CN100543102C - 涂覆的磨料 - Google Patents
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Abstract
一种涂覆的超硬磨料,其包含:超硬研磨材料的芯—其通常是金刚石或cBN基的,与该超硬研磨材料的外表面化学结合的金属碳化物、氮化物或碳氮化物内层,和物理沉积在该内层上的钨外层。该内层在金刚石磨料芯的情况下优选是碳化钛涂层,或者在cBN磨料芯的情况下是氮化钛或硼化钛涂层。
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,降低或者中和了任何可能提高的颗粒保持性。然后,在涉及到高的温度或时间的情形中,在粘结基质还含有通常用作金刚石合成用的溶剂/催化剂的金属的情况下,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。
另外,为了使涂层保护金刚石颗粒,必须在粘结基质与颗粒之间形成阻挡层。换句话说,它应该是不可渗透的并且致密的,以使得粘结基质的组分不能通过并且与颗粒表面接触。这些组分能够通过涂层的一种方式是借助于固态扩散通过涂层。作为选择,如果涂层是不完整的、破裂的或者多孔的,则这些组分可能通过涂层到达颗粒表面。涂层最初可能是致密的并且不可渗透的,但是在烧结过程期间可能由于例如与粘结基质熔合而因此发生相变,这导致了形成较少致密的合金或者可能是多孔的涂层,其使得粘结基质组分通过涂层到达颗粒表面。
美国专利No.5,024,680描述了一种用于提高在工具基质中的保持性的多重涂覆的金刚石砂粒(grit)。该涂覆的砂粒包括:与金刚石化学结合的强的碳化物前体,优选铬的金属碳化物的第一涂层,和与该第一金属涂层化学结合的抗氧化性碳化物前体,优选钨、钽或钼的第二金属涂层。可以加入合金金属例如镍的第三金属涂层。该涂覆的砂粒通过以下方式制备:通过金属汽相沉积将第一金属层涂覆在砂粒上,随后通过化学汽相沉积涂覆第二层金属。
众所周知的是一些元素比如Fe、Co和Ni可以将金刚石石墨化。在将碳化铬用作涂料的情形中,其对例如在铁的情况下防止这类石墨化并不特别有效,这限制了它的有效性。
该第二层还特别是厚的层。因此必须具有与第一层化学结合的第二层,这需要采用高温涂覆方法或者单独的加热步骤以产生这种化学结合。
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、氮化物或碳氮化物内层,和物理沉积在该内层上的钨外层。
优选通过物理汽相沉积来涂覆该外层。
该超硬研磨材料可以为金刚石或cBN基的。
内层在金刚石磨料芯的情况下优选是碳化钛涂层,或者在cBN磨料芯的情况下是氮化钛或硼化钛涂层。
由于外部的钨涂层通过物理汽相沉积涂覆,因此没有一部分钨涂层特别是钨涂层的内部被碳化。从而其形成了用于保护内层和基质的优良阻挡层。
外层的厚度一般为约0.05μm-约10μm,特别约0.2μm-约1μm。
优选实施方案的描述
以钛或碳化钛或者钛或氮化钛、硼化钛或硼氮化钛形式的Ti已经表现为是可分别用于金刚石和cBN基质的涂覆材料。由于它们能够化学结合在基质上、保护基质并且提高基质与粘结剂例如青铜或基质元素之间的粘结性,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高数量的铁类金属的情况下。
已经发现,钛基涂料的优点可以延伸至在将钨外涂层涂覆在钛基涂层上的情况下的其他应用。在以下情况下特别是这样的: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。这在以下情况下也是有用的:在金刚石颗粒的情况下,在涂覆的含金刚石的磨料部分烧结期间碳化钛涂料将被基质材料的组分例如青铜反应掉;钛基涂料将被用于形成涂覆的含金刚石的渗透性粉末金属部件例如采矿勘探钻孔用的钻头的液态浸透剂反应掉;或者钛基涂料将被用于使超磨蚀的组分固定在另一种金属或陶瓷材料上的青铜反应掉。
外部的钨层不具有碳化的内部,由于外层的目的主要是作为用于保护内层和基质的阻挡层并且通过保持薄的外部涂层可以获得足够的夹层粘结,因此这不是必须的。外层具有约0.05μm-约10μm,特别约0.2μm-约1μm的厚度。
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或低温CVD方法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。
使用冷涂覆技术例如优选的低温CVD法或PVD将钨外层沉积。这是一种低温方法,在其中产生了不足以造成显著的碳化物形成的热。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法的一个例子是溅射涂覆。在该方法中,通过激发源例如磁控管而产生钨金属蒸汽的熔剂(flux)。一些制品例如超磨蚀的砂粒或者放置在熔剂中的组件变成被钨金属覆盖。
本发明的涂覆的磨料的例子包括:
i)涂覆有碳化钛和钨的金刚石锯切砂粒(卤化物气体碳化钛涂层,随后将钨物理沉积(PVD))。尤其是具有高的青铜基质或者当采用渗透生产方法时用于生产锯切或钻孔用的研磨部件。
