CN110116221A - 一种以低钴含量烧结碳化钨为基体的聚晶金刚石复合片 - Google Patents
一种以低钴含量烧结碳化钨为基体的聚晶金刚石复合片 Download PDFInfo
- Publication number
- CN110116221A CN110116221A CN201811587201.0A CN201811587201A CN110116221A CN 110116221 A CN110116221 A CN 110116221A CN 201811587201 A CN201811587201 A CN 201811587201A CN 110116221 A CN110116221 A CN 110116221A
- Authority
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- China
- Prior art keywords
- diamond
- tungsten carbide
- matrix
- cemented tungsten
- cobalt content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010432 diamond Substances 0.000 title claims abstract description 226
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 223
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 120
- 239000010941 cobalt Substances 0.000 title claims abstract description 120
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000002131 composite material Substances 0.000 title claims abstract description 120
- 239000011159 matrix material Substances 0.000 title claims abstract description 102
- 238000000576 coating method Methods 0.000 claims abstract description 78
- 239000011248 coating agent Substances 0.000 claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 38
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 34
- 239000000956 alloy Substances 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 238000000151 deposition Methods 0.000 claims abstract description 11
- 238000007747 plating Methods 0.000 claims abstract description 10
- 230000008021 deposition Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 7
- 238000009792 diffusion process Methods 0.000 claims abstract description 5
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- 230000004044 response Effects 0.000 claims abstract description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 19
- 229910052804 chromium Inorganic materials 0.000 claims description 19
- 239000011651 chromium Substances 0.000 claims description 19
- 229910052721 tungsten Inorganic materials 0.000 claims description 16
- 239000010937 tungsten Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000470 constituent Substances 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 239000010955 niobium Substances 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 7
