CN102352512B - Method for preparing high-adhesion diamond coating with pulse laser - Google Patents
Method for preparing high-adhesion diamond coating with pulse laser Download PDFInfo
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- -1 pitch-dark Substances 0.000 claims 1
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- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 5
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- Cutting Tools, Boring Holders, And Turrets (AREA)
Abstract
The invention discloses a method for preparing a high-adhesion diamond coating with pulse laser, belonging to the fields of coated cutting tool industry and laser processing. In the method, a dual-laser shock processing (LSP) technology is used to perform selective Co removal treatment on the surface and subsurface of a YG serial hard alloy under the high-frequency and high-pressure action of laser shock waves, by virtue of the great hardness difference between Co and WC on the premise of not affecting the mechanical property of a cutting tool, at the same time, B ions are fed in the cutting tool by adopting laser shock waves with B ions, and the B ions react with Co during high temperature deposition to generate dense CoB and Co2B to prevent Co at the subsurface and core part of the cutting tool from spreading and migrating, thus remarkably improving the bonding strength. According to the method, the dual LSP technology is used to improve the bonding strength of the coated cutting tool and overcome the limitation of traditional measures, thus being an ideal technical means for improving the coating adhesion and the overall mechanical property of the coated cutting tool.
Description
Technical field
The present invention relates to laser processing and coated cutting tool field.Refer in particular to bonding strength between the inserted tool that adopts two laser impact intensified treatment technologies to improve diamond coatings and YG series and the method for coating and cutter integral body mechanics and mechanical property.
Background technology
Diamond has excellent specific properties such as high rigidity, high-wearing feature, high heat conductance, low-friction coefficient, low thermal coefficient of expansion, is as the very good cutter coat material of cutting tool wear-resistant coating.And Hardmetal materials has a series of premium propertiess such as hardness height, wear-resisting, intensity and toughness is better, heat-resisting, corrosion-resistant, particularly its high rigidity and wear resistance, it is a kind of application cutter material very widely, but along with industrial and science and technology, increasing difficult-to-machine material emerge in multitude, the performance of single Hardmetal materials can't satisfy current demand, has therefore produced cutting tool coated with hard alloy.The diamond-coated tools that with YG serial carbide alloy (WC-Co) is matrix is most widely used in the cutting difficult-to-machine material, has wide application market at the various nonferrous materials of cutting such as aluminum silicon alloy, pottery and various prepare composite.Yet, because the sticking power of diamond coatings on the inserted tool matrix is relatively poor, under the cutting force effect, be easy to come off from matrix, so had a strong impact on cutting ability and the work-ing life of diamond-coated tools, influenced an existence that key factor is exactly Co of bonding strength between diamond coatings and the inserted tool.Co has a following side effect: (1) is postponed and is hindered adamantine forming core and growth; (2) formation of the brill catalysis non-diamond carbon of high-vapor-pressure, amorphous carbon, graphite; (3) the C of Co has bigger dissolving power, when the high temperature deposition coating, can separate out a large amount of C, forms graphite linings between coating and matrix; (4) cobalt promotes adamantine second nucleation strongly.
Therefore diffusion and the transfer ability of how to reduce the Co on YG series top layer, thoroughly eliminating Co under the high temperature are the key points of preparation high adhesive force diamond coatings.Hard alloy substrate for YG series, presedimentary substrate surface state and character, especially the content of surface C o, surfaceness, surface property factors such as (surfactivity, surface geometry pattern, defect type and density, crystalline structure and lattice constant, surface energies) can the adamantine formation nuclear of remarkably influenced and coating quality, bonding strength.
