CN103320772A - Metal inner surface modification device and method - Google Patents
Metal inner surface modification device and method Download PDFInfo
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- CN103320772A CN103320772A CN2013102783444A CN201310278344A CN103320772A CN 103320772 A CN103320772 A CN 103320772A CN 2013102783444 A CN2013102783444 A CN 2013102783444A CN 201310278344 A CN201310278344 A CN 201310278344A CN 103320772 A CN103320772 A CN 103320772A
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Abstract
The invention discloses a metal inner surface modification device and method and belongs to the technical field of plasma surface modification. The method is characterized by comprising the following steps: generating plasmas on a metal inner surface by utilizing the principle of hollow-cathode discharge, and nitriding or depositing diamond like carbon, so as to improve the hardness, the wear resistance and the corrosion resistance of the metal inner surface; by taking a treated piece as a cathode, arranging the cathode inside, adjusting the distance and the vacuum degree between a workpiece and the cathode to reach the discharge condition, arranging an anode at the periphery of a cathode cavity, and adding a direct current pulse power supply between the anode and the cathode, wherein reaction gas is nitrogen or ammonia gas and carrier gas is argon gas during the nitriding, and the reaction gas is methane or acetylene and the carrier gas is argon gas in the process of depositing a hard carbon film. The method has the effects and advantages of simple process, low cost and high efficiency and is particularly suitable for treating the metal inner surface and pipe fittings of large draw ratios.
Description
Technical field
The invention belongs to the plasma surface modification technology field, relate to the deposition that surface chemistry blends hard carbon films, specially refer to metallic interior surface is realized that chemistry oozes or the method for thin film deposition, to improve the physical and chemical performances such as hardness, wear resistance and solidity to corrosion of metallic interior surface.
Background technology
Internal surface is that the workpiece class of working face is numerous, cylinder barrel, transport pipeline, ion accelerating tube, gun barrel, interior punch die and axle sleeve etc. such as engine, these workpiece are often destroyed because of forms such as inner wall abrasion, corrosion, for the hardness that improves the workpiece inwall, wear-resisting anti-and corrodibility, and then improve its working efficiency and life-span, the wall chemistry oozes or the deposit film technique means that is very important within it.But at present few about the relevant report of inner wall surface modification, compare the technical reserve critical shortage with the heavy demand of internal surface military service parts, develop therefore that the inner wall surface modification technology has and urgent realistic meaning.Pipe internal surface can not only be confined to the internal surface of tubular workpiece, but can be generalized to concave face on the complex part, hole and inner chamber.So processing research, pipe internal surface has great application potential.
At present the main method that adopts has plating, laser reinforcing processing, physical vapor deposition, plasma enhanced chemical vapor deposition, ion implantation etc.Electroplate and electroless plating is the preferred method of socket spare inner surface treatment, be characterized in that modified effect is good, can process the very little pipe fitting of internal diameter, I reaches several millimeters.But plating and electroless plating cause serious pollution to environment, and the wear resistance of coating is lower, and tack is poor.
Utilize fiber optic conduction laser, thereby make pipe internal surface laser quenching not be subjected to the restriction of pipe range, can realize the inner surface laser phase transformation strengthening of elongated tubular, but laser can only be applied to some special occasions; When using plasma is ion implantation, if processed socket internal diameter is too thin, because the sheath layer intersects, manages interior plasma potential and apply the current potential difference and will reduce, injection effect may reduce greatly as a result, even may not produce injection effect.There is the investigator to propose interior electrode method for this reason, namely in socket, places a ground-electrode.But because most external ion source that adopts, outer generation of plasma body diffuses into cylinder interior subsequently, must cause like this body internal plasma Density inhomogeneity, also just caused the axially inhomogeneous of implantation dosage, and when processing elongated tubular, this phenomenon is comparatively obvious.Generally speaking, interior electrode method has improved Implantation Energy, the ununiformity of implantation dosage is not provided terms of settlement.
Summary of the invention
The invention provides a kind of apparatus and method of metallic interior surface modification, to utilize hollow cathode effect, it is endoporus cathode glow area overlapping, glow current sharply increases in the overlap, produce highdensity plasma body in metallic interior surface, the realization chemistry oozes or deposits ganoine thin film, solves the metallic interior surface modification, improves internal surface hardness, wear resistance and corrosion proof purpose.