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- 239000010936 titanium Substances 0.000 claims description 7
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- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- -1 feature It is Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
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- 239000004332 silver Substances 0.000 claims description 5
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- 230000014759 maintenance of location Effects 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 3
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 claims description 3
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 claims description 3
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- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 3
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- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 description 1
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- PNAFSBCLQWEVBS-UHFFFAOYSA-N chromium yttrium Chemical compound [Cr].[Cr].[Cr].[Cr].[Cr].[Cr].[Cr].[Cr].[Cr].[Y] PNAFSBCLQWEVBS-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
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- E21B10/573—Button-type inserts with preformed cutting elements mounted on a distinct support, e.g. polycrystalline inserts characterised by support details, e.g. the substrate construction or the interface between the substrate and the cutting element
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- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
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- C—CHEMISTRY; METALLURGY
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
- C04B37/021—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles in a direct manner, e.g. direct copper bonding [DCB]
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- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
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- C—CHEMISTRY; METALLURGY
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- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
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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
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- 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
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
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- C—CHEMISTRY; METALLURGY
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- 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
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
- C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B10/00—Drill bits
- E21B10/46—Drill bits characterised by wear resisting parts, e.g. diamond inserts
- E21B10/56—Button-type inserts
- E21B10/567—Button-type inserts with preformed cutting elements mounted on a distinct support, e.g. polycrystalline inserts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2226/00—Materials of tools or workpieces not comprising a metal
- B23B2226/31—Diamond
- B23B2226/315—Diamond polycrystalline [PCD]
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明是关于一种具有涂层覆盖的、以低钴含量烧结碳化钨作为基体的聚晶金刚石复合片。该复合片是由聚晶金刚石层和烧结碳化钨基体构成，其中：聚晶金刚石层为未脱除触媒材料或脱除触媒材料(部分或全部)的，烧结碳化钨基体含有3％～10％(重量百分数)的钴或钴基合金作为粘结剂。涂层至少覆盖烧结碳化钨基体的部分表面，可扩展覆盖聚晶金刚石层的部分乃至全部表面。涂层为单层或者多层，但至少包含一金属或合金层。涂层的制备方法有物理气相沉积、化学气相沉积、热反应沉积和扩散、电镀、化学镀、或者它们的组合。本发明的聚晶金刚石复合片具有减少的残余应力、低脆性，以及优异的抗冲蚀耐磨性能和可钎焊性能。
Description
技术领域
本发明是关于一种用于切削工具、磨具及钻具上以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，属于道路桥梁建设、机械加工、石材加工、采矿、石油钻探及开采等领域。
背景技术
聚晶金刚石复合片(Polycrystalline Diamond Cutter,PDC)业已为人们所熟知，它是由一聚晶金刚石(Polycrystalline Diamond,PCD)层和硬质合金(烧结碳化物)支撑基体构成，聚晶金刚石复合片制备通常是在高温高压下、在触媒材料的辅助下、在烧结碳化物基体上、将细小的金刚石颗粒烧结粘合在一起，常见的金属触媒材料为钴、镍、铁及其它们的合金，该工艺即为常见的高温高压过程。聚晶金刚石复合片的支撑基体为烧结碳化物，例如：以钴作为粘结剂的烧结碳化钨。在高温高压烧结过程中，烧结碳化物基体中的钴或其它金属触媒材料可扩散至聚晶金刚石层中的金刚石颗粒间，作为触媒，它促进金刚石颗粒间的结合(金刚石与金刚石键结合，即Diamond-to-Diamond,简称D-D键结合)，形成聚晶金刚石层。另一种方法，先将金刚石颗粒与粉末状的触媒材料预先混合均匀，然后在高温高压下烧结，形成聚晶金刚石。
聚晶金刚石复合片也可通过钎焊方法，将制好的无基体支撑的聚晶金刚石层与烧结碳化物基体焊合在一起来制备。如前所述，无基体支撑的聚晶金刚石层可通过在高温高压下、在触媒材料的辅助下烧结而成。
人们认识到聚晶金刚石中的金属触媒材料(如：钴)对其热稳定性是非常有害的。金属触媒材料不仅促进金刚石的石墨化，而且，由于其热膨胀系数与金刚石有显著差异，导致形成高的热应力。为了改进聚晶金刚石的热稳定性，各种热稳定聚晶金刚石(ThermallyStable Polycrystalline Diamond,TSPCD)相继问世，它们或者是用非金属触媒材料、或者是将合成的聚晶金刚石中金属触媒材料部分或全部脱除掉。
