CN102321865B - Heat treated magnetron sputtering B-C-N ternary hard coat - Google Patents
Heat treated magnetron sputtering B-C-N ternary hard coat Download PDFInfo
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Abstract
The invention relates to a heat treated magnetron sputtering B-C-N ternary hard coat, wherein a plurality of transition coats consisting of Ti, TiN and Ti-B-C-N are formed on the surface of a metallic matrix so that the good combination performance between the B-C-N hard coat and the metallic matrix is increased; meanwhile, a proper graphite/boron composite target and corresponding sputtering process parameters are selected; the high-performance hard coat close to BC2N stoichiometric ratio is obtained; the thickness of the B-C-N in the coat is about 150 nm; the atomic percentage contents of elements of a film surface are as follows: 22.3% of B, 51.6% of C and 26.1% of N; and the surface hardness is about 14 GPa.
Description
Technical field
The present invention relates to a kind of technical field of material surface coating, especially a kind of through heat treated magnetron sputtering B-C-N ternary hard coat.
Background technology
According to mechanism's similarity of diamond and cube BN (c-BN), people's expected in theory can be synthesized the B-C-N ternary hard coat, and expects that it can have adamantine ultrahigh hardness and c-BN high-temperature stability, oxidation-resistance etc. concurrently.And through widely experimental study confirmation, synthetic B-C-N ternary hard coat is truly feasible, and the B-C-N ternary hard coat is certain hardness with superelevation the same as with cube BN diamond also, in addition, compare with hard coats such as diamond, carbonitrides, it also has the unrivaled use advantages such as the internal stress of stability at elevated temperature excellence, coating is low.Therefore, the B-C-N ternary hard coat not only becomes the study hotspot in hard coat field, and its practical application in corresponding field is also increasingly extensive, has immeasurable huge performance potential and wide application prospect.
And also very general for the preparation of the method for B-C-N ternary hard coat, the synthesis preparation method of routines such as chemical Vapor deposition process and physical vaporous deposition can be used for preparing the B-C-N ternary hard coat.But when using chemical gaseous phase depositing process, often its boron source gas etc. all has toxicity, all causes very large pressure for environment and production safety; Moreover, studies show that the result of chemical gaseous phase depositing process preparation, all trend towards obtaining hexangle type B-C-N ternary coating but not cube B-C-N ternary coating.Comparatively speaking, to be sputtered to the physical gas-phase deposite method of feature, because it uses solid phase target source usually, then safer convenience the particularly important is it and trends towards making a cube B-C-N ternary coating.
Yet, for the composition control of B-C-N ternary coating, with the problems such as elimination of the close attachment of matrix, coating internal stress on, still have various deficiencies, become the obstacle of restriction B-C-N ternary hard coat widespread use.
Summary of the invention
For the problems referred to above, purpose of the present invention namely is as rf magnetron sputtering B-C-N ternary hard coat preparation method selects suitable processing parameter, thereby obtains a kind of and the compact high-performance rigid B-C-N of matrix ternary hard coat.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is as follows:
At first, with the metal matrix material surface finish, and after in ultrasonic cleaner, respectively cleaning approximately 10min with acetone, alcohol and deionized water etc. respectively, dry up for subsequent use with nitrogen.
Subsequently, body material is placed on the sample table in the vacuum chamber, and the Ti target placed respectively different target position with graphite/boron composition target, wherein said graphite/boron composition target is that the boron with ring-type is enclosed within outside the graphite of disc-shaped, and the Area Ratio of graphite and boron is 2.5: 1-2: between 1, the purity of graphite is 99.999%, the purity of boron is 99.9%, and graphite/boron composition target and body material distance are 7-8cm.
Subsequently vacuum tightness in the vacuum chamber is extracted into≤5 * 10
-4Pa passes into the Ar that flow is 8-10sccm simultaneously, when gas pressure in vacuum is 2-4Pa, and pre-sputter 2-3min, the power of pre-sputter is 50-70W, with the surface of further cleaning body material.
The flow of keeping subsequently Ar is 8-10sccm, control body material temperature is 40-50 ℃, when gas pressure in vacuum is 1-1.5Pa, apply the negative bias of 100-150V to body material, remove simultaneously the baffle plate of Ti target, power with 50-70W carries out sputter, and sputtering time is 5-10min, to form the pure Ti coating of one deck.
