, and the use of the base material of the poor heat resistance such as paper, macromolecular material is restricted, energy expenditure is large simultaneously, is unfavorable for expanding its use range.
Usual cold plasma can be divided into two classes, and a class is thermal equilibrium plasma, and another kind of is nonthermal plasma.What traditional plasma film coating equipment adopted is thermal equilibrium plasma, and the electronics less due to wherein quality and the larger atom of quality and ion have identical temperature, therefore it is higher to have high-octane plasma temperature; And nonthermal plasma does not reach thermal equilibrium state due to the less electronics of quality wherein and the larger atom of quality and ion, cause the electronic temp of little quality very high and the atom of large quality and ion temperature very low, and what determine plasma temperature is atom and the ion of large quality, so plasma body bulk temperature is very low.
Because low-temperature plasma has, temperature is lower, electric density high, be widely used in the fields such as material surface modifying, biological sterilization, surface cleaning and sewage is clean at present, due to it, there is higher-energy simultaneously, low-temperature plasma also can as the carrier of material granule, make material granule have larger energy, be convenient to deposit film forming.
Summary of the invention
The deficiency that the object of the invention is for above-mentioned vacuum plasma coating technique and normal atmosphere high-temperature plasma coating technique provides a kind of atmospheric glow discharge low-temperature plasma coating technique, this technology coating temperature is low, effectively can solve the too high problem damaging substrate and complicated process of preparation of coating temperature that plated film field exists.
The technical solution adopted for the present invention to solve the technical problems is: provide a kind of atmospheric glow discharge low-temperature plasma coating technique, its step comprises: a, in the discharge vessel energising puncture low-temperature plasma process, the gas passed into by gas source is issued to voltage breakdown in the effect of the power supply being added with driving source, and conducting discharge excitation produces low-temperature plasma; B, powder body material importing process, powder body material local temperature under the effect of low-temperature plasma of feeding raises melts and accelerates; C, low-temperature plasma ejection plated film implementation procedure, powder body material sprays together with low-temperature plasma, is deposited on substrate surface and realizes plated film.
A kind of atmospheric glow discharge low-temperature plasma coating technique of the present invention, in step a, described discharge tube comprises gas and passes into mouth, negative electrode, anode, electrolyte barrier and spout, and low-temperature plasma temperature is 10-150 DEG C.
A kind of atmospheric glow discharge low-temperature plasma coating technique of the present invention, in step a, the optional DC pulse of driving source, interchange, radio frequency and microwave power supply.
A kind of atmospheric glow discharge low-temperature plasma coating technique of the present invention, in step a, the gas passed into can select Ar, N 2, O 2, H 2with air and mixed gas, passing into gas flow is 1-40L/min.
A kind of atmospheric glow discharge low-temperature plasma coating technique of the present invention, in stepb, powder lead-in mode is internal powder conveying mode, and powder feeding rate is 10-35g/min, and powder granule diameter is less than 10 μm.
A kind of atmospheric glow discharge low-temperature plasma coating technique of the present invention, in step c, the distance of spout and substrate is 80mm-150mm.
The present invention also has that coating temperature is low, plated film precision is high and the feature such as coating film thickness is thicker compared with traditional coating technique, and the contrast of itself and traditional coating technique is as follows:
Coating technique Thicknesses of layers Base reservoir temperature
PVD(vacuum PVD) 1-10μm 200-500℃
CVD(chemical vapour deposition) 1-50μm 400-2000℃
Thermospray 40-3000μm 300-750℃
Atmospheric glow discharge low-temperature plasma plated film 1-200μm 10-150℃
The present invention has following outstanding beneficial effect:
1, due to the present invention's utilization is that low-temperature plasma realizes plated film as carrier, so it is applicable to the plated film of the substrate material surface of the poor heat resistance such as paper, macromolecular material, reduce complicated process of preparation degree, avoid the problem damaging substrate because coating temperature is too high, expand use range.
2, due to the optional DC pulse of driving source of the present invention, interchange, radio frequency and microwave power supply, the gas passed into can select Ar, N 2, O 2, H 2with air and mixed gas, so it can be selected different driving sources according to differing materials and pass into gas, make coating effects better.
Accompanying drawing explanation
Accompanying drawing 1 is the schema of atmospheric glow discharge low-temperature plasma coating technique of the present invention;
Accompanying drawing 2 is the principle schematic of atmospheric glow discharge low-temperature plasma coating technique of the present invention;
Description of reference numerals: 1 substrate, 2 films, 3 low-temperature plasmas, 4 powder introducing ports, 5 anodes, 6 negative electrodes, 7 gases pass into mouth, 8 discharge tubes, 9 electrolyte barriers, 10 spouts.
Embodiment
