CN103160793A - Preparation method for super thick tin-titanium carbonitride (TIN-TICN) multi-layer composite thin film materials - Google Patents
Preparation method for super thick tin-titanium carbonitride (TIN-TICN) multi-layer composite thin film materials Download PDFInfo
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Abstract
The invention discloses a preparation method for super thick tin-titanium carbonitride (TIN-TICN) multi-layer composite thin film materials. According to the preparation method for the super thick TIN-TICN multi-layer composite thin film materials, the technology of direct current magnetron sputtering physical vapor deposition is used for preparing the TIN-TICN multi-layer composite thin film materials, the thickness of the TIN-TICN multi-layer composite thin film materials is 9.5-24.0 microns, and the TIN-TICN multi-layer composite thin film materials is uniform and compact in texture, smooth in surface, good in elasticity and adhesiveness, high in hardness, and good in anti-wear performance, and can be used in cutters for mechanical cutting and hole drilling and molds for processing and shaping.
Description
Technical field
The present invention relates to a kind of method with TiN-TiCN multi-layer compound film material of high rigidity and good wear resistance.
Background technology
Therefore TiN and TiCN thin-film material are with a wide range of applications in fields such as machinery, tribology, protection against corrosion, aerospace owing to all having high hardness, good resistance to wearing and corrodibility, fabulous chemical stability and the excellent characteristic such as good electroconductibility and thermal conductivity.TiN-TiCN MULTILAYER COMPOSITE mould material is controlled and the dislocation effect by layer thickness except the advantage that combines both, makes TiN-TiCN multi-layer compound film material internal stress aspect be greatly improved, and makes its thickness and bonding force all be significantly increased.
At present, the main method of preparation TiN-TiCN multi-layer compound film material has physical vapor deposition, electrochemical deposition, chemical Vapor deposition process etc.In these methods, it is particularly extensive that physical vapor deposition uses in industry, comprising vacuum-evaporation, sputter, ionic fluid and epitaxy etc.Magnetically controlled DC sputtering is as one of system relatively commonly used, simple to operate in sputter, in often being applied to produce.In addition, the TiN-TiCN multi-layer compound film material that has high rigidity and a good wearability has potential application prospect aspect cutter, mould.Yet, realize that the use of ultra-long time still has very large challenge, and it is of inadequate achievement especially to make super thick thin-film material have excellent performance.
Summary of the invention
Main purpose of the present invention is that to utilize magnetically controlled DC sputtering to prepare super thick and have a TiN-TiCN multi-layer compound film material of high rigidity and good abrasion resistance properties.
Principle of the present invention is that transition layer can reduce not matching relationship between layers effectively; Suitable Thickness Ratio and many bimolecular numbers of plies can be avoided the undue concentration of internal stress and the generation that causes film to come off between the layers.
The present invention adopts the TiN-TiCN multi-layer compound film material of magnetically controlled DC sputtering physical gas phase deposition technology preparation, the homogeneous densification of this film, and smooth surface, elasticity is good, and tack is good, has high hardness and excellent wear resistance.
Technical scheme of the present invention is, uses direct magnetic control equipment in room temperature, and base material need not any extra heating deposit and prepares TiN-TiCN multi-layer compound film material.
A kind of super thick TiN-TiCN multi-layer compound film material preparation method is characterized in that the method concrete steps are:
A adopts DC magnetron sputtering system equipment in deposition process;
B is fixed on monocrystalline silicon piece or steel disc on underboarding as base material, then underboarding is loaded in deposition chambers, vacuumizes; Vacuum tightness when the sediment chamber reaches 8.0 * 10
-4-6.0 * 10
-4During Pa, logical argon gas in the sediment chamber, is that 60-80%, pulse direct current negative bias are to carry out sputter clean base material 10-20min with argon (Ar) plasma body under the condition of 800-1100V in dutycycle;
C is 20-40sccm at argon flow amount, the distance of target and substrate is 10-15cm, the initial cavity chambers temp is at 30-40 ℃, galvanic current is 2-4sccm, dutycycle and negative bias are respectively under the condition of 60-80% and 0-100V, by gradual change ground adjusting nitrogen and methane flow, the pure titanium target of sputter, make the TiN-TiCN multi-layer compound film, depositing time is 100-260min;
After the D deposition finished, chamber temp was 125-135 ℃, when waiting for the chamber temp cool to room temperature, took out monocrystalline silicon piece or steel disc.