热稳定聚晶金刚石复合片(Thermally Stable Polycrystalline DiamondCutter,TSPDC)是指由热稳定聚晶金刚石层(TSPCD)和烧结碳化物基体构成的聚晶金刚石复合片。通常，热稳定聚晶金刚石复合片是通过脱除掉聚晶金刚石层中部分或全部金属触媒材料(如：钴)来获得的。脱除金属触媒材料的方法有化学、电化学及其它技术。最常见的是部分脱除金属触媒材料，即仅脱除聚晶金刚石层表面和亚表层中的金属触媒材料，深度一般是几十至几百微米、不超过1毫米，而聚晶金刚石层内部仍保留金属触媒材料。美国专利(April 2,2005；U.S.Pat.No.6,878,447B2；Polycrystalline Diamond PartiallyDepleted of Catalyzing Material)和(July 15,2003；U.S.Pat.No.6,592,985B2；Polycrystalline Diamond Partially Depleted of Catalyzing Material)是关于部分脱除金属触媒材料的聚晶金刚石复合片的。完全脱除金属触媒材料不仅耗时长，而且还会导致聚晶金刚石层变脆。部分脱除金属触媒材料的聚晶金刚石除了改善其热稳定性，而且还保持聚晶金刚石良好的抗冲击性能。部分脱除金属触媒材料的热稳定聚晶金刚石复合片具有优异的综合性能，在切削应用中如石油钻探取得极大的成功，得到广泛的应用。
聚晶金刚石复合片作为切削刀在各种切削工具上的应用非常成功，特别是在石油地质钻探工具上，但它们的早期失效仍影响其制备成品率、以及切削工具的性能和效率。聚晶金刚石复合片的早期失效表现为：在高温高压制备、钎焊、以及使用过程中聚晶金刚石层断裂、崩齿、开裂、分层。这些问题通常是与聚晶金刚石层与烧结碳化物基体界面间存在高的残余应力密切相关，而这种高的残余应力是由它们间显著的热膨胀系数差异所致。
发明内容
本发明的主要目的是提供一种以低钴含量烧结碳化钨为基体的、基体具有包覆涂层的聚晶金刚石复合片，通过减少聚晶金刚石层与烧结碳化物基体界面间的残余应力、增加冲击韧性、提高抗冲蚀耐磨性能、改善钎焊性，以提高聚晶金刚石复合片的质量、制备的成品率、避免早期失效、延长工具的使用寿命。
本发明的技术方案是：
一种以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，包括未脱除触媒材料或脱除触媒材料的聚晶金刚石层及低钴含量烧结碳化钨基体，其中：
按重量百分数计，低钴含量烧结碳化钨基体含有3～10％的钴或钴基合金作为粘结剂；
低钴含量烧结碳化钨基体表面至少部分被涂层所包覆。
所述的以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，低钴含量烧结碳化钨基体是以碳化钨作为唯一的碳化物组元的硬质合金，或者是除碳化钨外还含有其它碳化物组元的硬质合金，其它碳化物组元采用碳化钛、碳化钽、碳化铌的至少一种。
所述的以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，涂层中包含有金属或合金层，它是从下列金属或合金中选取：镍、铁、钴、钛、铌、锆、钒、钽、铪、铬、钨、钼、锰、银、铜、金、铂、钯，或者含有至少一种这些金属元素的合金。
所述的以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，涂层中包含有以碳化物形成金属元素钛、铌、锆、钒、钽、铪、铬、钨、钼或者含有至少一种这些金属元素的合金为结合层，它直接与聚晶金刚石复合片相接触。
所述的以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，涂层中包含有化合物层，它是从下列物质中选取：碳化物、硼化物、氮化物、氧化物、或它们的复合化合物。
所述的以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，涂层与聚晶金刚石复合片间为冶金结合，即在它们的界面上有碳化物形成，这些碳化物是在涂层制备、随后的热处理、或者钎焊至工具上时形成的。
所述的以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，产生涂层冶金结合的热处理为保温温度450℃～900℃、保持时间1分钟～120分钟。
所述的以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，涂层总厚度为0.1微米～100微米，最佳厚度为1微米～10微米。
所述的以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，涂层包覆低钴含量烧结碳化钨基体的全部表面、乃至聚晶金刚石层的部分或全部表面。
所述的以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，涂层的制备方法为物理气相沉积、化学气相沉积、热反应沉积和扩散、电镀、化学镀、或者它们的组合。
本发明的优点及有益效果是：
