CN100564475C - 涂覆的磨料 - Google Patents
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Abstract
一种涂覆的超硬磨料,其包含:超硬研磨材料,通常是金刚石或cBN基的芯,与该超硬研磨材料的外表面化学结合的金属碳化物、氮化物、硼化物或碳氮化物的内层,和金属碳氮化物特别是碳氮化钛的外层。优选通过物理汽相沉积来涂覆该外层。该内层由当使用热涂覆方法涂覆时能够在研磨材料的表面形成(单独或者结合地)碳化物、氮化物或硼化物的元素形成。
Description
发明背景
本发明涉及涂覆的磨料、它们的制备方法,以及用在含磨料工具中的涂覆的磨料。
磨料颗粒例如金刚石和立方氮化硼被普遍用于切削、研磨、钻孔、锯切和抛光应用。在这些应用中,将磨料颗粒与金属粉末混合物混合,然后在高温下烧结以形成粘结的切削元件。典型的粘结基质包含铁、钴、铜、镍和/或其合金。
在这些应用中的普遍问题是在烧结过程和随后的应用期间这些颗粒在粘结基质中的保留和对氧化性侵蚀的抵抗性。
通常通过用化学结合到颗粒上并熔合到粘结基质上的金属或合金涂覆磨料颗粒来解决这些问题。一般而言,使用化学汽相沉积(CVD)或物理汽相沉积(PVD溅射涂覆)技术。碳化钛是由于其对金刚石的优良粘合性而因此被提出作为磨料颗粒的涂料的一种材料的例子。碳化铬是可以使用的类似的涂料。
伴随着在粘结基质含有青铜或Cu的情况下使用碳化钛涂料的问题是这些材料会与碳化钛反应,这使得其可能被反应掉。然后,在粘结基质由被通常用作金刚石合成用的溶剂/催化剂的金属组成的情况下,金刚石颗粒容易受到金刚石颗粒表面石墨化的影响。这些金属的例子是Fe、Co和Ni。在熔融状态下,这些金属能够使金刚石溶解,金刚石当冷却时沉淀而形成石墨。该金刚石表面的石墨化过程不仅削弱了颗粒,而且还导致了颗粒在粘结中较差的保留。
在切削工具的生产期间,例如在含有金刚石颗粒的锯的部件的烧结期间,氧气可能作为表面氧化物、溶解于形成粘结基质的金属粉末中的氧气或以气态形式存在,或者由于涂覆碳化钛涂料的结果而以其本身存在。在烧结温度下,该氧气容易侵蚀金刚石颗粒的表面,这削弱了颗粒。
发明概述
一种涂覆的超硬磨料,其包含:超硬研磨材料的芯,与该超硬研磨材料的外表面化学结合的金属碳化物、氮化物、硼化物或碳氮化物的内层,和金属碳氮化物特别是碳氮化钛的外层。
优选通过物理汽相沉积来涂覆该外层。
该超硬研磨材料一般为金刚石或cBN基的,并且可以包括:金刚石或cBN砂粒(grit)、PCD基质、热稳定的PCD(TSPCD)基质、PcBN基质、CVD金刚石膜、单晶金刚石基质。
内层由当使用热涂覆方法作为内层涂覆时能够在研磨材料的表面形成(单独或者结合地)碳化物、氮化物或硼化物的元素形成。一般而言,这些元素来自于周期表的IVa、Va、VIa、IIIb和IVb族。内层在金刚石磨料芯的情形下优选是碳化钛或碳化铬涂层,或者在cBN磨料芯的情形下优选是氮化钛、硼化钛或硼氮化钛或者氮化铬、硼化铬或硼氮化铬涂层,尽管也可以使用其他金属例如钒、钼、钽、铟、锆、铌、钨、铝、硼或硅。
优选实施方案的描述
尽管本发明延伸至各种形式的涂覆的研磨材料,但为了方便,大部分将参照金刚石砂粒涂料来描述。
以碳化钛或者氮化钛和硼化钛形式的Ti已经表现为是可分别用于金刚石和cBN基质的涂覆材料。由于它们化学结合在基质上和保护基质的能力,因此它们特别地有用。然而正如在前已经提及的那样,它们并不适合于某些应用,特别是在青铜或铜的存在下在侵蚀性的烧结条件中将它们烧结的情况下,和在粘结基质含有例如铁类金属的情况下或者在氧气的存在下。
已经发现,钛涂料的优点可以延伸至在将金属碳氮化物特别是碳氮化钛的外涂层涂覆在钛涂层上的情况下使用金刚石砂粒的其他应用。在以下情形下特别是这样的:将金刚石砂粒用于含有铁类金属的金属粘结基质中以在烧结时形成研磨工具组件。这由其金属粘结基质形成了对Co、Fe和Ni扩散的阻挡层,这使得即使在烧结条件需要长的烧结时间和高温的情况下其也可以少的Cu含量用于Fe、Co和Cu热压工艺和用于纯铁粘结。这在碳化钛涂料的情况下也是有用的,在金刚石颗粒的情况下其将被金属材料的组分例如材料的青铜和铜焊料反应到另一种金属或陶瓷材料上,或者将粉末烧结或渗透以形成渗透的粉末材料。
其尤其可用于生产金刚石注入的(impregnated)工具例如锯条部件,钻孔机,金刚石线(diamond wire)的珠粒,尤其是在高含量的青铜或铜限制了碳化钛涂料的可用性、铜焊的金刚石层工具例如铜焊的金刚石线珠粒的制备、含有金刚石的金属基质复合物的制备、金刚石材料的铜焊例如将TSPCD、PCD和金刚石钻石粘结在钻体上、将CVD、单晶、TSPCD和PCD粘结在锯条、刀架、钻体等上的情况下。
另外,涂覆的金刚石注入的工具产生了改进的性能例如更长的工具寿命和更高的生产力。与需要排除氧气的含Ti的活性铜焊相反,将本发明的涂覆的金刚石颗粒用于铜焊应用使得能够采用在空气中进行的简单铜焊。
