CN1305023A - Plasma surface-alloying process for titanium alloy - Google Patents
Plasma surface-alloying process for titanium alloy Download PDFInfo
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Abstract
A plasma surface alloying process for Ti alloy features that dual-layer glow ion diffusion technique is used to form a single-or multi-element diffused alloy layer on the surface of Ti alloy. Said elements may be Mo, Ni, Cr, Nb, W, Pd, Ta and Zr. Said alloy layer has higher anticorrosion, antiwear and anti-oxidizing power. Said process can also be used to prepare marmem, superconductor alloy and hydrogen-bearing alloy.
Description
The invention belongs to the metal surface properties modification technical field.Category in particular to double glow plasma surface alloying technique and titanium alloy surface alloying.
Titanium alloy is the metallic substance of a new generation, because its high specific tenacity and good solidity to corrosion, be widely used in fields such as Aeronautics and Astronautics, chemical industry, the energy, oceans, the application aspect civilian also day by day increases, as joint prosthesis and some sports equipments etc.Yet also there are some problems in titanium alloy, as: frictional coefficient is big, wears no resistance; Corrosion stability is very poor in media such as hydrochloric acid, sulfuric acid, cyanogen fluoric acid; Be used for pyritous titanium alloy oxidation-resistance deficiency.Method by alloying has developed and many new titanium alloy, has solved some problems.But the inefficacy of titanium alloy often starts from the surface, and whole alloying can cause waste to a certain degree on the one hand, also has the problem that surface property and overall performance are difficult to take into account on the other hand.Therefore various process for modifying surface are all used on titanium alloy and are studied, as plating, ion nitriding, ion implantation, PVD, CVD, plasma spraying etc.Carry out alloying on the surface of titanium alloy and can improve its surface property effectively.Because what surface alloying formed is diffusion layer, can solve the bad problem of each type coating or film and matrix bond.None proven technique still so far in this field.Ion carburizing, glowdischarge carburizing, ion nitriding only can realize the infiltration of carbon, nitrogen, can't realize the infiltration of metallic element.Though traditional powder entrapping method, paste method can be carried out the infiltration of alloying element, but be difficult for realizing Composition Control that labor condition is poor, and environment is also had bigger pollution, therefore is difficult to be applied.Give full play to the application potential of titanium alloy, press for a kind of adaptation face width, can effectively control the surface-alloying process of infiltration layer composition and tissue.
Double glow plasma surface alloying technique in 1985 in the U. S. application patent, and it is granted, the patent No. is 4,520,268. the application of this technology on cutting tools also obtained Chinese patent, the patent No. is that present this technology of 87104358.0. is mainly used in ferrous materials, and obtains good effect.Titanium alloy surface alloying purpose is the double glow plasma surface alloying technique range of application is extended to the titanium alloy field, thereby discloses a kind of technical scheme of utilizing the glow discharge plasma characteristic metallic cementation process to be carried out the titanium alloy plasma surface alloying of effectively strengthening and controlling.The metallic cementation process is carried out under vacuum environment, has cleaning, free of contamination advantage.Double glow plasma surface alloying technique is applied to titanium or titanium alloy certain singularity, the chemical property of titanium or titanium alloy is active far beyond ferrous materials, hydrogen and oxidation are easily inhaled in its surface, and therefore vacuum tightness and the leak rate to double-layer metallic glow ion cementation equipment has higher requirement.In addition, titanium or titanium alloy might spontaneous combustion under frictional heat and high temperature even blast, so must be taken precautions against during the application double glow plasma surface alloying technique on titanium or titanium alloy.Heating temperature all far above the tempering temperature of ferrous materials, therefore, for improving the bulk strength of ferrous materials, also must be carried out subsequent heat treatment behind the metallic cementation when double glow plasma surface alloying technique was applied to ferrous materials.Yet the aging temp of titanium or titanium alloy just in time can be used as the temperature of titanium alloy metallic cementation.Therefore, double-layer metallic glow ion cementation can be used as the final processing of titanium alloy and state after not destroying the titanium alloy solution treatment.
The present invention can be a treated material with any titanium or titanium alloy material, the alloying element of selecting desire to add as required.Single element, multielement all can.The degree of depth of may command alloying layer and alloying element ratio and content.Diffusion layer can be formed and also the composite bed that settled layer adds diffusion layer can be obtained.Also can add reaction atmosphere simultaneously and carry out Combined Processing at metallic cementation.