1、本发明是关于一种以低钴含量的烧结碳化钨作为基体的聚晶金刚石复合片，并且烧结碳化钨表面至少部分为涂层所覆盖。低钴含量烧结碳化钨基体含有3％～10％(平均重量百分数)的钴或钴基合金作为烧结碳化钨的粘结剂。常规聚晶金刚石复合片的烧结碳化钨基体通常含有11％～16％(平均重量百分数)的钴或钴基合金作为烧结碳化钨的粘结剂。由于渗入至聚晶金刚石层中的钴粘结剂与金刚石存在显著的热膨胀系数差异，烧结碳化钨中的钴粘结剂含量会显著影响着聚晶金刚石层与烧结碳化钨基体界面的热错配度。烧结碳化钨中的粘结剂钴含量越高，它们的热错配度越严重，严重的热错配度会在高温高压制备以及随后的钎焊过程中产生高的残余应力。高的残余应力会使聚晶金刚石复合片在高温高压制备、钎焊、以及切削应用过程中，质量和性能发生蜕变，诸如：聚晶金刚石层断裂、崩齿、开裂、分层等。低钴含量的烧结碳化钨作为基体的聚晶金刚石复合片则有降低的界面残余应力，因而改进它们的成品率、加工和使用性能。进一步，由于低钴含量的烧结碳化钨有更高的硬度，它们具有更优的抗冲蚀和耐磨性能。经研究，烧结碳化钨中低钴含量不仅减少高温高压制备和钎焊过程中聚晶金刚石复合片的开裂，而且还提高冲击韧性。美国申请专利(Jun.21,2016；U.S.Appl.Pat.No.0,017,665A1；Reduced Length and Low CobaltContent Cutters and Drill Bit Made therewith)也提及含6％～10％(重量百分数)钴的烧结碳化钨基体，并未发现增加聚晶金刚石复合片脆性破坏几率。
2、本发明是关于一种以低钴含量的烧结碳化钨作为基体的聚晶金刚石复合片，并且烧结碳化钨表面至少部分为涂层所覆盖，烧结碳化钨中粘结剂钴含量的减少会损害它的钎焊性能，本发明观察到烧结碳化钨中钴含量减少显著恶化它与银基钎焊合金的浸润性。本发明中，在低钴含量烧结碳化钨基体上加涂层的目的就是为了改善钎焊性能、提高聚晶金刚石复合片与工具间的结合力。
3、本发明的聚晶金刚石复合片具有减少的残余应力、低脆性，以及优异的抗冲蚀耐磨性能和可钎焊性能。
附图说明
图1示意地显示一圆柱形的聚晶金刚石复合片的横截面，该聚晶金刚石复合片包括聚晶金刚石层和低钴含量烧结碳化钨基体；
图2示意地显示一圆柱形的聚晶金刚石复合片的横截面，该聚晶金刚石复合片包括聚晶金刚石层和低钴含量烧结碳化钨基体，其中低钴含量烧结碳化钨基体的全部外表面为涂层所覆盖；
图3示意地显示一圆柱形的聚晶金刚石复合片的横截面，该聚晶金刚石复合片包括聚晶金刚石层和低钴含量烧结碳化钨基体，其中低钴含量烧结碳化钨基体的侧面为涂层所覆盖；
图4示意地显示一圆柱形的聚晶金刚石复合片的横截面，该聚晶金刚石复合片包括聚晶金刚石层和低钴含量烧结碳化钨基体，其中聚晶金刚石层的全部外表面和低钴含量烧结碳化钨基体的侧面为涂层所覆盖；
图5示意地显示一圆柱形的聚晶金刚石复合片的横截面，该聚晶金刚石复合片包括聚晶金刚石层和低钴含量烧结碳化钨基体，并且它们的全部外表面为涂层所覆盖。
图中标记的含义：10低钴含量烧结碳化钨基体；12聚晶金刚石层；14涂层。
具体实施方式
在具体实施过程中，本发明是关于一种以低钴含量的烧结碳化钨作为基体的聚晶金刚石复合片，并且烧结碳化钨表面至少部分为涂层所覆盖。聚晶金刚石复合片是由聚晶金刚石层和硬质合金(烧结碳化物)基体所构成，聚晶金刚石层作为切削刃，而烧结碳化物作为支撑基体。聚晶金刚石复合片制备通常是在高温高压下、在触媒材料的辅助下、在烧结碳化物基体上、将细小的金刚石颗粒烧结粘合在一起的，金刚石颗粒间具有强的金刚石与金刚石键结合(Diamond-to-Diamond,简称D-D键结合)。聚晶金刚石复合片的基体是烧结碳化物，如：以钴作为粘结剂的烧结碳化钨。
聚晶金刚石复合片的支撑基体为烧结碳化物，例如：以钴作为粘结剂的烧结碳化钨。在高温高压烧结过程中，烧结碳化钨中的粘结剂钴或其它金属触媒材料可扩散至聚晶金刚石层中的金刚石颗粒间，作为触媒，它促进金刚石颗粒间的D-D键结合，形成聚晶金刚石层。另一种方法，先将金刚石颗粒与粉末状的触媒材料预先混合均匀，然后在高温高压下烧结，形成聚晶金刚石片。聚晶金刚石复合片也可通过将无支撑基体的聚晶金刚石片钎焊至烧结碳化物基体上来制备。
本发明中，聚晶金刚石复合片的低钴含量烧结碳化钨基体是指以钴作为粘结剂的烧结碳化钨，它是碳化钨颗粒与钴或钴基合金的复合材料，钴或钴基合金作为烧结碳化钨的粘结剂。烧结碳化钨是以碳化钨作为唯一的碳化物组元，也可以是除碳化钨外，还含有其它碳化物组元的复合材料，如：含有碳化钛、碳化钽、碳化铌等。
本发明中，聚晶金刚石复合片中的低钴含量烧结碳化钨基体含有3％～10％(平均重量百分数)的钴或钴基合金，钴或钴基合金作为低钴含量烧结碳化钨基体的粘结剂。
本发明是关于以低钴含量的烧结碳化钨为基体的聚晶金刚石复合片。图1示意显示一以低钴含量的烧结碳化钨为基体的聚晶金刚石复合片的横截面。聚晶金刚石复合片是由低钴含量烧结碳化钨基体10和聚晶金刚石层12组成，其中：低钴含量烧结碳化钨基体10作为支撑基体，而聚晶金刚石层12作为切削刃。