In order to reduce the Co content of tool surface, improve the bonding strength of the two, many scholars have proposed many more effective treatment processs, all can reduce the content of Co to a certain extent, improve bonding strength, as: little sandblast, plasma etching, the current sputter, chemical treatment, the plasma body tufftride method, transition layer etc. is handled and is applied in the carbide surface boronising, but the existence of current conventional process measure is big not enough, as: though the Co content of tool surface can be effectively removed in chemical treatment, improve bonding strength, but have certain limitation: (1) can't overcome Co and move and diffusion to poor Co layer when high temperature deposition; (2) there is accumulation in the distribution of Co in the hard alloy substrate, chemistry takes off Co and handles the ununiformity that can't avoid hole distribution and size, corrosion back Co accumulation area is converted into huge dell, be easy to form the loose WC layer of structure organization, thereby between coating and cutter bonding surface, form weak phase, influence the bonding strength of coating and cutter; (3) go Co hardness and all decline to some extent of bending strength of tool matrix afterwards, and the repeatability difference etc.; Though oozing the influence that B handles the Co that can thoroughly eliminate with, plasma body tufftride method and carbide surface, plasma etching improves bonding strength, but because the influence of high temperature, can form crisp phase η phase at the cutter blade, cause brittle rupture, and can't form certain residual compressive stress on the tool matrix surface, can't carry out modification to substrate surface, can't improve stressed condition, roughness of base material etc.Though the current sputtering method also can be removed the Co of tool surface to a certain extent, DeGrain also can't overcome the diffusion and a migration difficult problem of Co.Though traditional method can improve the bonding strength between coating and the cutter, effect is not clearly, and defective is also many, and the infringement that matrix is caused is also bigger.That is: all there is bigger limitation in traditional treatment process, as: (1) can't be on the tool matrix top layer and the residual compressive stress of the residual certain value of certain depth; (2) damage ratio that matrix is caused is bigger, as reducing hardness and the intensity of cutter; (3) form crisp phase η phase at the cutter blade, cause brittle rupture; (4) Co of place to go tool surface and migration, the diffusibility of thoroughly eliminating Co up hill and dale; (5) the technology more complicated for the treatment of measures.
Summary of the invention
The objective of the invention is to overcome current cutter preprocessing means can't be on the tool matrix top layer and the residual compressive stress of the residual certain value of certain depth, the damage ratio that matrix is caused is bigger, as reduce hardness and the intensity of cutter, form crisp phase η phase at the cutter blade, cause brittle rupture, the Co of place to go tool surface and the migration of thoroughly eliminating Co up hill and dale, diffusibility, limitation such as the technology more complicated for the treatment of measures, under the prerequisite of not damaging the tool matrix performance, adopted the influence that two times laser impact intensified preconditioning techniques have thoroughly been eliminated Co, proposed a kind of novel and effective and improved bonding strength between diamond coatings and the YG serial carbide alloy and the pretreatment process of overall performance.
Technical scheme of the present invention is:
The present invention adopts two reiforcing laser impact technologies to prepare the high adhesive force diamond coatings.At first cutter is carried out the laser reinforcing pre-treatment first time, utilize the greatest differences between the hardness of Co and WC, the hardness of Co is well below the hardness of WC, Co to tool surface and inferior top layer under the high-frequency and high-voltage effect of laser blast wave carries out etching, has improved the environment of diamond coatings deposition greatly; On this basis cutter is carried out the laser impact intensified processing second time, with B ion band feed tool matrix inside,
A kind of method that adopts pulse laser to prepare the high adhesive force diamond coatings, its concrete steps are:
(1) at first YG serial carbide alloy cutter is cleaned, selected cleaning reagent must be selected according to the complete processing of cutter.
(2) be coated on the tool matrix equably with pitch-dark, utilize the motion of computer control system control laser generator and numerical control five-axle worktable then, make laser beam see through optical mirror slip, through the effect of speculum with laser beam reflex to pitch-dark on, water is as restraint layer, select for use bigger laser energy that cutter is carried out the laser impact intensified processing cutter first time, laser energy is 200mJ ~ 2J, removes the Co on tool surface and top layer.
(3) clean the pitch-dark of tool surface with reagent again, measure the Co amount that contains on this tool surface and inferior top layer with X-ray energy spectrometer.
