CN101880866B - Method for preparing diamond-silicon carbide-cobalt disilicide composite interlayer of diamond coating on hard alloy - Google Patents
Method for preparing diamond-silicon carbide-cobalt disilicide composite interlayer of diamond coating on hard alloy Download PDFInfo
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- CN101880866B CN101880866B CN2010102057326A CN201010205732A CN101880866B CN 101880866 B CN101880866 B CN 101880866B CN 2010102057326 A CN2010102057326 A CN 2010102057326A CN 201010205732 A CN201010205732 A CN 201010205732A CN 101880866 B CN101880866 B CN 101880866B
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Abstract
The invention discloses a method for preparing a diamond-silicon carbide-cobalt disilicide composite interlayer of a diamond coating on a hard alloy and belongs to the technical field of diamond coatings. The method is characterized in that: direct current plasma-assisted hot filament chemical vapor deposition (CVD) technology is adopted, hydrogen, methane and tetramethylsilane are used as reactant gases, the diamond-silicon carbide-cobalt disilicide composite interlayer is deposited on the hard alloy of which the surface is etched for removing cobalt, the composite interlayer is subjected to isothermal treatment in an atmosphere of methane and hydrogen in a volume ratio of 1 percent, and a diamond thin film is deposited on the composite interlayer. The method has the advantages that: the cobalt disilicide generated in the composite interlayer improves the adhesive force between a CVD diamond coating and a hard alloy substrate and the toughness of the CVD diamond coating obviously. The process of the invention is easy to control, can be applied to hard alloy CVD diamond coating tools and parts and large-area CVD diamond coatings and has a promising industrial prospect.
Description
Technical field
The invention belongs to chemical vapor deposition (CVD) diamond coatings technical field, relate to the adhering method of a kind of raising CVD diamond coatings, specially refer to a kind of method that on wimet, prepares diamond-silicon carbide-silicon cobalt composite interlayer.
Background technology
Wimet (WC-Co) have the hardness height, wear-resisting, heat-resisting, than excellent comprehensive performances such as high-fracture toughness, be widely used in field of machining mainly as cutter material.In addition, wimet also is used for tools, mould and wear parts.Diamond has hardness the highest in the known substance, low-friction coefficient, the highest thermal conductivity and high excellent properties such as chemicalstability.Wear resistance, the life-span of instrument and parts be will increase substantially with chemical Vapor deposition process (CVD) diamond coated film on carbamide tool and parts, and working (machining) efficiency and working accuracy improved.
Though more than two decades has been carried out in the research that on hard alloy substrate, applies the CVD diamond thin, the adhesivity of CVD diamond coatings and hard alloy substrate still can not satisfy industrial application requirements.At present, the insufficient problem of CVD diamond thin adhesivity has become the major obstacle of its application.
The CVD diamond coatings has with the insufficient major cause of hard alloy substrate adhesivity: 1) conduct bonding cobalt mutually in the wimet; The effect of catalytic graphite is arranged in chemical vapor deposition processes; On the interface of diamond thin and matrix, promote that non-diamond forms mutually; 2) on the interface of diamond thin and matrix, there is micro-pore between diamond crystals and the matrix.The existence of these micro-pores has reduced the contact area of diamond thin and matrix, has weakened the bonding force of film and matrix; 3) thermal expansion coefficient difference of diamond and wimet is big; In the process of cooling after deposition of diamond thin films; In diamond coatings, produce big thermal stresses, especially coating edge place and produce high shearing stress, the shearing stress peak value causes coating in use to be peeled off from matrix.
At present, improve CVD diamond coatings and hard alloy substrate adhesivity and mainly contain two approach: the one, the method for employing chemical etching is removed the cobalt of carbide surface; The 2nd, the suitable middle layer of deposition between diamond coatings and wimet is to stop cobalt in the matrix to surface diffusion.