本发明中，聚晶金刚石复合片可以是未除脱触媒材料的聚晶金刚石复合片。未脱除触媒材料的聚晶金刚石复合片是指常规的聚晶金刚石复合片，它的聚晶金刚石层是由D-D键结合的金刚石颗粒和其间隙处分布的触媒材料(如：钴)所组成。它的热稳定性通常不超过750℃，热稳定聚晶金刚石复合片(TSPDC)是指由热稳定聚晶金刚石层(TSPCD)和烧结碳化物基体构成的聚晶金刚石复合片。通常，热稳定聚晶金刚石复合片是通过脱除掉聚晶金刚石层中部分或全部金属触媒材料(如：钴)来制备的。脱除金属触媒材料的方法有化学、电化学及其它技术。最常见的是部分脱除金属触媒材料，即仅脱除聚晶金刚石层表面和亚表层中的金属触媒材料，深度一般是几十至几百微米、不超过1毫米，而聚晶金刚石层内部仍保留金属触媒材料。完全脱除金属触媒材料不仅耗时长，而且还会导致聚晶金刚石层变脆。部分脱除金属触媒材料的聚晶金刚石除了改善其热稳定性，而且还保持聚晶金刚石良好的抗冲击性能。部分脱除金属触媒材料的热稳定聚晶金刚石复合片具有优异的综合性能，在切削应用中如石油钻探取得极大的成功，得到广泛的应用。
本发明中，涂层至少部分覆盖低钴含量烧结碳化钨基体，并且可部分乃至全部包覆聚晶金刚石层。
本发明中，涂层包括一金属或合金层，它至少是下列一种金属：镍、铁、钴、钛、铌、锆、钒、钽、铪、铬、钨、钼、锰、银、铜、金、铂、钯，或是含有至少一种这些金属元素的合金，例如镍-铬合金。
本发明中，涂层可以包括多层。但最外层一定为金属或合金层，它至少是下列一种金属：镍、铁、钴、钛、铌、锆、钒、钽、铪、铬、钨、钼、锰、银、铜、金、铂、钯，或是含有至少一种这些金属元素的合金。
本发明中，涂层可以包括多层。涂层中可包括一碳化物形成金属或合金层作为结合层，它与聚晶金刚石复合片直接接触，这些金属或合金是从钛、铌、锆、钒、钽、铪、铬、钨、钼，或者是含有至少一种这些金属元素的合金中选取。
本发明中，涂层可以包括多层。涂层中可包括一化合物层，它们是从碳化物、氮化物、硼化物、氧化物、或者它们的复合化合物中选取。它们最好是含有铝、铬或同时两者的化合物，这些化合物能够与氧反应形成连续致密的氧化物，可保护其下面的材料免于氧化，例如：氮化铬(CrN)、氮化铝铬(AlCrN)、氮化铝钛(AlTiN)、氮化铝钛硅(AlTiSiN)、氮化钛铝铬钇(TiAlCrYN)等。化合物层具有优异的抗氧化和耐磨性能，可保护聚晶金刚石复合片在钎焊及切削应用过程中免遭受热和机械损伤。
本发明中，涂层与聚晶金刚石复合片可为冶金结合。这种冶金结合可以是在涂层制备、附加热处理、以及钎焊至工具过程中形成。
本发明中，利用热处理来实现涂层与聚晶金刚石复合片的冶金结合。热处理可在真空、惰性或还原气氛炉中完成，温度为450℃～900℃，保持时间1分钟～120分钟。
本发明中，保护涂层总厚度为0.1微米～100微米，最好为1微米～10微米。
参照图2，本发明具有涂层覆盖、以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，该烧结碳化钨基体外表面全部为涂层所覆盖。图2示意地显示一具有涂层全部覆盖、以低钴含量烧结碳化钨为基体的聚晶金刚石复合片的横截面。由图可见，低钴含量烧结碳化钨基体10外表面全部为涂层14所包覆，低钴含量烧结碳化钨基体10作为聚晶金刚石层12的支撑基体。需要指出，图中的所有尺寸都不成比例，实际上涂层的厚度很小，为显示方便有意夸张放大，下面的图3～5也是如此。
参照图3，本发明具有涂层覆盖、以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，该烧结碳化钨基体外表面部分为涂层所覆盖。图3示意地显示一具有涂层覆盖、以低钴含量烧结碳化钨为基体的聚晶金刚石复合片的横截面，该烧结碳化钨基体外表面部分为涂层所覆盖。由图可见，低钴含量烧结碳化钨基体10侧表面为涂层14所包覆，低钴含量烧结碳化钨基体10作为聚晶金刚石层12的支撑基体。
参照图4，本发明具有涂层覆盖、以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，该烧结碳化钨基体部分外表面和聚晶金刚石层全部外表面为涂层所覆盖。图4示意地显示具有涂层覆盖、以低钴含量烧结碳化钨为基体的聚晶金刚石复合片的横截面，涂层覆盖烧结碳化钨基体部分外表面和聚晶金刚石层的全部外表面。由图可见，低钴含量烧结碳化钨基体10侧表面为涂层14所覆盖，并且聚晶金刚石层12的外表面也全部为涂层所覆盖，低钴含量烧结碳化钨基体10作为聚晶金刚石层12的支撑基体。
参照图5，本发明具有涂层覆盖、以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，聚晶金刚石复合片全部外表面为涂层覆盖。图5示意地显示具有涂层覆盖、以低钴含量烧结碳化钨为基体的聚晶金刚石复合片的横截面，涂层覆盖聚晶金刚石复合片全部外表面。由图可见，低钴含量烧结碳化钨基体10和聚晶金刚石层12的全部外表面为涂层14所包覆，低钴含量烧结碳化钨基体10作为聚晶金刚石层12的支撑基体。
本发明中，涂层可覆盖聚晶金刚石复合片全部或部分外表面，并且聚晶金刚石复合片的不同部位可有不同的涂层，例如：聚晶金刚石层有两层涂层，而烧结碳化钨基体有单层金属涂层、或者金属-化合物-金属的三层涂层。
本发明中，聚晶金刚石复合片可有各种不同的几何形状，包括对称和不对称的，例如：圆柱体、圆锥体、立方体、长方体、楔形体等。
本发明中，涂层可通过各种沉积方法来制备，包括物理气相沉积法、化学气相沉积法、热反应沉积和扩散、电镀、化学镀等，或者它们的组合。