(4) adopt the pitch-dark of flexible lamina technology preparation band B particle: ultra-fine B particle (nm level), pitch-dark, silica gel carry out proportioning according to certain ratio, and be equipped with promoting agent, initiator etc. and carry out polyreaction and make emulsion, fully rotate stirring in the Scattered Kettle with dispersion agent, defoamer under 65 ° of C ~ 90 ° C then and form, cooling obtains pad pasting then.
What (5) will prepare is coated in above the cutter that laser pre-treated crosses with ultra-fine B particle pitch-dark, the movement locus of the system of computerizeing control control laser apparatus and numerical control five-axle worktable, laser beam sees through optical mirror slip, the effect of passing through speculum reflexes to the pitch-dark last of band B particle with laser beam, water is as restraint layer, select for use less laser energy that cutter is carried out the laser impact intensified processing cutter second time, laser energy is 100mJ, the B ion is sent in the tool matrix, make Co and B that chemical reaction take place when high temperature deposition, generate stable, fine and close compound, stopped that the Co of cutter time top layer and heart portion is to poor cobalt layer diffusion and migration, thoroughly eliminated the influence of Co, and room temperature has been arrived in the slow cooling of diamond coatings constant voltage.
(6) take off flexible lamina, with hot filament CVD slow cooling measure deposit diamond coatings 6 ~ 8 hours, 850 ° of depositing temperatures, with the content of X-ray energy spectrometer measurement tool surface and inferior top layer Co, again with the critical load between scratch method measurement diamond coatings and the inserted tool.
The laser apparatus that the present invention adopts is the Nd:YAG solid statelaser, and laser energy is 100m J ~ 2J, and spot diameter is 0.8mm, and frequency is 8HZ, and pulsewidth 8ns, overlapping rate are 50%.Material adopts hot-wire chemical gas-phase deposition (CVD) deposition techniques diamond coatings for the YG6 carbide chip that Zhuzhou diamond cutting company limited produces.
The beneficial effect that the present invention can reach is:
(1) adopted and a kind ofly remove the Co of carbide tool surface and rely on laser blast wave to bring the B ion into base material inside by reiforcing laser impact technology, when high temperature deposition, generate stable compound, diffusion and the migration of Co have been hindered, thoroughly eliminate the influence of Co, significantly improve the bonding strength of coated cutting tool.This method can improve the hardness of matrix and bending strength etc., not only can not cause damage to the performance of matrix, can improve the performance on tool matrix surface on the contrary greatly, and favourable adamantine forming core improves sticking power.
(2) adopted the flexible lamina technology, prepared the flexible lamina with ultra-fine B particle, can carry out repeatedly laser impact intensified processing, and sticking power has been also very good.
(3) by after the laser impact intensified pre-treatment cutter, make tool surface to increase, thereby improve the forming core density of diamond coatings; After the laser-impact cutter, the dislocation desity of cutter increases greatly, has reduced the gap of crystal boundary etc., has weakened migration and the diffusibility of Co to a certain extent.
(4) use for the second time when laser impact intensified, bring the B ion into base material inside by laser blast wave, when high temperature deposition, chemical reaction takes place with the Co on inferior top layer, generate stable compound, hindered Co at high temperature to interfacial diffusion and migration, thoroughly eliminated the influence of Co, improve adamantine forming core density, improved adhesive force of coatings greatly.
(5) after the laser impact intensified cutter, can improve performance and the state on tool matrix surface greatly, for coating has been built an optimal deposition environment.
(6) after the laser-impact cutter, stay the pit of non-open type at tool surface, increased surface (micro-) roughness of cutter, increased " mechanical sealed effect " between coating and the tool matrix greatly, improved the bonding strength of coated cutting tool greatly.
(7) this method is to have utilized laser impact intensified stress effect, and therefore non-thermal effect can not form tensile stress in matrix, can not form crisp phase η phase at the cutter blade yet, cause brittle rupture, and can also make that matrix presents compressive stress state, improve the mechanical property of cutter greatly.
