CN104099576B

CN104099576B - A kind of W2N-Cu hard nanometer structural membrane and preparation method

Info

Publication number: CN104099576B
Application number: CN201410313488.3A
Authority: CN
Inventors: 喻利花; 许俊华; 赵洪舰
Original assignee: Jiangsu University of Science and Technology
Current assignee: Jiangsu University of Science and Technology
Priority date: 2014-07-02
Filing date: 2014-07-02
Publication date: 2016-05-11
Anticipated expiration: 2034-07-02
Also published as: CN104099576A

Abstract

Herein disclosure of the invention a kind of ganoine thin film and preparation method thereof, this film is taking pure W target, pure Cu target and pure Cr target as target, utilizes two confocal radio frequency reactive sputterings of target to be deposited on carbide alloy or ceramic matrix, divided thin film minor is W₂N-Cu, wherein W content is 85at.%-100at.%, and Cu content is 0at.%-15at.%, and film thickness is at 1-3 μ m. When deposition, vacuum is better than 3.0 × 10^-3Pa, with the argon gas starting the arc, nitrogen is reacting gas, argon nitrogen flow-rate ratio 10:(6-15), sputtering pressure 0.3Pa. The method production efficiency is high, and gained film has high rigidity and excellent frictional behaviour concurrently, can be used as the nanostructured ganoine thin film of DRY CUTTING under high speed, wide temperature range.

Description

A kind of W2N-Cu hard nanometer structural membrane and preparation method

Technical field

The present invention relates to a kind of coating and preparation method thereof, particularly a kind of W₂N-Cu hard nanometer structural membrane and preparationMethod, belongs to ceramic coating technical field.

Background technology

The development of modern processing, has proposed such as " high-speed and high-temperature ", " high accuracy ", " high reliability " cutter coatHigher service demand such as " long-lives ", except requiring coating to have the due high rigidity of ordinary cutting tool coating, excellentOutside high-temperature oxidation resistance, more need coating under wide temperature range, all to there is good friction and wear behavior. But, existing cutterAlthough coating all has higher hardness, their friction and wear behavior is all undesirable, is difficult to meet as high speed, the cutting of wide temperature rangeEtc. harsh service condition. Tungsten nitride is because having high-melting-point, high rigidity, stable chemical nature, low room temperature and high temperature friction coefficientBe subject to researcher pays close attention to good wear resistance. In recent years many scholar's research the mechanics of the system such as WTiN and WCNPerformance and friction and wear behavior, find to add after the third element, and mechanical property and friction and wear behavior all improve, but itsMiddle temperature friction and wear behavior is relatively poor. Therefore, wear-resistant with the wide temperature range of the desired desirable high rigidity of contemporary processing manufacturing industryCoating is compared, and the friction and wear behavior of this type of hard coat still has deficiency.

Summary of the invention:

The object of the invention is to overcome existing WN is hard nanometer structure composite film and multilayer film antioxygenic property and frictionThe shortcoming that polishing machine is undesirable, provides a kind of W₂N-Cu hard nanometer structural membrane, has compared with high efficiency, has concurrently high hardDegree and excellent in low high temperature friction and wear performance, can be used as at a high speed, the nanostructured ganoine thin film of DRY CUTTING under wide temperature range.

Another object of the present invention is to provide a kind of W₂The preparation method of N-Cu hard nanometer structural membrane.

The present invention tests by the following technical programs:

A kind of W₂N-Cu hard nanometer structural membrane, is taking pure W target, pure Cu target and pure Cr target as target, adopts two targets altogetherBurnt radio frequency reactive sputtering prepares on carbide alloy or ceramic matrix, (according to the name of film main component) film moleculeFormula is W₂N-Cu, film thickness is at 1-3 μ m; Wherein W content is that 85at.%-100at.%, Cu content are 0at.%-15at.％。

A kind of W₂The preparation method of N-Cu ganoine thin film, is taking pure W target, pure Cu target and pure Cr target as target, utilizes two targetsConfocal radio frequency reaction method deposits W on carbide alloy or ceramic matrix₂N-Cu ganoine thin film, when deposition, vacuum is better than 3.0 ×10^-3Pa, with the argon gas starting the arc, nitrogen is that reacting gas deposits, sputtering pressure 0.3Pa, argon nitrogen flow-rate ratio 10:(6-15);

W content is 85at.%-100at.%, and Cu content is 0at.%-15at.%;

Preferably, W content is 87.78at.%-100at.%, and Cu content is 0at.%-12.22at.%; Cu contentGood is 0at.%-11.04at.%, better 0at.%-4.85at.%, and the best is 1.9at.%, when W content is 98.1at.%,Cu content is 1.9at.%, and the hardness of film is up to 33.5GPa, and under dry cutting experiment, coefficient of friction and wear rate are 0.35 He1.64×10^-8mm³·N^-1mm^-1。

Aforesaid W₂The preparation method of N-Cu ganoine thin film, is characterized in that, deposits in advance CrN as transition on matrixLayer, Cr target sputtering power is 80-150W.

