CN101497985A - Single-phase hexagonal tungsten carbide hard coating material and low temperature synthesizing method thereof - Google Patents
Single-phase hexagonal tungsten carbide hard coating material and low temperature synthesizing method thereof Download PDFInfo
- Publication number
- CN101497985A CN101497985A CNA2009100665428A CN200910066542A CN101497985A CN 101497985 A CN101497985 A CN 101497985A CN A2009100665428 A CNA2009100665428 A CN A2009100665428A CN 200910066542 A CN200910066542 A CN 200910066542A CN 101497985 A CN101497985 A CN 101497985A
- Authority
- CN
- China
- Prior art keywords
- tungsten carbide
- phase
- temperature
- hexagonal tungsten
- hard coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
The invention relates to a single-phase hexagonal tungsten carbide hard coating material and a low-temperature synthetic method thereof, belonging to the technical field of thin-film materials. The invention mainly aims at solving the technical problems of reducing the synthesis temperature of the single-phase hexagonal tungsten carbide hard coating to 300 DEG C from more than 1000 DEG C in the prior art, and meanwhile, obviously improving the microhardness of the single-phase hexagonal tungsten carbide hard coating. The low-temperature synthetic method adopts a magnetron sputtering method and takes W as a target source and Ar, CH4 and N2 as discharge gases, wherein a deposition system adopts a direct-current electrical source, and a little bit of N-doping is carried out to the tungsten carbide coating and enables N to substitute partial C atoms, wherein the doping concentration of N atoms is 0.5-9 percent. The method can promote the generation of the hexagonal tungsten carbide, reduces the preparation temperature of the hexagonal tungsten carbide and improves the hardness. The invention can ensure that the hexagonal tungsten carbide coating can be applied to substrate materials with lower stability, reduces the production cost and broadens the application field.
Description
Technical field
The invention belongs to the thin-film material technical field, relate to a kind of low-temperature synthetic method of single-phase hexagonal tungsten carbide hard coating.
Technical background
Tungsten carbide coating is because it is good wear-resistant, shock-resistant, and antifatigue and corrosion resistance nature are extensively applied to cutter industry and aircraft industry.The exploitation of high quick burning oxygen tungsten carbide coating technology especially in recent years makes tungsten carbide coating replace traditional hard chrome coating gradually in the Application Areas of many particular requirements.The phase structure complexity of wolfram varbide comprises six side α-WC, six side α-W
2C, cube β-WC, cube β-WC
1-x, quadrature β-W
2C, monocline W
3C and four jiaos of WC etc.And its different in kind of different phase structures; for the hard supercoat aspect that requires mechanical property; six side α-WC are in hardness, and modulus all obviously is better than other mutually with the abrasion resistance properties aspect, so directly deposit the target that single-phase six side α-WC are research on base material always.But tungsten carbide coating is difficult to crystallization, and in most cases the phase composition of crystallization wolfram varbide is a cube β-WC
1-xOr heterogeneous coexistence.For six side α-WC, because it is a kind of high-temperature thermal stability phase, this makes single-phase six side α-WC be difficult to crystallization more.In the existing report, M.Katoh etc. (Jpn.J.Appl.Phys.1995,34,3628) use plasma enhanced chemical vapor deposition (PE-CVD) method to go out α-WC in monocrystalline W (110) 800 ℃ of epitaxys in surface.But the characteristics of this method are the template effects by base material forces the wolfram varbide crystallization, substrate is required high, and coat-thickness is lower, is difficult to practice.E.C.Weigert etc. (J.Vac.Sci.Technol.A 2008,26,23) are using magnetron sputtering (PVD) method deposition wolfram varbide to find only just can obtain single-phase α-WC more than 1040 ℃ on the substrates of different.