As shown in Figure 1 and Figure 2, a kind of atmospheric glow discharge low-temperature plasma coating technique of the present invention, its step comprises: S1, in discharge tube 8 energising puncture low-temperature plasma 3 process, pass into by gas the gas that mouth 7 passes into by gas source and be issued to voltage breakdown in the effect of the power supply being added with driving source, and conducting discharge excitation produces low-temperature plasma 3; S2, powder body material importing process, the powder body material sent into by powder introducing port 4 local temperature under the effect of low-temperature plasma 3 is raised melts and accelerates; S3, low-temperature plasma 3 spray plated film implementation procedure, and powder body material sprays spout 10 together with low-temperature plasma 3, are deposited on substrate 1 surface and form film 2.
In step sl, discharge tube 1 comprises gas and passes into mouth 7, negative electrode 6, anode 5, electrolyte barrier 9 and spout 10.Electrode materials can select resistant to elevated temperatures tungsten, copper, graphite, and discharge tube can adopt four fluorinated ethylene propylenes (Teflon), quartz, aluminum oxide, boron nitride.The optional DC pulse of driving source, interchange, radio frequency and microwave power supply; Added voltage range is 2-50KV, and pulses range is 7KHz-15MHz, preferred 20KHz-70KHz; When adopting DC pulse, pulsed voltage width 600nm-80 μm; When adopting radio-frequency power supply, power 10-300mW.The gas passed into can select Ar, N 2, O 2, H 2with air and mixed gas, passing into gas flow is 1-40L/min.
In step s 2, powder lead-in mode is internal powder conveying mode, and powder feeding rate is 10-35g/min, and powder granule diameter is less than 10 μm.
In step s3, spout 10 is 80mm-150mm with the distance of substrate 1.
In order to ensure the quality of plated film, the low-temperature plasma that can also the present invention be adopted after plated film terminates not pass into powder body material takes off fire for material, helps material crystallization.
Below in conjunction with the drawings and specific embodiments, the present invention is illustrated further:
Embodiment 1
The present embodiment selects gas to be N 2; Driving source is direct current pulse power source; Electrode materials selects Graphite Electrodes, and discharge tube adopts polytetrafluoroethylmaterial material to make.Coating process is as follows:
S1, by N 2pass into mouth 7 by gas and pass into discharge tube 1, its gas flow 6-20L/min; Add direct current pulse power source at anode 5 and negative electrode 6, voltage range is 2-15KV, and pulses range is 7KHz-50KHz, pulsed voltage width 600nm-80 μm; Low-temperature plasma 3 temperature produced is 10-100 DEG C.S2, by powder introducing port 4 import powder body material powder feeding rate be 10-25g/min, under the effect of low-temperature plasma 3 local temperature raise; S3, powder body material melt and accelerate to spray spout 10, are deposited on substrate 1 surface deposition and form film 2; Spout 10 and substrate 1 are apart from being 100mm-150mm.
Embodiment 2
The present embodiment selects gas to be Ar; Driving source adopts radio-frequency power supply; Electrode materials selects tungsten electrode, and discharge tube adopts alumina material to make.Coating process is as follows:
S1, Ar is passed into mouth 7 by gas pass into discharge tube 1, its gas flow 10-20L/min; Add radio-frequency power supply at anode 5 and negative electrode 6, power 10-300mW, pulses range is 7.17MHz-15MHz, is preferably 13.56MHz; Low-temperature plasma 3 temperature produced is 50-150 DEG C.S2, by powder introducing port 4 import powder body material powder feeding rate be 10-35g/min, under the effect of low-temperature plasma 3 local temperature raise.S3, powder body material melt and accelerate to spray spout 10, form film 2 at substrate 1 surface deposition; Spout 10 is 100mm-120mm with the distance of substrate 1.
Embodiment 3
The present embodiment selects gas to be N 2with Ar mixed gas; Driving source adopts AC power; Electrode materials selects copper electrode, and discharge tube adopts boron nitride material to make.Coating process is as follows:
S1, by N 2pass into mouth 7 by gas and pass into discharge tube 1, its gas flow 6-20L/min; Ar is passed into mouth 7 by gas and passes into discharge tube 1, its gas flow 1-10L/min; Add AC power at anode 5 and negative electrode 6, voltage range is 5-50KV, and pulses range is 20KHz-50KHz; Low-temperature plasma 3 temperature produced is 70-100 DEG C.S2, by powder introducing port 4 import powder body material powder feeding rate be 10-35g/min, under the effect of low-temperature plasma 3 local temperature raise.S3, powder body material melt and accelerate to spray spout 10, form film 2 at substrate 1 surface deposition; Spout 10 is 80mm-140mm with the distance of substrate 1.
Atmospheric glow discharge low-temperature plasma coating technique of the present invention, effectively can solve the normal atmosphere coating temperature that plated film field exists and too highly can damage the problem such as substrate and complicated process of preparation, the preparation of the materials such as field metallic substance, semiconductor material, compound-material and polymer such as printed electronics, 3D printing can be widely used in.
The above, be only preferred embodiment of the present invention, not does any pro forma restriction to the present invention.Any those of ordinary skill in the art, are not departing under technical solution of the present invention ambit, technology contents described above all can be utilized to make many possible variations and modification to technical solution of the present invention, or be revised as the Equivalent embodiments of equivalent variations.Therefore, every content not departing from technical solution of the present invention, according to technical spirit of the present invention to any change amendment made for any of the above embodiments, equivalent variations and modification, all belongs to the protection domain of the technical program.