Know-why of the present invention and feature are in vacuum electric-discharge device, and two negative electrodes are set: source electrode and workpiece, furnace shell serve as the anode of discharge.One cover direct supply (or direct current pulse power source) is set respectively between source electrode, workpiece and the anode, and voltage is adjustable continuously between 0～2000V, and the positive pole of power supply is connected with furnace shell, and negative pole is connected with workpiece with source electrode.Source electrode is made with desire co-diffusioning alloy element, can be different shapes such as flat board, circular arc, decides on the workpiece shape, and principle is and the workpiece profiling to guarantee the even infiltration of workpiece surface.Source electrode, workpiece spacing are 10～100mm, and simultaneously the two can be equipped with the auxiliary cathode with equi-potential own and profiling, and the distance of auxiliary cathode and source electrode and workpiece is between 20～60mm.Discharge medium is an argon gas, and operating air pressure is that 13.3～1330Pa. electric discharge device can be established the resistive heating parts, and the required part of heat energy that heats up is provided.Because titanium alloy is very easily inhaled hydrogen and oxidation, the final vacuum of metallic cementation equipment will reach 10
-1More than the Pa, when two brightness metallic cementations are used on iron to the about order of magnitude of vacuum requirements height.Leak rate must not be higher than 0.67Pa/hr simultaneously.
During metallic cementation, be evacuated to final vacuum 10
-1Charge into argon gas to the operating air pressure scope after Pa is above, the power-on aura that ignites.By ion bombardment heated parts and source electrode, also can be used resistive heating.Workpiece temperature can be at 600～1300 ℃, and the process time decides on the alloying layer thickness requirement.Source potential generally-800V～-2000V, the workpiece current potential-200V～-1000V, the source electrode alloying element is because the bombardment of positive ion sputters a large amount of active particles, these particles (atom, cluster, ion etc.) are to workpiece motion s, be adsorbed on workpiece surface, and infiltrate matrix formation alloyed layer by diffusion.
Advantage of the present invention is to form various alloy layers on the titanium or titanium alloy surface.According to the part applying working condition with to the requirement of surface physics, chemical property, can design the source electrode composition and carry out single element and infiltrate or multiple permeation, obtain having various alloy layers with different surfaces performance.In technological process, can realize effective control by the adjustment of processing parameter to layer surface composition, the degree of depth, tissue.Because plasma environment is to the reinforcement of surface alloying process, the traditional alloyage process of efficiency ratio that infiltrates process improves greatly.Whole process is carried out under vacuum condition, and is pollution-free, and the surface quality after labor condition and part are handled is all relatively good.By surface alloying, make titanium alloy material under the prerequisite of performance overall performance, have bigger adaptability.
Embodiment: the Ti6A14V sample, pure nickel material source electrode, size is 50 * 20mm, after in device, arranging, be evacuated to the limit after, charge into argon gas to operating air pressure, light aura and be warming up to 800 ℃, be incubated 4 hours.After soaking time arrives, continue to charge into argon gas, come out of the stove behind the cool to room temperature.Through check, alloy layer thickness is 60～70 μ m, and surface nickel content reaches 70%.
Claims (6)
1. plasma surface-alloying process for titanium alloy, it is characterized in that double glow plasma surface alloying technique is extended to titanium alloy surface alloying field, be implemented in titanium alloy surface and infiltrate alloying element and combinations thereof such as molybdenum, nickel, chromium, zirconium, niobium, tantalum, tungsten, molybdenum, vanadium, form the titanium alloy surface alloy layer; Concrete processing method is: two negative electrodes are set in the vacuum glow discharge device simultaneously, an alloying element that is infiltrated by desire is made, be called source electrode, another one is processed titanium alloy material, be called negative electrode, vacuum chamber housing is as shared anode, between anode and two negative electrodes, tunable voltage dc power supply is set respectively, after being evacuated to final vacuum and sending into an amount of argon gas, light aura, the alloying element particle of source electrode is sputtered out, and is deposited on titanium alloy surface, by 600～1000 ℃ the surface alloying layer that diffuses to form; In metallic cementation, can feed reactant gas and carry out Combined Processing, also can after metallic cementation, carry out thermo-chemical treatments such as carburizing or nitrogenize.
2. tunable voltage dc power supply according to claim 1, it is characterized in that source electrode and negative electrode are equipped with a cover direct supply or a direct current pulse power source separately, voltage output range is 0～2000V, and adjustable continuously, and two cover power supplys are common anode with the vacuum chamber housing of ground connection.
3. a kind of plasma surface-alloying process for titanium alloy according to claim 1 is characterized in that processing condition are to discharge air pressure at 13.3～133Pa, and final vacuum is not less than 10
-1Pa; Discharge medium can be rare gas elementes such as argon gas, also can add other atmosphere such as atmosphere such as nitrogen, ammonia and carry out Combined Processing; Source potential-800V～-2000V, the workpiece current potential-200V～-1000V; Source electrode workpiece spacing is 10～100mm; Can independently discharge between source electrode and the negative electrode, also can carry out equi-potential or the hollow cathode discharge of non-equi-potential.