Most of base materials can't bear 1000 ℃ high temperature, and the thermostability of heat sensitive substrates such as polymkeric substance is then poorer.The temperature for preparing α-WC in the above-mentioned background technology is more than 1000 ℃, and obviously, so high depositing temperature is difficult to satisfy the low temperature plated film needs of most of base materials.So for the range of application of widening α-WC coating and make its industrialization, the preparation technology in low temperature of researching and developing single-phase α-WC seems very necessary.
Summary of the invention
The problem to be solved in the present invention is, under the prerequisite that does not weaken coating performance, reduces the depositing temperature of single-phase α-WC coating, and a kind of low temperature deposition method is provided, and reduces to prepare difficulty, widens the range of application of single-phase α-WC coating.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of single-phase hexagonal tungsten carbide hard coating material, the N that mixes in tungsten carbide coating replaces the portion C atom with N, does not form the WN phase, and the atomic percentage conc scope of N is 0.5～9%; The phase structure of coated material is single-phase six side α-WC, and its spacer is P6m2; Each atoms of elements quantity ratio is in the coating: [W]/([C]+[N])=1:1.
A kind of low-temperature synthetic method that is used for above-mentioned single-phase hexagonal tungsten carbide hard coating material adopts magnetron sputtering method, is the target source with W, Ar, CH
4And N
2Be discharge gas, depositing system adopts direct supply, and concrete processing step is:
A) choose body material, comprise silicon chip, pottery, metal, organic or matrix material, before the deposition pre-treatment is polished, cleaned in substrate;
B) the depositing system vacuum chamber is evacuated to 2 * 10 with mechanical pump and molecular pump respectively
-4Below the Pa, then with Ar, CH
4And N
2Send into the vacuum chamber bottom, make it reach certain proportioning by the adjustments of gas flow, the pressure of regulating vacuum chamber simultaneously is that 0.6～2Pa, base reservoir temperature are 300～1000 ℃, bias voltage 0～-200V, deposition current 0.2～0.45A, gas flow Ar are 10～80sccm, CH
4Be 2～20sccm, N
2Be 0.3～15sccm;
C) deposition process keeps Ar and CH
4Flow is constant, by changing N
2N content in the flow control coating, depositing time 10～300 minutes.
Described polishing, cleaning pre-treatment comprise: make its attenuate 1.0～2.0 μ m with the substrate of waterproof abrasive paper corase grind earlier, use the fine grinding of 400#-1000# waterproof abrasive paper then, use the twin polishing of M2.5 diamond paste again, last acetone supersound process 10-30 minute, alcohol supersound process 10-30 minute, deionized water dries up after washing repeatedly.
The temperature rise rate of base reservoir temperature is controlled between the 1-10 ℃/min, reach the temperature that sets in base reservoir temperature after, be incubated 10-60 minute, remove and to be adsorbed on suprabasil air; Before deposition,, remove pollutent remaining on the target earlier to the pre-sputter of W target 5～15 minutes.
Described gas flow proportioning Ar:CH
4=4:1.
The constructional feature of single-phase α of the present invention-WC hard supercoat is:
(1) coating that deposits is single-phase α-WC, does not comprise the phase except that six side α-WC.
(2) the atomic percent scope of N content is 0.5～9%.
(3) each atoms of elements concentration ratio is about [W]/([C]+[N])=1:1 in the coating.
The depositing temperature scope of single-phase α of the present invention-WC hard supercoat is: 300～1000 ℃.
The outstanding feature of single-phase α of the present invention-WC hard supercoat is a low temperature depositing, and minimum deposition temperature reaches 300 ℃, can be used for the lower base material of thermostability, thereby has solved the problem that thermo-sensitive material is difficult to low temperature depositing hard supercoat; And,, make production cost significantly reduce owing to reduced depositing temperature.
α-WC the coating of method preparation of the present invention does not contain dephasign, compact structure, stable mechanical property.This preparation method is simple, economical, efficient, and the mechanical property ideal has a good application prospect.
Description of drawings
Fig. 1 is N in the superhard hard coat of wolfram varbide of the present invention
2Flow and concentration of element atomic percent graph of a relation.
