CN102321864B - B-C-N ternary hard coating - Google Patents
B-C-N ternary hard coating Download PDFInfo
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- CN102321864B CN102321864B CN 201110307465 CN201110307465A CN102321864B CN 102321864 B CN102321864 B CN 102321864B CN 201110307465 CN201110307465 CN 201110307465 CN 201110307465 A CN201110307465 A CN 201110307465A CN 102321864 B CN102321864 B CN 102321864B
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Abstract
The invention discloses a B-C-N ternary hard coating prepared through radio frequency (13.56MHz) magnetron sputtering. A Ti, TiN and Ti-B-C-N multi-layer transition coating is formed on the surface of a metal matrix to improve the bonding property of the B-C-N hard coating and the metal matrix; meanwhile, a proper graphite/boron composite target and corresponding sputtering process parameters areselected, a high-performance hard coating close to a stoichiometric ratio of BC2N is obtained, the thickness of B-C-N in the coating is about 150nm, the atomic percentage of elements B, C and N on the surface of a film is 23.4, 52.2 and 24.4, and the hardness of the surface is about 15GPa.
Description
Technical field
The present invention relates to a kind of technical field of material surface coating, especially a kind of 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 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 experimental study confirmation widely, synthetic B-C-N ternary hard coat is truly feasible, and B-C-N ternary hard coat is certain the same with cube BN hardness with superelevation with diamond also, in addition, compare with hard coats such as diamond, carbonitrides, it also has unrivaled use advantages such as the internal stress of stability at elevated temperature excellence, coating is low.Therefore, B-C-N ternary hard coat not only becomes the research focus 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, for example the synthesis preparation method of routine such as chemical Vapor deposition process and physical vaporous deposition can be used for preparing B-C-N ternary hard coat.But when being to use chemical gaseous phase depositing process, often its boron source gas etc. all has toxicity, all causes very big 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 control of the composition 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
At the problems referred to above, purpose of the present invention namely is to rf magnetron sputtering B-C-N ternary hard coat preparation method selects suitable processing parameter, thereby obtains a kind of and matrix bond high-performance rigid B-C-N ternary hard coat closely.
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 each cleans about 10min in ultrasonic cleaner with acetone, alcohol and deionized water etc. respectively, dry up standby with nitrogen.
Subsequently, body material is placed on the sample table in the vacuum chamber, and the Ti target placed different target position respectively 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 disk shape, and the area of graphite and boron ratio 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 feeds 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 Ar subsequently 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 the baffle plate of Ti target simultaneously, power with 50-70W carries out sputter, and sputtering time is 5-10min, to form the pure Ti coating of one deck.
Begin to feed the N that flow is 0.3-0.6sccm subsequently
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 Ar subsequently 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 Ar subsequently 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 B-C-N ternary hard coat.
Advantage of the present invention is: formed Ti, TiN, Ti-B-C-N multilayer tie coat at metal base surface, to improve B-C-N hard coat and metallic matrix good binding performance; Simultaneously, selected suitable graphite/boron composition target and corresponding splash-proofing sputtering process parameter for use, 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 for use the W6Mo5Cr4V2 rapid steel as body material, with its surface finish, and after each cleans about 10min in ultrasonic cleaner with acetone, alcohol and deionized water etc. respectively, dry up standby with nitrogen.
Subsequently, body material is placed on the sample table in the vacuum chamber, and the Ti target placed different target position respectively 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 disk shape, and graphite compares at 2.2: 1 with the area of boron, 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 feeds 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 Ar subsequently 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 the baffle plate of Ti target simultaneously, carry out sputter with the power of 60W, sputtering time is 7min, to form the pure Ti coating of one deck.
Begin to feed the N that flow is 0.4sccm subsequently
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 Ar subsequently 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 Ar subsequently 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.
After tested, the thickness of surperficial B-C-N hard coat is about 150nm, and the atoms of elements percentage composition of coatingsurface is 23.4B-52.2C-24.4N, and the hardness on surface is about 15GPa.Appearance is smooth smooth, and frictional coefficient is about 0.11 during 5mN.The placement a few days does not have the problem of obvious cracking, projection to occur in air.
Claims (1)
- One kind since the B-C-N ternary hard coat that makes of rf magnetron sputtering particularly prepared by following steps:At first, select for use 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 standby with nitrogen;Subsequently, body material is placed on the sample table in the vacuum chamber, and the Ti target placed different target position respectively 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 disk shape, and graphite compares at 2.2: 1 with the area of boron, 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 feeds 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 Ar subsequently 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 the baffle plate of Ti target simultaneously, carry out sputter with the power of 60W, sputtering time is 7min, to form the pure Ti coating of one deck;Begin to feed the N that flow is 0.4sccm subsequently 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 Ar subsequently 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 Ar subsequently 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;The frequency of described rf magnetron sputtering is 13.56MHz;The thickness of surface B-C-N hard coat is 150nm, and the atoms of elements percentage composition of coatingsurface is 23.4B-52.2C-24.4N, and the hardness on surface is 15GPa; Appearance is smooth smooth, and frictional coefficient is 0.11 during 5mN.
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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 (4)
| Title |
|---|
| 反应磁控溅射制备组分可控的B-C-N薄膜;管昌雨;《硕士学位论文》;20110121;19页-28页 * |
| 徐淑艳等.靶功率和基体偏压对BCN薄膜成分及结构的影响.《中国表面工程》.2009, |
| 管昌雨.反应磁控溅射制备组分可控的B-C-N薄膜.《硕士学位论文》.2011, |
| 靶功率和基体偏压对BCN薄膜成分及结构的影响;徐淑艳等;《中国表面工程》;20090831;图1 * |
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