Though adopt the method for chemical etching can remove the cobalt of carbide surface, under the condition of depositing diamond film (substrate temperature is 700 ℃-900 ℃ usually), the cobalt that matrix inside is not etched away can spread to the top layer.The cobalt that diffuses out still can suppress adamantine forming core and growth, promotes the formation of non-diamond phase.Moreover the method for cobalt of going chemical etching can not reduce the generation shearing stress peak stress in the CVD diamond coatings, thereby avoids the problem of disbonding.
Up to now, people have worked out the multiple middle layer that is suitable for diamond and wimet, like Cr, CrN, TiN/TiC or the like, but owing to need to introduce other coating technique, like magnetron sputtering technique, make the preparation process complicated, and cost is high.
With the immediate middle layer of the present invention diamond-silicon carbide composite package, carborundum films and films of cobalt silicate are arranged.1) patent (Jiang.Xin; Klages; Calus-Peter; Diamant-Siliciumcarbid-MischschichtVerfahren zu ihrer Herstellung und ihre Verwendung; Patent DE 42 10 508 C1 (1993)) and document (Vadali V.S.S.Srikanth, Xin Jiang, Arno
Deposition ofdiamond/ β-SiC nanocomposite films onto a cutting tool material; Surface &Coatings Technology 204 (2010) 2362) adopts microwave plasma CVD technique or heated filament CVD method; Prepare the diamond-silicon carbide composite package with hydrogen, methane and TMS, but do not utilize cobalt silicon, adhesion property has much room for improvement; 2) document (Gil Cabrl; Jan
Lindner; Jos é Gr á cio; Riccardo Polini; A study of diamond film deposition on WC-Co inserts for graphitemachining:Effectiveness of SiC interlayers prepared by HFCVD; Diamond Relat.Mater.17 (2008) 1008) adopt heated filament CVD method, with hydrogen and TMS depositing silicon carbide middle layer on the WC-6%Co wimet, but in the deposition process of CVD diamond thin, can not stop Co fully to surface diffusion.Do not contain diamond in addition in the middle layer, can't regulate thermal stresses in the diamond thin, reduce thermal stresses effectively, so adhesivity such as still has at raising through regulating in the middle layer adamantine content; 4) patent (elegant husband of the same colour, the coating method of diamond thin and the cemented carbide member of cladding diamond, patent CN200580018812.8 (2007)) adopts various CVD methods, feeds silicon unstripped gas, on wimet, forms cobalt silicide (CoSi, CoSi
2), but the cobalt silicide middle layer that makes, its thermal expansivity is bigger than wimet, can not reduce the shearing stress peak value in the diamond thin.
In sum, though compare with the coating in no middle layer, more than various middle layers in the adhesivity that has improved CVD diamond coatings and hard alloy substrate in varying degrees, facts have proved that require there is bigger distance in the adhesivity that is obtained from industrial application.
Summary of the invention
The technical problem that the present invention will solve is; A kind of method that on wimet, prepares diamond-silicon carbide-silicon cobalt composite interlayer for the CVD diamond coatings is provided; Solving CVD diamond coatings and the insufficient problem of hard alloy substrate adhesivity, the work-ing life of raising CVD diamond coatings on carbamide tool and parts.
For overcome existing middle layer can not stop fully Co to surface diffusion, can not further reduce at the interface the micro-pore between the diamond crystals and interface, can not effectively reduce the deficiencies such as shearing stress peak value in the diamond thin, the present invention provides a kind of method for preparing diamond-silicon carbide-silicon cobalt composite interlayer.