4. alloy source electrode according to claim 1 is characterized in that the alloying element that desire is infiltrated mainly refers to molybdenum, nickel, chromium, zirconium, niobium, tantalum, tungsten, molybdenum, vanadium etc., can be single element material, binary and multicomponent alloy, compound etc.; Source electrode can be made different geometrical shapies according to the situation of workpiece, as different shapes such as flat board, circular arc, brushes, or with the profiling of workpiece outside surface, to guarantee the even infiltration of alloying element at workpiece surface.
5. a kind of plasma surface-alloying process for titanium alloy according to claim 1, it is characterized in that workpiece can be the titanium alloy of pure titanium or any composition, treatment temp is between 600～1000 ℃, and workpiece surface can form pure diffusion layer, also can form the compisite seeping layer that settled layer adds diffusion layer; The tissue of infiltration layer and composition and thickness can be controlled by the adjusting process parameter.
6. a kind of plasma surface-alloying process for titanium alloy according to claim 1 is characterized in that source electrode and workpiece can set up equipotential with it auxiliary cathode; The spacing of auxiliary cathode and source electrode and negative electrode is between 20～60mm; Auxiliary cathode and source electrode can independently discharge between auxiliary cathode and the workpiece, also can produce hollow cathode discharge.
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|---|---|---|---|---|
| CN100426937C (en) * | 2005-04-05 | 2008-10-15 | 深圳市王博纳米热能技术有限公司 | Titanium nano electrothermal materials |
| CN101851744A (en) * | 2010-06-05 | 2010-10-06 | 太原理工大学 | Preparation method of multilayer composite modified layer with strong toughness on titanium alloy surface |
| CN101591784B (en) * | 2009-06-01 | 2010-11-10 | 太原理工大学 | Mechanical infiltration method for surface alloying of pure iron-based plate |
| CN101400287B (en) * | 2006-02-13 | 2011-02-09 | Seb公司 | Easy-clean cooking surface |
| CN102560411A (en) * | 2012-01-10 | 2012-07-11 | 北京工业大学 | Preparation method of anti-ablative coating on surface of titanium alloy |
| CN103194719A (en) * | 2012-01-05 | 2013-07-10 | 曾云发 | High-performance ceramic piston ring manufacturing technology |
| CN103225058A (en) * | 2012-12-20 | 2013-07-31 | 桂林电子科技大学 | High-temperature-oxidation-resistant austenitic stainless steel and preparation method thereof |
| CN103243306A (en) * | 2013-05-10 | 2013-08-14 | 太原理工大学 | Method for preparing Cu doped TiN alloy layer on surface of titanium alloy |
| CN104593718A (en) * | 2015-02-28 | 2015-05-06 | 深圳市华宇发真空离子技术有限公司 | Method for hardening austenitic stainless steel material |
| CN104862649A (en) * | 2015-04-07 | 2015-08-26 | 太原理工大学 | Preparation method for gradient titanium alloy-surface Ni/TiN composite modification layer |
| CN105154835A (en) * | 2015-09-15 | 2015-12-16 | 江苏省产品质量监督检验研究院 | Abrasion-resistant protection coating on surface of gamma-TiAl alloy and preparation method thereof |
| CN105385974A (en) * | 2015-11-30 | 2016-03-09 | 济南泰丽龙企业管理咨询有限公司 | Method for improving surface properties of suture line of nickel-titanium memory alloy |
| CN105483610A (en) * | 2015-11-27 | 2016-04-13 | 燕山大学 | Iron permeating method for surface strengthened titanium alloy |
| CN106048548A (en) * | 2016-06-16 | 2016-10-26 | 南京航空航天大学 | Preparation method of biological active nanocrystal beta-Ta coating |
| CN107419233A (en) * | 2017-06-26 | 2017-12-01 | 南京航空航天大学 | A kind of titanium aluminium base alloy surface protection coating and preparation method thereof |
| CN108070831A (en) * | 2017-12-18 | 2018-05-25 | 南京航空航天大学 | Ta-Zr alloy coats of TiAl-base alloy surfacecti proteon and preparation method thereof |
| CN108866502A (en) * | 2018-06-21 | 2018-11-23 | 太原理工大学 | A kind of titanium alloy surface high temperature coatings and preparation method thereof |
| CN108914082A (en) * | 2018-06-20 | 2018-11-30 | 太原理工大学 | A kind of surface treatment method of austenitic stainless steel |
| CN109554667A (en) * | 2018-12-04 | 2019-04-02 | 南京航空航天大学 | A kind of wear-resisting Nb-N co-penetration layer of TA15 alloy surface and the preparation method and application thereof |
| CN109797360A (en) * | 2019-03-14 | 2019-05-24 | 太原理工大学 | A kind of processing method improving titanium alloy surface wearability |
