CN103112212B - Titanium alloy fastener with coating as well as manufacturing method thereof - Google Patents
Titanium alloy fastener with coating as well as manufacturing method thereof Download PDFInfo
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- CN103112212B CN103112212B CN201310062333.2A CN201310062333A CN103112212B CN 103112212 B CN103112212 B CN 103112212B CN 201310062333 A CN201310062333 A CN 201310062333A CN 103112212 B CN103112212 B CN 103112212B
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Abstract
The invention provides a titanium alloy fastener with a coating as well as a manufacturing method and device thereof. The titanium alloy fastener comprises the complex aluminium coating, wherein the complex aluminium coating comprises a bonding layer, a blended layer and a functional layer which are sequentially stacked from inside to outside, and the coating is prepared through high ionization rate of middle-frequency magnetron sputtering and high deposition rate of direct-current magnetron sputtering. The titanium alloy fastener has the beneficial effects that environmental pollution is avoided, simultaneously the prepared aluminium coating is compact in structure, has good binding force and can meet long-term stable operating requirement of the fastener, and the quality of the titanium alloy fastener is improved.
Description
Technical field
The present invention relates to thin-film material technical field, relate in particular to the cated titanium alloy fastener of a kind of tool and manufacturing method and apparatus thereof.
Background technology
Titanium alloy is the desirable structural material of aircraft, is widely used in aircaft configuration.But titanium alloy passive potential is higher, easy and aluminium alloy, composite connector produce galvanic corrosion, also can make titanium alloy fastener liberation of hydrogen cause hydrogen embrittlement simultaneously, cause aircaft configuration to destroy.Before use high strength steel and aluminium alloy, cadmium plating coating has obtained and has been widely used as the method for protection aircraft steel construction piece.Adopt after titanium alloy structure part, cadmium plating is also the conventional method that prevents from producing between titanium alloy fastener and connector galvanic corrosion, but because easily causing, cadmium plating technique environmental pollution and the crisp phenomenon of the cadmium of cadmium plating in titanium alloy use procedure of titanium alloy hydrogen embrittlement, cadmium limits the application of titanium alloy fastener in aircaft configuration.
Developed at present some can be on metal and other material the method for deposited coatings, the technique of comparative maturity has hot dipping, spraying, bag plating, plating and physical vapour deposition (PVD).Front four kinds of methods application is subject to coating layer thickness, adhesion often, by the restriction of the factors such as the size and dimension of coating-Ti alloy securing member 1, be subject to certain restrictions.Physical gas-phase deposite method can obtain even thickness, aluminized coating that adhesion is good, and wherein cathodic sputtering, arc ion plating arc and hollow cathode depositing device all can use.Although evaporation plating has fireballing feature, its uniformity is poor, add ionization device after its adhesive force increase, but coating product needs complicated post processing, is unfavorable for producing in enormous quantities.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the object of this invention is to provide the cated titanium alloy fastener of a kind of tool and manufacturing method and apparatus thereof, it can effectively avoid environmental pollution and the crisp phenomenon of the cadmium of cadmium plating in titanium alloy use procedure of titanium alloy hydrogen embrittlement, cadmium, and can adopt good manufacturing method and apparatus to manufacture required coating.
To achieve these goals, the present invention adopts first aspect provides a kind of tool cated titanium alloy fastener, comprises securing member body, and described coating is clad aluminum coating;
Preferably, described clad aluminum coating is gradient composition grading structure.
Preferably, described clad aluminum coating is followed successively by binder course, blended layer and functional layer from inside to outside.
Preferably, described binder course is sputter aluminium coated.
Preferably, described blended layer is nanocrystalline aluminium and crystallite aluminium mixed layer.
Preferably, described functional layer is multilayer aluminum coating.
Second aspect present invention provides a kind of manufacture to have the method for the titanium alloy fastener of clad aluminum coating, it is characterized in that, carries out according to following steps: in advance securing member body is carried out to aura cleaning,
1) then use intermediate frequency sputtering target sputtering sedimentation transition metal aluminum on described securing member body, form binder course;
2) with d.c. sputtering target and described intermediate frequency sputtering target sputtering sedimentation blend aluminium composite bed on described binder course, form blended layer;
3) continue with described intermediate frequency sputtering target and described d.c. sputtering target sputtering sedimentation multilayer aluminum coating in described blended layer, form functional layer;
Above-mentioned binder course, blended layer, functional layer form described clad aluminum coating.
Preferably, described step 1) be at 100-450 DEG C, 0.1-0.5Pa ,-800V carries out under the condition of-1000V; Described step 2) be at 100-450 DEG C, 0.3-0.8Pa ,-100V carries out under the condition of-250V; Described step 3) be at 100-350 DEG C, 0.2-0.8Pa ,-50V carries out under the condition of-150V.