Technical scheme of the present invention is to adopt direct-current plasma auxiliary heat wire chemical gas phase deposition technology; With hydrogen, methane and TMS (TMS) is reactant gases; Depositing diamond-silit-cobalt silicide composite interlayer, depositing diamond film on this composite interlayer then on the wimet that goes through surface etch after cobalt is handled.The step that realizes this technical scheme is following:
The first step: adopt chemical etching method to remove the cobalt of carbide surface;
Second step: in the bortz powder suspension liquid, go the wimet of cobalt to carry out the preparatory forming core of ultrasonic diamond and handle to the surface;
The 3rd step: on the basis in second step, adopting the auxiliary heated filament CVD method of direct-current plasma, is reactant gases with hydrogen and methane, and wimet is carried out Bias-enhanced Nucleation;
The 4th step: adopting the auxiliary heated filament CVD method of direct-current plasma, is reactant gases with hydrogen, methane and TMS (TMS), depositing diamond-silit-cobalt silicide composite interlayer.Wherein the cobalt silicide of composite interlayer be through Co by matrix to surface diffusion, and generate with TMS or with SiC reaction.In the deposition process, on hard alloy substrate, add positive bias;
The 5th step: on the basis in the 4th step, close TMS, than being isothermal processes some hrs under 1% the atmosphere,, form stable cobalt silicide so that the Co in the matrix fully spreads at methane and hydrogen volume; In the isothermal process, on matrix, add positive bias;
The 6th step: from the heated filament stove, take out by the plating matrix, in the bortz powder suspension liquid, plating piece is carried out the preparatory forming core of ultrasonic diamond and handle;
The 7th step: on the basis in the 6th step, adopting the auxiliary heated filament CVD method of direct-current plasma, is the reactant gases depositing diamond film with hydrogen and methane.
Said diamond-silicon carbide-silicon cobalt composite interlayer; Its deposition pressure scope is 0.5～10kPa; The substrate temperature scope is 700 ℃～900 ℃, and the filament temperature scope is 1800 ℃～2600 ℃, and it is 0.01%～0.5% that TMS accounts for total gas volume mark scope; It is 0.4%～2% that methane accounts for total gas volume mark scope, and the corresponding bias current scope of matrix positive bias is 0～6A.
The silicide that forms cobalt in the said diamond-silicon carbide-silicon cobalt composite interlayer has Co
2Si or CoSi, or both and deposit.Utilize Co in chemical vapor deposition processes by the behavior of matrix to film surface diffusion, make Co and TMS or with the stable Co of SiC reaction shape generation and compound-cobalt silicide of Si.Cobalt silicide not only eliminated the Co catalytic graphite effect, stop that Co spreads to diamond thin; And play the effect of caking agent at diamond crystals and SiC intergranule; And because of its low Young's modulus and good plasticity strengthen the toughness of diamond coatings, thereby improve the adhesivity of diamond coatings and hard alloy substrate.
Said diamond-silicon carbide-silicon cobalt composite interlayer can through regulate TMS flow, bias voltage, in hydrogen and methane atmosphere isothermal processes time and to the cobalt etch amount what etc. parameter control the relative content and the structure of diamond in the composite interlayer, silit and cobalt silicide.Increase the volume(tric)fraction of TMS in total gas, the relative content of silit increases in the composite package, and the relative content of diamond and cobalt silicide reduces.When each flow rate of reactive gas of deposition process is constant, can prepare composite interlayer.In composite interlayer, the relative content of silit should be greater than diamond, and the cobalt silicide relative content is between 0 to 30%; When in deposition process, reducing the TMS flow gradually, silit and cobalt silicide content are reduced gradually and diamond content increases gradually, thus preparation complex gradient middle layer.The complex gradient middle layer since its Young's modulus and thermal expansivity between the Young's modulus of matrix and diamond thin and thermal expansivity, change; Can reduce the shearing stress peak value in the diamond thin, thereby improve the adhesivity of diamond coatings and hard alloy substrate.
Between filament and matrix, apply bias voltage, when matrix can promote diamond film during for positive bias, along with the raising of positive bias, adamantine relative content increases in the composite package, the relative content reduction of silit and cobalt silicide.
