乐投英超

RENZAOJINGANGSHITUCENGYONGYINGZHIHEJINJITIBIAOMIANYUCHULIYANJIU

发布时间:2016-08-17 16:24:57

摘 要:从孔隙的形成、界面非人造金刚石物的形成以及较高残余应力等3个不利方面,分析和综述了影响金刚石涂层与硬质合金基体粘结性的主要因素。着重对浸蚀基体表面除去Co相或浸蚀WC相,在基体与涂层之间形成中间过渡层或中间化合物,基体表面机械或热处理等硬质合金基体表面预处理,改善涂层与基体粘结性的3种方法和途径进行了阐述。

乐投英超YOUYUJINGANGSHIYUYINGZHIHEJINZAIREPENGZHANGXISHU、DANXINGMOLIANG、HUAXUEJIYUANZIJIEGOUDENGXINGNENGSHANGYOUHENDACHAYI,YOUQISHIYINGZHIHEJINJITIZHONGZHANJIEXIANGCoDECUNZAI,BUJINJIANGDILEJINGANGSHIDEJINGHEXINGHELV,ERQIECUJINLEZAITUCENGYUJITIJIEMIANSHANGXINGCHENGFEIJINGANGSHIDETANWUZHI,YANZHONGYINGXIANGLEJINGANGSHITUCENGDEZHILIANGHEZHANJIEXING。RUHESHIJINGANGSHIYUYINGZHIHEJINXINGNENGSHANGDECHAYIDEDAOPIPEI,JIANSHAOCoXIANGDUITUCENGYUJITIJIEMIANSHANGJINGANGSHIBOMOSHENGZHANGDEFUMIANYINGXIANG,SHIGAISHANTUCENGYUJITIZHANJIEXIAOGUODEGUANJIANSUOZAI。

大多数研究认为,改善人造金刚石涂层与硬质合金基体粘结效果的途径,不外乎有下列3条:1)采用低Co或无Co硬质合金基体;2)涂层之前,对硬质合金基体表面进行适当预处理;3)严格控制人造金刚石乐投英超涂层 工艺和方法。其中硬质合金基体表面预处理,可以从根本上消除或减弱Co的负面影响,已受到世界各国研究人员的广泛重视。目前,有关硬质合金基体表面预处理的研究着重在以下3个方面:1)浸蚀基体表面除去Co相或WC相;2)在基体与涂层之间形成中间过渡层或中间化合物;3)基体表面机械或热处理。相对于未作表面预处理的硬质合金基体来说,上述3种方法都对涂层与基体的粘结效果有了较大改善,有些方法已在实际生产中得到了应用。为了寻找改善涂层与基体粘结效果更好的方法和途径,必须首先了解影响人造金刚石涂层与硬质合金基体粘结性的各种因素。

1 YINGXIANGTUCENGYUJITIZHANJIEXINGDE3GEBULIYINSU

人造金刚石与硬质合金在物理和化学等性能上的较大差异,以及硬质合金基体中粘结相Co对涂层与基体界面上人造金刚石薄膜生长的负面影响,是造成人造金刚石涂层与硬质合金基体粘结性较差的根本原因。深入分析CVD金刚石涂层硬质合金的过程和效果认为,造成人造金刚石涂层与硬质合金基体粘结性较差的直接因素有:在涂层与基体界面上有孔隙形成;在涂层与基体界面上存在非金刚石物质;较高的残余应力。首先,孔隙的形成,是由于较低的人造金刚石形核密度所致。金刚石晶核在硬质合金表面生长之前,在涂层与基体界面上有一个形核过程,形核密度低,将导致界面上的孔隙增加。由于人造金刚石次形核的数量有限,在随后的晶核生长过程中,也无法填充这些孔隙。因此,涂层之后,界面上有孔隙形成。而硬质合金基体中的粘结相Co对人造金刚石的形核极为不利。对含Co量为3%~10%的硬质合金上人造金刚石的形核率进行了研究,发现含Co量>6%时,人造金刚石在硬质合金上的形核率极低。这导致了现在大多数的研究都集中在含Co量<6%的硬质合金上进行。