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| CN110760788A (en) * | 2019-10-29 | 2020-02-07 | 长春奥普光电技术股份有限公司 | Modification treatment method for surface hardness of cast titanium alloy |
| CN110983257A (en) * | 2019-11-29 | 2020-04-10 | 南京航空航天大学 | Surface treatment method for improving corrosion resistance and anti-icing performance of titanium alloy surface |
| CN111074199A (en) * | 2019-12-03 | 2020-04-28 | 太原理工大学 | Preparation method of high-entropy alloy layer on surface of tungsten alloy |
| CN111519150A (en) * | 2020-05-29 | 2020-08-11 | 太原理工大学 | Preparation method of binary or multi-component alloy layer |
| CN114717507A (en) * | 2022-05-20 | 2022-07-08 | 西安理工大学 | Low-temperature ionic nitriding method for synchronously improving wear resistance and fatigue resistance of titanium alloy |
| CN114941120A (en) * | 2022-05-24 | 2022-08-26 | 西北有色金属研究院 | Method for hardening surface of beta titanium alloy |
| CN115449743A (en) * | 2022-09-20 | 2022-12-09 | 江西省科学院应用物理研究所 | Alloy surface modification layer and preparation method thereof |
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2000
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| CN100426937C (en) * | 2005-04-05 | 2008-10-15 | 深圳市王博纳米热能技术有限公司 | Titanium nano electrothermal materials |
| CN101400287B (en) * | 2006-02-13 | 2011-02-09 | Seb公司 | Easy-clean cooking surface |
| CN101591784B (en) * | 2009-06-01 | 2010-11-10 | 太原理工大学 | Mechanical infiltration method for surface alloying of pure iron-based plate |
| CN101851744A (en) * | 2010-06-05 | 2010-10-06 | 太原理工大学 | Preparation method of multilayer composite modified layer with strong toughness on titanium alloy surface |
| CN101851744B (en) * | 2010-06-05 | 2012-11-14 | 太原理工大学 | Preparation method of multilayer composite modified layer with strong toughness on titanium alloy surface |
| CN103194719B (en) * | 2012-01-05 | 2016-03-02 | 曾云发 | High-performance ceramic piston ring manufacturing technology |
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| CN103243306B (en) * | 2013-05-10 | 2015-01-14 | 太原理工大学 | Method for preparing Cu doped TiN alloy layer on surface of titanium alloy |
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| CN104862649A (en) * | 2015-04-07 | 2015-08-26 | 太原理工大学 | Preparation method for gradient titanium alloy-surface Ni/TiN composite modification layer |
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| CN105483610A (en) * | 2015-11-27 | 2016-04-13 | 燕山大学 | Iron permeating method for surface strengthened titanium alloy |
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| CN106048548A (en) * | 2016-06-16 | 2016-10-26 | 南京航空航天大学 | Preparation method of biological active nanocrystal beta-Ta coating |
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| CN108914082A (en) * | 2018-06-20 | 2018-11-30 | 太原理工大学 | A kind of surface treatment method of austenitic stainless steel |
| CN108914082B (en) * | 2018-06-20 | 2020-05-26 | 太原理工大学 | Surface treatment method of austenitic stainless steel |
| CN108866502A (en) * | 2018-06-21 | 2018-11-23 | 太原理工大学 | A kind of titanium alloy surface high temperature coatings and preparation method thereof |
| CN109554667A (en) * | 2018-12-04 | 2019-04-02 | 南京航空航天大学 | A kind of wear-resisting Nb-N co-penetration layer of TA15 alloy surface and the preparation method and application thereof |
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| CN110983257A (en) * | 2019-11-29 | 2020-04-10 | 南京航空航天大学 | Surface treatment method for improving corrosion resistance and anti-icing performance of titanium alloy surface |
| CN111074199A (en) * | 2019-12-03 | 2020-04-28 | 太原理工大学 | Preparation method of high-entropy alloy layer on surface of tungsten alloy |
| CN111074199B (en) * | 2019-12-03 | 2022-02-18 | 太原理工大学 | Preparation method of high-entropy alloy layer on surface of tungsten alloy |
| CN111519150A (en) * | 2020-05-29 | 2020-08-11 | 太原理工大学 | Preparation method of binary or multi-component alloy layer |
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| CN114717507A (en) * | 2022-05-20 | 2022-07-08 | 西安理工大学 | Low-temperature ionic nitriding method for synchronously improving wear resistance and fatigue resistance of titanium alloy |
| CN114717507B (en) * | 2022-05-20 | 2024-01-19 | 西安理工大学 | Low-temperature ion nitriding method for synchronously improving wear resistance and fatigue resistance of titanium alloy |
| CN114941120A (en) * | 2022-05-24 | 2022-08-26 | 西北有色金属研究院 | Method for hardening surface of beta titanium alloy |
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