(8) the inventive method is to integrate mechanical pretreatment and the method for taking off Co, resistance Co.
(9) very simply and practical, repeatability and controllability are good for technology of the present invention, are a kind of harmless preconditioning techniques.
Description of drawings
The invention will be further described below in conjunction with accompanying drawing:
Fig. 1 prepares the principle schematic of high adhesive force diamond coatings for adopting pulse laser
Among the figure, 1, the numerical control five-axle worktable; 2, computer control system; 3, Nd:YAG Solid State Laser producer; 4, optical frames; 5, speculum; 6, apply the water constraint layer device; 7, cutter; 8, pitch-dark; 9, with the flexible lamina of ultra-fine B particle; 10, hot-wire chemical gas-phase deposition device; 11, laser beam; 12, X-ray energy spectrometer.
Embodiment
As Fig. 1, realize that the device of invention comprises device numerical control five-axle worktable 1, computer control system 2, Nd:YAG Solid State Laser producer 3, optical mirror slip 4, speculum 5, applies water constraint layer device 7, hot wire process deposition apparatus 11, X-ray energy spectrometer 13.
Cutter 8 is fixed on the numerical control five-axle worktable 1 after with alcohol wash, on cutter 7, evenly apply one deck pitch-dark 8 then, unlatching applies water constraint layer device 6, control restraint layer thickness is 2mm, start computer control system 2, send instruction, control Nd:YAG Solid State Laser producer 3, making Nd:YAG Solid State Laser producer 3 send energy is 200mJ ~ 2J, pulsewidth is the laser pulse of 8ns, the facular model of laser beam 11 is adjustable, spot diameter 0.8mm among the present invention, the laser beam 11 that Nd:YAG Solid State Laser producer 3 produces is accurately controlled the hot spot dimensional energy distribution by optical mirror slip 4, changes the direction of laser beam 11 through the effect of speculum, arrive on pitch-dark 8, simultaneously, the movement locus of computer control system 2 control numerical control five-axle worktable 1 is finished for the first time laser impact intensified, removes the Co of tool surface, with residual pitch-dark 8 above the alcohol wash cutter 7, the Co that contain that measure cutters 7 surfaces and inferior top layer with X-ray energy spectrometer 12 measure; Stick flexible lamina 9 with ultra-fine B particle at cutter 7, unlatching applies water constraint layer device 6, control restraint layer thickness is 2mm, start computer control system 2 again, send instruction, act on Nd:YAG Solid State Laser producer 3, Nd:YAG Solid State Laser producer 3 sends the laser beam that energy is 100mJ, other laser parameters are selected for use and for the first time identical parameter, the facular model of laser beam 11 is adjustable, spot diameter is that the laser beam 11 that Nd:YAG Solid State Laser producer produces is accurately controlled the hot spot dimensional energy distribution by optical mirror slip 4, and the effect of process speculum changes the direction of laser beam 11, arrives on the flexible lamina 9 with ultra-fine B particle, simultaneously, the movement locus of computer control system 2 control numerical control five-axle worktable 1 is finished for the second time laser impact intensified, after finishing, takes off the pad pasting with ultra-fine B particle 9; With high-frequency induction cutter 7 is heated to 850 ° in deposition apparatus, adopting hydrogen and methane is carbon source, and gas purity is 99.999%, and methane is 1% with the hydrogen volume ratio, and total flux remains on 100sccm, base vacuum degree variation range 1 ~ 3 * 10
-22000 ° of filament temperatures, carrying out 850 °, deposition pressure with heated filament deposition apparatus 10 is that 5KPa, surrounding gas temperature are that 100 ° ~ 200 ° deposit diamond coatings 7 hours are to room temperature, measure the Co amount that contains on tool surface and inferior top layer then with X-ray energy spectrometer 12, again with the critical load between scratch method measurement diamond coatings and the inserted tool; Measure the unrelieved stress of diamond coatings inside with the X diffractometer.
