CN1037862C - 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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- CN1037862C CN1037862C CN 93119434 CN93119434A CN1037862C CN 1037862 C CN1037862 C CN 1037862C CN 93119434 CN93119434 CN 93119434 CN 93119434 A CN93119434 A CN 93119434A CN 1037862 C CN1037862 C CN 1037862C
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- diamond film
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- carbide substrate
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Abstract
The present invention provides a simple and effective manufacture method for hard alloy tools of chemical vapor deposition diamond film coatings. Before the chemical vapor deposition is carried out, high energy laser beams (excimer laser, carbon dioxide laser or YAG laser) are firstly used for processing the substrate surface of the hard alloy tool, so the bonding force between the diamond film and the substrate is strengthened, and the service performance of the diamond film coating tools is improved. The present invention can obtain the diamond coating with good bonding force by any existing diamond film low pressure chemical vapor deposition processes, and the present invention can also realize that the diamond films only deposit on tool tips, cutting edges and near regions by a special masking process.
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) to handle the method for carbide substrate surface, improves the bonding force between chemical vapor deposition diamond film and the substrate, prepares 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 have mostly had complex process, are 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
4-10
5℃/second) 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 (0.2-10mm/s) 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% from nominal composition (6wt%).Laser energy density is less than 0.5J/cm
2Shi Buneng plays the effect of removing cobalt and surface roughening, when energy density then can not be removed cobalt owing to what laser beam caused to the stirring action in surperficial molten bath during greater than 4.0J/cm2 effectively.The diamond chemical vapour deposition can be adopted microwave plasma CVD, or hot filament CVD, or method such as dc plasma jet is carried out.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 carry 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, and is less to the penetrativity of material surface layer, helps making smelting zone to concentrate on the extremely surface of substrate.Simultaneously because most of material surfaces absorb very greatly to excimer laser, reflect very for a short time, so laser energy utilizing rate is very high.(see the explanation of accompanying drawing 2 if adopt special masking method, inventor's patent applied for, application number 93119435.0), make 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 that diamond film is 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.It is worthy of note that the present invention and Japanese Patent JP3-166369 there is no something in common.The described invention of JP3-166369 is the method for a kind of laser assisted chemical vapor deposition (CVD) diamond film.Its principle is that the gas that utilizes the energy of laser photon to make to contain C and H (is to adopt CH in JP3-166369
4And H
2) disassociation, form required reaction active groups, thereby deposit in conjunction with good diamond film at substrate surface.It and common its dissimilarity of hot filament CVD diamond film deposition method comparison only are to make the method for the gaseous dissociation that contains C and H, common heated filament CVD relies on hot filament (2000-2600 ℃) heated air to make it to decompose, the described laser assisted CVD of JP3-166369 method is then outside the effect of hot filament, also rely in addition the photon energy of the high energy laser beam of having introduced to promote the decomposition of gas, to quicken the process of diamond nucleation and growth.In addition the described invention of JP03-166369 is also mentioned and is adopted laser irradiation that the Si-Si atomic bond of surface of silicon is interrupted before deposition, form unsaturated outstanding key, make the surface of silicon activation, thereby reach the effect that improves diamond film forming core density and strengthen diamond film and silicon substrate bonding force.Owing to require to interrupt the Si-Si atomic bond of surface of silicon, therefore require the energy of laser photon must be higher than bound energy between substrate atoms (Si atom) (～1.8eV).The present invention then is a kind of method that promotes diamond film and carbamide tool substrate bonding force, the essence of this method is the preceding special pre-treatment (laser irradiation processing) to cemented carbide substrate of a kind of diamond film deposition, the principle of institute's foundation is a high energy laser beam to modification (roughening) effect to carbide substrate surface of the preferential evaporation of the cobalt in the Wimet (about 1400 ℃ of the fusing point of cobalt, and the fusing point of WC is up to more than 3000 ℃) and laser beam.The cobalt of carbide surface is removed effectively, thereby the diamond film that makes good quality can be on cemented carbide substrate with the chemical gaseous phase depositing process growth, and laser beam is further strengthened diamond film and cemented carbide substrate bonding force to the roughening effect of carbide substrate surface.The heat effect of the laser that the present invention utilizes, therefore the energy to laser photon there is no particular requirement.Therefore, adopt laser beam that the width of cloth of substrate is shone pretreated method although all described in the described invention of the present invention and JP03-166369, both are all inequality at the scope aspects of purpose, content, principle and the claim of invention.The purpose that adopts the pretreatment process of JP3-166369 is an activation substrate surface (substrate of mainly mentioning in the literary composition is a silicon), and the present invention to adopt the purpose of laser pre-treated mainly be in order to remove carbide substrate surface to the deleterious cobalt of diamond film deposition.It is pointed out that in addition cemented carbide substrate,, can not guarantee to draw the result that the present invention will reach even adopt the pretreatment process of JP3-166369 because only at laser beam energy (not being photon energy) greater than 0.5J/cm
2Shi Caineng reaches the effect of removing the cobalt in the Wimet effectively.Usually use non-focusing laser beam at the pretreatment process of JP3-166369, its energy density also deficiency so that cobalt produces preferential evaporation.
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.As shown in Figure 1a, YG6 (WC-6wt%Co) 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 press above-mentioned processing condition scope deposition after 15 hours in microwave plasma CVD equipment, 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, application number: 93119435.5), 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.
Claims (1)
1. 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, remove the cobalt on Wimet utmost point top layer, and make suitably roughening of surface simultaneously, can adopt all known diamond film chemical gaseous phase depositing process at present then, finish the coated of diamond film; Suitable laser energy density must be adopted when cemented carbide substrate is carried out pre-treatment, excimer laser can be adopted, or carbon dioxide laser, or YAG laser, under the situation that adopts excimer laser, laser beam energy density should be at 0.5J/cm
2To 4.0J/cm
2Between, sweep velocity 0.2-10mm/s.
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 |
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| CN1102219A CN1102219A (en) | 1995-05-03 |
| CN1037862C true CN1037862C (en) | 1998-03-25 |
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| 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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Families Citing this family (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 |
| 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 |
| CN102352512B (en) * | 2011-10-26 | 2013-07-17 | 江苏大学 | Method for preparing high-adhesion diamond coating with pulse laser |
| CN103286537B (en) * | 2013-06-26 | 2016-03-30 | 洛阳理工学院 | A kind of preparation method with high-wearing feature coated cutting tool |
| 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 |
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