CN1102219A - New process of chemical gas-phase deposition of diamond coating for hard alloy tool - Google Patents
New process of chemical gas-phase deposition of diamond coating for hard alloy tool Download PDFInfo
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- CN1102219A CN1102219A CN 93119434 CN93119434A CN1102219A CN 1102219 A CN1102219 A CN 1102219A CN 93119434 CN93119434 CN 93119434 CN 93119434 A CN93119434 A CN 93119434A CN 1102219 A CN1102219 A CN 1102219A
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- diamond film
- diamond
- cemented carbide
- carbide substrate
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- Chemical Vapour Deposition (AREA)
Abstract
The present invention provides a simple and effective method for preparing diamond film coating on hard alloy tool by using chemical vapour phase deposition, i.e. before chemical vapour phase deposition, said invention uses high-energy laser beam (quasi-molecular laser or carbon dioxide laser or YAG laser) to treat the substrate surface of hard alloy tool to strengthen the binding force between the diamond film and substrate surface so as to raise the service performance of tool with diamond film coating. It can use any existent diamond film low-pressure chemical vapour phase deposition technology to obtain the diamond coating with good binding force, and can use a special masking process, and also can implement the diamond film deposition only on the tip end and cutting edge of tool and its nearby zone.
Description
The invention belongs to the technology that on Wimet, prepares the ultrahard diamond coated tool with chemical gaseous phase depositing process, the present invention adopts excimer laser (or carbon dioxide laser, YAG laser) method of processing carbide substrate surface, improve the bonding force between chemical vapor deposition diamond film and the substrate, prepare high performance diamond film coating layer carbamide tool.
Diamond coating for hard alloy tool has begun on market (Japan) and has occurred, and has demonstrated very remarkable cutting ability (when the cutting silumin, it is tens of to hundreds of times to improve life tools, and can improve suface processing quality greatly).But, because the existence of the cobalt phase in the Wimet makes the diamond thin vapor phase growth be difficult to carry out.Cobalt promotes the generation of graphite, thereby the overslaugh growth of diamond also finally causes diamond film and very fragile the combining of cemented carbide substrate.At this problem, from 86 years, existing up to a hundred patents were delivered in the Japan and the U.S..These patent attempts are passed through: (1) reduces the content of cobalt in the Wimet as far as possible, adds special additive, or adopts non-cemented carbide substrate (as JP01-255630/1989, JP02-4934/1990, JP03-17738/1991, JP02-102881/1990 etc.); (2) adopt acid liquor etching, electrolytic etching, plasma body etch and at H
2O-O
2The method of high temperature carbonization treatment is removed the cobalt of carbide surface layer (as JP63-53269/1988 in the atmosphere, JP03-183774/1991, JP02-88782/1990, JP03-54180/1991 etc.), (3) apply metal or compound barrier layer (as JP62-86161/1987, JP63-153275/1988, JP0-254728/1990, JP03-260069/1991, JP04-2401/1992 etc.), (4) adopt various surface modifying treatments to make the substrate surface roughening (as JP62-57804/1987, JP02-170792, JP03-20467/1991, JP-0448076/1992 etc.), (5) adopt special deposition technique to obtain discontinuous diamond thin (JP01-242960/1989), or composition, the gradient film that grain-size changes is (as JP03-219778, JP59-93869/1984, JP03-253369/1991 etc.), the multilayer complex films of (6) preparation complexity is (as US PATENT 4919974,4992082,4998421 etc.), eliminate the harmful effect of cobalt, strengthen the bonding force between diamond thin and cemented carbide substrate, in the hope of obtaining practical diamond coating for hard alloy tool, yet all these patents have all only partly solved the bonding force problem, and mostly have complex process, be difficult to the high shortcoming that gets of control and cost.
The object of the present invention is to provide a kind of simple and feasible new Method of processing a substrate of any invention different from the past, in the cobalt of removing the surface, make surface roughening, thereby strengthen the bonding force between diamond thin and the cemented carbide substrate greatly, prepare the diamond film coating layer carbamide tool of practicability.
The present invention adopts the intense laser beam scanning carbide substrate surface of focusing, and under the effect of laser beam, the fusing point cobalt more much lower than wolfram varbide optionally evaporated, and carbide surface layer is by instantaneous (millisecond magnitude) fusing, and then at a terrific speed (10
-4Second-10
-5Second) cooled and solidified, cause the roughening of carbide surface.Because cobalt is from the removal of upper layer, the chemical vapour deposition of diamond thin no longer is subjected to the influence that graphite is separated out, and because the effect of surface roughening, the bonding force of diamond thin and cemented carbide substrate is improved further.