Fig. 2 is the phase structure of the tungsten carbide coating under the different N content.
Fig. 3 is the coating hardness test result under the different N content among the embodiment 2.
Embodiment
Further specify detailed content of the present invention and embodiment thereof below in conjunction with the accompanying drawing illustrated embodiment:
The present invention realizes by following technique means: utilize magnetron sputtering method to mix the minor N element in tungsten carbide coating, make the N atom replace the portion C atom.The adding of N element can promote the formation of single-phase α-WC, thereby reduces the preparation temperature of α-WC significantly, all right crystal grain thinning of the adding of N simultaneously, the mechanical property of enhancing coating.
The present invention is the one-tenth nuclear barrier that reduces α-WC by the adulterated mode of N, promotes the generation of α-WC under the low temperature.This method has avoided the traditional preparation process method need improve the problem that temperature reaches the thermodynamic condition of α-WC growth.
The preparation method of single-phase α of the present invention-WC coating hard supercoat is: adopt magnetron sputtering method, W is the target source, Ar, CH
4And N
2Be discharge gas, depositing system adopts direct supply; With silicon chip, pottery, metal, organic, matrix material etc. are as substrate; Earlier substrate is polished pre-treatment such as cleaning before the deposition.Earlier the depositing system vacuum chamber is evacuated to 2 * 10 with mechanical pump and molecular pump respectively during deposition
-4Below the Pa, regulating base reservoir temperature then is 300～1000 ℃, bias voltage 0～-200V, deposition pressure 0.6～2Pa, deposition current 0.2～0.45A, depositing time 10～300 minutes.Gas flow Ar is 10～80sccm, CH
4Be 2～20sccm, N
2Be 0.3～15sccm.
Pre-treatment need be polished, be cleaned to above-mentioned substrate before deposition, can make its attenuate 1.0～2.0 μ m with the substrate of waterproof abrasive paper corase grind earlier, use the fine grinding of 400#-1000# waterproof abrasive paper then, use the twin polishing of M2.5 diamond paste again, last acetone supersound process 10 minutes, alcohol supersound process 10 minutes, deionized water dries up after washing repeatedly.Can guarantee the bonding force between substrate and the coating like this.
Make coating of fine qualities, temperature rise rate need be controlled between the 1-10 ℃/min; After reaching the temperature that sets in base reservoir temperature, be incubated 10-60 minute, can remove like this and be adsorbed on suprabasil air; Elder generation is to the pre-sputter of W target 5～15 minutes, to remove pollutent remaining on the target before deposition.
The concrete preparation method of embodiment 1 single-phase α of the present invention-WC coating hard supercoat.
Base material is an example with Si (100), and substrate need be passed through acetone, alcohol and washed with de-ionized water successively before experiment.To guarantee itself and coating's adhesion.Experiment adopts magnetically controlled sputter method to carry out the coating deposition.This depositing system is the DPS-III type ultrahigh vacuum(HHV) multi-target magnetic control sputtering equipment that Shenyang scientific instrument company of the Chinese Academy of Sciences produces.With W is the target source, Ar, CH
4And N
2Be discharge gas, discharge electrode adopts direct supply.Before the deposited coatings, the vacuum of magnetic control sputtering system is evacuated to 2 * 10 with molecular pump
-4Below the Pa, then with Ar, CH
4And N
2Send into from the vacuum chamber bottom, regulate under meter and make gas flow reach certain proportioning, take out the pressure of valve regulation vacuum chamber by the side between vacuum chamber and the molecular pump.The processing condition of deposition process are: 300 ℃～1000 ℃ of base reservoir temperatures, and bias voltage 0～-200V, deposition pressure 0.6～2Pa, deposition current 0.2～0.45A, depositing time 10～300 minutes.Keep Ar and CH
4Flow is constant, and by changing the N content in the N2 flow control coating, the coating N atomic percentage conc that obtains thus is between 0.5～9%.
