CN1279207C - TiN/SiO2 nanometer multilayer film and its preparation method - Google Patents
TiN/SiO2 nanometer multilayer film and its preparation method Download PDFInfo
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- CN1279207C CN1279207C CN 200410053490 CN200410053490A CN1279207C CN 1279207 C CN1279207 C CN 1279207C CN 200410053490 CN200410053490 CN 200410053490 CN 200410053490 A CN200410053490 A CN 200410053490A CN 1279207 C CN1279207 C CN 1279207C
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Abstract
The present invention relates to a superhard nano TiN/SiO2 multilayer film and a preparation process thereof, which belongs to the technical field of ceramlc films. The high-hardness nano Tin/SiO2 multilayer film is formed by that a TiN layer and a SiO2 later are alternatively deposited on a metallic or ceramic substrate, the thickness of the Tin layer is from 2 to 9 nm, and the thickness of the SiO2 later is from 0.45 to 1.2 nm. The high-hardness nano Tin/SiO2 multilayer film of the present invention has the preparation process that the surface of the metallic or ceramic substrate is treated by mirror polishing first; then the TiN layer and the SiO2 layer are alternatively deposited on the metallic or ceramic substrate by a two-sided target radio frequency sputtering technique to obtain the high-hardness nano TiN/SiO2 multilayer film, wherein both the TiN layer and the SiO2 layer are made from Sputtering target materials. The present invention has good oxidation resistance at high temperatures and high hardness, the hardness is higher than 33GPa, the maximum hardness can reach 45GPa, and the maximum elastic modulus reaches 460GPa. The present invention is used as a coating for fly-cutters and other wear-resistant workpieces serving at high temperatures, and has high application value.
Description
Technical field
What the present invention relates to is a kind of metal or ceramic membrane and preparation method thereof, particularly a kind of TiN/SiO
2Nano-multilayer film and preparation method thereof is used for the ceramic membrane technical field.
Background technology
The high speed cutting of cutting speed 〉=100m/min and DRY CUTTING become the main flow of cutting technology development just day by day because its mechanical workout efficient height is low in the pollution of the environment, and this processing technology is to the demands for higher performance of cutter coat.Not only require cutter coat hardness height, frictional coefficient is little, but also need have higher resistance of oxidation.Existing cutter coat does not satisfy these requirements as yet comprehensively.As the TiN coating, hardness HV25 ± 2GPa, oxidizing temperature is about 500 ℃; The hardness of TiCN coating is up to HV40, and oxidation resistance temperature but has only 400 ℃; Best at present TiAlN coating hardness is HV35 ± 5GPa, and antioxidant property can reach 800 ℃, but still can not satisfy the needs of high speed cutting and the harsh service condition of DRY CUTTING.Owing to have the excellent high-temperature chemical stability, oxide ceramics is acknowledged as the hard coat that has potential application foreground most, and regrettably the mechanical property of oxide coating, especially hardness is far away from nitride, and is not good as the cutter coat result of use separately.
Through the retrieval of prior art is found, in present existing report and the patent (as U.S. Pat 6565957, US6638571, US5766782 and Chinese patent 95108982.X etc.) with Al
2O
3Pottery and other mechanically resistant material, as TiN, TiC, TiCN and (Ti, Al) N etc. uses together and forms compound coating or multi-layer film structure, wherein Al
2O
3Pottery is used to provide the high-temperature oxidation resistance of coating.Although above-mentioned oxycompound coating has improved the high-temperature oxidation resistance of coating to a great extent, its hardness descends to some extent, has influenced the effective performance that is coated with layer function.On the other hand, find in the nano-multilayer film that forms with the nanometer scale alternating deposit by two kinds of materials, to exist the unusual superhard effect that raises of hardness the nineties in 20th century.This type of film is made up of two kinds of different materials of shearing modulus, borrows by means of the interface contraposition and moves the retardation that reaches crack propagation, and the mechanical properties such as hardness, Young's modulus and breaking tenacity of film are improved to a great extent.
William D.Sproul is at " SCIENCE " 1996,273 (16): " NewRoutes in the preparation of mechanically hard films " (" science " magazine of publishing an article on the 889-892, " new way of mechanics ganoine thin film preparation "), point out and to prepare the multilayer film that oxide multilayered film or oxide compound and nitride are formed by means of the unusual superhard effect that raises of nanometer multilayer film hardness, make it have high hardness and excellent antioxidant property simultaneously.The scientific and technical personnel in this field have done a large amount of tests and research, yet still do not have the report of success up to now.In prior art is further retrieved and analyzed, still there be not to find the report identical or similar so far with the technology of the present invention theme.
