WO2018113088A1 - 一种具有二硼化钛-金刚石复合涂层的工件及其制备方法 - Google Patents

一种具有二硼化钛-金刚石复合涂层的工件及其制备方法 Download PDF

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WO2018113088A1
WO2018113088A1 PCT/CN2017/074824 CN2017074824W WO2018113088A1 WO 2018113088 A1 WO2018113088 A1 WO 2018113088A1 CN 2017074824 W CN2017074824 W CN 2017074824W WO 2018113088 A1 WO2018113088 A1 WO 2018113088A1
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coating
diamond
titanium diboride
workpiece
substrate
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PCT/CN2017/074824
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English (en)
French (fr)
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唐永炳
王陶
张松全
蒋春磊
陈光海
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中国科学院深圳先进技术研究院
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/067—Borides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/271—Diamond only using hot filaments
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications

Definitions

  • the invention relates to the technical field of diamond coating preparation, in particular to a workpiece with a titanium diboride-diamond composite coating and a preparation method thereof.
  • Diamond-coated cemented carbide tools have attracted wide attention due to their excellent performance.
  • the application of the tool has been greatly hindered and industrial development has become The main bottleneck in the process.
  • the main reasons for the insufficient adhesion of the diamond film on the cutting tool are: (1) the binder Co in the cemented carbide matrix inhibits the diamond growth, and is favorable for the poor adhesion of the graphite deposit; (2) in the diamond At the interface between the film and the substrate, there are tiny pores between the diamond grains and the matrix. The existence of these tiny pores reduces the contact area between the diamond film and the substrate, and weakens the bonding force between the film and the substrate. (3) Diamond film and The thermal expansion coefficients of the matrix materials vary greatly, and there is a strong residual thermal stress between the two materials, especially the sharper blade edge of the cemented carbide tool, which causes the film to stratify with the substrate.
  • the first aspect of the present invention provides a workpiece having a titanium diboride-diamond composite coating, which solves the diamond coating and the substrate by providing a titanium diboride coating between the diamond coating and the workpiece substrate. Insufficient bonding force, low density of diamond film and slow deposition rate.
  • the present invention provides a workpiece having a titanium diboride-diamond composite coating comprising a workpiece substrate and a titanium diboride coating and a diamond coating disposed in sequence on the surface of the workpiece substrate.
  • the invention provides a titanium diboride layer between the surface of the workpiece substrate and the diamond coating layer, and the titanium diboride is used as the intermediate layer to fill the discontinuous region of the surface structure of the substrate; at the same time, the growth rate and deposition process of the subsequent diamond film can be improved.
  • the nucleation density in the material greatly promotes the growth of the diamond film.
  • the use of titanium diboride as the intermediate layer can effectively improve the bonding force between the diamond coating and the tool base, and a diamond film having high bonding strength and uniform density can be obtained even in the blade edge portion.
  • the titanium diboride coating has a thickness of 20-500 nm, and the titanium diboride coating has ultrafine nanocrystals with a grain size of 20-50 nm. Further optionally, the titanium diboride coating has a thickness of 80-200 nm. A suitable thickness of the titanium diboride coating can perfectly block the diffusion of cobalt to the surface of the substrate without causing a weakening of the bonding strength between the diamond and the substrate due to the excessive thickness of the intermediate layer.
  • the diamond coating has a thickness of 2-8 ⁇ m, and further has a thickness of 4-6 ⁇ m.
  • the crystal grains of the diamond coating are nanometer grade (ie, within 100 nm) or micrometer grade (ie, 1-5 micrometers), specifically 10-80 nm, 1-4 microns.
  • the diamond grains in the coating are at the nanometer level, the graphite phase in the coating increases, The fracture toughness of the coating is higher; when the diamond grains in the coating are on the order of microns, the hardness and strength of the coating will be higher. Different structural properties can meet different needs of people for workpieces.
  • the material of the workpiece base may be cemented carbide, stainless steel, silicon nitride or silicon carbide.
  • the workpiece base can be a tool or other tool (such as a mold), mechanical parts, and the like.
  • the titanium diboride coating is prepared by physical vapor deposition (PVD), and the diamond coating is prepared by hot filament vapor deposition.
  • PVD physical vapor deposition
  • the titanium diboride coating grown by PVD can effectively block the metal cobalt diffused to the surface by the matrix, and eliminate the catalytic effect of the metal cobalt on the graphite, thereby facilitating the obtaining of a diamond coating with good bonding force, high purity of the diamond and good crystal form.
  • the workpiece with the titanium diboride-diamond composite coating provided by the first aspect of the invention improves the bonding between the diamond coating and the workpiece substrate by providing a titanium diboride coating between the diamond coating and the workpiece substrate.
  • the force solves the problem that the diamond coating has insufficient binding force to the substrate, the diamond film has low nucleation density and the deposition speed is slow.