Embodiment
The sticking power of laser impact intensified raising diamond coatings and YG6 inserted tool
Clean YG6 inserted tool 7 surfaces with industrial spirit or acetone soln, then in surface-coated layer of even pitch-dark 8, select Nd:YAG Solid State Laser producer 3 for use, laser energy is 200m ~ 2J, spot diameter is 0.8mm, frequency is 8HZ, pulsewidth 8ns, overlapping rate is 50%, the movement locus of the system of computerizeing control 2 control Nd:YAG Solid State Laser producers 3 and numerical control five-axle worktable 1, laser beam 11 sees through the spatial distribution that optical mirror slip 4 is regulated laser energy, it is pitch-dark surperficial 9 to make that through speculum 5 laser beam 12 is radiated, and starts to apply water constraint layer device 6, and cutter 7 matrixes are carried out the shock peening first time, remove residual pitch-dark 8 of tool surface with industrial spirit again, again with the content of X-ray energy spectrometer 12 surface measurements and the surperficial 15um of the distance Co of place; Select ultra-fine B particle (nm level), silicon gel, pitch-dark ratio according to 3:2:2 for use, being equipped with promoting agent, initiator etc. carries out polyreaction and makes emulsion, rotate stirring with dispersion agent, defoamer, carbon dust etc. down at 85 ° again and form, cooling obtains the pad pasting 9 of pad pasting-band B particle of 2mm then; The pad pasting 9 of this band B particle is attached on the cutter of crossing through laser-impact 7, adjusts laser energy, laser energy is selected 100mJ for use, and other laser parameters are selected for use with for the first time identical parameter and carried out the laser impact intensified processing second time, after finishing, take off pad pasting 9; With high frequency induction heater cutter is heated to 850 °, adopting hydrogen and methane is carbon source, and gas purity is 99.999%, and methane is 1% with the hydrogen volume ratio, and total flux remains on 100sccm, base vacuum degree variation range 1 ~ 3 * 10
-2, 2000 ° of filament temperatures, carrying out 850 °, deposition pressure with heated filament deposition apparatus 10 is that envrionment temperature is that 140 ° of C deposit diamond coatings 7 hours are to the greenhouse in 5KPa, the container.After 7 hours, measure the Co amount that contains on cutters 7 surfaces with X-ray energy spectrometer 12, and apart from 15um(top layer of tool surface) the Co amount that contains located, with the critical load between scratch method measurement diamond coatings and the inserted tool.
Can see from measuring result: the YG6 carbide chip is carried out after the laser-impact first time, the Co amount that contains of tool surface drops to 0 from 6%, the Co content on inferior top layer (15um place) is 1.35%, after impacting for the second time, adopt the hot-wire chemical gas-phase deposition technology, 850 ° of depositing temperatures, deposition pressure are 240 ° of depositions of 5KPa, ambient temperature after 7 hours, and the Co content of measuring tool surface with X-ray energy spectrometer still is 0, inferior top layer (15um place) to contain that Co measures be 0.The employing pressing in method records the critical load 〉=3KN between diamond coatings and the cutter, and critical load 〉=1.5KN that traditional method obtains.