Begin subsequently to pass into the N that flow is 0.3-0.6sccm
2And the flow of keeping Ar is that 8-10sccm, gas pressure in vacuum are that the negative bias of 1-1.5Pa, body material is that the temperature of 100-150V, body material is 40-50 ℃, continuation is carried out sputter with the power of 50-70W, and sputtering time is 15-25min, to form one deck Ti-N binary coating.
The flow of keeping subsequently Ar is that 8-10sccm, gas pressure in vacuum are that the negative bias of 1-1.5Pa, body material is 100-150V, and the temperature of rising body material is 250-300 ℃, N
2Flow be 0.8-1sccm, remove the baffle plate of graphite/boron composition target, the power that the Ti target is kept with 50-70W carries out sputter, and graphite/boron composition target carries out sputter with 100-110W power, sputtering time is 15-25min, to form Ti-B-C-N quaternary coating.
The flow of keeping subsequently Ar is that 8-10sccm, gas pressure in vacuum are that the negative bias of 1-1.5Pa, body material is that the temperature of 100-150V, body material is 250-300 ℃, closes Ti target baffle plate and keeps graphite/boron Film by Sputtering of Composite Target, N
2Flow raise and to be 3.5-4.5sccm, sputtering power is increased to 130-140W, sputtering time is 80-100min, to form the B-C-N ternary hard coat.
Keep subsequently the inert atmosphere of Ar, under 700-750 ℃ temperature coating is carried out anneal, the treatment time is 60-90min.
Advantage of the present invention is: formed Ti, TiN, Ti-B-C-N multilayer tie coat at metal base surface, to improve the good bonding properties of B-C-N hard coat and metallic matrix; Simultaneously, selected suitable graphite/boron composition target and corresponding splash-proofing sputtering process parameter, obtained close to BC
2The high-performance rigid coating of N stoichiometric ratio.
Embodiment
Below, the present invention is described in detail by specific embodiment.
The B-C-N ternary hard coat that a kind of because radio frequency (13.56MHz) magnetron sputtering makes is particularly prepared by following steps:
At first, select the W6Mo5Cr4V2 rapid steel as body material, with its surface finish, and after in ultrasonic cleaner, respectively cleaning approximately 10min with acetone, alcohol and deionized water etc. respectively, dry up for subsequent use with nitrogen.
Subsequently, body material is placed on the sample table in the vacuum chamber, and the Ti target placed respectively different target position with graphite/boron composition target, wherein said graphite/boron composition target is that the boron with ring-type is enclosed within outside the graphite of disc-shaped, and the Area Ratio of graphite and boron was at 2.2: 1, the purity of graphite is 99.999%, the purity of boron is 99.9%, and graphite/boron composition target and body material distance are 8cm.
Subsequently vacuum tightness in the vacuum chamber is extracted into≤5 * 10
-4Pa passes into the Ar that flow is 9sccm simultaneously, when gas pressure in vacuum is 3Pa, and pre-sputter 2min, the power of pre-sputter is 60W, with the surface of further cleaning body material.
The flow of keeping subsequently Ar is 9sccm, and control body material temperature is 40 ℃, when gas pressure in vacuum is 1.5Pa, apply the negative bias of 130V to body material, remove simultaneously the baffle plate of Ti target, carry out sputter with the power of 60W, sputtering time is 7min, to form the pure Ti coating of one deck.
Begin subsequently to pass into the N that flow is 0.4sccm
2, and the flow of keeping Ar is that 9sccm, gas pressure in vacuum are that the negative bias of 1.5Pa, body material is that the temperature of 130V, body material is 40 ℃, continues to carry out sputter with the power of 60W, sputtering time is 20min, to form one deck Ti-N binary coating.
The flow of keeping subsequently Ar is that 9sccm, gas pressure in vacuum are that the negative bias of 1.5Pa, body material is 130V, and the temperature of rising body material is 270 ℃, N
2Flow be 0.9sccm, remove the baffle plate of graphite/boron composition target, the power that the Ti target is kept with 60W carries out sputter, and graphite/boron composition target carries out sputter with 110W power, sputtering time is 20min, to form Ti-B-C-N quaternary coating.
The flow of keeping subsequently Ar is that 9sccm, gas pressure in vacuum are that the negative bias of 1.5Pa, body material is that the temperature of 130V, body material is 270 ℃, closes Ti target baffle plate and keeps graphite/boron Film by Sputtering of Composite Target, N
2Flow raise and to be 4sccm, sputtering power is increased to 140W, sputtering time is 90min, to form the B-C-N ternary coating.