QICI,JIEMIANSHANGXINGCHENGDEFEIJINGANGSHIWU,DUIJINGANGSHITUCENGDEZHI LIANGHEZHANJIEXINGYOUJIDADEHAICHU。MehlmannDENGGUANCHADAO, ZAIJINGANGSHICHENJISHENGZHANGGUOCHENGZHONG,JITIZHONGDECoHUIXIANGTUCENGFANGXIANGKUOSAN,ZHISHITUCENGZHONGXINGCHENGXUDUOHANBAOHECDEQIUXINGCoLIZI,ZHEIHUIYANZHONGYINGXIANGJINGANGSHITUCENGDEZHILIANG。LINGWAI,CoDECUNZAIHAICUJINLETUCENGYUJITIDEJIEMIANSHANGXINGCHENGFEIJINGANGSHIWU,RUSHIMO,FEIJINGCDENG。CONGC-CoERYUANXIANGTUKEZHI,CZAICoZHONGYOUJIAODADERONGJIEDU,SUIZHEWENDUDEJIANGDI,CZAICoZHONGDERONGJIEDUXIAJIANG,XICHUDECHUIKUOSANDAOJITIBIAOMIAN,XINGCHENGZHANJIEXINGCHADELEISHIMOBOMO。CONGRELIXUESHANGLAIJIANG,ZAICHENJITIAOJIANXIASHIMOSHICDEWENDINGXINGTAI。YINCI,ZAICHENJILENGQUEGUOCHENGZHONG,CONGCoZHONGXICHUDECHUIKUOSANDAOJITIBIAOMIAN,XINGCHENGZHANJIEXINGCHADELEISHIMOBOMO。

ZUIHOU,JIAOGAOCANYUYINGLIDECHANSHENG,SHIYOUYURENZAOJINGANGSHITUCENGHEYINGZHIHEJINJITIDEREPENGZHANGXISHUXIANGCHAJIAODAZAOCHENGDE。JINGANGSHIDEXIANREPENGZHANGXISHUWEI3.1×106/℃,ERYINGZHIHEJINDEXIANREPENGZHANGXISHUWEI(415~711)×106/℃(SUICoHANLIANGBUTONGERBIANHUA)。JIEGUO,JINGANGSHITUCENGSHOUCANYUYAYINGLI,ERYINGZHIHEJINJITISHOUCANYULAYINGLI,CANYUYINGLIYUEDA,RENZAOJINGANGSHITUCENGYUYINGZHIHEJINJITIDEZHANJIEXINGYUECHA。

上述研究表明,在人造金刚石乐投英超沉积过程中,硬质合金基体中的Co,不仅影响人造金刚石涂层的质量,同时,对金刚石的形核与生长,以及粘结性都极为不利。因此,要改善金刚石涂层与硬质合金基体的粘结性,必须克服上述3个不利因素。其中,消除或减弱Co的负面影响,是解决问题的关健所在。

2 GAISHANZHANJIEXINGDEGEZHONGBIAOMIANYUCHULIFANGFAHETUJING

2.1JINSHIJITIBIAOMIANCHUQUCoXIANGHUOWCXIANG

乐投英超2.1.1 YIBUFACHUCo

CoYIRONGYUGEZHONGSUANHUOHUNHESUAN,RU:LIUSUAN、YANSUAN、XIAO SUANDENG,SHENGCHENGCoSUANYAN。SUOWEIDEYIBUFACHUCo,JIZHIYONGYI ZHONGSUANHUOHUNHESUANJIEZHI,DUIJITIBIAOMIANJINXINGYICIJINSHICHUCo,SHIYIZHONGJIANDAN、DILIANQIEJIAOYOUXIAODEBIAOMIANCHUCoFANGFA。SHANGSHIJI90NIANDAICHUQIYIQIANDEYANJIUBAODAOJIAODUO。BIAO1LIECHULEYOUGUANZHEIFANGMIANYANJIUDEXIANGXIQINGKUANG。

乐投英超2.1.2 ERBUFACHUCo

乐投英超JINGUANGEZHONGSUANHUOHUNHESUANKEYIRONGJIEQUCo,DANSHI,YINGZHIHEJINJITIBIAOMIANDEWCQUEBUYIBEISUANJINSHI。ZHONGSUOZHOUZHI,WCZAIJITIZHONGDEBILIGAODA85%YISHANG,ZAIBIAOMIANYEZHANYOU TONGYANGDEBILI。BIAOMIANDALIANGWCDECUNZAI,JIANGZUAIGEZHONGSUANDUICoDESHENRUJINSHI。GUJIANDANDEYIBUFAJINSHICHUCo,BUNENGYOUXIAO、SHENRUDICHUQUJITIBIAOMIANDECo。WEILEXIAOCHUWCDUISUAN JINSHIDEZUAIYINGXIANG,BIXUKAOLVSHOUXIANCHUQUWCXIANG。SHANGSHIJI90NIANDAIZHONGQIFAZHANQILAIDE、XIANYONGMurakamiJIJINSHICHUWCXIANG、ZAIYONGSUANJINSHICHUCoXIANGDEERBUFA,MUQIANYISHOUDAOSHIJIEGEGUODEGAODUZHONGSHI,BINGZAIYANJIUHEYINGYONGDANGZHONGQUDELEHENHAODEXIAOGUO。JINJINIANLAIYOUGUANERBUFADEYANJIUXIANGXIQINGKUANGJIANBIAO2。