Technical scheme of the present invention is: the device of metallic interior surface modification is to utilize hollow cathode effect to produce plasma body in cavity, realizes that plasma oozes or plasma activated chemical vapour deposition.Processed is negative electrode, according to processed surface shape, increases negative electrode identical with cathode material, profile similarity, forms double cathode.Reactant gases evenly is incorporated in the cavity between negative electrode and the negative electrode by negative electrode, and the residual gas after the reaction needs be extracted out by mechanical pump by around the cathode inner surface edge.Satisfy Pd=0.5～10Torrcm relation between negative electrode and cathode spacing d and the vacuum chamber reaction pressure P, molybdenum anode processed is positioned at around the cavity edge, and the negative electrode and positive electrode spacing is 2～5 times of double cathode spacing.
The metallic interior surface modification is to pass into reactant gases, adds the DC pulse bias voltage between the anode and cathode, controls processed temperature, carries out that chemistry oozes or thin film deposition.Under the effect of hollow cathode plasma, processed is heated between 400～700 ° of C, passes into the mixed gas of nitrogen or ammonia and argon gas, to the inner surface of pipe fitting nitriding; During the deposition hard carbon thin film, processed workpiece and water-cooled copper electrode contact are controlled between 50～300 ° of C the temperature of processed workpiece, pass into the mixed gas of acetylene or methane and argon gas, add pulsed voltage and deposit hard carbon thin film at inner surface of pipe fitting.
Effect of the present invention and benefit are: can process the pipe fitting of big L/D ratio and the internal surface of various complicated shapes; Can realize that chemistry oozes, comprise that single element blends multiple permeation, also can carry out thin film deposition, as depositing hard carbon films etc.; Surface modification efficient is high.
Description of drawings
Accompanying drawing 1 is inner surface of pipe fitting reforming apparatus schematic diagram.
Among the figure: 1 power supply; 2 processed pipe fittings; 3 negative electrode air taking ports; 4 negative electrodes; 5 anodes; 6 insulating ceramic pipes; 7 bleeding points; 8 vacuum measurements; 9 seal washers; 10 silica tubes; 11 tongued and grooved flanges.
Embodiment
Be described in detail the specific embodiment of the present invention below in conjunction with technical scheme and accompanying drawing.
The specific embodiment of the invention is, at first, vacuumizes and makes reaction chamber reach base vacuum～10
-3Torr passes into argon gas and carries out surface cleaning and activating pretreatment 5-20min to processed to 0.05Torr, passes in proportion afterwards reactant gases.In nitrogen or ammonia and the argon gas mixed gas, nitrogen or ammonia ratio are 20～80%, regulate vacuum tightness 5 * 10
-2Between～the 5Torr, add pulsed voltage 0～10kV or electric current 0～5A between anode and cathode, under the effect of hollow cathode plasma, processed is heated between 400～700 ° of C naturally, and nitriding time is 0.5～4h.
During the deposition hard carbon films, change reactant gases into acetylene or methane and argon gas mixed gas, acetylene or methane ratio are 5～40%, and the water flowing cooling guarantees that workpiece temperature is between 50～300 ° of C.Regulate vacuum tightness 5 * 10
-2Between～the 5Torr, add pulsed voltage 0～10kV or electric current 0～5A, hard carbon films depositing time 0.5～4h between anode and cathode.
Embodiment 1:
As shown in Figure 1, the adjustment cathode spacing is 5mm, and cathode and anode spacing 20mm is evacuated to 10
-3Torr passes into argon gas to 0.05Torr, adds dc pulse voltage 2kV, plasma clean sample 10min.Pass into 40% nitrogen, the pressure of adjusting vacuum chamber is 3Torr, adds direct current pulse power source, and discharging current maintains 0.3A, and underlayer temperature is 500 ° of C approximately, and the reaction times is 2h.