W of the present invention₂N-Cu ganoine thin film is to adopt high-purity W target and the confocal RF-reactively sputtered titanium of Cu target, is deposited on hardOn alloy or ceramic matrix, prepare, film thickness is at 1-3um, and Cu content is at 0at.%-15at.%, when Cu content isWhen 1.9at.%, the hardness of film is up to 33.5GPa, and under dry cutting experiment, coefficient of friction and wear rate be 0.35 and 1.64 ×10^-8mm³·N^-1mm^-1, this hard coat has comprehensively possessed high rigidity, the good characteristics of high-wearing feature. Cu content isWhen 11.04at.%, hardness is 22.1GPa, and the coefficient of friction between 25～600 DEG C is between 0.3～0.4, and wear rate is lower than 8.9×10^-8mm³·N^-1mm^-1, this hard coat has comprehensively possessed anti abrasive feature within the scope of wide temperature range.

Brief description of the drawings

Fig. 1 is embodiment of the present invention gained W₂N-Cu composite membrane is with the XRD collection of illustrative plates of the increase gained of Cu content, wherein illustrationThat Cu content is the XRD collection of illustrative plates of 81.98at.%, visible W₂N-Cu film has and W₂The face-centred cubic structure that N film is similar is thinFilm is mainly the growth of (200) preferred orientation. Cu content during lower than 12.22at.%, does not detect Cu phase diffraction maximum in collection of illustrative plates, whenWhen Cu content is 81.98at.%, Cu phase diffraction maximum in collection of illustrative plates, detected. (according to the main component W of composite membrane, Cu, N, inventionPeople is by film called after W₂N-Cu)。

Fig. 2 is embodiment of the present invention gained W₂The variation relation of N-Cu film hardness (GPa) and Cu content (at.%); WithThe increase of Cu content, the microhardness of film first raises and reduces afterwards, and in the time that Cu content is 1.9at.%, hardness is up to33.5GPa。

Fig. 3 is embodiment of the present invention gained W₂Average friction coefficient and wear rate and Cu under the dry cutting experiment of N-Cu composite membraneThe variation relation curve of content, with the increase of Cu content, the average friction coefficient of film reduces gradually, and wearing and tearing take the lead in reducing afterIncrease, when Cu content is 11.04at.%, it is minimum that wear rate reaches, and is 0.9 × 10^-8mm³·N^-1mm^-1, now coefficient of friction is0.3。

Fig. 4 is embodiment of the present invention gained W₂Under the dry cutting experiment of N-Cu composite membrane, average friction coefficient and wear rate are with rubbingWiping temperature (DEG C) variation relation curve. Known, raise with temperature, W₂The coefficient of friction of N-Cu composite membrane subtracts after first increasing graduallyLittle, and wear rate increases gradually.

Detailed description of the invention

Below with reference to preferred embodiment, technical scheme of the present invention is described:

W of the present invention₂N-Cu ganoine thin film completes on JGP-450 high-vacuum multi-target magnetic control sputtering equipment, adoptsHigh-purity W target and the confocal RF-reactively sputtered titanium of Cu target, be deposited on carbide alloy or ceramic matrix and prepare. This magnetic control sputtering deviceHave three sputtering targets, be arranged on respectively in three water cooled holder, three stainless steel baffle plates are arranged on respectively before three targets, pass throughComputer is controlled automatically. Pure W target (99.99%), pure Cu target (99.99%) and pure Cr target (99.9%) are arranged on independently and penetrate respectivelyFrequently on negative electrode, target diameter is 75mm. The carbide alloy such as high-speed steel or ceramic matrix surface are done to mirror finish processing, to vacuumThe indoor purity that is filled with is 99.999% Ar, N₂Mist, on the matrix at the carbide alloy such as high-speed steel or potteryAdopt pure W target and pure Cu target to carry out the confocal RF-reactively sputtered titanium method deposition of two targets and generate W₂N-Cu ganoine thin film. Deposition W₂N-CuBefore film, isolate substrate and ion district by baffle plate, first carry out sputter 5-10 minute with Ar ion pair target, to remove targetThe impurity on material surface, avoids impurity to bring in film. On matrix, deposit the pure CrN of 100-200nm as transition zone, to strengthenFilm-substrate cohesion. Sputtering time is 2-3h, and film thickness is 1-3 μ m.