  • the present invention provides a method of preparing a workpiece having a titanium diboride-diamond composite coating, comprising the steps of:
  • the pre-processing comprises: sandblasting the workpiece substrate, and then ultrasonically cleaning with acetone and ethanol respectively; or chemically etching the workpiece substrate;
  • a titanium diboride coating is prepared on the workpiece substrate by physical vapor deposition, and a diamond coating is prepared on the titanium diboride coating by hot filament vapor deposition to obtain titanium diboride- Diamond composite coated workpiece.
  • the chemical etching treatment includes an alkali washing for 8-15 minutes and a pickling treatment for 5-15 seconds.
  • the deposition condition of the titanium diboride coating prepared by physical vapor deposition is as follows: using titanium diboride as a target, the power of the target is 2.2-2.7 kW, between the target and the sample. Spacing is 70 In centimeters, the deposition pressure is 0.9-1.2 Pa, the cavity temperature is 320-380 ° C, the substrate frame is biased at 150 V, and the bias current is 1.0-1.5 A. Optionally, the substrate frame rotates at a speed of 20 revolutions per minute during the deposition process, the direction of rotation is clockwise, and the deposition time is 20 minutes. Before the depositing the titanium diboride coating, the workpiece substrate is subjected to ion source cleaning.
  • the parameters of the ion source cleaning are: argon gas (Ar) acts as an ion source, and the power is 1.6-1.9 kW; the gas pressure in the chamber is 0.9-1.2Pa, the cavity temperature is 320-380 ° C; the base frame rotation speed is 20 rev / min, and the cleaning time is 20 minutes.
  • Ar argon gas
  • the deposition condition of the diamond coating prepared by hot-wire vapor deposition is as follows: hydrogen and methane are used as reaction gases, methane accounts for 0.6%-2% of total gas volume, and vacuum chamber pressure ranges from 3-10 kPa; filament temperature The range is 1800-2800 ° C, the substrate temperature range is 700-1000 ° C; the treatment time is 1-4 h, and a diamond coating is prepared, and the crystal grains of the diamond coating are on the order of micrometers.
  • the deposition condition of the diamond coating prepared by hot-wire vapor deposition is as follows: hydrogen and methane are used as reaction gases, methane accounts for 3%-6% of total gas volume, and vacuum chamber pressure ranges from 0.5 to 4 kPa; filament temperature The range is 1500-2400 ° C, the substrate temperature range is 500-800 ° C; the treatment time is 1-4 h, and a diamond coating is prepared, and the crystal grains of the diamond coating are on the nanometer scale.
  • the workpiece substrate After the preparation of the titanium diboride coating, before the preparation of the diamond coating layer, the workpiece substrate is further subjected to sand blasting, and then ultrasonically washed with acetone and ethanol respectively to obtain a better deposition preparation diamond coating. The surface of the layer.
  • the preparation method of the workpiece with titanium diboride-diamond composite coating provided by the invention is combined with physical vapor deposition and hot wire chemical vapor deposition, and the process is simple, wherein the preparation time of the titanium diboride coating is only about 20 minutes.
  • the PVD equipment used can realize automatic production, and does not need to use flammable, explosive and toxic gases in the preparation process, and has the advantages of high efficiency, fast, safe and automatic production.
  • Example 1 is a schematic cross-sectional structural view of a workpiece having a titanium diboride-diamond composite coating prepared in Example 1 of the present invention
  • Example 2 is a cross-sectional high-frequency scanning electron micrograph of a workpiece having a titanium diboride-diamond composite coating prepared in Example 1 of the present invention
  • Example 3 is an indentation diagram of a titanium diboride-diamond composite coating in Example 1 of the present invention.
  • Example 4 is a high-power scanning electron micrograph of a hot-wire vapor deposition on a titanium diboride coating prepared in Example 1 of the present invention for 10 minutes.
  • a method for preparing a workpiece having a titanium diboride-diamond composite coating comprising the steps of:
  • the first step using a commercially available silicon carbide cemented carbide blade as the substrate, the substrate is subjected to wet blasting of white corundum, the pressure is 300 kPa, the sand particle size is 800 mesh, and then the cemented carbide substrate is ultrasonically irradiated in acetone and alcohol, respectively. Wash for 15 minutes;
  • argon (Ar) acts as an ion Source
  • ion source voltage is 70V
  • current is 250A
  • power is 1.6Kw
  • intracavity pressure is 1.0Pa
  • cavity The temperature is 320-380 ° C; the substrate frame rotation speed is 20 rpm, the cleaning time is 20 minutes; the
  • base frame rotation speed is 20 rev / min, the direction of rotation is clockwise;
  • base frame bias is 150V, bias current is 1.5A;
  • target voltage is 420V, current is 6.5A, power is 2.7Kw;
  • cavity The internal temperature is 320-380 ° C, the deposition time is 20 minutes, and the obtained titanium diboride coating thickness is 70-80 nm;
  • the third step using hot-wire chemical vapor deposition method, using hydrogen and methane as reaction gases, depositing a micro-diamond film, the deposition conditions: the distance between the filament and the sample is 10 mm, the distance between the filament and the filament is 8 mm; the flow rate of methane gas is 16 sccm
  • the hydrogen gas flow rate is 800 sccm, the methane to hydrogen volume ratio is maintained at about 2%;
  • the vacuum chamber pressure range is 4 kPa;
  • the filament temperature range is 2600 ° C, the substrate temperature range is 900 ° C; and the treatment time is 1.5 h.