Summary of the invention
The objective of the invention is to overcome the deficiency of existing titanium nitride Quito tunic high-temperature oxidation resistance, a kind of TiN/SiO is provided
2Nano-multilayer film and preparation method thereof.
The present invention is achieved by the following technical solutions, TiN/SiO of the present invention
2Nano-multilayer film is by TiN layer and SiO
2Layer alternating deposit formed on matrix, and matrix is metal or pottery.Wherein the thickness of TiN layer is 2～9nm, SiO
2The thickness of layer is 0.45～1.2nm, and the total thickness of nano-multilayer film is 2～6 μ m.
Nano-multilayer film of the present invention is by control SiO
2The thickness of layer makes SiO
2Layer produces crystallization by means of the crystalline structure of TiN layer less than 1.2nm the time, and with the epitaxy of TiN layer coherence, form the polycrystalline superstructure.This constitutional features makes nano-multilayer film present the superhard effect that the consistency and elasticity modulus raises, and the hardness of multilayer film is higher than 33GPa, and maximum hardness reaches 45GPa.
TiN/SiO of the present invention
2The manufacture craft of super hard nano multilayer film is as follows:
At first metal or ceramic matrix surface are done the mirror polish processing, then by on the matrix of metal or pottery, adopting double-target radio frequency sputtering method alternating deposit TiN layer and SiO
2Layer is produced TiN/SiO
2Nano-multilayer film, wherein TiN and SiO
2Material adopts sputtering target material to provide.
Described double-target radio frequency sputter, its TiN target and SiO
2Target is respectively by independently radio frequency cathodic control.
Described double-target radio frequency sputter, its sputter gas are Ar, and dividing potential drop is P
Ar=1.7～9.0 * 10
-1Pa.
Described double-target radio frequency sputter, by matrix at TiN and SiO
2Alternately stop before the target and obtain to have the nano-multilayer film of composition modulated structure, the thickness of each layer is by the power and the residence time control of matrix before target of sputtering target.
The power of described sputtering target and the matrix residence time before target is respectively: TiN target sputtering power is 100W, and depositing time is 10～100 seconds, SiO
2The target sputtering power is 30～120W, and depositing time is 5 seconds.
Described matrix, its temperature are room temperature～300 ℃.
The present invention has substantive distinguishing features and marked improvement, and the present invention will have the SiO of excellent high temperature oxidation resistance energy
2Pottery is incorporated in the multilayer film materials system, by optimized design of structure, makes this kind film when having the intrinsic high-temperature oxidation resistance of oxide ceramics, obtains the excellent mechanical property of high rigidity.The maximum hardness of gained multilayer film of the present invention can reach 45GPa, and high elastic coefficient can reach 460GPa, has very big using value on the mould of being on active service under high speed cutting tool, the hot conditions and other wear-resisting workpiece.
Description of drawings
Fig. 1 TiN/SiO of the present invention
2High hardness nanocomposite multi-layer film structure synoptic diagram.
Among the figure: SiO
2 Layer 1, TiN layer 2, matrix 3.
Embodiment
As shown in Figure 1, this nano-multilayer film is by SiO
2Layer 1 and TiN layer 2 alternating deposit are formed SiO on the matrix 3 of metal or pottery
2The thickness of layer 1 is 0.45～1.2nm, and the thickness of TiN layer 2 is 2～9nm, and the total thickness of nano-multilayer film is 2～6 μ m.
SiO
2 Layer 1 forms the polycrystalline superstructure less than 1.2nm the time.
Provide embodiment below in conjunction with content of the present invention:
Example one
TiN/SiO of the present invention
2The concrete processing parameter of the making method of multilayer film is: TiN target sputtering power is 100W, and depositing time is 15 seconds, SiO
2The target sputtering power is 30W, and depositing time is 5 seconds, and substrate temperature is a room temperature.The TiN/SiO that obtains thus
2The thickness of TiN layer is 2.2nm in the multilayer film, SiO
2Bed thickness is 0.45nm, and the hardness of film is 33GPa.