乐投英超ERBUFACHUCoYOUBIJIAOHAODEXIAOGUO,DANSHI,HaubnerDENGRENWEIJINSHIFACHUCo,HUISHIJITIBIAOMIANCHANSHENGKONGXI,ZHEIXIEKONGXIZAITUCENGZHIHOURENGCANLIUZAIJITIYUTUCENGDEJIEMIANSHANG,YINGXIANGJITIYUTUCENGDEZHANJIEXIAOGUO。WEILEJIEJUEJIEMIANSHANGCANLIUKONGXIDEWENTI,ZAIJITIYUTUCENGZHIJIANXINGCHENGZHONGJIANGUODUCENGHUOZHONGJIANHUAHEWUDEYANJIUYINQILERENMENGUANGFANDEXINGQU。

2.2 ZAIJITIYUTUCENGZHIJIANXINGCHENGZHONGJIANGUODUCENGHUOZHONGJIANHUAHEWU

乐投英超YONGCVD,PVDHUOPCVDDENGGONGYIFANGFA,KEYIZAIYINGZHIHEJINJITIBIAOMIANSHANGZHIDEGEZHONGZHONGJIANGUODUCENGHUOZHONGJIANHUAHEWU,YOUXIAODIXIAOCHUHUOJIANRUOCoDEFUMIANYINGXIANG,GAISHANJINGANGSHITUCENGYUYINGZHIHEJINJITIDEZHANJIEXING。YOUGUANYANJIUXIANGJIANBIAO3。ZHIBEIDEGEZHONGZHONGJIANGUODUCENG,KEYIWANQUANFUGAIZAIJITIBIAOMIANSHANG,FANGZHICoDEFUMIANYINGXIANG,DANJINGANGSHIDEXINGHELVQUEHENDI,SHICHENJIBIANDEKUNNAN。

在基体表面原位形成各种稳定的Co中间化合物(如:硼化物、硅化物、铝化物等),看来是一种更好的改善人造金刚石乐投英超涂层与基体粘结效果的方法。文献介绍了表面原位CoxBy的形成,在沉积初始过程中,加入B化物[B(C2H5)3],可以促进人造金刚石的生长,虽然表面形成的CoxBy中间化合物很薄,却能有效地阻止Co相的迁移,并使Co的蒸气压下降几个数量级。但 是,在这种CoxBy中间化合物上生长的金刚石呈明显的片状,并没有改善金刚石涂层与硬质合金基体的 粘结性。看来有关这方面的研究仍需深入。

2.3 JITIBIAOMIANJIXIECHULIHUORECHULI

乐投英超2.3.1 JITIBIAOMIANJIXIECHULI

JITIBIAOMIANJIXIEYUCHULICHULECHANGYONGDEWEIFENPAOGUANGWAI,WENXIANJIESHAOLEYIZHONGXINYINGDESHUICHONGJIYINGZHIHEJINBIAOMIANDEJIXIEYUCHULIFANGFA,QIGONGYICANSHU:SHUIYALIWEI50MPa;SHUICHONGJISHIJIANWEI40s;PENZUIZHIBIAOMIANJULIWEI45mm;PENZUIZHIJINGWEI115mm;PENZUIJIAODUWEI20°。CAIYONGZHEIZHONGGONGYI,KEYISHIK10YINGZHIHEJINJITIBIAOMIANZHONGDECoHANLIANGJIANGDI50%,CONGERGAISHANJINGANGSHITUCENGYUJITIDEZHANJIEXIAOGUO。BUGUOGAIFANGFAZHISHIHEYUDICoYINGZHIHEJINDEBIAOMIANYUCHULI。

2.3.2 JITIBIAOMIANRECHULI

JITIBIAOMIANRECHULIDEYANJIUYOUBUSHAOBAODAO,XIAMIANFENBIEJIANDANJIESHAOYOUGUANJIGUANGRECHULI、DENGLIZITANDANGONGSHEN、YONGH2DENGLIZIYUANWEITUOTAN、DUOXINGQITIZHONGJIAREDENGFANGMIANDEYANJIU。

美国的DongGulee研究了用激光热处理WC-6%Co基体表面的过程。研究采用的工艺为:λ=248 nm;Τ=25ns;激光能量=117J/cm2~716J/cm2。用激光处理改变基体,在界面上创造三维热和成分梯度,是改善金刚石涂层与基体粘结效果的有效方法之一。研究结果表明,随着激光能量增加,基体表面的表面粗糙度增加,致使金刚石涂层的表面粗糙度也增加,结果改善了人造金刚石涂层与基体的粘结效果。