ii)涂覆有碳化钛和钨的金刚石磨轮砂粒或微米砂粒(卤化物气体碳化钛涂层,随后将钨物理沉积)。尤其是当采用青铜粘结时用于生产砂轮。
iii)涂覆有氮化钛或硼化钛(单独或者结合地)和钨的cBN磨轮砂粒或微米砂粒(卤化物气体钛基涂层,随后将钨物理沉积)。尤其是当采用青铜粘结时用于生产砂轮。
iv)碳化钛加上钨涂覆的PCD。用作将碳化钨半成品铜焊用的切削工具插件。
v)氮化钛或硼化钛(单独或者结合地)加上钨涂覆的PCBN。用作将碳化钨半成品铜焊用的切削工具插件。
vi)碳化钛加上钨涂覆的CVD或单晶。用作将碳化钨半成品铜焊用的切削工具插件,或者用作烧结或铜焊成打磨机柱台(dresser post)的打磨机原木(dresser log)。
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、40/45US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10,000克拉40/45 US筛目大小的该TiC涂覆的金刚石放置在带有旋转圆筒和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。将溅射功率升高至5000W,同时使圆筒旋转以确保在所有金刚石颗粒上均匀涂覆。在溅射7.5小时后,在从腔室中取出之前将涂覆的金刚石冷却10小时。
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些微黯淡的金属银/灰色。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具有非常光滑的表面形态的均匀涂层。颗粒破裂并且在SEM上观察涂层横截面。可以看见两个明显的涂层。测量该涂层的钨部分具有约0.45微米的厚度。该特定的涂层得到了5.9%的测定结果。用于该批料的这种尺寸的TiC涂层通常具有0.77%的测定结果。因此,5.9%的剩余值归因于TiC内层顶上的钨层。当使用XRD分析时,发现了金刚石、TiC和W。XRF分析表现出87%的W和13%的Ti。
Claims (5)
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、氮化物或碳氮化物内层,和物理沉积在该内层上的钨外层,其中没有一部分钨涂层被碳化,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,其中通过物理汽相沉积使外层沉积。
3.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况下是碳化钛涂层,或者在cBN基的芯的情况下是氮化钛或硼化钛涂层。
4.根据权利要求1或2的涂覆的超硬磨料,其中外层的厚度为0.05μm-10μm。
5.根据权利要求1或2的涂覆的超硬磨料,其中外层的厚度为0.2μm-1μm。
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EP1709136B1 (en) * | 2004-01-15 | 2008-03-26 | Element Six Limited | Coated abrasives |
KR20100022072A (ko) | 2007-05-22 | 2010-02-26 | 엘리먼트 씩스 리미티드 | 코팅된 cbn |
WO2009013716A2 (en) * | 2007-07-23 | 2009-01-29 | Element Six Limited | Placing of superhard material |
WO2009013714A1 (en) * | 2007-07-23 | 2009-01-29 | Element Six Limited | Air brazeable material |
DE102008039459B4 (de) * | 2008-08-25 | 2014-06-26 | Center For Abrasives And Refractories Research & Development C.A.R.R.D. Gmbh | Beschichtete Feststoffpartikel |
GB0903822D0 (en) | 2009-03-06 | 2009-04-22 | Element Six Ltd | Polycrystalline diamond body |
US9004199B2 (en) * | 2009-06-22 | 2015-04-14 | Smith International, Inc. | Drill bits and methods of manufacturing such drill bits |
US8689909B2 (en) * | 2010-10-29 | 2014-04-08 | Baker Hughes Incorporated | Inserts, polycrystalline diamond compact cutting elements, earth-boring bits comprising same, and methods of forming same |