  • the thickness of the diamond film formed on the surface of the titanium diboride coating is about 2.5 ⁇ m, that is, a workpiece having a titanium diboride-diamond composite coating is prepared.
  • FIG. 1 is a schematic cross-sectional structural view of a workpiece having a titanium diboride-diamond composite coating prepared in Example 1 of the present invention; in the figure, 10 is a cemented carbide substrate, 20 is a titanium diboride coating, and 30 is a diamond. Thin film coating.
  • the titanium diboride-diamond composite coating includes a titanium diboride coating 20 and a diamond thin film coating 30 which are sequentially disposed on the surface of the cemented carbide substrate 10.
  • Example 2 is a cross-sectional high-frequency scanning electron micrograph of a workpiece having a titanium diboride-diamond composite coating prepared in Example 1 of the present invention; the cemented carbide substrate 10 and the titanium diboride coating 20 can be clearly seen in the figure. And a diamond film 30. At the portion where the diamond film 30 is in contact with the titanium diboride coating 20, extremely fine nano-diamond particles (having an average particle diameter of 100 nm) are grown, which greatly improves the strength and bonding force of the film.
  • FIG. 3 is an indentation diagram of a titanium diboride-diamond composite coating according to Embodiment 1 of the present invention. As can be seen from the figure, after a load of 150 Kg, the composite coating has only 5 extremely fine particles. Cracks, and the phenomenon that large-area diamond films fall off along the crack direction does not occur. The coating is only in the contour of the indenter Two small areas of diamond film peeling off appeared on the line. Therefore, the composite coating has excellent adhesion to the substrate.
  • Example 4 is a high-power scanning electron micrograph of a hot-wire vapor deposition on a titanium diboride coating prepared in Example 1 of the present invention for 10 minutes.
  • the grain size is 5.3 ⁇ 10 9 cm -2 .
  • the diamond film has substantially covered the entire surface of the substrate.
  • the titanium diboride coating as the intermediate layer can effectively increase the growth rate of the diamond film and the nucleation density during the deposition process, and greatly promote the growth of the diamond film.
  • a method for preparing a workpiece having a titanium diboride-diamond composite coating comprising the steps of:
  • the first step using the YG6X (WC-6%Co) hard end mill sold in the domestic market as the substrate, the substrate is subjected to alkaline washing for 10 minutes and pickling treatment for 10 seconds to complete chemical etching;
  • the second step depositing a single layer of titanium diboride coating on the surface of the cemented carbide by phase deposition (PVD).
  • the ion source cleaning of the cemented carbide substrate is as follows: argon (Ar) acts as an ion source, the ion source voltage is 70V, the current is 250A, the power is 1.6Kw; the intracavity pressure is 1.0Pa, the cavity temperature 320-380 ° C; substrate rotation speed of 20 rev / min, cleaning time of 20 minutes; redeposition of a single layer of titanium diboride coating, the parameters are: the distance between the target and the sample is 70cm, the deposition pressure is 1.0Pa The base frame rotates at a speed of 20 rpm, and the direction of rotation is clockwise; the base frame is biased at 150 V and the bias current is 1.5 A; the applied target voltage is 380 V, the current is 6.0 A, and the power is 2.2 kW. The time was 30 minutes and the resulting titanium diboride coating was 120
  • the third step using a hot wire chemical vapor deposition method, using hydrogen and methane as reaction gases, depositing a nano-diamond film, the deposition conditions: the filament and the sample spacing is 10 mm, the filament and filament spacing is 8 mm; the methane gas flow is 40 sccm The hydrogen gas flow rate is 800sccm, the methane to hydrogen volume ratio is maintained at about 5%; the vacuum chamber pressure range is 4kPa; the filament temperature range is 2200°C, and the substrate temperature is The circumference is 800 ° C; the treatment time is 3 h.
  • the thickness of the diamond film formed on the surface of the titanium diboride coating is about 4 micrometers, that is, the workpiece having the titanium diboride-diamond composite coating is prepared.
  • a method for preparing a workpiece having a titanium diboride-diamond composite coating comprising the steps of:
  • the first step using the silicon nitride blade sold on the domestic market as the substrate, the substrate is subjected to wet blasting of white corundum, the pressure is 300 kPa, the grain size of the sand is 800 mesh, and then the cemented carbide substrate is respectively made in acetone and alcohol. Ultrasonic cleaning for 15 minutes;
  • the second step depositing a single layer of titanium diboride coating on the surface of the cemented carbide by phase deposition (PVD).
