阅读说明：本技术 一种在钛合金表面制备强附着力钼层的方法 (A method of strong adhesive force molybdenum layer is prepared in titanium alloy surface ) 是由 马捷 程文涛 李洪义 魏建忠 吴龙 于 2019-09-03 设计创作，主要内容包括：一种在钛合金表面制备强附着力钼层的方法,属于金属材料表面改性技术领域。在经过预处理的钛上先磁控溅射Cu形成薄膜后化学气相沉积W,在此基础上再上化学气相沉积Mo,形成Cu/W/Mo复合涂层。本发明提供的钛合金表面制备强附着力钼层的技术,旨在通过磁控溅射铜薄膜提高W涂层和钛基体的结合力,增加W层避免钛基体在后续化学气相沉积Mo过程中受高温影响而发生的氢脆和侵蚀,并且能够提高钛和钼的结合力,进而得到既可以保护钛基体不被破坏又能与钛结合力良好的钼复合涂层,改善钛的性能缺陷,大大扩宽了钛的应用范围。(A method of strong adhesive force molybdenum layer being prepared in titanium alloy surface, belongs to technical field of metal material surface modification.In the chemical vapor deposition W after elder generation magnetron sputtering C u on pretreated titanium forms film, goes up chemical vapor deposition Mo again on this basis, form Cu/W/Mo composite coating.Titanium alloy surface provided by the invention prepares the technology of strong adhesive force molybdenum layer; it is intended to improve the binding force of W coating and Titanium base by magnetron sputtering Copper thin film; increase W layer avoid Titanium base subsequent chemistry vapor deposition Mo during influenced by high temperature and the hydrogen embrittlement occurred and erosion; and it can be improved the binding force of titanium and molybdenum; and then it not only can protect Titanium base and be not destroyed but also can be with the good molybdenum composite coating of titanium binding force; the performance deficiency for improving titanium, has widened the application range of titanium significantly.)

1. a kind of method for preparing strong adhesive force molybdenum layer in titanium alloy surface, which comprises the following steps:

(1) magnetron sputtering C u: being matrix by target, the TA1 by cleaning pretreatment of Cu；It first vacuumizes and is again heated to 375 DEG C After start starter pre-sputtering, copper 3h is sputtered after pre-sputtering 30s on Titanium base, room temperature is finally down to and takes out sample；

(2) chemical vapor deposition W: test is with WF₆And H₂For reaction gas, H₂For protective gas, with step (1) magnetron sputtering copper Titanium afterwards is matrix, WF₆And H₂Gas flow is controlled by needle-valve and flowmeter；On-test, first leads to H₂It is rear to wait reaction into reaction chamber Room is heated to W deposition required temperature, while WF₆Laggard promoting the circulation of qi is heated, WF is then passed to₆Carry out chemical vapor deposition, WF₆ And H₂Molar ratio=1:5；Technological temperature is 450 DEG C, process time 10min；

(3) chemical vapor deposition Mo: test is with MoF₆And H₂For reaction gas, Ar is protective gas, with step (2) chemical gaseous phase Titanium after depositing W is matrix, this step is tested Following step (2) and carried out；MoF in test₆And H₂Gas flow is by needle-valve and stream Meter control first leads to Ar into slowly closing H again after reaction chamber when this step starts₂, temperature needed for reaction chamber is heated to molybdenum deposition Degree, while MoF₆Laggard promoting the circulation of qi is heated, H is then passed to₂After turn off Ar, then logical MoF₆Carry out chemical vapor deposition, MoF₆With H₂Molar ratio=1:5；Technological temperature is 600 DEG C -800 DEG C, process time 30min.

2. a kind of method for preparing strong adhesive force molybdenum layer in titanium alloy surface described in accordance with the claim 1, which is characterized in that step Suddenly the rectangular stainless steel tube that (2) and (3) chemical vapor deposition equipment are side length 25mm length 1000mm, with tube furnace point Start chemical vapor deposition after not being heated to each autoreaction required temperature；Step (2) parameter: WF₆And H₂Molar ratio=1:5, technique Temperature is 450 DEG C, process time 10min；Step (3) parameter: MoF₆And H₂Molar ratio=1:5, technological temperature be 650 DEG C- 750 DEG C, process time 30min.

3. a kind of method for preparing strong adhesive force molybdenum layer in titanium alloy surface described in accordance with the claim 1, which is characterized in that step Suddenly (1) sputtering parameter: pre-sputtering 30S, sputtering time 3h, sputtering power 200W, 375 DEG C of sputter temperature.