Embodiment 2:
As shown in Figure 2, the adjustment cathode spacing is 10mm, and cathode and anode spacing 40mm is evacuated to 10
-3Torr passes into argon gas to 0.05Torr, and to substrate holder water flowing cooling, underlayer temperature is no more than 300 ° of C.Add dc pulse voltage 2kV, plasma clean sample 10min.Pass into 20% acetylene gas, the pressure of adjusting vacuum chamber is 0.5Torr, adds direct current pulse power source, and discharging current maintains 0.2A, and the reaction times is 2h.
Claims (2)
1. the device of a metallic interior surface modification, to utilize hollow cathode effect in cavity, to produce highdensity plasma body, realize the modification of metallic interior surface, can realize that chemistry oozes, also can deposit hard carbon films, improve the physical and chemical performances such as hardness, wear resistance and solidity to corrosion of metallic interior surface, it is characterized in that processed is negative electrode, according to processed surface shape, increase negative electrode identical with cathode material, profile similarity, form double cathode; Reactant gases evenly is incorporated in the cavity between negative electrode and the negative electrode by negative electrode, and the residual gas after the reaction needs be extracted out by mechanical pump by around the cathode inner surface edge; Satisfy the Pd=0.5-10Torrcm relation between negative electrode and cathode spacing d and the vacuum chamber reaction pressure P, molybdenum anode processed is positioned at around the cavity edge, and the negative electrode and positive electrode spacing is 2-5 times of double cathode spacing; Pass into reactant gases, add the DC pulse bias voltage between the anode and cathode, control processed temperature, carry out that chemistry oozes or thin film deposition.
2. metallic interior surface modification is characterized in that:
A) at first, vacuumize and make reaction chamber reach base vacuum～10
-3Torr passes into argon gas and carries out surface cleaning and activating pretreatment 5-20min to processed to 0.05Torr, passes in proportion afterwards reactant gases; In nitrogen or ammonia and the argon gas mixed gas, nitrogen or ammonia ratio are 20～80%, regulate vacuum tightness 5 * 10
-2Between～the 5Torr, add pulsed voltage 0～10kV or electric current 0～5A between anode and cathode, under the effect of hollow cathode plasma, processed is heated between 400～700 ° of C naturally, and nitriding time is 0.5～4h;
When b) depositing hard carbon films, change reactant gases into acetylene or methane and argon gas mixed gas, acetylene or methane ratio are 5～40%, and the water flowing cooling guarantees that workpiece temperature is between 50～300 ° of C; Regulate vacuum tightness 5 * 10
-2Between～the 5Torr, add pulsed voltage 0～10kV or electric current 0～5A, hard carbon films depositing time 0.5～4h between anode and cathode.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104313567A (en) * | 2014-09-12 | 2015-01-28 | 湖州鑫隆镀膜科技有限公司 | Metal chromium production technology for replacing electroplating technology |
| CN105648424A (en) * | 2016-03-29 | 2016-06-08 | 北京航空航天大学 | Device and method for coating inner walls of hollow cathode discharge reducer metal tubes |
| CN107217228A (en) * | 2017-05-18 | 2017-09-29 | 清华大学 | Improve the method and bearing of bearing anti-wear performance |
| CN107937880A (en) * | 2017-09-20 | 2018-04-20 | 深圳市创新维度科技有限公司 | A kind of method of metal surface properties modification and products thereof and purposes |
| CN108342708A (en) * | 2018-03-22 | 2018-07-31 | 深圳大学 | A kind of carbon method for implanting and its modified cutter, mold |
| RU2671522C1 (en) * | 2017-08-14 | 2018-11-01 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" | Method of internal cylindrical surface plasma strengthening |
| CN109518121A (en) * | 2018-11-21 | 2019-03-26 | 中国航发哈尔滨东安发动机有限公司 | A method of regulating and controlling thin-wall titanium alloy part deformation using hollow cathode effect |