Keep subsequently the inert atmosphere of Ar, under 720 ℃ temperature coating is carried out anneal, the treatment time is 80min.
After tested, the thickness of surperficial B-C-N hard coat is about 150nm, and the atomic percentage conc of the element of coatingsurface is 22.3B-51.6C-26.1N, and the hardness on surface is about 14GPa.Appearance is smooth smooth, and frictional coefficient is about 0.95 during 5mN.The placement a few days does not have the problem of obvious cracking, projection to occur in air.
Claims (1)
1. B-C-N ternary hard coat that is made by rf magnetron sputtering is particularly prepared by following steps:
At first, select the W6Mo5Cr4V2 rapid steel as body material, with its surface finish, and after in ultrasonic cleaner, respectively cleaning 10min with acetone, alcohol and deionized water respectively, dry up for subsequent use with nitrogen;
Subsequently, body material is placed on the sample table in the vacuum chamber, and the Ti target placed respectively different target position with graphite/boron composition target, wherein said graphite/boron composition target is that the boron with ring-type is enclosed within outside the graphite of disc-shaped, and the Area Ratio of graphite and boron was at 2.2: 1, the purity of graphite is 99.999%, the purity of boron is 99.9%, and graphite/boron composition target and body material distance are 8cm;
Subsequently vacuum tightness in the vacuum chamber is extracted into≤5 * 10
-4Pa passes into the Ar that flow is 9sccm simultaneously, when gas pressure in vacuum is 3Pa, and pre-sputter 2min, the power of pre-sputter is 60W, with the surface of further cleaning body material;
The flow of keeping subsequently Ar is 9sccm, and control body material temperature is 40 ℃, when gas pressure in vacuum is 1.5Pa, apply the negative bias of 130V to body material, remove simultaneously the baffle plate of Ti target, carry out sputter with the power of 60W, sputtering time is 7min, to form the pure Ti coating of one deck;
Begin subsequently to pass into the N that flow is 0.4sccm
2, and the flow of keeping Ar is that 9sccm, gas pressure in vacuum are that the negative bias of 1.5Pa, body material is that the temperature of 130V, body material is 40 ℃, continues to carry out sputter with the power of 60W, sputtering time is 20min, to form one deck Ti-N binary coating;
The flow of keeping subsequently Ar is that 9sccm, gas pressure in vacuum are that the negative bias of 1.5Pa, body material is 130V, and the temperature of rising body material is 270 ℃, N
2Flow be 0.9sccm, remove the baffle plate of graphite/boron composition target, the power that the Ti target is kept with 60W carries out sputter, and graphite/boron composition target carries out sputter with 110W power, sputtering time is 20min, to form Ti-B-C-N quaternary coating;
The flow of keeping subsequently Ar is that 9sccm, gas pressure in vacuum are that the negative bias of 1.5Pa, body material is that the temperature of 130V, body material is 270 ℃, closes Ti target baffle plate and keeps graphite/boron Film by Sputtering of Composite Target, N
2Flow raise and to be 4sccm, sputtering power is increased to 140W, sputtering time is 90min, to form the B-C-N ternary coating;
Keep subsequently the inert atmosphere of Ar, under 720 ℃ temperature coating is carried out anneal, the treatment time is 80min;
The frequency of rf magnetron sputtering is 13.56MHz;
The thickness of surface B-C-N hard coat is 150nm, and the atomic percentage conc of the element of coatingsurface is 22.3B-51.6C-26.1N, and the hardness on surface is 14GPa, and appearance is smooth smooth, and frictional coefficient is 0.95 during 5mN.
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| CN 201110307491 CN102321865B (en) | 2011-10-11 | 2011-10-11 | Heat treated magnetron sputtering B-C-N ternary hard coat |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525734A (en) * | 2009-03-31 | 2009-09-09 | 西安交通大学 | Method for preparing boron, carbon and nitrogen hard coating |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525734A (en) * | 2009-03-31 | 2009-09-09 | 西安交通大学 | Method for preparing boron, carbon and nitrogen hard coating |
Non-Patent Citations (2)
| Title |
|---|
| 王玉新，等，."沉积参量对硼碳氮薄膜光透过性质的影响".《动能材料》.2008,第39卷(第6期),第935-941页. |
| 王玉新,等,."沉积参量对硼碳氮薄膜光透过性质的影响".《动能材料》.2008,第39卷(第6期),第935-941页. * |
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