Technical field

The invention belongs to technical field of metal material surface modification, in particular to a kind of strong attached in titanium alloy surface preparation Put forth effort the method for molybdenum layer.

Technical background

Titanium is the important new structure metal of one kind that last century mid-term grows up, titanium and its alloy have density it is small, The excellent comprehensive performances such as specific strength is high, specific stiffness is high, anti-fatigue life is long, high-temperature mechanics and croop property are good are extensive Be applied to aerospace, biochemical industry, automobile ship etc..Titanium surface hardness is low, wears no resistance, and corrosion resistance is paid no attention to Think, although titanium is easy to be formed on its surface oxidation film, protective effect is extremely limited, and titanium is caused to be unable to satisfy in real life greatly The normal use requirement of most cases, greatly limits the application of titanium.Molybdenum belongs to refractory metal, therefore one with refractory metal Number of features: because having good thermal conductivity, low-expansion coefficient, elevated temperature strength is high, the performances such as wear resistant corrosion resistant and it is extensive Applied to the fields such as metallurgy, agricultural, aerospace, electronic chemical.Therefore the performance that process for modifying surface can be used to improve titanium mentions Height application, and current titanium alloy surface prepares molybdenum layer and produces many problems, and hydrogen embrittlement and erosion, matrix easily occurs under hot environment The problems such as combining difference with coating is especially prominent.The principle of sputter coating is the plasma that low density gas is generated in abnormal glow discharge Body bombards cathode targets surface under the action of electric field, and the molecule of target material surface, atom, ion and electronics etc. are splashed It shoots out, the particle for being sputtered out is formed along certain direction directive matrix surface in matrix surface with certain kinetic energy Coating.Magnetron sputtering has the characteristics that high-speed low temperature, and the film of formation is uniform, quality of forming film is high, plated film rate is fast, finished product quantity More and technique stability is good.Chemical vapor deposition (CVD) is to make gas under the activation and driving of heat, light and plasma etc. Chemistry hair occurs on gas-solid interface and answers for state substance, so that a material preparation technology of stable, solid deposit be made.CVD tool There is a uniformly coating complex shape part, coating purity obtained is high, matrix and coating is firmly combined, deposition velocity is fast, equipment is simple The advantages that single operation facilitates.

Summary of the invention

The purpose of the present invention is overcoming the performance deficiency of titanium, one kind is provided in titanium alloy surface and prepares strong adhesive force molybdenum layer simultaneously It prevents titanium from the method for hydrogen embrittlement and erosion occurs under high temperature when depositing molybdenum layer, copper atom is splashed to titanium using magnetron sputtering technique On piece prepares Copper thin film, then using the method direct chemical vapor deposition on Copper thin film at a lower temperature of chemical vapor deposition Tungsten starts chemical vapor deposition molybdenum after being finally raised to certain temperature on this basis, prepares Cu/W/Mo composite coating.It is made Standby sample out carries out Mechanics Performance Testing using the automatic scratching instrument of WS-2005 coating adhesion, wherein composite coating binding force It can reach 168.5N, the binding force 65.8N of CVD molybdenum coating direct higher than titanium alloy sample surface；Directly change in metallic titanium surface Learn vapor deposition molybdenum, hydrogen embrittlement and erosion and molybdenum coating and Titanium base occur at high temperature and combines insecure for titanium, coating easily occur Whole peeling phenomenon, coating binding force 65.8N, and in titanium sheet after magnetron sputtering copper again chemical vapor deposition tungsten be made and titanium The Cu/W composite coating that matrix is well combined, deposits molybdenum after being warming up to 650 DEG C -750 DEG C on this basis, and it is multiple to obtain Cu/W/Mo Coating is closed, binding force can reach 168.5N, the binding force between molybdenum coating and Titanium base greatly improved, and Titanium base does not go out What incumbent damage.Titanium alloy surface provided by the invention prepares the technology of molybdenum coating, and the knot of W and Ti is improved by increasing Cu film With joint efforts, increasing intermediate layer W, from there is hydrogen embrittlement under high temperature environment in titanium and erosion is got ready to prevent when subsequent deposition Mo. The excellent molybdenum coating of binding force is finally obtained, the binding force between molybdenum coating and Titanium base had both been greatly improved, avoids coating in titanium On fall off easily, and prevent titanium from hydrogen embrittlement and erosion occurring during the deposition process, good protection carried out to Titanium base, in turn Improve the performance of titanium.