Said isothermal processes in hydrogen and methane atmosphere is meant diamond-silicon carbide-silicon cobalt composite interlayer at its depositing temperature, in direct-current plasma, is to handle some hrs in 1% hydrogen and the methane atmosphere in the volume ratio of methane and hydrogen.In the reason process, Co can be diffused into the surface from matrix herein, in the middle layer and the surface form cobalt silicide with SiC reaction, with the blocking layer of the Co that forms densification.Simultaneously, sedimentary Si and C fully react the SiC amount that makes in the composite package increases to some extent.In addition, in isothermal processes, the non-diamond phase on atomic hydrogen etching composite package surface is for follow-up diamond nucleation provides a purified SiC surface.The diamond and the SiC of subsequent growth are combined closely more, reduced the micro-pore between diamond crystals at the interface, thereby improve diamond adhesivity above that.
In hydrogen and methane atmosphere, after the isothermal processes, when adamantine relative content in diamond-silicon carbide-silicon cobalt composite interlayer is enough big, can add the preparatory forming core of ultrasonic diamond.The flow of TMS is transferred to zero, direct continued growth diamond thin on laminated film.The gas that feed this moment has only methane and hydrogen, and methane is 0.4～2% with the hydrogen volume ratio, and air pressure range is 0.5～10kPa; The substrate temperature scope is 700 ℃～900 ℃; The filament temperature scope is 1800 ℃～2600 ℃, and the bias current scope is 0～6A, and depositing time is 2～8 hours.
The middle layer of the present invention's preparation can be applicable to the CVD diamond coatings of cobalt base alloy and cobalt-containing alloy, also can be applicable to the CVD diamond-silicon carbide coating of wimet, cobalt base alloy and cobalt-containing alloy.
Effect of the present invention and benefit are to have made full use of the effect of cobalt silicide at diamond-silicon carbide-silicon cobalt composite interlayer: one of which, the cobalt silicide (Co that Co and Si form
2Si CoSi) has eliminated the effect of Co catalytic graphite; Its two, cobalt silicide has stoped the Co in the matrix to spread to diamond coatings; Its three, cobalt silicide has the effect of bonding diamond crystal grain and SiC crystal grain; Its four, cobalt silicide has low Young's modulus and good plasticity, thereby strengthens the toughness of diamond coatings; They are five years old; Because the existence of cobalt silicide; Young's modulus and the thermal expansivity that can make the gradient middle layer changes to adamantine Young's modulus and thermal expansivity gradually by the Young's modulus and the thermal expansivity of matrix; Make shear Stress Distribution arrive composite interlayer, thereby reduce the shearing stress peak value in the CVD diamond coatings effectively.Therefore diamond-silicon carbide-silicon cobalt composite interlayer has significantly improved the adhesivity of diamond thin and hard alloy substrate.Processing parameter of the present invention is easy to control, but large-area preparation CVD diamond coatings has wide industrialization prospect.
Description of drawings
Accompanying drawing is to utilize the application's method on wimet, to prepare the cross-sectional structure synoptic diagram of diamond-silicon carbide-silicon cobalt composite interlayer and top layer diamond coatings.
Among the figure: 1 hard alloy substrate; 2 diamond-silicon carbide-silicon cobalt composite interlayers; 3 diamond coatings; 4 cobalt silicides; 5 diamonds; 6 silit.
Embodiment
Be described in detail embodiment of the present invention below in conjunction with technical scheme and accompanying drawing.
As matrix, prepare diamond-silicon carbide-silicon cobalt composite interlayer and top layer diamond coatings with the YG6X that sells on the home market (WC-6%Co) carbide chip above that, its practical implementation step is following:
The first step: matrix is carried out conventional pre-treatment, and with wimet ultrasonic cleaning 10 minutes, again it being immersed in proportioning was KOH: K in alcohol
3[Fe (CN)
6]: H
2O=1: in the solution of 1: 10 (mass ratio) 10 minutes, being immersed in proportioning then was H
2SO
4: H
2O
2In the solution of=1: 10 (volume ratios) 1 minute, with the cobalt of etching carbide surface.