The key point for preparing this coating is a flowrate proportioning, particularly Ar and CH
4Flowrate proportioning, CH
4The too high meeting of flow makes coating that surplus carbon phenomenon take place and amorphous carbon occurs, crosses to hang down to cause the carbon source deficiency, W occurs
2C or W
3The C phase, optimal flowrate proportioning is Ar:CH
4=4:1.The Ar of present embodiment and CH
4Flow adopts 20 and 5sccm respectively, N
2Flow 0.3～15sccm.
Embodiment 2 preparation methods' optimum process condition.
Technological process is with embodiment 1,400 ℃ of base reservoir temperatures, negative bias 60-120V, deposition pressure 0.7-0.9Pa, deposition current 0.25-0.30A, flowrate proportioning Ar:CH
4=20:5sccm, N
2Flow is 0.3-2.5sccm, depositing time 120 minutes.The N content of resultant coating is 0.5-9%.Temperature in this processing parameter is the minimum temperature condition that makes single-phase six sides α-WC coating.
The coating sample of embodiment 2 is carried out the vickers microhardness test, and its result consults shown in Figure 3, and it is to be that substrate deposits the hardness of N content between 0.5～9% (atomic percent) with N content synoptic diagram with Si (100).As seen from Figure 3, along with the increase of N content, hardness value raises.Show among Fig. 3 when N content during at 4.7-9%, when just coating presents single-phase six sides α-WC, coating hardness is 44.3-50GPa, does not compare with carrying out the adulterated coating of N (25.2GPa), and hardness improves about 20GPa., and this illustrates that the generation of single-phase six side α-WC makes coating hardness increase substantially.
Embodiment 4 selects different base materials to carry out coating deposition, hardness test.
The present invention also can be used for other base material, for example: organic, pottery, metal, matrix material substrate etc., depositing operation is identical with embodiment 1, and hardness test is identical with embodiment 2.Find to be the optimum N doping content of single-phase six side α-WC all between 0.5～9% by different base being carried out the coating deposition, and hardness all is significantly increased before mixing, and illustrates that single-phase α-WC coating that the method for this invention deposits is not influenced by base material.
Claims (5)
1, a kind of single-phase hexagonal tungsten carbide hard coating material is characterized in that: the N that in tungsten carbide coating, mixes, replace the portion C atom with N, and do not form the WN phase, the atomic percentage conc scope of N is 0.5～9%; The phase structure of coated material is single-phase six side α-WC, and its spacer is P6m2; Each atoms of elements quantity ratio is in the coating: [W]/([C]+[N])=1:1.
2, a kind of low-temperature synthetic method that is used for the described single-phase hexagonal tungsten carbide hard coating material of claim 1 is characterized in that: adopting magnetron sputtering method, is the target source with W, Ar, CH
4And N
2Be discharge gas, depositing system adopts direct supply, and concrete processing step is:
A) choose body material, comprise silicon chip, pottery, metal, organic or matrix material, before the deposition pre-treatment is polished, cleaned in substrate;
B) the depositing system vacuum chamber is evacuated to 2 * 10 with mechanical pump and molecular pump respectively
-4Below the Pa, then with Ar, CH
4And N
2Send into the vacuum chamber bottom, make it reach certain proportioning by the adjustments of gas flow, the pressure of regulating vacuum chamber simultaneously is that 0.6～2Pa, base reservoir temperature are 300～1000 ℃, bias voltage 0～-200V, deposition current 0.2～0.45A, gas flow Ar are 10～80sccm, CH
4Be 2～20sccm, N
2Be 0.3～15sccm;
C) deposition process keeps Ar and CH
4Flow is constant, by changing N
2N content in the flow control coating, depositing time 10～300 minutes.
