CN100351427C - Process for preparing nano composite ultra-hard film material by industrial equipment - Google Patents
Process for preparing nano composite ultra-hard film material by industrial equipment Download PDFInfo
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- CN100351427C CN100351427C CNB200510041774XA CN200510041774A CN100351427C CN 100351427 C CN100351427 C CN 100351427C CN B200510041774X A CNB200510041774X A CN B200510041774XA CN 200510041774 A CN200510041774 A CN 200510041774A CN 100351427 C CN100351427 C CN 100351427C
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Abstract
The present invention discloses a method for preparing nanometer composite superhard thin film materials by industrial devices. Industrial pulse direct current plasma is used for assisting a chemical vapor deposition device to prepare an nc-TiN/a-Si3N4 nanometer thin film material. The present invention has the specific method that high-speed steel with the hardness HRC of 60 after 1170 DEG C quenching and 550 DEG C tempering is soaked in acetone for ultrasonic cleaning after surface deoiling and polishing, the high-speed steel is subsequently dewatered by alcohol, and then the high-speed steel is put into an industrial pulse direct current PCVD vacuum furnace as a base material to prepare the nc-TiN/a-Si3N4 nanometer thin film material. The nanometer composite superhard thin film material has an optimized organization structure and excellent mechanical properties. The optimum technique comprises that pulsed voltage is 700 V, duty ratio is 1:1, pulse frequency is 17KHz, temperature is 520 DEG C, air pressure is from 180 to 200 Pa, N2 flow capacity is 180 ml/min, H2 flow capacity is 800 ml/min, Ar flow capacity is 70 ml/min, TiCl4 (carrying H2) flow capacity is 20 ml/min, SiCl4 flow capacity is 5 ml/min, and sedimentation time is 2 h.
Description
Technical field
The invention belongs to the thin-film material preparation field, further relate to a kind of employing industrial equipments, promptly pulsed dc plasma assistant chemical vapor deposition equipment prepares the method for nano composite super-hard film material.
Background technology
Superhard material is meant the material of microhardness 〉=40GPa, as cubic boron nitride H
v=48GPa, diamond H
v=70-90GPa etc., the generation of this class material high rigidity generally is owing to bonding strength high between the material atom, than short atom gap and high atom proportioning.As everyone knows, the existence of material Dislocations, microfissure, actual hardness and intensity etc. often will be lower than the several orders of magnitude of desirable index.Can dislocation, microfissure be inhibited by the nanometer microstructure design for obtaining superhard material, stop the strengthening mechanism acquisitions such as dislocation motion.Nano composite structure design now can obtain such superhard material.Veprek carried out such ideal to nano composite structure to be described: the crystalline phase of nano-scale (2-5nm) evenly is embedded in the noncrystal substrate, as shown in Figure 1.Because crystalline phase material number of dislocations in nano-scale range is few, and the crystal boundary of crystalline phase is amorphous phase, and therefore, only dislocation is obstructed in the athletic meeting of crystal boundary edge, also is that the viscous deformation of material is inhibited, and will obviously improve the hardness and the intensity of material.By this thinking design nano composite structure, then the nitride of transition metal is made nanometer crystalline phase and nonmetallic nitride and is made amorphous phase and can form such nano composite structure: namely be expressed as with general formula: nc-MnN/a-Si
3N
4Wherein, M represents titanium (Ti), tungsten (W), vanadium magnesium-yttrium-transition metals such as (V).Present nc-TiN/a-Si
3N
4, nc-W
2N/a-Si
3N
4, nc-VN/a-Si
3N
4These Development of Superhard Nanocomposite Films obtain in practice.
Because the special institutional framework of nano composite super-hard film material has the advantages such as high rigidity, high tenacity, high elastic modulus and the steady oxidisability of anti-height at macro-mechanical property.Requiring wear-resistant, the machinery of corrosion-resistant and high-temperature resistant, electronics, chemical field that great application prospect is arranged.
Yet,, comprising: physical vapor deposition (PVD) such as reaction magnetocontrol sputtering, vacuum arc vapor deposition because the particular requirement of nano composite structure obtains this class material at present and mainly adopts CVD (Chemical Vapor Deposition) method; Chemical vapour deposition such as radio-frequency plasma assistant chemical vapor deposition (R.F.PCVD), direct-current plasma assistant chemical vapor deposition (D.C.PCVD).At present, this class material all is to exist with form of film.