DC magnetron sputtering system equipment used in the present invention is produced by Shenyang scientific instrument company limited of the Chinese Academy of Sciences, and its model is JS-650.This equipment mainly is comprised of deposition chambers, one year target plate, a underboarding, a direct supply, a grid bias power supply and a series of vacuum pump, wherein carrying target plate and underboarding is vis-a-vis, direct supply is connected to and carries on target plate, and grid bias power supply is connected to underboarding.
The performance of the TiN-TiCN multi-layer compound film material that the present invention obtains:
(1) the TiN-TiCN multi-layer compound film thickness of the method preparation is 9.5-24.0 μ m, with steel ball and Si
3N
4Ball is antithesis, and in atmospheric environment, rotating speed is that 600rpm and one way coasting distance are under the condition of 5mm, and can surpass 11 hours its working time, and not worn out;
(2) the TiN-TiCN multi-layer compound film consistency and elasticity modulus of the method preparation is respectively 20.7-30.1GPa and 299.4-389.2GPa;
(3) little (stress＜0.2GPa), tack is good for the TiN-TiCN multi-layer compound film internal stress of the method preparation;
(4) it is fast that the method prepares TiN-TiCN multilayer film sedimentation rate, and can carry out the Large-Area-Uniform deposition.
The reason that the present invention has above-mentioned performance is: high galvanic current makes the ionization level of sputter gas improve, and sedimentation rate increases; The slow increase gradually of nitrogen and methane is conducive to the transition of interlayer, has improved matching between layers, the sticking power of enhanced film; The suitable Thickness Ratio of TiN layer and TiCN layer is conducive to slow down the stress that high thickness brings; The TiCN layer add the great friction coefficient and relative low hardness that has improved the TiN film, and the further optimization of the raising that is added with the bonding force that is beneficial to the TiCN film of TiN layer and tribological property.
The present invention can be used on the mould of the cutter of cut mechanically and boring and machine-shaping.
Embodiment
In order to understand better the present invention, describe by example.
Embodiment 1:
Clean substrate: use respectively each 10min of dehydrated alcohol and acetone soln ultrasonic cleaning ground (N100 type silicon chip and 2520-310S high-temperature steel), dry up and be placed in reaction chamber.Vacuumize: with efficient molecular pump, reaction chamber is vacuumized.Substrate surface treatment: when vacuum tightness is in 6.0 * 10
-4During Pa, logical argon gas in the sediment chamber, is to carry out sputter clean base material 10min with argon (Ar) plasma body under the condition of 80% pulse direct current negative bias 1100V in dutycycle, with zone of oxidation and other impurity of removing the surface.Deposition: argon gas, nitrogen and methane blended gas are passed in reaction chamber, be adjusted to 1-5 ° holding back flapper valve (control chamber pressure), the distance of target and substrate is 10cm, dutycycle is 80% negative bias 100V, initial chamber temp remains under the condition of 40 ℃ and opens direct supply (electric current is 4A), and the pure titanium target of sputter is regulated nitrogen and methane flow by gradual change, total depositing time is 260min, obtains the bimolecular number of plies and be 30 TiN-TiCN multi-layer compound film.
Utilize field emission scanning electron microscope (FESEM) that thin-membrane section is observed and find, film thickness is 23.50 μ m, can significantly observe TiCN layer and TiN layer, and even compact, and base material is in conjunction with good.The analysis of application high-resolution-ration transmission electric-lens obtains the TiN layer and shows as the polycrystalline state structure, and the TiCN layer shows as the structure that non-crystalline state is mixed with crystalline state.Be pressed into experiment by nanometer and show, the consistency and elasticity modulus of this film is respectively 20.7-22.2GPa and 299.4-301.3GPa.The bonding force that scratch experiment records between high-temperature steel (2520-310S) and film is about 24-30N.Use the UMT tester for friction between, the load that applies is 4N, and operation surpasses 11 hours, and not worn out yet, it is with Si
3N
4Ball is that the polishing scratch degree of depth of antithesis ball is about 6 μ m, and the polishing scratch degree of depth take steel ball as the antithesis ball is about 12 μ m.
Embodiment 2:
As described in Example 1, total depositing time is changed to 180min, obtain the bimolecular number of plies and be 20 TiN-TiCN multi-layer compound film.