Preferably, described step 1) to 3) step is to carry out under ar gas environment, the thickness of described binder course, blended layer, functional layer is respectively 30-50nm, 0.5-5um, 5-30um.
Third aspect present invention provides a kind of manufacture to have the device of the titanium alloy fastener of clad aluminum coating, it is characterized in that: comprise vacuum chamber, be positioned at the heater in vacuum chamber centre, what be positioned near the first intermediate frequency sputtering target vacuum chamber one side inwall and be positioned at centre forms the second intermediate frequency sputtering target to target with described the first intermediate frequency sputtering target, is positioned near the some d.c. sputtering targets of vacuum chamber opposite side inwall.
The invention has the beneficial effects as follows: this coating securing member not only has good decay resistance, aluminized coating has good adhesive force simultaneously.Adopt after this coating securing member, not only the weight of aircraft alleviates to some extent, has avoided the galvanic corrosion problem of securing member and aluminium alloy element simultaneously, makes the aerospace equipments such as aircraft have good dependability.In addition, traditional titanium alloy cadmium plating can cause serious environmental pollution and titanium alloy fastener hydrogen embrittlement, has a strong impact on the use of titanium alloy fastener.And adopt magnetron sputtering technique on titanium alloy fastener, to prepare nano combined aluminized coating, not only avoid problem of environmental pollution, the aluminized coating compact structure of preparation simultaneously, adhesion is good, can meet the work of securing member long-term stability, improve the product quality of titanium alloy fastener.
Brief description of the drawings
Fig. 1 is institute's employing manufacturing installation schematic diagram in the present invention;
Fig. 2 is clad aluminum coating structure schematic diagram of the present invention;
Fig. 3 is titanium alloy fastener surface topography;
Fig. 4 is titanium alloy fastener cross section metallograph.
In figure, 1, titanium alloy fastener 2, d.c. sputtering target 3, fire door 4, vacuum orifice 5, intermediate frequency sputtering target 6, furnace wall 7, heater 8, functional layer 9, blended layer 10, binder course 11, securing member body
Detailed description of the invention
As shown in Figure 1, the invention provides a kind of device of manufacturing the cated titanium alloy fastener of tool, this device comprises vacuum chamber, and vacuum chamber is surrounded by furnace wall 6, and vacuum chamber height is 0.5-1.5m, and diameter is 700-1500mm.Vacuum chamber side is provided with fire door 3, to facilitate the handling of titanium alloy fastener 1.Vacuum chamber is provided with vacuum orifice 4, vacuumizes unit and by vacuum orifice 4, vacuum chamber is vacuumized, and vacuumizing unit can be made up of diffusion pump and mechanical pump, also can adopt molecular pump, and end vacuum can reach 5 × 10-4Pa.The centre of vacuum chamber is heater 7, and heating power 10-30 kilowatt improves the efficiency of heating surface.Intermediate frequency sputtering target 5 is arranged on the left side, furnace wall, and a target is arranged on furnace wall, and another is arranged on by heater position in stove, and two targets form to target, by ac power supply.Other four d.c. sputtering targets 2 are arranged on the right of furnace wall, and titanium alloy fastener 1 is contained on 1 of titanium alloy fastener.This layout increases considerably vacuum chamber ionic medium volume density, and titanium alloy fastener is immersed in plasma completely.Coating sedimentation rate, hardness, adhesive force are greatly improved.Due to target structure is optimized, Distribution of Magnetic Field is more even, makes electric arc evenly burning on target surface, has improved the uniformity of coating.