Example two
TiN/SiO of the present invention
2The concrete processing parameter of the making method of multilayer film is: TiN target sputtering power is 100W, and depositing time is 15 seconds, SiO
2The target sputtering power is 40W, and depositing time is 5 seconds, and substrate temperature is 200 ℃.The TiN/SiO that obtains thus
2The thickness of TiN layer is 2.2nm in the multilayer film, SiO
2Bed thickness is 0.6nm, and the hardness of film is 45GPa.
Example three
TiN/SiO of the present invention
2The concrete processing parameter of the making method of multilayer film is: TiN target sputtering power is 100W, and depositing time is 15 seconds, SiO
2The target sputtering power is 60W, and depositing time is 5 seconds, and substrate temperature is 100 ℃.The TiN/SiO that obtains thus
2The thickness of TiN layer is 2.2nm in the multilayer film, SiO
2Bed thickness is about 1.2nm, and the hardness of film is 33.5GPa.
Example four
TiN/SiO of the present invention
2The concrete processing parameter of the making method of multilayer film is: TiN target sputtering power is 100W, and depositing time is 60 seconds, SiO
2The target sputtering power is 40W, and depositing time is 5 seconds, and substrate temperature is 150 ℃.The TiN/SiO that obtains thus
2The thickness of TiN layer is 9nm in the multilayer film, SiO
2Bed thickness is about 0.6nm, and the hardness of film is 37GPa.
Example five
TiN/SiO of the present invention
2The concrete processing parameter of the making method of multilayer film is: TiN target sputtering power is 100W, and depositing time is 15 seconds, SiO
2The target sputtering power is 50W, and depositing time is 5 seconds, and substrate temperature is 300 ℃.The TiN/SiO that obtains thus
2The thickness of TiN layer is 2.0nm in the multilayer film, SiO
2Bed thickness is 0.7nm, and the hardness of film is 44GPa.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 200410053490 CN1279207C (en) | 2004-08-05 | 2004-08-05 | TiN/SiO2 nanometer multilayer film and its preparation method |
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|---|---|---|---|
| CN 200410053490 CN1279207C (en) | 2004-08-05 | 2004-08-05 | TiN/SiO2 nanometer multilayer film and its preparation method |
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| CN1587434A CN1587434A (en) | 2005-03-02 |
| CN1279207C true CN1279207C (en) | 2006-10-11 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100395060C (en) * | 2006-02-16 | 2008-06-18 | 华南理工大学 | A kind of TiN double-layer film coating on the surface of cutting tool material and its preparation method |
| CN100424224C (en) * | 2006-07-20 | 2008-10-08 | 上海交通大学 | Reaction and magnetically controlled sputtering process of preparing hard nanometer layered TiN/SiO2 coating |
| CN100557072C (en) * | 2006-07-25 | 2009-11-04 | 震虎精密科技股份有限公司 | Surface hardening method of cutter |
| KR101257375B1 (en) * | 2007-02-22 | 2013-04-23 | 미츠비시 쥬고교 가부시키가이샤 | Surface film member, process for producing the surface covering member, cutting tool, and machine tool |
| CN101398123B (en) * | 2007-09-29 | 2011-03-02 | 中国人民解放军装甲兵工程学院 | A WS2/MoS2 solid lubricating multilayer film and its preparation method |
| CN102011092B (en) * | 2010-12-17 | 2012-02-01 | 上海理工大学 | High-hardness high-elastic-modulus CrAlN/SiO2 nano multilayer coating material and preparation method thereof |
| KR101471257B1 (en) * | 2012-12-27 | 2014-12-09 | 한국야금 주식회사 | Multilayered thin layer for cutting tools and cutting tools comprising the same |
| CN103943532B (en) * | 2014-04-22 | 2017-01-18 | 上海华力微电子有限公司 | Monitoring wafer for monitoring oxygen-free environment of furnace tube and manufacturing method and monitoring method of monitoring wafer |
| CN105648410A (en) * | 2014-11-11 | 2016-06-08 | 基准精密工业（惠州）有限公司 | Titanium nitride/titanium carbide coating, preparation method thereof and coated part with titanium nitride/titanium carbide coating |
| CN109518142A (en) * | 2019-01-27 | 2019-03-26 | 佛山市南海区晶鼎泰机械设备有限公司 | A kind of PVD technique for vacuum coating of aluminum alloy surface |
| CN110408895B (en) * | 2019-07-23 | 2021-11-19 | 慈溪市宜美佳铝业有限公司 | High-temperature-resistant PVD (physical vapor deposition) coating for die and preparation method thereof |
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