3, the low-temperature synthetic method of a kind of single-phase hexagonal tungsten carbide hard coating material according to claim 2, it is characterized in that: described polishing, cleaning pre-treatment comprise: make its attenuate 1.0～2.0 μ m with the substrate of waterproof abrasive paper corase grind earlier, use the fine grinding of 400#-1000# waterproof abrasive paper then, use the twin polishing of M2.5 diamond paste again, last acetone supersound process 10-30 minute, alcohol supersound process 10-30 minute, deionized water dries up after washing repeatedly.
4, the low-temperature synthetic method of a kind of single-phase hexagonal tungsten carbide hard coating material according to claim 2, it is characterized in that: the temperature rise rate of base reservoir temperature is controlled between the 1-10 ℃/min, after reaching the temperature that sets in base reservoir temperature, be incubated 10-60 minute, remove and be adsorbed on suprabasil air; Before deposition,, remove pollutent remaining on the target earlier to the pre-sputter of W target 5～15 minutes.
5, the low-temperature synthetic method of a kind of single-phase hexagonal tungsten carbide hard coating material according to claim 2 is characterized in that: described gas flow proportioning Ar:CH
4=4:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100665428A CN101497985A (en) | 2009-02-19 | 2009-02-19 | Single-phase hexagonal tungsten carbide hard coating material and low temperature synthesizing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100665428A CN101497985A (en) | 2009-02-19 | 2009-02-19 | Single-phase hexagonal tungsten carbide hard coating material and low temperature synthesizing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101497985A true CN101497985A (en) | 2009-08-05 |
Family
ID=40945254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100665428A Pending CN101497985A (en) | 2009-02-19 | 2009-02-19 | Single-phase hexagonal tungsten carbide hard coating material and low temperature synthesizing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101497985A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102400026A (en) * | 2011-12-21 | 2012-04-04 | 吉林大学 | Nitrogen-containing germanium carbon alloy membrane material and preparation method thereof |
| CN108130517A (en) * | 2017-12-26 | 2018-06-08 | 浙江大学 | A kind of electrically conducting transparent WC crystalline films and preparation method thereof |
| CN108165941A (en) * | 2017-12-26 | 2018-06-15 | 浙江大学 | The polycrystalline WC films and its low temperature preparation method of a kind of high stoichiometric ratio |
| CN108193178A (en) * | 2017-12-26 | 2018-06-22 | 浙江大学 | A kind of crystalline state WC hard alloy film and its buffer layer technique room temperature growth method |
| CN110062861A (en) * | 2016-12-07 | 2019-07-26 | H.E.F.公司 | Friction plate, mechanical system and implementation method including this friction plate |
| US11117196B2 (en) * | 2018-03-19 | 2021-09-14 | Sumitomo Electric Industries, Ltd. | Surface-coated cutting tool |
| CN114945708A (en) * | 2020-01-21 | 2022-08-26 | 瓦尔特公开股份有限公司 | PVD coated cemented carbide cutting tool with improved coating adhesion |
-
2009
- 2009-02-19 CN CNA2009100665428A patent/CN101497985A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102400026B (en) * | 2011-12-21 | 2014-12-10 | 吉林大学 | Nitrogen-containing germanium carbon alloy membrane material and preparation method thereof |
| CN102400026A (en) * | 2011-12-21 | 2012-04-04 | 吉林大学 | Nitrogen-containing germanium carbon alloy membrane material and preparation method thereof |
| CN110062861A (en) * | 2016-12-07 | 2019-07-26 | H.E.F.公司 | Friction plate, mechanical system and implementation method including this friction plate |
| CN110062861B (en) * | 2016-12-07 | 2022-05-13 | H.E.F.公司 | Friction plate, mechanical system comprising such a friction plate and method of implementation |
| CN108130517B (en) * | 2017-12-26 | 2019-10-29 | 浙江大学 | A kind of electrically conducting transparent WC crystalline film and preparation method thereof |