  • the ion source cleaning of the cemented carbide substrate is as follows: argon (Ar) acts as an ion source, the ion source voltage is 70V, the current is 250A, the power is 1.6Kw; the intracavity pressure is 1.0Pa, the cavity temperature 320-380 ° C; substrate rotation speed of 20 rev / min, cleaning time of 20 minutes; redeposition of a single layer of titanium diboride coating, the parameters are: the target and sample spacing between 70cm, deposition pressure is 1.2Pa The base frame rotation speed is 20 rev / min, the rotation direction is clockwise; the base frame is biased to 150V, the bias current is 1.5A; the applied target voltage is 380V, the current is 6A, the power is 2.2Kw; the deposition time For 60 minutes, the resulting titanium diboride coating has a thickness of about 240 nm
  • the third step using hot-wire chemical vapor deposition method, using hydrogen and methane as reaction gases, depositing a micro-diamond film, the deposition conditions: the distance between the filament and the sample is 10 mm, the distance between the filament and the filament is 8 mm; the flow rate of methane gas is 8 sccm
  • the hydrogen gas flow rate is 800sccm, the methane to hydrogen volume ratio is maintained at about 1%; the vacuum chamber pressure range is 4kPa; the filament temperature range is 2600°C, the substrate temperature range is 900°C; the treatment time is 3h, and the titanium diboride coating is applied.
  • the diamond film formed on the surface has a thickness of about 5 ⁇ m, that is, a workpiece having a titanium diboride-diamond composite coating is prepared.
  • a method for preparing a workpiece having a titanium diboride-diamond composite coating comprising the steps of:
  • the first step using a YG8 (WC-8% Co) carbide indexing blade sold on the domestic market as a substrate, performing a chemical etching on the substrate for 10 minutes of alkaline washing and 10 seconds of pickling treatment;
  • the second step depositing a single layer of titanium diboride coating on the surface of the cemented carbide by phase deposition (PVD).
  • the ion source cleaning of the cemented carbide substrate is as follows: argon (Ar) acts as an ion source, the ion source voltage is 70V, the current is 250A, the power is 1.6Kw; the intracavity pressure is 1.0Pa, the cavity temperature 320-380 ° C; substrate rotation speed of 20 rev / min, cleaning time of 20 minutes; redeposition of a single layer of titanium diboride coating, the parameters are: the distance between the target and the sample is 70cm, the deposition pressure is 1.0Pa The rotation speed of the base frame is 20 rpm, the direction of rotation is clockwise; the bias of the base frame is 150V, the bias current is 1.5A; the target voltage is 380V, the current is 6A, the power is 2.2Kw, the deposition time For 30 minutes, the resulting titanium diboride coating has a thickness of
  • the third step the white corundum wet blasting treatment of the substrate, the pressure is 300 kPa, the sand particle size is 800 mesh, and then the cemented carbide is ultrasonically cleaned in acetone and alcohol for 15 minutes.
  • the fourth step using hot-wire chemical vapor deposition method, using hydrogen and methane as reaction gases, depositing nano-diamond film, the deposition conditions: the distance between the filament and the sample is 10 mm, the distance between the filament and the filament is 8 mm; the flow rate of methane gas is 24 sccm
  • the hydrogen gas flow rate is 800 sccm, the methane to hydrogen volume ratio is maintained at about 3%; the vacuum chamber pressure range is 2 kPa; the filament temperature range is 2000 ° C, the substrate temperature range is 750 ° C; and the treatment time is 3 h.
  • the thickness of the diamond film formed on the surface of the titanium diboride coating is about 4 micrometers, that is, the workpiece having the titanium diboride-diamond composite coating is prepared.