物理气相沉积法包括热蒸发、溅射和离子镀方法。它们是在相对较低的温度下进行，一般不超过500℃。它们适合用于在聚晶金刚石复合片上制备涂层，并且成本低、可规模化生产。
化学气相沉积法是在高温下进行，其温度可达1000℃。在化学气相沉积过程中，聚晶金刚石复合片有热损伤的风险，因为它的热稳定温度通常不超过750℃。因此，加工工艺参数一定要恰当选取，以避免沉积过程中造成聚晶金刚石复合片的热损伤。用化学气相沉积法在聚晶金刚石复合片上制备涂层的优点之一是：伴有碳化物产生的冶金结合界面会形成。
热反应沉积和扩散的方法包括盐浴法和固体装箱法。它们是在500℃～1250℃高温下进行，因此，当温度超过700℃时，加工工艺参数一定要恰当选取，以避免沉积过程中造成聚晶金刚石复合片的热损伤。伴有碳化物产生的冶金结合界面可能会在涂层制备过程中形成。
电镀和化学镀是在电解质溶液中进行，其温度不超过100℃。该方法要求待镀件必须是电导体，而聚晶金刚石复合片的聚晶金刚石层是不导电的，故它们是不能直接用来包覆聚晶金刚石复合片层的。但是，它们可用于包覆聚晶金刚石复合片的烧结碳化钨基体，以及在已有导电的包覆层的聚晶金刚石复合片上制备多层包覆。
下面所给出的实施例仅是对本发明的进一步描述，权利要求包括但不限于所述的实施例内容。
实施例1：制备以低钴含量的烧结碳化钨作为基体的聚晶金刚石复合片
在高温高压条件下，制备以低钴含量的烧结碳化钨作为基体的1313聚晶金刚石复合片。1313聚晶金刚石复合片为圆柱状，其外观尺寸为13毫米直径、13毫米高。该聚晶金刚石复合片由一2毫米高的聚晶金刚石层和11毫米高的烧结碳化钨基体组成。烧结碳化钨基体是以碳化钨作为唯一的碳化物组元及以钴作为粘结剂，其名义化学重量百分数组成为91％WC和9％Co。高温高压制备条件为温度1450℃～1550℃和压力5GPa～6GPa，高温高压制备的成品率为100％。
实施例2：用物理气相沉积法-离子镀法、制备铬、氮化铝钛和镍铬合金三层涂层覆盖聚晶金刚石复合片
用实施例1中制备的、以低钴含量的烧结碳化钨作为基体的、1313聚晶金刚石复合片作为试样。离子镀法是物理气相沉积方法之一，也称为离子辅助沉积。本实施例是用离子镀法在以低钴含量的烧结碳化钨作为基体的聚晶金刚石复合片表面包覆铬、氮化铝钛和铬三层，包覆层覆盖聚晶金刚石层的全部外表面及烧结碳化钨基体的侧表面。聚晶金刚石复合片试样经在丙酮溶液中超声清洗、干燥后，放入离子镀机器腔中。机器腔中有三种靶：铬靶、铝钛合金靶和镍铬合金靶。首先，点燃铬靶，沉积铬，沉积温度为450℃，沉积时间为30分钟，沉积铬层厚度约为1微米。然后，点燃铝钛合金靶，沉积氮化铝钛。此时，向离子镀机器腔中导入氮气，沉积时间为1.5小时，沉积氮化铝钛层厚度约为4微米。最后，点燃镍铬合金靶，沉积镍铬合金，沉积温度为450℃，沉积时间为30分钟，沉积镍铬合金层厚度约为1微米。聚晶金刚石复合片的保护障碍层为三层，内层金属铬作为结合层、中间层氮化铝钛化合物作为抗氧化耐磨层、最外层镍铬合金作为抗氧化和可钎焊层。制得的涂层连续、致密、无裂纹等缺陷。
实施例3：具有涂层的、以低钴含量的烧结碳化钨作为基体的聚晶金刚石复合片的热处理
对具有涂层的、以低钴含量的烧结碳化钨作为基体的聚晶金刚石复合片进行热处理，在涂层与聚晶金刚石复合片之间形成冶金结合。试验所用试样为实施例2中已包覆铬、氮化铝钛和镍铬合金三层的聚晶金刚石复合片。热处理是在流动氩气保护下、在电阻炉中进行的。电阻炉的加热速度为约10℃/min，保持温度630℃，保持时间1小时。随后冷却是在电阻炉中、在流动氩气保护下完成的。热处理后的涂层连续、致密、无裂纹等缺陷。
实施例4：热处理后的、具有涂层的、以低钴含量的烧结碳化钨作为基体的聚晶金刚石复合片的钎焊
对经热处理的、具有涂层的、以低钴含量的烧结碳化钨作为基体的聚晶金刚石复合片进行钎焊试验。试验所用试样为实施例3中热处理的、包覆有铬、氮化铝钛和镍铬合金三层的聚晶金刚石复合片。钎焊材料为银基合金，其名义化学重量百分数组成：56％Ag、22％Cu、17％Zn、5％Sn，它的液相线和固相线分别为620℃和650℃。钎焊是用火焰加热，在空气中进行的，估计钎焊温度为650℃至750℃。聚晶金刚石复合片被钎焊到一低合金钢试块上。力学试验表明，本发明的、经热处理的、具有涂层的、以低钴含量的烧结碳化钨作为基体的聚晶金刚石复合片的钎焊结合强度比未有涂层的以低钴含量的烧结碳化钨作为基体的聚晶金刚石复合片的高约15％以上。并且，钎焊后，没有观察到任何裂纹出现，钎焊优异性能的涂层有效地改善以低钴含量的烧结碳化钨作为基体的聚晶金刚石复合片的钎焊性能。
本发明中，具有涂层的、以低钴含量的碳化钨作为基体的聚晶金刚石复合片可应用于各种切削工具上作为切削刀刃，例如：石油地质钻探钻头、钻探扩孔器工具等。组装方法为钎焊。
本发明中，以低钴含量的碳化钨作为基体的聚晶金刚石复合片其在聚晶金刚石层与碳化钨基体间界面的残余应力会减少。因而，聚晶金刚石复合片的制备和加工成品率以及使用性能会提高，其上的可钎焊涂层还会改善钎焊性能、增加工具基体的把持力。进一步，涂层还可减少钎焊过程中的热损伤、改善使用过程中的抗冲蚀和耐腐蚀性能。本发明的、以低钴含量的碳化钨作为基体的、聚晶金刚石复合片的制备及加工方法成本经济、方便易行、适合工业批量生产。