Below with nc-TiN/a-Si
3N
4Nano composite super-hard film material is example, existing preparation method analyzed, and in the various PVD methods, nc-TiN/a-Si
3N
4Chemical composition in the material is denitrogenated and is derived from N
2Outside the decomposition, all the other all adopt target that the stoicheiometry that needs in the thin-film material is provided, such as titanium target, silicon target etc.Obviously, processing parameters such as control sputtering source voltage, electric current and the vacuum that this method must be appropriate, depositing temperature are to guarantee to obtain stoichiometric and high-quality nano composite structure.But homogeneity or sight line when the main drawback of this method is plated film are relatively poor, to complex part outside particularly internal surface also can't realize even plating.
In radio frequency and direct current PCVD method, Veprek adopts dc source or radio-frequency power supply, and these two kinds of methods exist the arc discharge of plated film homogeneity question, particularly dc source inevitable in practice equally, and this is totally unfavorable to practical application.At present, adopt these two kinds of PCVD methods to prepare nc-TiN/a-Si
3N
4Nano composite super-hard film material, the equipment of its use is the test-type skinny device.
Summary of the invention
For defective or deficiency that above-mentioned prior art exists, purpose of the present invention is intended to propose a kind of pulsed dc plasma assistant chemical vapor deposition equipment (Pul sedD.C.PCVD) that is suitable for commercial Application, for the preparation of nc-TiN/a-Si
3N
4The method of nano composite super-hard film material.
For achieving the above object, solution of the present invention is: a kind of method of preparing nano composite ultra-hard film material by industrial equipment, adopt industrial pulse direct-current plasma assistant chemical vapor deposition equipment to prepare nc-TiN/a-Si
3N
4Nano film material is characterized in that, comprises the following steps:
1) will be through 1170 ℃ of quenchings, the hardness after 550 ℃ of tempering is the high-speed steel of HRC=60 Ultrasonic Cleaning in the immersion acetone after surface degreasing, polishing, dehydration of alcohol;
2) put into then industrial pulse direct current PCVD vacuum drying oven and carry out nc-TiN/a-Si as matrix material
3N
4The deposition of nano composite film;
3) adopt SiCl
4Do the Si source, when Si is 7-10 percentage atom content, a-Si
3N
4Content is the 16-20 volumn concentration;
4) pulsed dc plasma assistant chemical vapor deposition processing condition are: pulsed voltage 700V, dutycycle 1: 1, pulse-repetition 17KHz, 520 ℃ of temperature, air pressure 180-200Pa, N
2180ml/min, H
2800ml/min, Ar70ml/min, TiCl
4To carry H
2Be expressed as 20ml/min, SiCl
45ml/min, depositing time 2h;
The ne-TiN/a-Si that under pulse direct-current plasma assistant chemical vapor deposition process conditions, obtains
3N
4Nano film material, 3 microns of film thicknesses, nc-TiN crystal grain are the 5-7 nanometer, a-Si
3N
4Be non crystalline structure, nc-TiN is embedded in the noncrystal substrate, its microhardness H
vBetween 40-60GPa.
The pulsed dc plasma assistant chemical vapor deposition equipment that the present invention adopts is industrial equipment rather than test-type equipment; Preparation process has been used pulse dc power, has effectively avoided arc discharge and hollow cathode effect to the burn of surface of the work in the deposition process, has guaranteed the uniformity of thin film deposition and the stability of quality, has adopted SiCl
4Make Si source rather than SiH
4Utilize this inventive method, can be at surface of the work, particularly the complex-shaped surface mould inner surface obtains equally distributed nc-TiN/a-Si
3N
4Nano composite super-hard film material, and have preferably bond strength and mechanical property, can directly apply to industrial production, improve service life and the production efficiency of workpiece.
Description of drawings
Fig. 1 is a nano composite super-hard film material microtexture synoptic diagram.
The embodiment that provides below in conjunction with the contriver is described in further detail the present invention.
Embodiment
The nc-TiN/a-Si of the present invention's preparation
3N
4Nano film material adopts the industrial pulse direct-current plasma assistant chemical vapor deposition equipment (obtained national inventing patent, patent No. zl 991159594) of developing voluntarily, finishes nc-TiN/a-Si at vacuum chamber
3N
4The deposition of nano composite film.
Specific embodiment of the present invention is:
Will be through 1170 ℃ of quenchings, the hardness after 550 ℃ of tempering is the high-speed steel of HRC=60 Ultrasonic Cleaning in the immersion acetone after surface degreasing, polishing, dehydration of alcohol is put into then industrial pulse direct current PCVD vacuum drying oven and is carried out nc-TiN/a-Si as matrix material
3N
4The nano film material deposition.