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Abstract

一种具有二硼化钛-金刚石复合涂层的工件，包括工件基体（10），以及依次设置于所述工件基体表面的二硼化钛涂层（20）和金刚石涂层（30）。以及一种具有二硼化钛-金刚石复合涂层的工件的制备方法。通过在金刚石涂层与工件基体之间设置二硼化钛涂层，提高了金刚石涂层与工件基体之间的结合力，解决了金刚石涂层与基体结合力不足，金刚石薄膜形核密度低和沉积速度慢的问题。

Description

一种具有二硼化钛-金刚石复合涂层的工件及其制备方法
本申请要求了2016年12月21日提交中国专利局的，申请号201611194326.8，发明名称为“一种具有二硼化钛-金刚石复合涂层的工件及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及金刚石涂层制备技术领域，特别是涉及一种具有二硼化钛-金刚石复合涂层的工件及其制备方法。
背景技术
金刚石涂层硬质合金刀具由于具有优异的性能而受到人们的广泛关注，但由于金刚石涂层与硬质合金刀具之间的粘合力不足，从而极大阻碍了该刀具的应用，成为工业发展中的主要瓶颈。而导致金刚石薄膜在切削刀具上的粘附性不足的主要原因有：(1)硬质合金基体中的粘结剂Co抑制金刚石生长，而有利于粘附性差的石墨沉积；(2)在金刚石薄膜与基体的界面上，金刚石晶粒与基体之间存在微小孔隙，这些微小孔隙的存在，减少了金刚石薄膜与基体的接触面积，削弱了薄膜与基体间的结合力；(3)金刚石膜与基体材料之间热膨胀系数相差很大，并且两者之间存在较强的残余热应力，特别是硬质合金刀具较为尖锐的刀刃部位，造成薄膜与基体分层。
目前，为提高金刚石涂层与硬质合金基体粘附性主要有两条途径：一是采用表面脱Co处理；二是在金刚石涂层与硬质合金之间沉积合适的中间层，以阻止基体中的钴向表面扩散。表面脱Co处理法虽然在一定程度上能够改善金刚石 涂层与基体粘着性，但基体中Co的缺失会大大降低基体本身的硬度、强度、弹性模量等性能，因而，硬质合金表面所沉积生成的金刚石薄膜也无法满足实际的需求。而现有设置中间层的方法大都制备过程复杂，且金刚石涂层与硬质合金刀具之间的粘附力提高有限。
发明内容
鉴于此，本发明第一方面提供了一种具有二硼化钛-金刚石复合涂层的工件，通过在金刚石涂层与工件基体之间设置二硼化钛涂层，解决了金刚石涂层与基体结合力不足，金刚石薄膜形核密度低和沉积速度慢的问题。
第一方面，本发明提供了一种具有二硼化钛-金刚石复合涂层的工件，包括工件基体，以及依次设置于所述工件基体表面的二硼化钛涂层和金刚石涂层。
本发明通过在工件基体表面与金刚石涂层之间设置二硼化钛层，二硼化钛作为中间层，填充了基体表面组织结构不连续区域；同时能够提高后续金刚石薄膜的生长速度以及沉积过程中的形核密度，极大促进金刚石薄膜的生长。此外，采用二硼化钛作为中间层，能够有效提高金刚石涂层与刀具基体之间的结合力，即使在刀具刀刃部分也能得到结合强度高、均匀致密的金刚石薄膜。
可选地，所述二硼化钛涂层的厚度为20-500nm，所述二硼化钛涂层的晶粒为超细纳米晶，晶粒尺寸为20-50nm。进一步可选地，所述二硼化钛涂层的厚度为80-200nm。适合的二硼化钛涂层厚度能够完美的阻挡住钴向基体表面扩散，而且不会引起由于中间层过厚使金刚石与基体之间的结合强度的减弱。
所述金刚石涂层的厚度为2-8μm，进一步地厚度为4-6μm，所述金刚石涂层的晶粒为纳米级别(即100nm以内)或微米级别(即1-5微米)，具体可以是10-80nm、1-4微米。当涂层中金刚石晶粒为纳米级别时，涂层中石墨相增加， 涂层的断裂韧性更高；当涂层中金刚石晶粒为微米级别时，涂层硬度、强度会更高。不同结构性能可以满足人们对工件的不同需求。
所述工件基体的材质可以是硬质合金、不锈钢、氮化硅或碳化硅。工件基体可以是刀具或其他工具(如模具)、机械零部件等。
所述二硼化钛涂层采用物理气相沉积(PVD)方式制备得到，所述金刚石涂层采用热丝气相沉积的方式制备得到。PVD所生长的二硼化钛涂层能够有效阻挡基体向表面扩散的金属钴，消除金属钴对石墨的催化作用，从而有利于获得结合力良好、金刚石纯度高、晶型好的金刚石涂层。
本发明第一方面提供的具有二硼化钛-金刚石复合涂层的工件，通过在金刚石涂层与工件基体之间设置二硼化钛涂层，提高了金刚石涂层与工件基体之间的结合力，解决了金刚石涂层与基体结合力不足，金刚石薄膜形核密度低和沉积速度慢的问题。
第二方面，本发明提供了一种具有二硼化钛-金刚石复合涂层的工件的制备方法，包括以下步骤：