优选使用用于涂覆内层的热涂覆方法和用于涂覆外层的PVD方法而形成涂覆的磨料颗粒。
金刚石砂粒颗粒是常规用于生产金属粘结的工具的那些。它们通常是均匀大小的,一般为0.1-10mm。这类金刚石砂粒颗粒的例子包括:0.1-60微米的微米砂粒、40微米-200微米的磨轮砂粒、180微米-2毫米的锯切砂粒、1毫米-10毫米的单晶、几平方毫米-至多200毫米直径圆盘的CVD插件、几平方毫米-104毫米直径圆盘的PCD插件、0.1-60微米的微米范围的cBN砂粒、40微米-200微米的磨轮砂粒、几毫米-至多104mm直径圆盘的PCBN插件。
在热涂覆方法中首先将金刚石颗粒涂覆以提供内层,该内层可以是金属层或者金属碳化物、氮化物或碳氮化物层。在cBN的情形中,这种内涂层将通常是金属氮化物或硼化物或者硼氮化物层。在该热涂覆方法中,在用于进行这种粘结的合适的热条件下将金属基的涂料涂覆在金刚石基质上。可以使用的典型热涂覆技术包括:例如涉及由金属卤化物气相沉积的方法、CVD法或热扩散真空涂覆或者金属汽相沉积方法。优选的是由金属卤化物气相沉积和CVD法。
在涉及由金属卤化物气相沉积的方法中,在合适的气态环境(例如包含一种或多种以下条件的非氧化环境:惰性气体、氢气、烃、减压)中将要被涂覆的颗粒暴露于含有要被涂覆的金属(例如Ti)的金属卤化物下。该金属卤化物可由作为该方法一部分的金属生成。
将混合物进行热循环,在这期间金属卤化物将Ti传送到颗粒的表面,在那里其被释放并且化学结合在颗粒上。
使用CVD法或者冷涂覆技术例如优选的PVD将外金属碳氮化物层沉积。这是一种低温方法,在其中产生了不足以使得碳化物显著地化学结合在基质上的热。因此,如果单独使用,则其将导致对金刚石颗粒差的粘合性。用于涂覆外涂层的PVD法的一个例子是活性溅射涂覆:其中在涂覆期间引入活性气体例如烃气体和/或氮气。气体与通过溅射方法形成的金属蒸汽反应,使得碳氮化物沉积。在该方法中,可以将Ti∶(C,N)和C∶N的比例最优化以进一步增强外层的性能。
外层通常由来自于IVa、Va、VIa族金属例如钛和铬、来自于IIIb和IVb族金属例如铝以及一些元素例如硼和硅的碳化物、氮化物、硼化物、氧化物和硅化物(单独或者结合地)组成,但优选由碳化钛、碳氮化钛、氮化钛、硼化钛或硼氮化钛组成。
现在将参照以下非限定性实施例仅仅作为例子来描述本发明。
实施例
在CVD法中将来自于Element Six的、40/45 US筛目大小的金刚石砂粒涂覆,以根据本领域普遍公知的常用方法制得TiC涂覆的金刚石。然后将该CVD TiC涂覆的金刚石用作第二涂覆步骤用的基质。
将1,000克拉40/50 US筛目大小的该TiC涂覆的金刚石放置在带有旋转圆筒、带有大的纯钛金属板作为目标物的磁控管溅射涂覆机中。将涂覆腔室排空、引入氩气并且打开电源以形成等离子体。在目标物上将溅射功率升高至10A(400V),同时使圆筒旋转以确保在20sccm氩气压力下在所有金刚石颗粒上均匀涂覆。在5sccm下将C4H10气体与氮气一起引入以实现70%的光发射测量值。将与碳和氮气反应的钛连续溅射2小时。之后,在从腔室中取出之前将涂覆的金刚石冷却。
对该涂覆的金刚石进行分析,这由X-射线衍射法、X-射线荧光法、涂层的化学测定、光学和扫描电子显微图像分析和颗粒破裂及随后在SEM上进行横截面分析所组成。
肉眼看出该涂层表现出暗红色/类似铜的颜色。该颜色表现出均匀分布于每一颗粒上,并且每一颗粒表现出是相同的。该涂层看起来是均匀的并且没有任何未涂覆的区域。SEM上的观察再次表现出带有稍微粗糙的表面形态的均匀涂层。在SEM上还观察到破裂的颗粒。两层结构清楚地显现,TiCN层的厚度约0.2微米。该特定的涂层得到了1.03%的测定结果。用于该批料的这种尺寸的TiC涂层通常具有0.45%的测定结果。因此,1.03%的剩余值归因于TiC顶上的TiCN层。当使用XRD分析时,发现了TiC和TiCN。XRF分析表现出100%的Ti。
Claims (9)
1.一种涂覆的超硬磨料,其包含:超硬研磨材料的芯,与该超硬研磨材料的外表面化学结合的金属碳化物、氮化物或硼化物的内层,和沉积在该内层上的金属碳氮化物的外层,其中所述超硬研磨材料是金刚石或cBN基的超硬研磨材料。
2.根据权利要求1的涂覆的超硬磨料,其中外层由碳氮化钛形成。
3.根据权利要求1或2的涂覆的超硬磨料,其中通过物理汽相沉积使外层沉积。
4.根据权利要求1或2的涂覆的超硬磨料,其中超硬研磨材料选自:金刚石或cBN砂粒、PCD基质、热稳定的PCD基质、PcBN基质、CVD金刚石膜,和单晶金刚石基质。
5.根据权利要求1或2的涂覆的超硬磨料,其中使用热涂覆方法由能够在研磨材料的表面单独或者结合地形成碳化物、氮化物或硼化物的元素形成内层。
6.根据权利要求5的涂覆的超硬磨料,其中该元素选自周期表的IVa、Va、VIa、IIIb和IVb族。