Claims (4)
1. method that adopts pulse laser to prepare the high adhesive force diamond coatings, it is characterized in that, adopt the laser impact intensified Co technology of taking off, there are two kinds of elements of Co and WC in the inserted tool, utilize the greatest differences between the hardness of Co and WC, the hardness of Co is well below the hardness of WC, and the Co to tool surface and inferior top layer under the high-frequency and high-voltage effect of laser blast wave carries out etching; Concrete steps are:
(A) at first YG serial carbide alloy cutter is cleaned
(B) be coated on the tool matrix equably with pitch-dark, water is as restraint layer, utilize the motion of computer control system control laser generator and numerical control five-axle worktable then, make laser beam see through optical mirror slip, through the effect of speculum with laser beam reflex to pitch-dark on, cutter is carried out the laser impact intensified processing cutter first time, remove the Co of tool surface;
(C) clean the pitch-dark of tool surface with reagent again, measure the Co amount that contains on tool surface and inferior top layer with X-ray energy spectrometer;
(D) adopt the pitch-dark of flexible lamina technology preparation band B particle, ultra-fine nm level B particle, pitch-dark, silica gel carry out proportioning according to the ratio of 3:2:2, and be equipped with promoting agent, initiator carries out polyreaction and makes emulsion, fully rotate stirring in the Scattered Kettle with dispersion agent, defoamer under 65 ° of C ~ 90 ° C then and form, cooling obtains pad pasting then;
What (E) will prepare is coated in above the cutter that laser pre-treated crosses with ultra-fine B particle pitch-dark, utilize the movement locus of computer control system control laser apparatus and numerical control five-axle worktable, make laser beam see through optical mirror slip, through the effect of speculum laser beam is reflexed on band B particle pitch-dark, water carries out the laser impact intensified processing cutter second time as restraint layer to cutter, and the B ion is sent in the tool matrix, during high temperature deposition, hinder Co to tool surface diffusion and migration;
(F) take off flexible lamina, with hot filament CVD slow cooling measure deposit diamond coatings 6 ~ 8 hours, 850 ° of C of depositing temperature, with the content of X-ray energy spectrometer measurement tool surface and inferior top layer Co, again with the critical load between scratch method measurement diamond coatings and the inserted tool.
2. the described a kind of method that adopts pulse laser to prepare the high adhesive force diamond coatings of claim 1 is characterized in that, the laser parameter that twice laser impact intensified processing selected for use is that spot diameter is 0.8mm, and frequency is 8HZ, and pulsewidth 8ns, overlapping rate are 50%.
3. claim 1 or 2 described a kind of methods that adopt pulse laser to prepare the high adhesive force diamond coatings is characterized in that step (B) laser energy is 200mJ ~ 2mJ.
4. claim 1 or 2 described a kind of methods that adopt pulse laser to prepare the high adhesive force diamond coatings is characterized in that step (E) laser energy is 100mJ.
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| 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 |
| CN104112042B (en) * | 2014-08-26 | 2017-12-08 | 同济大学 | A kind of diamond coatings film base interface bond strength measuring method based on molecular dynamics |
| CN108559970B (en) * | 2017-12-06 | 2019-11-01 | 上海交通大学 | The HFCVD batch preparation of complicated shape diamond-coated tools |
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| 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 |
| CN110054184B (en) * | 2019-05-29 | 2021-03-26 | 上海梁为科技发展有限公司 | Method for prolonging service life of diamond compact and diamond compact |
| EP4022110B1 (en) * | 2019-08-30 | 2023-07-12 | AB Sandvik Coromant | A method of treating a coated cutting tool |
| CN111944988B (en) * | 2020-08-11 | 2021-11-16 | 湖南泰嘉新材料科技股份有限公司 | Laser shock strengthening method for metal band saw blade |
| CN112139601B (en) * | 2020-09-24 | 2021-12-07 | 湖南泰嘉新材料科技股份有限公司 | Method for preparing lattice microstructure on surface of metal band saw blade and band saw blade |
| CN113621788B (en) * | 2021-07-20 | 2022-10-11 | 中国科学院上海光学精密机械研究所 | Constraint layer material suitable for laser shock peening and preparation method thereof |
| CN114150276B (en) * | 2022-02-09 | 2022-04-29 | 中国航空制造技术研究院 | Laser coating device |
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| JP2628601B2 (en) * | 1988-07-12 | 1997-07-09 | 富士通株式会社 | Diamond coated cemented carbide and method of diamond coating of cemented carbide |
| CN1037862C (en) * | 1993-10-28 | 1998-03-25 | 北京科技大学 | New process of chemical gas-phase deposition of diamond coating for hard alloy tool |
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