提供工件基体，对所述工件基体进行前处理；所述前处理包括对所述工件基体进行喷砂处理，然后分别采用丙酮和乙醇超声清洗；或对所述工件基体进行化学刻蚀处理；
采用物理气相沉积的方式在所述工件基体上制备二硼化钛涂层，再采用热丝气相沉积的方式在所述二硼化钛涂层上制备金刚石涂层，得到具有二硼化钛-金刚石复合涂层的工件。
所述化学刻蚀处理包括进行8-15分钟的碱洗以及5-15秒的酸洗处理。
本发明中，所述采用物理气相沉积的方式制备二硼化钛涂层的沉积条件为：以二硼化钛为靶材，施加靶材的功率为2.2-2.7kW，靶材与样品之间间距为70 厘米，沉积气压为0.9-1.2Pa，腔内温度为320-380℃，基体架所加偏压为150V，偏流为1.0-1.5A。可选地，沉积过程中基体架旋转速度为20转/分钟，旋转方向为顺时针方向，沉积时间为20分钟。所述沉积二硼化钛涂层之前先对所述工件基体进行离子源清洗，所述离子源清洗的参数为：氩气(Ar)充当离子源，功率为1.6-1.9kW；腔内气压为0.9-1.2Pa，腔内温度为320-380℃；基体架转速为20转/分钟，清洗时间为20分钟。
所述采用热丝气相沉积的方式制备金刚石涂层的沉积条件为：以氢气和甲烷为反应气体，甲烷占总气体体积范围为0.6％-2％，真空室气压范围为3-10kPa；灯丝温度范围为1800-2800℃，基体温度范围为700-1000℃；处理时间为1-4h，制备得到金刚石涂层，所述金刚石涂层的晶粒为微米级别。
所述采用热丝气相沉积的方式制备金刚石涂层的沉积条件为：以氢气和甲烷为反应气体，甲烷占总气体体积范围为3％-6％，真空室气压范围为0.5-4kPa；灯丝温度范围为1500-2400℃，基体温度范围为500-800℃；处理时间为1-4h，制备得到金刚石涂层，所述金刚石涂层的晶粒为纳米级别。
在制备完所述二硼化钛涂层之后，制备所述金刚石涂层之前进一步包括对所述工件基体进行喷砂处理，然后分别采用丙酮和乙醇超声清洗，以获得更好的沉积制备金刚石涂层的表面。
本发明提供的具有二硼化钛-金刚石复合涂层的工件的制备方法，采用物理气相沉积与热丝化学气相沉积相结合，工艺简单，其中二硼化钛涂层的制备时间只有约20分钟，所用PVD设备能实现自动化生产，且制备过程中不需要用到易燃、易爆、有毒气体，具有高效快捷、安全、自动化生产的优势。
本发明的优点将会在下面的说明书中部分阐明，一部分根据说明书是显而易见的，或者可以通过本发明实施例的实施而获知。
附图说明
图1为本发明实施例1制备的具有二硼化钛-金刚石复合涂层的工件的横截面结构示意图；
图2为本发明实施例1制备的具有二硼化钛-金刚石复合涂层的工件的横截面高倍扫描电镜图；
图3为本发明实施例1中二硼化钛-金刚石复合涂层的压痕图；
图4为本发明实施例1制备的在二硼化钛涂层上热丝气相沉积10分钟后的高倍扫描电镜图。
具体实施方式
以下所述是本发明实施例的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明实施例原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明实施例的保护范围。
下面分多个实施例对本发明实施例进行进一步的说明。其中，本发明实施例不限定于以下的具体实施例。在不变主权利的范围内，可以适当的进行变更实施。
实施例1
一种具有二硼化钛-金刚石复合涂层的工件的制备方法，包括以下步骤：
第一步：以市售碳化硅硬质合金刀片作为基体，对基体进行白刚玉湿喷砂处理，其压强为300kPa，砂粒度为800目，然后分别在丙酮和酒精中将硬质合金基体超声清洗15分钟；
第二步：采用物相沉积(PVD)法，在硬质合金基体表面沉积二硼化钛涂层：首先，对硬质合金基体进行离子源清洗，其参数为：氩气(Ar)充当离子源，离子源电压为70V，电流为250A，功率为1.6Kw；腔内气压为1.0Pa，腔内 温度为320-380℃；基体架转速为20转/分钟，清洗时间为20分钟；再沉积单层二硼化钛涂层，参数为：靶材与样品之间间距为70cm，沉积气压为1.2Pa；基体架旋转速度为20转/分钟，旋转方向为顺时针方向；基体架所加偏压为150V，偏流为1.5A；靶材电压为420V，电流为6.5A，功率为2.7Kw；腔内温度为320-380℃，沉积时间为20分钟，所得二硼化钛涂层厚度为70-80nm；
第三步：采用热丝化学气相沉积法，以氢气和甲烷为反应气体，沉积微米金刚石薄膜，其沉积条件：灯丝与样品间距为10毫米，灯丝与灯丝间距为8毫米；甲烷气体流量为16sccm，氢气气体流量为800sccm，甲烷与氢气体积比保持在2％左右；真空室气压范围为4kPa；灯丝温度范围为2600℃，基体温度范围为900℃；处理时间为1.5h。二硼化钛涂层表面所形成的金刚石薄膜厚度为2.5微米左右，即制备得到具有二硼化钛-金刚石复合涂层的工件。
