CN101605918B - 多晶金刚石(pcd)材料 - Google Patents

多晶金刚石(pcd)材料 Download PDF

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CN101605918B
CN101605918B CN2008800040270A CN200880004027A CN101605918B CN 101605918 B CN101605918 B CN 101605918B CN 2008800040270 A CN2008800040270 A CN 2008800040270A CN 200880004027 A CN200880004027 A CN 200880004027A CN 101605918 B CN101605918 B CN 101605918B
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H·S·L·斯赫比
K·乃杜
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Abstract

本发明用于包含粘结金刚石颗粒的第一相和散布在第一相之间的第二相的多晶金刚石材料。该第二相含有金属钒形式或碳化钒形式或碳化钒钨形式或者两种或更多种这些形式的钒，并且该第二相可以在该多晶金刚石材料中以该材料的1-8质量％存在。

Description

多晶金刚石(PCD)材料
发明背景
本发明涉及具有改善的抗磨损性、抗氧化性以及热稳定性的多晶金刚石(PCD)材料的制备。
多晶金刚石材料在本领域中是公知的。常规地，通过如下方式形成PCD：将金刚石颗粒与合适的粘合剂/催化剂结合产生生坯，并使该生坯经受高的温度和压力以使粘合剂/催化剂能够促进颗粒之间的晶间金刚石与金刚石粘结。所述高的温度和压力通常是金刚石处于热力学稳定的那些温度和压力。烧结的PCD具有足够的抗磨损性和硬度以用于侵蚀性磨损、切削和钻孔应用。
用于PCD的粘合剂/催化剂一般是VIII族金属，Co是最常见的。常规地，PCD含有80-95体积％金刚石，其余是粘合剂/催化剂。
将金刚石、粘合剂/催化剂和任何附加的添加剂混合的最常见方法包括球磨。与此伴随的问题是，最通常产生金刚石、粘合剂/催化剂和任何添加剂的不均匀分布。这导致烧结产生具有降低的性能例如抗磨损性、韧性、抗氧化性和热稳定性的较差PCD材料(由瑕疵的存在所证明)。
困扰PCD的问题是热劣化。存在多种热劣化的诱因，一个这样的诱因是PCD基质中金刚石的石墨化。已知金刚石的石墨化是由粘合剂/催化剂与金刚石的反应诱发的。这一般发生在约750℃。热劣化的另一个诱因是金刚石的氧化和粘合剂/催化剂的氧化。
上述问题的一个解决方案从烧结的PCD的表面除去粘合剂/催化剂。这包括初始烧结PCD，然后对PCD进行酸处理以除去粘合剂/催化剂。这是个多阶段过程。以一个步骤产生热稳定的PCD将是有益的。
GB 2408735公开了如下的PCD材料，该材料包含粘结金刚石晶体的第一相、以及用于促进金刚石粘结的粘合剂/催化剂材料和与该粘合剂/催化剂反应的材料之间的反应产物的第二相。据称，该反应产物具有与粘合剂/催化剂材料相比更接近粘结金刚石的热膨胀系数，因此提供更加热稳定的PCD。在烧结前将粘合剂/催化剂和反应材料与金刚石一起球磨。说明书中提供的唯一实施例是使用Si和SiC作为与粘合剂/催化剂反应的材料。建议可使用钒，但没有提供给出该工艺细节的实施例。另外，建议形成金属间化合物VCo3、VCo和V3Co。
US 6454027公开了包含多个由PCD、PCBN或其混合物形成的微粒的PCD材料。这些微粒进一步分布在由金属陶瓷材料形成的连续第二基质内。给出的金属陶瓷的例子是WC，然而还可使用碳化钒。形成这种烧结坯体的目的是相对于常规PCD材料改善断裂韧性和抗碎裂性的性能而基本上不损害抗磨损性。
GB 2372276描述了含有第一相和第二相的PCD的制备，所述第一相包含多晶金刚石，所述第二相选自氧化物细粒、金属碳化物和金属细粒、氮化物、或它们的混合物。该PCD对于轧辊和锤钎头显示出改善的韧性。该专利的公开内容关注于提高的韧性而不牺牲抗磨损性。
US 4643741公开了通过将预处理的金刚石晶体与硅粉末一起混合，使该混合物经受高压和高温而形成的多晶金刚石本体。该热稳定多晶金刚石本体的特征在于金刚石晶体均匀分布在该本体内。此外，金刚石晶体被β-碳化硅覆盖。
CA 2553567公开了制备涂覆的超硬研磨材料的方法。使用金属卤化物气相沉积、CVD法和热扩散法由周期表的IVa、Va、VIa、IIIb和IVb族元素使磨料颗粒涂覆有内层。钒属于要求涂覆到该研磨材料上的金属。