Wherein, selecting substrate is that the composition of single crystalline Si sheet (100) to film, phase structure, anti-oxidant and hardness are studied;Selecting substrate is the research that stainless composite membrane carries out friction and wear behavior. Substrate is ultrasonic at acetone and absolute ethyl alcohol respectivelyIn ripple, each 10-15min that cleans, to remove greasy dirt and the dust of matrix surface, packs the rotatable base of vacuum chamber into after flash bakingOn horse. Target is about 11cm to the distance of substrate. Vacuum chamber base vacuum is better than 3.0 × 10^-3After Pa, pass into purity and be99.999% the argon gas starting the arc. Operating air pressure remains on 0.3Pa, simultaneously Ar, N₂Flow-rate ratio keeps 10:10, prepares a series ofWith the W of Cu content (0at.%-12.22at.%)₂N-Cu film.

Embodiment 1 to 5 shown in table 1 has investigated the W under different Cu content₂The hardness of N-Cu film, and dry cutting is realAverage friction coefficient under testing and wear rate:

Table 1

Embodiment 6-8 shown in table 2 has investigated film that Cu content is 11.04at.% under differentiated friction test temperatureCoefficient of friction and wear rate:

Table 2

	Embodiment 6	Embodiment 7	Embodiment 8
				W content	88.96at.％	88.96at.％	88.96at.％
Cu content	11.04at.％	11.04at.％	11.04at.％
				Friction test temperature	200℃	400℃	600℃
Coefficient of friction	0.4	0.36	0.34
				Wear rate	2.2×10^-7	5.5×10^-7	8.9×10^-7

Below only having enumerated W content is 87.78at.%-100at.%, and Cu content is 0at.%-12.22at.%, argon nitrogenThe situation of flow-rate ratio 10:10, wherein Cu content be 0at.% only as a comparison with reference to example, Cu content is 11.04at.% conductHigh temperature friction example, in practical operation, can operate is that W content is 85at.%-100at.%, Cu content is 0at.%-15at.%, sputtering pressure 0.3Pa, the argon nitrogen flow-rate ratio 10:(6-15 of deposition process).

Claims

1. a W₂N-Cu hard nanometer structural membrane, it is characterized in that taking pure W target, pure Cu target and pure Cr target as target, adoptsThe confocal radio frequency reactive sputtering of two targets prepares on carbide alloy or ceramic matrix, at deposition W₂N-Cu hard nanometer structureBefore film, the CrN that deposit thickness is 100-200nm in advance on matrix is as transition zone, W₂N-Cu hard nanometer structural membraneIn in the atomic percentage conc of W and Cu element, the atomic percentage conc of W is 85at.%≤W < 100at.%, the atom hundred of CuDividing content is 0at.% < Cu≤15at.%, W₂N-Cu hard nanometer structural membrane thickness is at 1-3 μ m.

2. W claimed in claim 1₂The preparation method of N-Cu hard nanometer structural membrane, it is characterized in that with pure W target, pure CuTarget and pure Cr target are target, utilize two confocal radio frequency reactive sputterings of target to be deposited on carbide alloy or ceramic matrix, in depositionW₂Before N-Cu hard nanometer structural membrane, the CrN that deposit thickness is 100-200nm in advance on matrix, as transition zone, depositsW₂When N-Cu hard nanometer structural membrane, vacuum is better than 3.0 × 10^-3Pa, with the argon gas starting the arc, nitrogen is reacting gas, argon nitrogenFlow-rate ratio 10:(6-15), sputtering pressure 0.3Pa, W₂In N-Cu hard nanometer structural membrane, contain with the atom percentage of W and Cu elementAmount meter, the atomic percentage conc of W is 85at.%≤W < 100at.%, the atomic percentage conc of Cu be 0at.% < Cu≤15at.％。

3. W claimed in claim 2₂The preparation method of N-Cu hard nanometer structural membrane, is characterized in that Cr target sputtering power is80-150W。

4. W claimed in claim 2₂The preparation method of N-Cu hard nanometer structural membrane, is characterized in that the atom percentage of Cu containsAmount is 0at.% < Cu≤12.22at.%.

5. W claimed in claim 2₂The preparation method of N-Cu hard nanometer structural membrane, is characterized in that Cu content 1.9at.%≤Cu≤11.04at.％。

6. W claimed in claim 2₂The preparation method of N-Cu hard nanometer structural membrane, is characterized in that Cu content is 0at.%<Cu≤4.85at.％。