Adopt SiCl
4Do the Si source, wherein processing condition are: pulsed voltage 700V, dutycycle 1: 1, pulse-repetition 17KHz, 520 ℃ of temperature, air pressure 180-200Pa, N
2180ml/min, H
2800ml/min, Ar70ml/min, TiCl
4(carry H
2) 20ml/min, SiCl
45ml/min depositing time 2h.
Under above-mentioned process conditions, obtained nc-TiN/a-Si
3N
4Nano film material detects by analysis, and 3 microns of film thicknesses (μ m), nc-TiN crystal grain are 5-7 nanometer (nm), a-Si
3N
4Be non crystalline structure, nc-TiN is embedded in the noncrystal substrate, its microhardness H
vBetween 40-60GPa.
In the technology preparation, found that silicone content is to nc-TiN crystallite dimension, a-Si
3N
4Content, film hardness have the best of breed scope, namely when Si is 7-10 percentage atom content (at.%), and a-Si
3N
4Content is 16-20 volumn concentration (vol.%); The nc-TiN crystallite dimension is 5-7 nanometer (nm).This nano composite structure is the ideal tissue that obtains excellent mechanical property.
Claims (1)
1. the method for a preparing nano composite ultra-hard film material by industrial equipment adopts industrial pulse direct-current plasma assistant chemical vapor deposition equipment to prepare nc-TiN/a-Si
3N
4Nano film material is characterized in that, comprises the following steps:
1) will be through 1170 ℃ of quenchings, the hardness after 550 ℃ of tempering is the high-speed steel of HRC=60 Ultrasonic Cleaning in the immersion acetone after surface degreasing, polishing, dehydration of alcohol;
2) put into then industrial pulse direct current PCVD vacuum drying oven and carry out nc-TiN/a-Si as matrix material
3N
4The deposition of nano composite film;
3) adopt SiCl
4Do the Si source, when Si is 7-10 percentage atom content, a-Si
3N
4Content is the 16-20 volumn concentration;
4) the plasma auxiliary chemical vapor deposition processing condition are: pulsed voltage 700V, dutycycle 1: 1, pulse-repetition 17KHz, 520 ℃ of temperature, air pressure 180-200Pa, N
2180ml/min, H
2800ml/min, Ar70ml/min, TiCl
4To carry H
2Be expressed as 20ml/min, SiCl
45ml/min, depositing time 2h;
The nc-TiN/a-Si that under above-mentioned pulsed dc plasma assistant chemical vapor deposition process conditions, obtains
3N
4Nano film material, 3 microns of film thicknesses, nc-TiN crystal grain are the 5-7 nanometer, a-Si
3N
4Be non crystalline structure, nc-TiN is embedded in the noncrystal substrate, its microhardness H
vBetween 40-60GPa.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510041774XA CN100351427C (en) | 2005-03-09 | 2005-03-09 | Process for preparing nano composite ultra-hard film material by industrial equipment |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510041774XA CN100351427C (en) | 2005-03-09 | 2005-03-09 | Process for preparing nano composite ultra-hard film material by industrial equipment |
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| Publication Number | Publication Date |
|---|---|
| CN1654708A CN1654708A (en) | 2005-08-17 |
| CN100351427C true CN100351427C (en) | 2007-11-28 |
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|---|---|---|---|
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2919308B1 (en) * | 2007-07-23 | 2009-12-11 | Commissariat Energie Atomique | PROCESS FOR THE PREPARATION OF NANOCOMPOSITE MATERIAL BY CHEMICAL VAPOR DEPOSITION |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263953A (en) * | 1999-12-29 | 2000-08-23 | 西安交通大学 | Industrial pulse or DC plasma and chemical gas-phase deposition equipment for strenthening surface of tool or mould |
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2005
- 2005-03-09 CN CNB200510041774XA patent/CN100351427C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1263953A (en) * | 1999-12-29 | 2000-08-23 | 西安交通大学 | Industrial pulse or DC plasma and chemical gas-phase deposition equipment for strenthening surface of tool or mould |
Non-Patent Citations (3)
| Title |
|---|
| Ti-Si-N纳米复相薄膜及Si含量对脉冲直流PCVD镀膜质量的影响 马大衍等.金属学报，第39卷第10期 2003 * |
| 脉冲直流PCVD制备Ti-Si-N薄膜的电化学腐蚀行为 马大衍等.稀有金属材料与工程，第33卷第7期 2004 * |
| 脉冲直流等离子体增强化学气相沉积Ti-Si-N纳米薄膜的摩擦磨损特性 马大衍等.摩擦学学报，第23卷第6期 2003 * |
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