CN104099576A

CN104099576A - Hard film and preparation method thereof

Info

Publication number: CN104099576A
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: 2014-10-15
Anticipated expiration: 2034-07-02
Also published as: CN104099576B

Abstract

The invention discloses a hard film and a preparation method thereof. The film uses a pure W target, a pure Cu target and a pure Cr target as targets, and deposits the targets on a hard alloy or ceramic matrix by using a double-target confocal radio frequency reaction sputtering method; the molecular formula of the film is W2N-Cu, wherein the content of W is 85-100 at.%, the content of Cu is 0-15 at.%, and the thickness of the film is 1-3 microns. In the deposition, the vacuum degree is superior to 3.0*10-3 Pa; the arc is started with argon; the argon is reaction gas; the flow ratio of the argon to nitrogen is 10: (6-15); and the sputtering pressure is 0.3 Pa. The method is high in production efficiency; the obtained film has high hardness and excellent friction performance, and can be used as a dry-cut hard film with a nanometer structure under high speed and wide temperature range.

Description

A kind of ganoine thin film and preparation method

Technical field

The present invention relates to a kind of coating and preparation method thereof, particularly a kind of W ₂n-Cu hard nanometer structural membrane and preparation method, belong to ceramic coating technical field.

Background technology

The development of modern processing, cutter coat has been proposed higher service demand such as " high-speed and high-temperature ", " high precision ", " high reliability " " long lifetime ", except requiring coating to have the high-temperature oxidation resistance of the due high rigidity of ordinary cutting tool coating, excellence, more need coating under wide temperature range, all to there is good friction and wear behavior.But although existing cutter coat all has higher hardness, their friction and wear behavior is all undesirable, be difficult to the service condition meeting as high speed, wide temperature range cutting etc. are harsh.Tungsten nitride receives investigator's concern because having high-melting-point, high rigidity, stable chemical nature, low room temperature and high temperature friction coefficient and good wear resistance.In recent years many scholar's research mechanical property and the friction and wear behavior of the system such as WTiN and WCN, find to add after the third element, mechanical property and friction and wear behavior all improve, but wherein warm friction and wear behavior is relatively poor.Therefore,, compared with the wide temperature range abrasion-resistant coatings of the desired desirable high rigidity of contemporary processing manufacturing industry, 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 antioxidant property and the undesirable shortcoming of friction and wear behavior, and a kind of W is provided ₂n-Cu hard nanometer structural membrane, has compared with high efficiency, have concurrently high rigidity and excellent in low high temperature friction and wear performance, can be used as at a high speed, the nanostructure ganoine thin film of DRY CUTTING under wide temperature range.

Another object of the present invention is to provide a kind of W ₂the preparation method of N-Cu hard nanometer structural membrane.The present invention tests by the following technical programs:

A kind of W ₂n-Cu hard nanometer structural membrane, is taking pure W target, pure Cu target and pure Cr target as target, adopts two confocal radio frequency reactive sputterings of target to prepare on Wimet or ceramic matrix, and (according to the name of film main component) divided thin film minor is W ₂n-Cu, film thickness is at 1-3 μ m; Wherein W content is that 85at.%-100at.%, Cu content are 0at.%-15at.%.

A kind of W ₂the preparation method of N-Cu ganoine thin film, is taking pure W target, pure Cu target and pure Cr target as target, utilizes two confocal radio frequency reaction methods of target to deposit W on Wimet or ceramic matrix ₂n-Cu ganoine thin film, when deposition, vacuum tightness is better than 3.0 × 10 ^-3pa, with the argon gas starting the arc, nitrogen is that reactant gases deposits, sputtering pressure 0.3Pa, argon nitrogen throughput 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 content is preferably 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, under dry cutting experiment, frictional coefficient and wear rate are 0.35 and 1.64 × 10 ^-8mm ³n ^-1mm ^-1.

Aforesaid W ₂the preparation method of N-Cu ganoine thin film, is characterized in that, deposits in advance CrN as transition layer on matrix, and Cr target sputtering power is 80-150W.

W of the present invention ₂n-Cu ganoine thin film is to adopt high-purity W target and the confocal RF-reactively sputtered titanium of Cu target, be deposited on and prepare on Wimet or ceramic matrix, film thickness is at 1-3um, Cu content is at 0at.%-15at.%, in the time that Cu content is 1.9at.%, the hardness of film is up to 33.5GPa, and under dry cutting experiment, frictional coefficient and wear rate are 0.35 and 1.64 × 10 ^-8mm ³n ^-1mm ^-1, this hard coat has comprehensively possessed high rigidity, the good characteristics of high-wearing feature.When Cu content is 11.04at.%, hardness is 22.1GPa, and the frictional coefficient between 25～600 DEG C is between 0.3～0.4, and wear rate is lower than 8.9 × 10 ^-8mm ³n ^-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 W ₂n-Cu composite membrane is with the XRD figure spectrum of the increase gained of Cu content, and wherein illustration is that Cu content is the XRD figure spectrum of 81.98at.%, visible W ₂n-Cu film has and W ₂the face-centred cubic structure that N film is similar, film is mainly the growth of (200) preferred orientation.Cu content during lower than 12.22at.%, does not detect Cu phase diffraction peak in collection of illustrative plates, in the time that Cu content is 81.98at.%, Cu phase diffraction peak detected in collection of illustrative plates.(according to the main component W of composite membrane, Cu, N, contriver is by film called after W ₂n-Cu).