乐投英超RIBENDONGJINGDAXUEDETakayasuSatoDENGYANJIULEYONG TANDANGONGSHENDENGLIZIYUCHULIYINGZHIHEJIN(WC21%TaC25%Co)JITIDEGUOCHENG,YANJIUCAIYONGDEGONGYIRUXIA:DENGLIZIQIANGGONGLVWEI4MHz,5kW~10kW;QITIYALIHELIUSUWEI45Pa,100sccm;QITICHENGFENWEIN2∶C2H2=100∶0~90∶10;JITIWENDUWEI450℃~900℃;CHULISHIJIANWEI60min。

乐投英超XRDFENXIBIAOMING,YUCHULIZHIHOU,JITIBIAOMIANYOUCo2N HEWCXIANGCUNZAI,WEIFAXIANWCDEFENJIEFANYINGHEDULIDEW XIANGCUNZAI。Co2NDEXINGCHENG,YOUXIAODIFANGZHILECoDEYINGXIANG。YUCHULIWENDUWEI600℃,C2H2DENONGDUWEI5%SHI,XIAOGUOZUIJIA。SEMFENXIBIAOMING,YUCHULIQIANHOU,BIAOMIANDEBIAOMIANCUCAODUBIANHUABUDA。CHUANTONGJINSHICoXIANGDEFANGFA,CHUCoBUCHEDI,HUICHANSHENGFEIJINGANGSHIWU,RUFEIJINGTAN。YOUYUBUXUYONGHUAXUEFAJINSHICHUCo,GUJITIDEJIXIEQIANGDUBUHUIJIANGDI。

CappelliDENGYANJIULEJINSHICHUQUCoXIANGZHIHOU,ZAIQINGQI ZHONGYONGDENGLIZIDUIJITIBIAOMIANJINXINGYUANWEITUOTANCHULI,FAXIANCHEN JISHI,JITIBIAOMIANZHONGXINTANHUA,XINGCHENGXITANHUAWU,CONGERSHISHENGZHANGDEJINGANGSHIJINGTIGENGJIAWENDING[22]。TUOTANDUIJITIBIAOMIANCoHANLIANGYOUHENDAYINGXIANG,CONGERYINGXIANGYINGZHIHEJINDEZHILIANG[23]。DUIYUGAOTAN(C>6121%)YINGZHIHEJINLAISHUO,YUANWEITUOTANHOU,BIAOMIANCHANLIANGDIYUNEIBU,GUNEIBUDEYEXIANGDUOYUBIAOMIAN,ZAOCHENGYEXIANGXIANGBIAOMIANLIUDONG,JIEGUOJITIBIAOMIANDECoHANLIANGZENGGAO。ZHEISHUOMING,YINGZHIHEJINYUANWEITUOTANCHULIDUIJINGANGSHICHENJIDEYINGXIANG,HAIYOUDAIYUJINYIBUKAOCHA。

乐投英超ZAIDUOXINGQIFENZHONG,DUIJITIJINXINGRECHULI,YOUYUGAOWENZHENGFA,KEYICHUQUJITIBIAOMIANDECoXIANG,BINGSHIWCZHANGDA,DAOZHIJITIBIAOMIANDEBIAOMIANCUCAOZENGJIA。ZHEIYANGZHIDEDERENZAOJINGANGSHITUCENG(30ΛmHOUDU)SHIYANG,TUCENGYUJITIDEZHANJIEXINGDEDAOLEGAISHAN,ZAIJIAGONGYAGONGJINGAlHEJINSHI,QIXINGNENGYUPCD(20ΛmHOUDU)DEXIANGDANG。

H2DENGLIZIYUANWEITUOTANYUDUOXINGQITIZHONGJIAREZHEILIANGZHONGFANG FAYAOQIUYANGEKONGZHIGONGYI,YIDADAODUIBIAOMIANCENGSHENDUHECHENGFEN KONGZHI,ERQIEZHEILIANGZHONGFANGFADERECHULIGONGYIHENJIEJIN,JIAREWENDUWEI800℃~1000℃,BAOWENSHIJIANWEI30min~3h。

3 JIESHUYU

硬质合金基体中的Co是影响人造金刚石涂层与基体粘结性的关键因素,采用适当的表面预处理,可以从根本上有效地消除或减弱Co的负面影响,改善金刚石涂层与硬质合金基体的粘结性。浸蚀表面预处理,是一种简单、低廉、且适合于批量生产的方法。制备各种中间过渡层或中间化合物的表面预处理,可以消除浸蚀法产生的界面孔隙的影响,但如何消除中间过渡层对金刚石形核率的影响,仍值得进一步深入研究。表面机械或热处理,对工艺的要求十分严格,用于批量生产,需要增加设备投资。3种表面预处理方法各有千秋,由于各研究对象基体性能的差别,以及采用的涂层工艺和方法的不同,很难评价哪一种方法最佳。可以肯定的是,目前国外批量生产已采用的是浸蚀法。国内有关这方面的研究报道不多,深入系统地开展浸蚀法的研究,对我国人造金刚石涂层硬质合金产品的开发,具有深远的意义。

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