GB2509790B (en) | 2013-03-27 | 2015-02-25 | Hardide Plc | Superabrasive material with protective adhesive coating and method for producing said coating |
WO2016003439A1 (en) * | 2014-07-01 | 2016-01-07 | Diamond Innovations, Inc. | Glass coated cbn abrasives and method of making them |
CN104669129B (zh) * | 2015-02-11 | 2018-06-22 | 河南富莱特超硬磨具有限公司 | 一种陶瓷镀钛cbn砂轮及其制备方法 |
DE102017201487A1 (de) | 2017-01-31 | 2018-08-02 | Gühring KG | Verfahren zum Beschichten von soliden Diamantwerkstoffen |
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 |
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- 2005-01-13 UA UAA200608934A patent/UA83722C2/ru unknown
- 2005-01-13 JP JP2006548467A patent/JP4790630B2/ja not_active Expired - Fee Related
- 2005-01-13 DE DE602005019851T patent/DE602005019851D1/de active Active
- 2005-01-13 ZA ZA200605820A patent/ZA200605820B/xx unknown
- 2005-01-13 WO PCT/IB2005/000056 patent/WO2005078041A1/en active Application Filing
- 2005-01-13 CN CNB2005800064977A patent/CN100543102C/zh active Active
- 2005-01-13 EP EP05702226A patent/EP1709135B1/en active Active
- 2005-01-13 RU RU2006129353/02A patent/RU2368489C2/ru not_active IP Right Cessation
- 2005-01-13 AU AU2005213529A patent/AU2005213529A1/en not_active Abandoned
- 2005-01-13 AT AT05702226T patent/ATE460468T1/de not_active IP Right Cessation
- 2005-01-13 US US10/586,394 patent/US20070160830A1/en not_active Abandoned
- 2005-01-13 KR KR1020067014945A patent/KR101104051B1/ko not_active IP Right Cessation
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KR20070003834A (ko) | 2007-01-05 |
JP4790630B2 (ja) | 2011-10-12 |
CA2553564A1 (en) | 2005-08-25 |
CA2553564C (en) | 2012-08-07 |
UA83722C2 (ru) | 2008-08-11 |
RU2006129353A (ru) | 2008-02-20 |
ZA200605820B (en) | 2009-01-28 |
IL176854A0 (en) | 2006-10-31 |
EP1709135A1 (en) | 2006-10-11 |
WO2005078041A1 (en) | 2005-08-25 |
EP1709135B1 (en) | 2010-03-10 |
RU2368489C2 (ru) | 2009-09-27 |
CN1926215A (zh) | 2007-03-07 |
US20070160830A1 (en) | 2007-07-12 |
AU2005213529A1 (en) | 2005-08-25 |
JP2007517954A (ja) | 2007-07-05 |
ATE460468T1 (de) | 2010-03-15 |
KR101104051B1 (ko) | 2012-01-06 |
DE602005019851D1 (de) | 2010-04-22 |
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