Under the situation that adopts excimer laser, the energy density of laser beam is generally 0.5-4.0J/cm
2, sweep velocity is generally 0.2-10mm/s.100 sodium seconds of pulsewidth, 10 hertz of frequencies.The carbamide tool substrate generally adopts diamond-impregnated wheel to be ground to desired shape (pressing the carbamide tool national standard), and clamping is on stepper motor driven X-Y sample bench, by the energy density (0.5-4.0J/cm that selects then
2) and sweep velocity carry out laser treatment.The calculating of doing in the XPS spectrum before and after the laser treatment from the WC-6wt%Co cemented carbide substrate shows that after the process laser treatment, cobalt surface content can be reduced to about 0.6wt%.The diamond chemical vapour deposition can be adopted microwave plasma CVD, or hot filament CVD, or method such as dc plasma jet carries out, and under the situation that adopts microwave plasma CVD, typical processing condition are: H
2: 50-500sccm, CH
4: 0.2-10sccm, underlayer temperature: 600-1000 ℃, microwave power: 200-2000W depositing time: 5-15 hour, before carrying out the diamond film chemical vapour deposition, should be in ultrasonic bath carries out 20 minutes activation treatment with bortz powder foot couple substrate.Typical diamond film thickness is below the 10um, except that excimer laser, also can adopt carbon dioxide laser and YAG laser, the excimer laser wavelength is very short, penetrativity to the material surface layer is less, help making smelting zone to concentrate on the extremely surface of substrate, simultaneously because most of material surfaces absorb very big to excimer laser, reflect very little, therefore laser energy utilizing rate is very high, (see the explanation of accompanying drawing 2 if adopt special masking method, inventor's patent applied for), makes the activation treatment of having only wedge angle and cutting edge near zone to be subjected to being suspended in the bortz powder in the ultrasonic bath, after through the microwave plasma CVD deposition, can also realize diamond film only in wedge angle and cutting edge near zone deposition, the adamantine cutter predicted performance of this local growth is much more excellent than the cutter of even growing diamond.
The invention has the advantages that the aforesaid laser treatment of employing can improve the bonding force between chemistry for gas phase depositing diamond film and the substrate widely, prepares high performance diamond film coating carbamide tool.The present invention compares with existing other method, and technology is simple, and cost is lower, and adopts special masking process can also realize a diamond growth at carbamide tool wedge angle and cutting edge and near zone thereof.
The present invention is further illustrated below in conjunction with accompanying drawing.
Fig. 1 is the influence of high energy laser beam irradiation to bonding force between diamond film and the cemented carbide substrate, and as shown in Figure 1a, YG6(WC-6wt%Co) the inserted tool energy density is 2.5J/cm
2Excimer laser beam handle.Lasing aperture is a rectangle, and area is approximately 3 * 0.5mm
2, sweep velocity is 0.4mm/s, and pulse-repetition is 10Hz, is divided into 3 scanning roads, between each scanning road a little gap is arranged, and presses above-mentioned processing condition scope deposition after 15 hours in microwave plasma CVD equipment, and the growing state of diamond film is shown in Fig. 1 b.All regional diamond thin and cemented carbide substrate of handling through excimer laser beam are adhered to well, and peel off fully without the regional diamond film of excimer laser beam processing, and the regional diamond film between two scanning roads partly peels off.
Fig. 2 is for adopting special masking method (inventor's patent applied for), make the synoptic diagram that has only wedge angle and cutting edge near zone energy growing diamond.Present method may further comprise the steps: [1] laser radiation, and [2] mask process, [3] activation treatment (adopting the ultrasonic bath of suspension diamond fine powder), [4] remove mask, [5] gas phase depositing diamond film.
Diamond film can a reason in carbamide tool wedge angle and cutting edge and near zone growth be the activation particle (being likely the diamond chips that embeds the surface) that high energy laser beam has been burnt substrate surface, therefore adopt mask process can only allow wedge angle and cutting edge and near zone be subjected to subsequently activation treatment, like this when the removal mask carries out chemical vapour deposition later on, because the forming core of diamond in masked areas is suppressed, just can only grow up into the diamond thin of continuous densification at wedge angle and the preferential forming core of cutting edge part through activation treatment.
Embodiment 2YG6(WC-6wt%Co) the inserted tool energy density is 2.0J/cm
2Excimer laser beam handle (cutter front, and side 0.5mm scope), and then deposition 15 hours in the microwave plasma, all wedge angles and cutting edge place diamond film and cemented carbide substrate are adhered to very good.
Claims (3)
1, a kind of technology that on cemented carbide substrate, prepares the diamond film coating instrument with low-pressure chemical vapor deposition method, it is characterized in that adopting laser beam that cemented carbide substrate is carried out pre-treatment before the depositing diamond film, promptly adopt suitable sample clamping device that the laser beam of focusing can be scanned on sample surfaces, the energy density of laser beam should be able to be removed the cobalt on utmost point top layer fully, can reach simultaneously the suitable roughening on surface again, carry out after the above-mentioned processing, can adopt present all diamond film chemical gaseous phase depositing process to finish the coated of diamond film, comprise microwave plasma CVD, hot filament CVD, plasma spraying (PLASMA JET) and other existing technology.
2, according to claim 1 on cemented carbide substrate low-pressure chemical vapor deposition method prepare the technology of diamond film coating instrument, it is characterized in that to adopt excimer laser, or carbon dioxide laser, or YAG laser carries out pre-treatment to cemented carbide substrate, under the situation that adopts excimer laser, typical processing condition are: energy density 0.5-4.0J/cm
2, sweep velocity 0.2-10.0mm/cm
2, 100 nanoseconds of pulsewidth, 10 hertz of frequencies.