7.根据权利要求1或2的涂覆的超硬磨料,其中该内层在金刚石基的芯的情形下是碳化钛或碳化铬涂层,或者在cBN基的芯的情形下是氮化钛、硼化钛或硼氮化钛或者氮化铬、硼化铬或硼氮化铬涂层。
8.根据权利要求1的涂覆的超硬磨料,其中该内层是碳化钛或碳化铬涂层,且该芯是金刚石基的。
9.根据权利要求1的涂覆的超硬磨料,其中该内层是氮化钛、硼化钛或硼氮化钛或者氮化铬、硼化铬或硼氮化铬涂层,且该芯是cBN基的。
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US (2) | US20070160839A1 (zh) |
EP (1) | EP1709136B1 (zh) |
JP (1) | JP4861831B2 (zh) |
KR (1) | KR101114680B1 (zh) |
CN (1) | CN100564475C (zh) |
AT (1) | ATE390468T1 (zh) |
AU (1) | AU2005213530A1 (zh) |
CA (1) | CA2553566C (zh) |
DE (1) | DE602005005634T2 (zh) |
ES (1) | ES2304684T3 (zh) |
IL (1) | IL176850A0 (zh) |
RU (1) | RU2372371C2 (zh) |
UA (1) | UA83414C2 (zh) |
WO (1) | WO2005078042A1 (zh) |
ZA (1) | ZA200606016B (zh) |
Families Citing this family (11)
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WO2008077135A1 (en) * | 2006-12-19 | 2008-06-26 | Acme United Corporation | Cutting instrument |
US20100275523A1 (en) * | 2007-03-22 | 2010-11-04 | Klaus Tank | Abrasive compacts |
CN102061466B (zh) * | 2009-11-12 | 2014-07-30 | 三菱综合材料株式会社 | 表面包覆切削工具 |
TW201412633A (zh) * | 2012-06-30 | 2014-04-01 | Diamond Innovations Inc | 獨特立方氮化硼晶體與製造彼之方法 |
GB201215469D0 (en) * | 2012-08-30 | 2012-10-17 | Element Six Ltd | Diamond constructions, tools comprising same and method for making same |
JP5784679B2 (ja) * | 2013-08-12 | 2015-09-24 | エレメント シックス アブラシヴェス エス.エー. | 多結晶質研磨材料成形体 |
JP6880652B2 (ja) * | 2016-10-26 | 2021-06-02 | 富士フイルムビジネスイノベーション株式会社 | 転写装置及び画像形成装置 |
JP6922184B2 (ja) * | 2016-10-26 | 2021-08-18 | 富士フイルムビジネスイノベーション株式会社 | クリーニングブレード及び画像形成装置 |
JP6968346B2 (ja) * | 2017-08-01 | 2021-11-17 | 福井県 | 工具用ダイヤモンド粒及びその製造方法 |
CN109202754B (zh) * | 2018-10-31 | 2021-01-22 | 长沙理工大学 | 一种磨粒预沉积TiN的电镀CBN砂轮及其制备方法 |
CN114634796A (zh) * | 2022-02-18 | 2022-06-17 | 厦门雷昂科技有限公司 | 一种改性金刚石磨粒的制备方法 |
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2005
- 2005-01-13 ES ES05702227T patent/ES2304684T3/es active Active
- 2005-01-13 EP EP05702227A patent/EP1709136B1/en active Active
- 2005-01-13 CN CNB2005800047280A patent/CN100564475C/zh not_active Expired - Fee Related