图1为本发明实施例1制备的具有二硼化钛-金刚石复合涂层的工件的横截面结构示意图；图中，10为硬质合金基体，20为二硼化钛涂层，30为金刚石薄膜涂层。二硼化钛-金刚石复合涂层即包括依次设置在硬质合金基体10表面的二硼化钛涂层20和金刚石薄膜涂层30。
图2为本发明实施例1制备的具有二硼化钛-金刚石复合涂层的工件的横截面高倍扫描电镜图；图中能够清楚的看到硬质合金基体10、二硼化钛涂层20以及金刚石薄膜30。在金刚石薄膜30与二硼化钛涂层20相接触的部位生长的均是极细的纳米金刚石颗粒(平均粒径为100纳米)，极大地提高了薄膜的强度以及结合力。
图3为本发明实施例1中二硼化钛-金刚石复合涂层的压痕图；从图中可以看出，经过150Kg的载荷压载之后，该复合涂层只出现了5道极细的裂纹，而且并没用出现沿裂纹方向大面积金刚石薄膜脱落的现象。该涂层只在压头轮廓 线上出现了两块小面积的金刚石薄膜脱落。因而说明该复合涂层与基体的结合力极好。
图4为本发明实施例1制备的在二硼化钛涂层上热丝气相沉积10分钟后的高倍扫描电镜图。其晶粒度达到5.3×109cm-2，从图中可以看出，此时金刚石薄膜已经基本铺满整个基体表面。由此可见二硼化钛涂层作为中间层能够有效提高金刚石薄膜的生长速度以及沉积过程中的形核密度，极大促进金刚石薄膜的生长。
实施例2
一种具有二硼化钛-金刚石复合涂层的工件的制备方法，包括以下步骤：
第一步：以国内市场上出售的YG6X(WC-6％Co)硬质合立铣刀作为基体，对基体进行10分钟的碱洗以及10秒的酸洗处理完成化学刻蚀；
第二步：采用物相沉积(PVD)法，在硬质合金表面沉积单层二硼化钛涂层。首先，对硬质合金基体进行离子源清洗，其参数为：氩气(Ar)充当离子源，离子源电压为70V，电流为250A，功率为1.6Kw；腔内气压为1.0Pa，腔内温度为320-380℃；基体架转速为20转/分钟，清洗时间为20分钟；再沉积单层二硼化钛涂层，参数为：靶材与样品之间间距为70cm，沉积气压为1.0Pa；基体架旋转速度为20转/分钟，旋转方向为顺时针方向；基体架所加偏压为150V，偏流为1.5A；施加靶材电压为380V，电流为6.0A，功率为2.2kW，沉积时间为30分钟，所得二硼化钛涂层厚度为120nm。
第三步：采用热丝化学气相沉积法，以氢气和甲烷为反应气体，沉积纳米金刚石薄膜，其沉积条件：灯丝与样品间距为10毫米，灯丝与灯丝间距为8毫米；甲烷气体流量为40sccm，氢气气体流量为800sccm，甲烷与氢气体积比保持在5％左右；真空室气压范围为4kPa；灯丝温度范围为2200℃，基体温度范 围为800℃；处理时间为3h。二硼化钛涂层表面所形成的金刚石薄膜厚度为4微米左右，即制备得到具有二硼化钛-金刚石复合涂层的工件。
实施例3
一种具有二硼化钛-金刚石复合涂层的工件的制备方法，包括以下步骤：
第一步：以国内市场上出售的氮化硅刀片作为基体，对基体进行白刚玉湿喷砂处理，其压强为300kPa，砂粒度为800目，然后分别在丙酮和酒精中将硬质合金基体超声清洗15分钟；
第二步：采用物相沉积(PVD)法，在硬质合金表面沉积单层二硼化钛涂层。首先，对硬质合金基体进行离子源清洗，其参数为：氩气(Ar)充当离子源，离子源电压为70V，电流为250A，功率为1.6Kw；腔内气压为1.0Pa，腔内温度为320-380℃；基体架转速为20转/分钟，清洗时间为20分钟；再沉积单层二硼化钛涂层，参数为：靶材与样品之间间距为70cm，沉积气压为1.2Pa；基体架旋转速度为20转/分钟，旋转方向为顺时针方向；基体架所加偏压为150V，偏流为1.5A；施加靶材电压为380V，电流为6A，功率为2.2Kw；沉积时间为60分钟，所得二硼化钛涂层厚度约为240nm；
第三步：采用热丝化学气相沉积法，以氢气和甲烷为反应气体，沉积微米金刚石薄膜，其沉积条件：灯丝与样品间距为10毫米，灯丝与灯丝间距为8毫米；甲烷气体流量为8sccm，氢气气体流量为800sccm，甲烷与氢气体积比保持在1％左右；真空室气压范围为4kPa；灯丝温度范围为2600℃，基体温度范围为900℃；处理时间为3h，二硼化钛涂层表面所形成的金刚石薄膜厚度为5微米左右，即制备得到具有二硼化钛-金刚石复合涂层的工件。
实施例4
一种具有二硼化钛-金刚石复合涂层的工件的制备方法，包括以下步骤：
第一步：以国内市场上出售的YG8(WC-8％Co)硬质合金转位刀片作为基体，对基体进行10分钟的碱洗以及10秒的酸洗处理完成化学刻蚀；