Claims (6)

1. an atmospheric glow discharge low-temperature plasma coating technique, it is characterized in that, its step comprises: a, in the discharge vessel energising puncture low-temperature plasma process, the gas passed into by gas source is issued to voltage breakdown in the effect of the power supply being added with driving source, and conducting discharge excitation produces low-temperature plasma; B, powder body material importing process, the powder body material local temperature rising under the effect of low-temperature plasma being sent into discharge tube inside by powder introducing port is melted and accelerates; C, low-temperature plasma ejection plated film implementation procedure, powder body material sprays together with low-temperature plasma, is deposited on substrate surface and realizes plated film.
2. a kind of atmospheric glow discharge low-temperature plasma coating technique according to claim 1, it is characterized in that, in step a, described discharge tube comprises gas and passes into mouth, negative electrode, anode, electrolyte barrier and spout, and low-temperature plasma temperature is 10-150 DEG C.
3. a kind of atmospheric glow discharge low-temperature plasma coating technique according to claim 1, is characterized in that, in step a, and the optional DC pulse of driving source, interchange, radio frequency and microwave.
4. a kind of atmospheric glow discharge low-temperature plasma coating technique according to claim 1, it is characterized in that, in step a, the gas passed into can select Ar, N 2, O 2, H 2with air and mixed gas, passing into gas flow is 1-40L/min.
5. a kind of atmospheric glow discharge low-temperature plasma coating technique according to claim 1, is characterized in that, in stepb, powder lead-in mode is internal powder conveying mode, and powder feeding rate is 10-35g/min, and powder granule diameter is less than 10 μm.
6. a kind of atmospheric glow discharge low-temperature plasma coating technique according to claim 1, is characterized in that, in step c, the distance of spout and substrate is 80mm-150mm.
CN201310033588.6A 2013-01-29 2013-01-29 Airglow-discharge low-temperature plasma coating technique Active CN103060740B (en)

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CN105922566B (en) * 2015-11-17 2018-06-29 中研智能装备有限公司 A kind of plasma cladding directly manufactures 3D printing device and method
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CN101555588A (en) * 2009-03-18 2009-10-14 成都同明新材料技术有限公司 Low-temperature plasma system based on atmosphere pressure glow discharge

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CN101555588A (en) * 2009-03-18 2009-10-14 成都同明新材料技术有限公司 Low-temperature plasma system based on atmosphere pressure glow discharge

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Effective date of registration: 20151209

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Patentee after: INFINITE MATERIALS TECHNOLOGY CO., LTD.

Address before: 610017, No. 2006, West Avenue, Chengdu hi tech Zone (West District, Sichuan)

Patentee before: University of Electronic Science and Technology of China

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Address after: 315000 Ningbo High-tech Zone Ningbo New Material Innovation Center East District No. 1 10-4-1, Zhejiang Province

Patentee after: Ningbo Xinghe Material Technology Co., Ltd.

Address before: 315040 No. 1299 Juxian Road, Ningbo High-tech Zone, Zhejiang Province

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