The mode that this device is manufactured the cated titanium alloy fastener of tool is as follows: utilize the high ionization level of medium frequency magnetron sputtering and the high deposition rate of magnetically controlled DC sputtering to prepare Aluminium composite coating.In order to improve the adhesion of coating and titanium alloy fastener matrix, after aura cleaning finishes, intermediate frequency sputtering target 5 (to target) is opened, utilize high-power medium frequency magnetron sputtering to prepare 30-50nm binder course, its process is for passing into argon gas, glow discharge is by argon gas ionization, utilize its high ionization level, by further aluminium atom ionization, the negative high bias voltage that adds 800-1000V on titanium alloy fastener 1, utilizes high bias suction-operated, and aluminium ion is adsorbed to the surface of high-speed motion to titanium alloy fastener 1, form the diffusion of atom level, cause last metallurgical binding.In addition argon ion high-speed striking titanium alloy fastener 1 surface of ionization, the one, unstable surface conjunction aluminium lamination can be sputtered away; The 2nd, hit coating surface, allow coating become fine and close, change the poor shortcoming of the low coating adhesion of conventional magnetically controlled DC sputtering ionization level.After binder course preparation, now, intermediate frequency sputtering target 5 continues to open, and d.c. sputtering target 2 is opened, and power progressively strengthens simultaneously, and adopting the object of d.c. sputtering target 2 is further to improve the sedimentation rate of coating.But because d.c. sputtering target 2 easily forms column crystal, be unfavorable for the Corrosion Protection of titanium alloy fastener, continue to open intermediate frequency sputtering target 5 for this reason, utilize the crystallization process of the high ionization level blocking-up direct current target sputtered aluminum of intermediate frequency sputtering target 5, significantly reduce the grain size of aluminium, it is become to micron from large column crystal brilliant.Because the power of direct current target progressively increases, the crystal grain of blended layer will progressively become a mixture nanocrystalline and that micron is brilliant from binder course nanocrystalline.This structure has formed the gradual change in gradient constituent structure, can improve the structural compatibility of surface functional layer and blended layer, reduces coating stress, improves the adhesion of coating.Coating layer thickness is controlled at 0.5-5um.After blended layer preparation finishes, middle RF sputtering and d.c. sputtering target are opened jointly, titanium alloy fastener 1 in rotary course through before intermediate frequency target time the brilliant aluminium lamination of depositing nano, when before titanium alloy fastener 1 rotates to direct current target, to prepare the brilliant aluminium lamination of micron, by continuous rotation titanium alloy fastener 1, will form the membrane structure of the multilayer aluminium lamination of the brilliant aluminium lamination formation of nanocrystalline aluminium lamination and micron, multi-layer film structure one is to reduce coating stress, the 2nd, can improve the density of coating, improve corrosion resistance.Every layer of nanocrystalline aluminum layer thickness of intermediate frequency magnetic control is 10-50nm, and every layer of magnetically controlled DC sputtering aluminum layer thickness is 50-100nm.Functional layer gross thickness is 5-30um.
Introduce the concrete mode of manufacturing the titanium alloy fastener with clad aluminum coating below:
Embodiment 1:
Under 100 DEG C, ar gas environment, to titanium alloy fastener 1 after aura cleans and finishes, at 0.1Pa, the thick transition metal Al binder course of-800V condition deposition 30nm; At 0.3Pa, the thick blend aluminium composite bed of-100V condition deposition 0.5um; Then under 100 DEG C ,-50V bias voltage, 0.2Pa air pressure conditions, deposit 5um functional layer; In functional layer, intermediate frequency sputtered aluminum nanometer layer thickness is 20nm, and d.c. sputtering aluminium lamination nanometer layer thickness is 80nm, and preparation finishes rear naturally cooling, obtains clad aluminum coated on titanium alloy securing member.
Embodiment 2:
Under 200 DEG C, ar gas environment, to titanium alloy fastener 1 after aura cleans and finishes, at 0.2Pa, the thick transition metal Al binder course of-800V condition deposition 40nm; At 0.4Pa, the thick blend aluminium composite bed of-150V condition deposition 2um; Then under 150 DEG C ,-100V bias voltage, 0.5Pa air pressure conditions, deposit 10um functional layer; In functional layer, intermediate frequency sputtered aluminum nanometer layer thickness is 30nm, and d.c. sputtering aluminium lamination nanometer layer thickness is 70nm, and preparation finishes rear naturally cooling, obtains clad aluminum coated on titanium alloy securing member.
Embodiment 3:
Under 250 DEG C, ar gas environment, to titanium alloy fastener after aura cleans and finishes, at 0.4Pa, the thick transition metal Al binder course of-900V condition deposition 50nm; At 0.6Pa, the thick blend aluminium composite bed of-250V condition deposition 4um; Then under 200 DEG C ,-150V bias voltage, 0.5Pa air pressure conditions, deposit 20um functional layer; In functional layer, intermediate frequency sputtered aluminum nanometer layer thickness is 40nm, and d.c. sputtering aluminium lamination nanometer layer thickness is 100nm, and preparation finishes rear naturally cooling, obtains clad aluminum coated on titanium alloy securing member.
Embodiment 4:
Under 450 DEG C, ar gas environment, to titanium alloy fastener after aura cleans and finishes, at 0.5Pa, the thick transition metal Al binder course of-1000V condition deposition 50nm; At 0.8Pa, the thick blend aluminium composite bed of-250V condition deposition 5um; Then under 350 DEG C ,-150V bias voltage, 0.8Pa air pressure conditions, deposit 30um functional layer; In functional layer, intermediate frequency sputtered aluminum nanometer layer thickness is 15nm, and d.c. sputtering aluminium lamination nanometer layer thickness is 90nm, and preparation finishes rear naturally cooling, obtains clad aluminum coated on titanium alloy securing member.