第二步：采用物相沉积(PVD)法，在硬质合金表面沉积单层二硼化钛涂层。首先，对硬质合金基体进行离子源清洗，其参数为：氩气(Ar)充当离子源，离子源电压为70V，电流为250A，功率为1.6Kw；腔内气压为1.0Pa，腔内温度为320-380℃；基体架转速为20转/分钟，清洗时间为20分钟；再沉积单层二硼化钛涂层，参数为：靶材与样品之间间距为70cm，沉积气压为1.0Pa；基体架旋转速度为20转/分钟，旋转方向为顺时针方向；基体架所加偏压为150V，偏流为1.5A；施加靶材电压为380V，电流为6A，功率为2.2Kw，沉积时间为30分钟，所得二硼化钛涂层厚度约120nm；
第三步：对基体进行白刚玉湿喷砂处理，其压强为300kPa，砂粒度为800目，然后分别在丙酮和酒精中将硬质合金超声清洗15分钟。
第四步：采用热丝化学气相沉积法，以氢气和甲烷为反应气体，沉积纳米金刚石薄膜，其沉积条件：灯丝与样品间距为10毫米，灯丝与灯丝间距为8毫米；甲烷气体流量为24sccm，氢气气体流量为800sccm，甲烷与氢气体积比保持在3％左右；真空室气压范围为2kPa；灯丝温度范围为2000℃，基体温度范围为750℃；处理时间为3h。二硼化钛涂层表面所形成的金刚石薄膜厚度为4微米左右，即制备得到具有二硼化钛-金刚石复合涂层的工件。
需要说明的是，根据上述说明书的揭示和和阐述，本发明所属领域的技术人员还可以对上述实施方式进行变更和修改。因此，本发明并不局限于上面揭示和描述的具体实施方式，对本发明的一些等同修改和变更也应当在本发明的权利要求的保护范围之内。此外，尽管本说明书中使用了一些特定的术语，但这些术语只是为了方便说明，并不对本发明构成任何限制。

Claims (10)

  1. 一种具有二硼化钛-金刚石复合涂层的工件，其特征在于，包括工件基体，以及依次设置于所述工件基体表面的二硼化钛涂层和金刚石涂层。
  2. 如权利要求1所述的具有二硼化钛-金刚石复合涂层的工件，其特征在于，所述二硼化钛涂层的厚度为20-500nm，所述二硼化钛涂层的晶粒为超细纳米晶。
  3. 如权利要求1所述的具有二硼化钛-金刚石复合涂层的工件，其特征在于，所述金刚石涂层的厚度为2-8μm，所述金刚石涂层的晶粒为纳米或微米级别。
  4. 如权利要求1所述的具有二硼化钛-金刚石复合涂层的工件，其特征在于，所述工件基体的材质为硬质合金、不锈钢、氮化硅或碳化硅。
  5. 如权利要求1所述的具有二硼化钛-金刚石复合涂层的工件，其特征在于，所述二硼化钛涂层采用物理气相沉积方式制备得到，所述金刚石涂层采用热丝气相沉积的方式制备得到。
  6. 一种具有二硼化钛-金刚石复合涂层的工件的制备方法，其特征在于，包括以下步骤：
    提供工件基体，对所述工件基体进行前处理；所述前处理包括对所述工件基体进行喷砂处理，然后分别采用丙酮和乙醇超声清洗；或对所述工件基体进行化学刻蚀处理；
    采用物理气相沉积的方式在所述工件基体上制备二硼化钛涂层，再采用热丝气相沉积的方式在所述二硼化钛涂层上制备金刚石涂层，得到具有二硼化钛-金刚石复合涂层的工件。
  7. 如权利要求6所述的制备方法，其特征在于，所述采用物理气相沉积的方式制备二硼化钛涂层的沉积条件为：以二硼化钛为靶材，施加靶材的功率为 2.2-2.7kW，靶材与样品之间间距为70厘米，沉积气压为0.9-1.2Pa，腔内温度为320-380℃，基体架所加偏压为150V，偏流为1.0-1.5A。
  8. 如权利要求6所述的制备方法，其特征在于，所述采用热丝气相沉积的方式制备金刚石涂层的沉积条件为：以氢气和甲烷为反应气体，甲烷占总气体体积范围为0.6％-2％，真空室气压范围为3-10kPa；灯丝温度范围为1800-2800℃，基体温度范围为700-1000℃；处理时间为1-4h，制备得到金刚石涂层，所述金刚石涂层的晶粒为微米级别。
  9. 如权利要求6所述的制备方法，其特征在于，所述采用热丝气相沉积的方式制备金刚石涂层的沉积条件为：以氢气和甲烷为反应气体，甲烷占总气体体积范围为3％-6％，真空室气压范围为0.5-4kPa；灯丝温度范围为1500-2400℃，基体温度范围为500-800℃；处理时间为1-4h，制备得到金刚石涂层，所述金刚石涂层的晶粒为纳米级别。
  10. 如权利要求6所述的制备方法，其特征在于，在制备完所述二硼化钛涂层之后，制备所述金刚石涂层之前进一步包括对所述工件基体进行喷砂处理，然后分别采用丙酮和乙醇超声清洗。
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