- 2005-01-13 US US10/586,393 patent/US20070160839A1/en not_active Abandoned
- 2005-01-13 CA CA2553566A patent/CA2553566C/en not_active Expired - Fee Related
- 2005-01-13 AT AT05702227T patent/ATE390468T1/de active
- 2005-01-13 UA UAA200608935A patent/UA83414C2/uk unknown
- 2005-01-13 AU AU2005213530A patent/AU2005213530A1/en not_active Abandoned
- 2005-01-13 ZA ZA200606016A patent/ZA200606016B/en unknown
- 2005-01-13 DE DE602005005634T patent/DE602005005634T2/de active Active
- 2005-01-13 WO PCT/IB2005/000057 patent/WO2005078042A1/en active IP Right Grant
- 2005-01-13 RU RU2006129350/04A patent/RU2372371C2/ru not_active IP Right Cessation
- 2005-01-13 KR KR1020067014943A patent/KR101114680B1/ko not_active IP Right Cessation
- 2005-01-13 JP JP2006548468A patent/JP4861831B2/ja not_active Expired - Fee Related
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2006
- 2006-07-13 IL IL176850A patent/IL176850A0/en unknown
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2009
- 2009-04-30 US US12/432,805 patent/US20090205260A1/en not_active Abandoned
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US20030192259A1 (en) * | 2000-12-04 | 2003-10-16 | D'evelyn Mark Philip | Abrasive diamond composite and method of making thereof |
Also Published As
Publication number | Publication date |
---|---|
ZA200606016B (en) | 2007-11-28 |
CN1918259A (zh) | 2007-02-21 |
JP4861831B2 (ja) | 2012-01-25 |
DE602005005634T2 (de) | 2009-05-14 |
RU2372371C2 (ru) | 2009-11-10 |
AU2005213530A1 (en) | 2005-08-25 |
WO2005078042A1 (en) | 2005-08-25 |
RU2006129350A (ru) | 2008-02-20 |
EP1709136A1 (en) | 2006-10-11 |
JP2007517955A (ja) | 2007-07-05 |
CA2553566A1 (en) | 2005-08-25 |
IL176850A0 (en) | 2006-10-31 |
ES2304684T3 (es) | 2008-10-16 |
UA83414C2 (uk) | 2008-07-10 |
EP1709136B1 (en) | 2008-03-26 |
KR101114680B1 (ko) | 2012-03-05 |
KR20070003833A (ko) | 2007-01-05 |
US20070160839A1 (en) | 2007-07-12 |
ATE390468T1 (de) | 2008-04-15 |
US20090205260A1 (en) | 2009-08-20 |
CA2553566C (en) | 2012-06-19 |
DE602005005634D1 (de) | 2008-05-08 |
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