| CN108193178A (en) * | 2017-12-26 | 2018-06-22 | 浙江大学 | A kind of crystalline state WC hard alloy film and its buffer layer technique room temperature growth method |
| CN108165941A (en) * | 2017-12-26 | 2018-06-15 | 浙江大学 | The polycrystalline WC films and its low temperature preparation method of a kind of high stoichiometric ratio |
| CN108193178B (en) * | 2017-12-26 | 2019-10-29 | 浙江大学 | A kind of crystalline state WC hard alloy film and its buffer layer technique room temperature growth method |
| CN108165941B (en) * | 2017-12-26 | 2019-10-29 | 浙江大学 | A kind of the polycrystalline WC film and its low temperature preparation method of high stoichiometric ratio |
| CN108130517A (en) * | 2017-12-26 | 2018-06-08 | 浙江大学 | A kind of electrically conducting transparent WC crystalline films and preparation method thereof |
| US11117196B2 (en) * | 2018-03-19 | 2021-09-14 | Sumitomo Electric Industries, Ltd. | Surface-coated cutting tool |
| CN114945708A (en) * | 2020-01-21 | 2022-08-26 | 瓦尔特公开股份有限公司 | PVD coated cemented carbide cutting tool with improved coating adhesion |
| CN114945708B (en) * | 2020-01-21 | 2023-11-21 | 瓦尔特公开股份有限公司 | PVD coated cemented carbide cutting tool with improved coating adhesion |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101497985A (en) | Single-phase hexagonal tungsten carbide hard coating material and low temperature synthesizing method thereof | |
| CN102586777B (en) | Preparation method for CBN (Cubic Boron Nitride) coated cutter based on micrometer/nanometer diamond transition layer | |
| CN103668095B (en) | A kind of high power pulse plasma enhancing combined magnetic-controlled sputter deposition apparatus and using method thereof | |
| CN101444985B (en) | Amorphous carbon coating and preparation method and application thereof | |
| CN107130222A (en) | High-power impulse magnetron sputtering CrAlSiN nano-composite coatings and preparation method thereof | |
| US5747118A (en) | Plasma enhanced chemical transport process for forming diamond films | |
| CN105908126B (en) | The AlTiN composite coatings and preparation method of a kind of high Al content | |
| CN101457359B (en) | Method for preparing Ti-Si-N nanocrystalline-amorphous composite superhard coating | |
| CN108728802B (en) | Multilayer high-temperature-resistant Ti/Zr co-doped diamond-like coating and preparation method thereof | |
| CN105543803B (en) | A kind of the diamond/carbon boron composite coating and preparation method of cemented carbide substrate | |
| CN105977379B (en) | A kind of oxycarbide film and resistance-variable storing device | |
| CN105624642A (en) | Method for directly depositing diamond film on graphite substrate | |
| CN106283052B (en) | A kind of two-dimensional material regulation silicon-carbon composite construction hydrogen resistance coating and preparation method thereof | |
| CN111647851B (en) | Zr-B-N nano composite coating with high hardness and high toughness and preparation method thereof | |
| CN108588822A (en) | The method of uninterrupted dynamic in-situ synthetic single crystal and super nano-diamond composite | |
| CN102094179A (en) | RB-SiC base reflector surface modified layer structure and preparation method thereof | |
| CN102817008B (en) | Preparation method of Ag-Ti-codoped diamond like carbon (DLC) film | |
| CN103628036B (en) | The preparation method of cubic boron nitride coated cutting tool | |
| CN105274485A (en) | Preparation method for Cr-Si-C-N nano composite film | |
| CN113215551B (en) | Method for preparing TaC | |
| CN108330455A (en) | A kind of Cr2The regulatable coating production of AlC phase purity | |
| CN100465334C (en) | Preparation method of diamond film coating layer bearing supporter | |
| CN104561906A (en) | Gradient boron carbide film and preparation method thereof | |
| CN1133756C (en) | Multi-layer compounded superhard C3N4/MN film and its synthesizing equipment and process | |
| TANAKA et al. | Preparation of carbon nitride films from g-C3N4 by ion-beam-assisted deposition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090805 |