Fig. 2 is embodiment of the present invention gained W ₂the variation relation of N-Cu film hardness (GPa) and Cu content (at.%); With the 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 to 33.5GPa.

Fig. 3 is embodiment of the present invention gained W ₂the variation relation curve of average friction coefficient and wear rate and Cu content under the dry cutting experiment of N-Cu composite membrane, with the increase of Cu content, the average friction coefficient of film reduces gradually, and wearing and tearing take the lead in reducing rear increase, when Cu content is 11.04at.%, it is minimum that wear rate reaches, and is 0.9 × 10 ^-8mm ³n ^-1mm ^-1, now frictional coefficient is 0.3.

Fig. 4 is embodiment of the present invention gained W ₂under the dry cutting experiment of N-Cu composite membrane average friction coefficient and wear rate with friction temperature (DEG C) variation relation curve.Known, raise with temperature, W ₂the frictional coefficient of N-Cu composite membrane reduces after first increasing gradually, and wear rate increases gradually.

Embodiment

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

W of the present invention ₂n-Cu ganoine thin film completes on JGP-450 high-vacuum multi-target magnetic control sputtering equipment, adopts high-purity W target and the confocal RF-reactively sputtered titanium of Cu target, is deposited on Wimet or ceramic matrix and prepares.This magnetic control sputtering device has three sputtering targets, is arranged on respectively in three water cooled holder, and three stainless steel baffle plates are arranged on respectively before three targets, automatically control by computer.Pure W target (99.99%), pure Cu target (99.99%) and pure Cr target (99.9%) are arranged on respectively independently on radio frequency negative electrode, and target diameter is 75mm.The Wimet such as rapid steel or ceramic matrix surface are done to mirror polish processing, be 99.999% Ar, N to being filled with purity in vacuum chamber ₂mixed gas, generates W by adopting pure W target and pure Cu target to carry out the confocal RF-reactively sputtered titanium method deposition of two targets on the matrix at the Wimet such as rapid steel or pottery ₂n-Cu ganoine thin film.Deposition W ₂before N-Cu film, isolate substrate and ion district by baffle plate, first carry out sputter 5-10 minute with Ar ion pair target, to remove the impurity of target material surface, avoid impurity to bring in film.On matrix, deposit the pure CrN of 100-200nm as transition layer, to strengthen film-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 each 10-15min that cleans in acetone and dehydrated alcohol ultrasonic wave respectively, to remove greasy dirt and the dust of matrix surface, packs in the rotatable substrate frame of vacuum chamber after flash baking.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 be 99.999% the argon gas starting the arc.Operating air pressure remains on 0.3Pa, simultaneously Ar, N ₂throughput ratio keeps 10:10, prepares the W of a series of different Cu content (0at.%-12.22at.%) ₂n-Cu film.

Embodiment 1 to 5 shown in table 1 has investigated the W under different Cu content ₂the hardness of N-Cu film, and average friction coefficient and wear rate under dry cutting experiment:

Table 1

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

Table 2

?	Embodiment 6	Embodiment 7	Embodiment 8
				W content	88.96at.％	88.96at.％	88.96at.％
Cu content	11.04at.％	11.04at.％	11.04at.％
				Rub(bing)test temperature	200℃	400℃	600℃
Frictional coefficient	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.%, Cu content is 0at.%-12.22at.%, the situation of argon nitrogen throughput ratio 10:10, wherein Cu content is that 0at.% is only as a comparison with reference to example, Cu content be 11.04at.% as high temperature friction example, in actually operating, can operate is that W content is 85at.%-100at.%, Cu content is 0at.%-15at.%, sputtering pressure 0.3Pa, the argon nitrogen throughput ratio 10:(6-15 of deposition process).

Claims

1. a ganoine thin film, it is characterized in that taking pure W target, pure Cu target and pure Cr target as target, adopts two confocal radio frequency reactive sputterings of target to prepare on Wimet or ceramic matrix, and molecular formula is W ₂n-Cu, wherein W content is 85at.%-100at.%, and Cu content is 0at.%-15at.%, and film thickness is at 1-3 μ m.

2. the preparation method of ganoine thin film claimed in claim 1, it is characterized in that 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 Wimet or ceramic matrix, and when deposition, vacuum tightness is better than 3.0 × 10 ^-3pa, with the argon gas starting the arc, nitrogen is reactant gases, argon nitrogen throughput ratio 10:(6-15), sputtering pressure 0.3Pa, W content is 85at.%-100at.%, Cu content is 0at.%-15at.%.

3. the preparation method of ganoine thin film claimed in claim 2, is characterized in that depositing in advance CrN on matrix as transition layer, and Cr target sputtering power is 80-150W.

4. the preparation method of ganoine thin film claimed in claim 2, is characterized in that Cu content is 0at.%-12.22at.%.

5. the preparation method of ganoine thin film claimed in claim 2, is characterized in that Cu content is 1.9at.%-11.04at.%.

6. the preparation method of ganoine thin film claimed in claim 2, is characterized in that Cu content is 0at.%-4.85at.%.

7. the preparation method of ganoine thin film claimed in claim 2, is characterized in that Cu content is 1.9at.%.

8. the preparation method of ganoine thin film claimed in claim 2, is characterized in that Cu content is 11.04at.%.