Utilize field emission scanning electron microscope (FESEM) that thin-membrane section is observed and find, film thickness is 16.13 μ m, can significantly observe TiCN layer and TiN layer, and even compact, and base material is in conjunction with good.Be pressed into experiment by nanometer and show, the consistency and elasticity modulus of this film is respectively 24.4-26.7GPa and 338.6-367.7GPa.The bonding force that scratch experiment records between high-temperature steel (2520-310S) and film is about 24-30N.Know that by the test of UMT tester for friction between the film wear resistance is good.
Embodiment 3:
As described in Example 1, total depositing time is changed to 100min, obtain the bimolecular number of plies and be 10 TiN-TiCN multi-layer compound film.
Utilize field emission scanning electron microscope (FESEM) that thin-membrane section is observed and find, film thickness is 9.68 μ m, can significantly observe TiCN layer and TiN layer, and even compact, and base material is in conjunction with good.Be pressed into experiment by nanometer and show, the consistency and elasticity modulus of this film is respectively 27.0-30.1GPa and 355.0-389.2GPa.The bonding force that scratch experiment records between high-temperature steel (2520-310S) and film is about 34-38N.Know that by the test of UMT tester for friction between the film wear resistance is good.
Claims (1)
1. super thick TiN-TiCN multi-layer compound film material preparation method is characterized in that the method concrete steps are:
A adopts DC magnetron sputtering system equipment in deposition process;
B is fixed on monocrystalline silicon piece or steel disc on underboarding as base material, then underboarding is loaded in deposition chambers, vacuumizes; Vacuum tightness when the sediment chamber reaches 8.0 * 10
-4-6.0 * 10
-4During Pa, logical argon gas in the sediment chamber, is that 60-80%, pulse direct current negative bias are to carry out sputter clean base material 10-20min with argon plasma under the condition of 800-1100V in dutycycle;
C is 20-40sccm at argon flow amount, the distance of target and substrate is 10-15cm, the initial cavity chambers temp is at 30-40 ℃, galvanic current is 2-4sccm, dutycycle and negative bias are respectively under the condition of 60-80% and 0-100V, by gradual change ground adjusting nitrogen and methane flow, the pure titanium target of sputter, make the TiN-TiCN multi-layer compound film, depositing time is 100-260min;
After the D deposition finished, chamber temp was 125-135 ℃, when waiting for the chamber temp cool to room temperature, took out monocrystalline silicon piece or steel disc.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105154880A (en) * | 2015-09-08 | 2015-12-16 | 上海应用技术学院 | Preparation process of TiCN multilayer composite coating layer on slotting cutter surface of steam turbine rotor |
| CN105220120A (en) * | 2015-10-27 | 2016-01-06 | 中国科学院兰州化学物理研究所 | The method of a kind of MULTILAYER COMPOSITE fullerene film industrialization in motor car engine |
| CN107488850A (en) * | 2016-06-13 | 2017-12-19 | 沈阳科蓝纳米涂层技术有限公司 | A kind of preparation method of titanium carbonitride coating |
| CN109652764A (en) * | 2019-01-25 | 2019-04-19 | 广东工业大学 | A kind of bulk metal ceramic material and its preparation method and application based on PVD technique |
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| CN101081557A (en) * | 2007-06-26 | 2007-12-05 | 广州有色金属研究院 | Metallic carbide/adamantine (MeC/DLC) nanometer multi-layer film material and method for preparing the same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105154880A (en) * | 2015-09-08 | 2015-12-16 | 上海应用技术学院 | Preparation process of TiCN multilayer composite coating layer on slotting cutter surface of steam turbine rotor |
| CN105154880B (en) * | 2015-09-08 | 2018-01-26 | 上海应用技术学院 | Turbo rotor groove milling cutter surface TiCN multi-layer composite coatings preparation technologies |
| CN105220120A (en) * | 2015-10-27 | 2016-01-06 | 中国科学院兰州化学物理研究所 | The method of a kind of MULTILAYER COMPOSITE fullerene film industrialization in motor car engine |
| CN107488850A (en) * | 2016-06-13 | 2017-12-19 | 沈阳科蓝纳米涂层技术有限公司 | A kind of preparation method of titanium carbonitride coating |
| CN109652764A (en) * | 2019-01-25 | 2019-04-19 | 广东工业大学 | A kind of bulk metal ceramic material and its preparation method and application based on PVD technique |
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