3, according to claim 1,2 described on cemented carbide substrate low-pressure chemical vapor deposition method prepare the technology of diamond film coating instrument, it is characterized in that under the situation that adopts microwave plasma CVD typical processing condition are: H
2: 50-500sccm, CH
4: 0.2-10sccm, underlayer temperature: 600-1000 ℃, microwave power: 200-2000W, depositing time: 5-15 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93119434 CN1037862C (en) | 1993-10-28 | 1993-10-28 | New process of chemical gas-phase deposition of diamond coating for hard alloy tool |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93119434 CN1037862C (en) | 1993-10-28 | 1993-10-28 | New process of chemical gas-phase deposition of diamond coating for hard alloy tool |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1102219A true CN1102219A (en) | 1995-05-03 |
| CN1037862C CN1037862C (en) | 1998-03-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93119434 Expired - Fee Related CN1037862C (en) | 1993-10-28 | 1993-10-28 | New process of chemical gas-phase deposition of diamond coating for hard alloy tool |
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|---|---|
| CN (1) | CN1037862C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093453C (en) * | 1998-12-28 | 2002-10-30 | 王光 | Manufacture of diamond film cutter and tool |
| CN100387753C (en) * | 2005-10-14 | 2008-05-14 | 南京航空航天大学 | Method for mfg. diamond coating on spherical substrate and device thereof |
| CN100462478C (en) * | 2007-03-28 | 2009-02-18 | 山东大学 | Microwave plasma back-coating and re-coating method for CVD diamond coating cutter |
| CN101422776A (en) * | 2001-10-26 | 2009-05-06 | 康奈可压缩机株式会社 | The method of coating fluorocarbon resin |
| CN101200802B (en) * | 2006-12-13 | 2010-05-12 | 上海坤孚企业(集团)有限公司 | Engine inner surface ceramic treatment method |
| CN101967638A (en) * | 2010-10-11 | 2011-02-09 | 南京航空航天大学 | Preparation method of diamond film inner wall of fracture well head |
| CN102352512A (en) * | 2011-10-26 | 2012-02-15 | 江苏大学 | Method for preparing high-adhesion diamond coating with pulse laser |
| CN103286537A (en) * | 2013-06-26 | 2013-09-11 | 洛阳理工学院 | Method for preparing coated cutting tool with high abrasion resistance |
| CN105081782A (en) * | 2014-05-23 | 2015-11-25 | 上海精韧激光科技有限公司 | Hard material machining method |
| CN109207955A (en) * | 2018-10-25 | 2019-01-15 | 东华大学 | The not damaged pretreating process of hard alloy substrate suitable for diamond coatings preparation |
| CN112376102A (en) * | 2020-11-07 | 2021-02-19 | 江苏美玛技术有限公司 | Preparation method of high-performance cutter coating material |
-
1993
- 1993-10-28 CN CN 93119434 patent/CN1037862C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093453C (en) * | 1998-12-28 | 2002-10-30 | 王光 | Manufacture of diamond film cutter and tool |
| CN101422776A (en) * | 2001-10-26 | 2009-05-06 | 康奈可压缩机株式会社 | The method of coating fluorocarbon resin |
| CN100387753C (en) * | 2005-10-14 | 2008-05-14 | 南京航空航天大学 | Method for mfg. diamond coating on spherical substrate and device thereof |
| CN101200802B (en) * | 2006-12-13 | 2010-05-12 | 上海坤孚企业(集团)有限公司 | Engine inner surface ceramic treatment method |
| CN100462478C (en) * | 2007-03-28 | 2009-02-18 | 山东大学 | Microwave plasma back-coating and re-coating method for CVD diamond coating cutter |
| CN101967638B (en) * | 2010-10-11 | 2011-12-07 | 南京航空航天大学 | Preparation method of diamond film inner wall of fracture well head |
| CN101967638A (en) * | 2010-10-11 | 2011-02-09 | 南京航空航天大学 | Preparation method of diamond film inner wall of fracture well head |
| CN102352512A (en) * | 2011-10-26 | 2012-02-15 | 江苏大学 | Method for preparing high-adhesion diamond coating with pulse laser |
| CN103286537A (en) * | 2013-06-26 | 2013-09-11 | 洛阳理工学院 | Method for preparing coated cutting tool with high abrasion resistance |
| CN105081782A (en) * | 2014-05-23 | 2015-11-25 | 上海精韧激光科技有限公司 | Hard material machining method |
| CN105081782B (en) * | 2014-05-23 | 2018-07-20 | 上海精韧激光科技有限公司 | The processing method of hard material |
| CN109207955A (en) * | 2018-10-25 | 2019-01-15 | 东华大学 | The not damaged pretreating process of hard alloy substrate suitable for diamond coatings preparation |
| CN112376102A (en) * | 2020-11-07 | 2021-02-19 | 江苏美玛技术有限公司 | Preparation method of high-performance cutter coating material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1037862C (en) | 1998-03-25 |
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