需要理解到的是，以上所述仅是本发明实施方式之一，对于本领域普通技术人员来说，在不脱离本发明原理的前提下，还可作出若干改进和润色，这些改进和润色也应视为本发明的保护范围。
Claims (10)
1.一种以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，其特征在于，包括未脱除触媒材料或脱除触媒材料的聚晶金刚石层及低钴含量烧结碳化钨基体，其中：
按重量百分数计，低钴含量烧结碳化钨基体含有3～10％的钴或钴基合金作为粘结剂；
低钴含量烧结碳化钨基体表面至少部分被涂层所包覆。
2.根据权利要求1所述的以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，其特征在于，低钴含量烧结碳化钨基体是以碳化钨作为唯一的碳化物组元的硬质合金，或者是除碳化钨外还含有其它碳化物组元的硬质合金，其它碳化物组元采用碳化钛、碳化钽、碳化铌的至少一种。
3.根据权利要求1所述的以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，其特征在于，涂层中包含有金属或合金层，它是从下列金属或合金中选取：镍、铁、钴、钛、铌、锆、钒、钽、铪、铬、钨、钼、锰、银、铜、金、铂、钯，或者含有至少一种这些金属元素的合金。
4.根据权利要求1所述的以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，其特征在于，涂层中包含有以碳化物形成金属元素钛、铌、锆、钒、钽、铪、铬、钨、钼或者含有至少一种这些金属元素的合金为结合层，它直接与聚晶金刚石复合片相接触。
5.根据权利要求1所述的以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，其特征在于，涂层中包含有化合物层，它是从下列物质中选取：碳化物、硼化物、氮化物、氧化物、或它们的复合化合物。
6.根据权利要求1所述的以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，其特征在于，涂层与聚晶金刚石复合片间为冶金结合，即在它们的界面上有碳化物形成，这些碳化物是在涂层制备、随后的热处理、或者钎焊至工具上时形成的。
7.根据权利要求6所述的以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，其特征在于，产生涂层冶金结合的热处理为保温温度450℃～900℃、保持时间1分钟～120分钟。
8.根据权利要求1所述的以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，其特征在于，涂层总厚度为0.1微米～100微米，最佳厚度为1微米～10微米。
9.根据权利要求1所述的以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，其特征在于，涂层包覆低钴含量烧结碳化钨基体的全部表面、乃至聚晶金刚石层的部分或全部表面。
10.根据权利要求1所述的以低钴含量烧结碳化钨为基体的聚晶金刚石复合片，其特征在于，涂层的制备方法为物理气相沉积、化学气相沉积、热反应沉积和扩散、电镀、化学镀、或者它们的组合。
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| CN110527891A (zh) * | 2019-09-16 | 2019-12-03 | 东华大学 | 低钴硬质合金表面金刚石涂层及其制备方法 |
| CN110757912A (zh) * | 2019-11-20 | 2020-02-07 | 聊城全超新材料有限公司 | 一种聚晶金刚石复合片及其制备方法 |
| CN112855033A (zh) * | 2021-03-02 | 2021-05-28 | 广东钜鑫新材料科技股份有限公司 | 聚晶金刚石复合片、其制造方法、pdc轴承组件及切削刀具 |
| CN112981407A (zh) * | 2021-02-03 | 2021-06-18 | 四川伽锐科技有限公司 | 一种环脱聚晶金刚石复合片及其加工方法 |
| CN113667874A (zh) * | 2020-05-15 | 2021-11-19 | 四川大学 | 一种ya类梯度硬质合金材料及其制备方法和用途 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110391095B (zh) * | 2019-08-23 | 2020-08-14 | 浙江大学 | 单面内氧化银氧化锡氧化铟电接触材料及其制备方法 |
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| CN112981407A (zh) * | 2021-02-03 | 2021-06-18 | 四川伽锐科技有限公司 | 一种环脱聚晶金刚石复合片及其加工方法 |
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