| CN109518122A (en) * | 2018-12-05 | 2019-03-26 | 中国航发哈尔滨东安发动机有限公司 | The asymmetric revolution class titanium alloy component ionic nitriding control method of thin-walled large scale |
| CN109609889A (en) * | 2018-12-05 | 2019-04-12 | 中国航发哈尔滨东安发动机有限公司 | A kind of thin-walled bivalve layer titanium alloy bushing high-temperature ammonolysis superfinishing deformation control method |
| CN109680243A (en) * | 2018-12-05 | 2019-04-26 | 中国航发哈尔滨东安发动机有限公司 | The asymmetric revolution class titanium alloy component of thin-walled small-medium size nitrogenizes deformation control method |
| CN111647879A (en) * | 2020-04-20 | 2020-09-11 | 中国科学技术大学 | Chemical vapor deposition device and method |
| CN112025202A (en) * | 2020-08-21 | 2020-12-04 | 广东粤江鸿锐电力科技发展有限公司 | Method for repairing straight gear |
| CN113198804A (en) * | 2021-04-30 | 2021-08-03 | 辽宁科技大学 | Method and apparatus for cleaning inner wall of slender pipeline by inert gas ionization |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104313567A (en) * | 2014-09-12 | 2015-01-28 | 湖州鑫隆镀膜科技有限公司 | Metal chromium production technology for replacing electroplating technology |
| CN105648424A (en) * | 2016-03-29 | 2016-06-08 | 北京航空航天大学 | Device and method for coating inner walls of hollow cathode discharge reducer metal tubes |
| CN107217228B (en) * | 2017-05-18 | 2019-11-22 | 清华大学 | Improve the method and bearing of bearing wear-resisting property |
| CN107217228A (en) * | 2017-05-18 | 2017-09-29 | 清华大学 | Improve the method and bearing of bearing anti-wear performance |
| RU2671522C1 (en) * | 2017-08-14 | 2018-11-01 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" | Method of internal cylindrical surface plasma strengthening |
| CN107937880A (en) * | 2017-09-20 | 2018-04-20 | 深圳市创新维度科技有限公司 | A kind of method of metal surface properties modification and products thereof and purposes |
| CN107937880B (en) * | 2017-09-20 | 2020-03-10 | 深圳市中科摩方科技有限公司 | Method for modifying surface of metal material, product and application thereof |
| CN108342708A (en) * | 2018-03-22 | 2018-07-31 | 深圳大学 | A kind of carbon method for implanting and its modified cutter, mold |
| CN109518121A (en) * | 2018-11-21 | 2019-03-26 | 中国航发哈尔滨东安发动机有限公司 | A method of regulating and controlling thin-wall titanium alloy part deformation using hollow cathode effect |
| CN109518121B (en) * | 2018-11-21 | 2021-09-10 | 中国航发哈尔滨东安发动机有限公司 | Method for regulating and controlling deformation of thin-wall titanium alloy part by using hollow cathode effect |
| CN109609889A (en) * | 2018-12-05 | 2019-04-12 | 中国航发哈尔滨东安发动机有限公司 | A kind of thin-walled bivalve layer titanium alloy bushing high-temperature ammonolysis superfinishing deformation control method |
| CN109680243A (en) * | 2018-12-05 | 2019-04-26 | 中国航发哈尔滨东安发动机有限公司 | The asymmetric revolution class titanium alloy component of thin-walled small-medium size nitrogenizes deformation control method |
| CN109518122A (en) * | 2018-12-05 | 2019-03-26 | 中国航发哈尔滨东安发动机有限公司 | The asymmetric revolution class titanium alloy component ionic nitriding control method of thin-walled large scale |
| CN109680243B (en) * | 2018-12-05 | 2021-11-09 | 中国航发哈尔滨东安发动机有限公司 | Thin-wall medium-small-size asymmetric rotation type titanium alloy part nitriding deformation control method |
| CN109609889B (en) * | 2018-12-05 | 2021-11-09 | 中国航发哈尔滨东安发动机有限公司 | High-temperature nitriding ultra-precision deformation control method for thin-wall double-shell titanium alloy bushing |
| CN111647879A (en) * | 2020-04-20 | 2020-09-11 | 中国科学技术大学 | Chemical vapor deposition device and method |
| CN112025202A (en) * | 2020-08-21 | 2020-12-04 | 广东粤江鸿锐电力科技发展有限公司 | Method for repairing straight gear |
| CN113198804A (en) * | 2021-04-30 | 2021-08-03 | 辽宁科技大学 | Method and apparatus for cleaning inner wall of slender pipeline by inert gas ionization |
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