Preparation method provided by the invention, which is characterized in that preparation process the following steps are included:

(1) magnetron sputtering C u: being matrix by target, the TA1 by cleaning pretreatment of Cu.It first vacuumizes and is again heated to Start starter pre-sputtering after 375 DEG C, sputter copper 3h on Titanium base after pre-sputtering 30s, is finally down to room temperature and takes out sample.

(2) chemical vapor deposition W: test is with WF₆And H₂For reaction gas, H₂For protective gas, splashed with step (1) magnetic control Titanium after penetrating copper is matrix, WF₆And H₂Gas flow is controlled by needle-valve and flowmeter.On-test, first leads to H₂It is rear etc. into reaction chamber Reaction chamber is heated to W deposition required temperature, while WF₆Laggard promoting the circulation of qi is heated, WF is then passed to₆Chemical vapor deposition is carried out, WF₆And H₂Molar ratio=1:5；Technological temperature is 450 DEG C, process time 10min.

(3) chemical vapor deposition Mo: test is with MoF₆And H₂For reaction gas, Ar is protective gas, with step (2) chemistry Titanium after vapor deposition W is matrix, this step is tested Following step (2) and carried out.MoF in test₆And H₂Gas flow is by needle-valve And flowmeter control, Ar is first led to when this step starts into slowly closing H again after reaction chamber₂, reaction chamber is heated to molybdenum deposition institute Temperature is needed, while MoF₆Laggard promoting the circulation of qi is heated, H is then passed to₂After turn off Ar, then logical MoF₆Chemical vapor deposition is carried out, MoF₆And H₂Molar ratio=1:5；Technological temperature is 650 DEG C -750 DEG C, process time 30min.

Chemical vapour deposition reaction equipment is the rectangular stainless steel tube of side length 25mm length 1000mm, is arrived with diamond heating React required temperature, WF₆、MoF₆And H₂Molar ratio is all 1:5.

Compared with prior art, the beneficial effects of the present invention are:

The direct chemical vapor deposition molybdenum of titanium alloy surface can be formed more within the scope of 650 DEG C -750 DEG C in sample surfaces Complete molybdenum layer, but be easy to cause and fall off in conjunction with situation difference.And since depositing temperature is relatively high, cause titanium in deposition molybdenum mistake Hydrogen embrittlement and erosion occur in journey, therefore improves the combination effect of coating and matrix and the protection of Titanium base is become and need to solve The problem of.Titanium alloy surface prepares W transition zone, can both improve the combination situation between molybdenum coating and titanium alloy substrate, improves coating With the binding force of matrix, and disbonding is avoided, prevents hydrogen and titanium from contacting caused by hydrogen embrittlement and vapor deposition occurs and corrode, into And protect Titanium base.

The present invention first uses and prepares Copper thin film in the method titanium sheet of magnetron sputtering, then uses the side of chemical vapor deposition Method deposits tungsten in Copper thin film surface low-temperature, finally chemical vapor deposition molybdenum on this basis, prepares purity is high, compactness It is good, the strong Cu/W/Mo composite coating of binding force.Prepared sample using the automatic scratching instrument of WS-2005 coating adhesion into Row Mechanics Performance Testing directly carries out chemical vapor deposition in Titanium base, and hydrogen embrittlement and erosion and coating and matrix knot occur for titanium Close it is insecure easily there is coating entirety peeling phenomenon, coating binding force 65.8N, and the chemical gas after magnetron sputtering copper in titanium sheet The molybdenum layer that phase deposits tungsten redeposition molybdenum obtains, binding force can reach 168.5N, the binding force between coating and matrix greatly improved, And there is not any damage in Titanium base.Technical solution of the present invention is reproducible, simple to operation, and excellent effect is obvious.

Detailed description of the invention

Fig. 1: macro morphology (a) and titanium alloy surface after the direct CVD molybdenum of titanium alloy surface increase CVD after intermediate layer The macro morphology (b) of molybdenum

Fig. 2: titanium alloy surface CVD molybdenum composite coating, which combines, tries hard to.

Fig. 3: titanium alloy surface increases CVD molybdenum composite coating sectional view after intermediate layer.

Specific embodiment:

Titanium alloy surface of the present invention illustrated below prepares the specific embodiment of the method for strong adhesive force molybdenum layer.Below Embodiment will be helpful to researcher in this field and further understand the present invention, but the invention is not limited in any way.It should , it is noted that for those of ordinary skill in the art, under the premise for not departing from present inventive concept, can also make Several adjustment and improvement.These are all within the scope of protection of the present invention.