Fig. 2 is the structural representation of the clad aluminum coating for preparing, and binder course 10, blended layer 9, functional layer 8 be the stacked periphery that is arranged on securing member body 11 from inside to outside.
Fig. 3 is the prepared clad aluminum coated on titanium alloy of the present invention fastener surface electron microscopic pattern, the as can be seen from the figure titanium alloy fastener smooth surface after coating, coating densification.
Fig. 4 is the prepared clad aluminum coated on titanium alloy securing member of the present invention cross section metallographic microscope shape appearance figure, and as can be seen from the figure coatings and substrate is in conjunction with good, and coating layer thickness is even.
Tool of the present invention has the following advantages: the first, and compared with conventional DC magnetically controlled sputter method, the method ionization level that medium frequency magnetron sputtering that the present invention adopts and magnetically controlled DC sputtering combine is high, has overcome that magnetron sputtering method ionization level is low causes the problem that adhesion is lower; The second, coating structure of the present invention adopts three-decker, forms structure gradual change, and coatings and substrate is metallurgical binding, has good adhesive force; The 3rd, compared with the column crystal aluminium lamination of preparing with conventional magnetically controlled DC sputtering, during the present invention adopts, the method for RF sputtering and d.c. sputtering codeposition significantly reduces aluminized coating crystallite dimension, forms nanocrystalline-microcrystalline coating.Increase substantially the density of coating; The 4th, the employing of high power DC sputtering technology in the present invention, has increased substantially the sedimentation rate of coating, coating layer thickness, and coating layer thickness can reach 35um; Five, the present invention adopts the auxiliary magnetically controlled DC sputtering technology of medium frequency magnetron sputtering close with existing coating apparatus, and coating apparatus is simple in structure simultaneously, is easy to control, and prospects for commercial application is good.
Above example of the present invention is had been described in detail, but described content is only preferred embodiment of the present invention, can not be considered to for limiting practical range of the present invention.All equalization variation and improvement etc. of doing according to the present patent application scope, within all should still belonging to patent covering scope of the present invention.
Claims (7)
1. the cated titanium alloy fastener of tool, comprise securing member body, it is characterized in that: described coating is clad aluminum coating, described clad aluminum coating is followed successively by binder course, blended layer and functional layer from inside to outside, and described blended layer is nanocrystalline aluminium and the brilliant aluminium mixed layer of micron.
2. securing member as claimed in claim 1, is characterized in that: described clad aluminum coating is gradient composition grading structure.
3. securing member as claimed in claim 1 or 2, is characterized in that: described binder course is sputter aluminium coated.
4. securing member as claimed in claim 1 or 2, is characterized in that: described functional layer is multilayer aluminum coating.
5. manufacture has a method for the titanium alloy fastener of clad aluminum coating, it is characterized in that, carries out according to following steps: in advance securing member body is carried out to aura cleaning,
1) then use intermediate frequency sputtering target sputtering sedimentation transition metal aluminum on described securing member body, form binder course;
2) with d.c. sputtering target and described intermediate frequency sputtering target sputtering sedimentation blend aluminium composite bed on described binder course, form blended layer;
3) continue with described intermediate frequency sputtering target and described d.c. sputtering target sputtering sedimentation multi-layer nano aluminized coating in described blended layer, form functional layer;
Above-mentioned binder course, blended layer, functional layer form described clad aluminum coating.
6. method as claimed in claim 5, is characterized in that: described step 1) be at 100-450 DEG C, 0.1-0.5Pa ,-800V carries out under the condition of-1000V; Described step 2) be at 100-450 DEG C, 0.3-0.8Pa ,-100V carries out under the condition of-250V; Described step 3) be at 100-350 DEG C, 0.2-0.8Pa ,-50V carries out under the condition of-150V.
7. the method as described in claim 5 or 6, is characterized in that: described step 1) to 3) step is to carry out under ar gas environment, the thickness of described binder course, blended layer, functional layer is respectively 30-50nm, 0.5-5um, 5-30um.
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| CN105779999B (en) * | 2016-02-01 | 2018-06-22 | 中原工学院信息商务学院 | A kind of material of high mechanical strength part |
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| CN102732832B (en) * | 2012-06-28 | 2014-04-09 | 南京航空航天大学 | Titanium alloy surface high temperature oxidation resistance and wear resistance oxide gradient coat, and preparation method thereof |
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Address after: 300300 Tianjin Huaming Industrial Park in Dongli Binhai District headquarters B06 Applicant after: Aerospace Precision Products Co., Ltd. Address before: 300300 Tianjin Huaming Industrial Park in Dongli Binhai District headquarters B06 Applicant before: Aerospace Fine Co., Ltd. |
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