Second step: in containing the alcohol suspension liquid of diamond powder and micron and nano powder with ultrasonic 60 minutes of wimet with preparatory forming core, used the alcohol ultrasonic cleaning then 10 minutes.
The 3rd step: the hard alloy substrate that pre-treatment is intact is put into Vakuumkammer, adopts the auxiliary heated filament CVD method of direct-current plasma, feeds hydrogen and methane, and the volume ratio of hydrogen and methane is 1.5%, and Bias-enhanced Nucleation 30min is to increase the diamond nucleation rate.
The 4th step: feed TMS depositing diamond-silit-cobalt silicide composite interlayer, TMS accounts for 0.15% of total gas volume, and the volume ratio of methane and hydrogen is 1%, deposits 6 hours.Following parameter remains unchanged in whole deposition process: filament and substrate surface distance is 8mm, and filament temperature is about 2200 ℃, and air pressure is 1.5kPa, and substrate temperature about 800 ℃ and bias current are 1.5A.
The 5th step: on the basis in the 4th step, close TMS, and at methane and hydrogen volume than being isothermal processes composite package coated substrate 6 hours under 1% the atmosphere, Co is fully spread, with the blocking layer of the Co that forms densification.
The 6th step: from the heated filament stove, take out the composite package coated substrate, repeated for second step, it is carried out the preparatory forming core of diamond again handle.
The 7th step: adopting the auxiliary heated filament CVD method of direct-current plasma, is 1% in the volume ratio of hydrogen and methane, atmosphere under, depositing diamond film is 6 hours on the composite interlayer of ultrasonic preparatory forming core processing.
Claims (1)
1. method that on wimet, prepares diamond-silicon carbide-silicon cobalt composite interlayer for diamond coatings; Adopt direct-current plasma auxiliary heat wire chemical gas phase deposition technology; With hydrogen, methane and TMS (TMS) is reactant gases; Depositing diamond-silit-cobalt silicide composite interlayer on the wimet go cobalt to handle through surface etch after, sedimentation chemistry vapour deposition (CVD) diamond thin on this composite interlayer then is characterized in that:
A) described diamond-silicon carbide-silicon cobalt composite interlayer; Its deposition pressure scope is 0.5～10kPa; The substrate temperature scope is 700 ℃～900 ℃, and the filament temperature scope is 1800 ℃～2600 ℃, and it is 0.01%～0.5% that TMS accounts for total gas volume mark scope; It is 0.4%～2% that methane accounts for total gas volume mark scope, and the corresponding dc bias current scope of matrix positive bias is 0～6A;
B) described diamond-silicon carbide-silicon cobalt composite interlayer; After its deposition, close TMS, at methane and hydrogen volume than being isothermal processes 2～8 hours in 1% the atmosphere; And air pressure range is 0.5～10kPa; The substrate temperature scope is 700 ℃～900 ℃, and the filament temperature scope is 1800 ℃～2600 ℃, and the dc bias current scope is 0～6A;
C) in the described diamond-silicon carbide-silicon cobalt composite interlayer, the relative content of silit is greater than diamond, and the relative content of cobalt silicide is between greater than 0 to 30%;
D) described diamond-silicon carbide-silicon cobalt composite interlayer, through regulate TMS (TMS) flow, bias voltage, the time, the amount of etching Co of isothermal processes is controlled the relative content and the structure of diamond in the composite interlayer, silit and cobalt silicide in hydrogen and methane atmosphere;
E) preparation diamond-silicon carbide-silicon cobalt complex gradient middle layer; Deposition parameter is same a); And in deposition process, reduce TMS (TMS) flow gradually, thereby silit and cobalt silicide content are reduced gradually and diamond content increases gradually.
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| CN105039928B (en) * | 2015-06-17 | 2017-06-30 | 姜辛 | A kind of preparation method of diamond/silicon carbide three dimensional composite structure and its product of preparation |
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