WO 2006032984描述了用基质前体材料涂覆磨料颗粒，然后进行处理使所述磨料颗粒适合于烧结。该基质前体材料可转变为氧化物、氮化物、碳化物、氧氮化物、碳氧化物、或碳氮化物、或其单质形式。例如然后可将氧化物转变为碳化物。
发明概述
根据本发明，提供了一种多晶金刚石材料(PCD材料)，该多晶金刚石材料包含粘结的金刚石颗粒的第一相，和散布在第一相之间的第二相，该第二相含有金属形式、碳化物形式或碳化钒钨形式的钒，或者两种或更多种这些钒形式的混合物。该PCD材料具有优异的抗氧化性、抗磨损性和热稳定性。
碳化钒钨可以是混合碳化物形式或者作为碳化钒钨化合物。
PCD材料中存在的金属形式或碳化钒形式或碳化钒钨形式的钒的量通常为该材料的1-8质量％，更优选2-6质量％。
本发明的要点是存在金属形式、碳化钒形式或碳化钒钨形式的钒。第二相基本上没有任何钒金属间化合物例如钒钴金属间化合物。任何这样的金属间化合物是不可通过XRD分析检测到的。
第二相将优选含有金刚石催化剂以辅助第一相中金刚石与金刚石粘结的产生。优选的金刚石催化剂是钴、铁和镍或含有这样的金属的合金。在本发明的该形式中，第二相优选基本上仅由金刚石催化剂和一种或多种钒形式的钒构成。第二相中的任何其它组分仅以痕量存在。
优选钒或碳化钒或碳化钒钨的氧含量尽可能低。优选地，钒或碳化钒或碳化钒钨的氧含量小于1000ppm，优选小于100ppm且更优选小于10ppm。这可通过确保在烧结的初生(green)状态产物中使用或存在纯钒或碳化钒得以实现。
金刚石颗粒可以是单峰的，即该金刚石将具有单一的平均颗粒尺寸，或者是多峰的，即该金刚石将包含具有多于一种平均颗粒尺寸的颗粒的混合物。
本发明的PCD材料优选呈粘结到胶结碳化物基材表面的PCD层形式，从而形成复合金刚石坯体。粘合剂/催化剂的来源将典型地(至少部分)来自碳化物基材。该碳化物优选为碳化钨形式，所述碳化钨是用于第二相的钨的来源。
可以通过如下方式制得本发明的PCD材料：通过使金刚石颗粒物料与可含有钒或碳化钒的第二相材料接触，形成初生状态产物，并使该初生状态产物经受适于产生PCD的提高的温度和压力条件，在该条件下金刚石为热力学稳定的。初生状态产物的氧含量优选尽可能低并优选低于上述极限。
第二相材料还可以含有金刚石催化剂。
附图简要描述
图1是本发明PCD材料的实施方案的SEM分析；
图2图解了热稳定性测试的结果，
图3图解了抗磨损性测试的结果，
图4图解了抗氧化性测试的结果，和
图5是本发明PCD材料的另一个实施方案的SEM分析。
优选实施方案的描述
本发明涉及通过将钒或碳化钒或碳化钒钨纳入第二相中来改进PCD材料。纳入这些多种形式的钒的结果是，制备的PCD材料将具有改善的抗磨损性、抗氧化性和热稳定性。
可在烧结前将钒或碳化钒引入材料或初生状态产物内。钒或碳化钒的这些引入方法包括本领域中公知的机械混合和碾磨技术，例如球磨(湿式或干式)、振动磨和磨碎机碾磨(attritor milling)。还可以使用其它技术例如使选择的碳化钒结合到PCD起始材料内的前体法。这些技术包括国际公开WO 2006032984中描述的方法。
可以使用包括PVD、CVD和电沉积的另外的已知技术。
尤其对于碳化钒，认为非常有利的特别方法包括使用例如溶胶-凝胶技术使金刚石颗粒涂覆有水合氧化物前体材料。这些描述于国际公开WO2006032984中的前体可易于转变为非常细的颗粒(包括纳米碳化钒)的紧密组合体。紧密的金刚石-碳化钒涂层可包括如下形式：粘着涂覆有碳化钒的金刚石，或附着到金刚石表面的纳米碳化钒的不连续岛状物。
在粉末状态中，优选钒或碳化钒的颗粒尺寸与金刚石颗粒的颗粒尺寸相当。甚至更优选钒或碳化钒比金刚石颗粒更细。
还可有利地在HpHT合成循环期间通过从外部来源渗透将钒或碳化钒添加剂引入金刚石层中。这种外部来源可以是在胶结碳化物基材和金刚石层之间引入的隔片或粉末层。在制备胶结碳化物基材所需的早期胶结或烧结步骤中，还可以通过将钒添加剂纳入到碳化物基材的胶结相中将其引入。其它类似方法例如在金刚石层的周围使用环形源对本领域技术人员将是显而易见的。在每种这些情形中，将必须选择渗透剂源的量，或者用条件选择来控制渗透的程度，以便在PCD层中获得最终所需的钒化合物水平。
还优选钒或碳化钒或碳化钒钨的氧含量保持尽可能低，保持在低于1000ppm，优选低于100ppm且最优选低于10ppm的水平。
钒或碳化钒或碳化钒钨可以按新的显微组织形式存在于第二相中。这些显微组织形式包括：沿金刚石粘合剂/催化剂界面分散/析出的含钒析出物，远离金刚石粘合剂/催化剂界面以偏析方式形成的含钒析出物，或在金刚石与粘合剂/催化剂之间涂覆金刚石表面的全部或部分的含钒析出物。使用本领域已知的既定电子显微镜技术例如TEM、SEM、HRTEM或HRSEM可观测到这些显微组织或形式。含钒析出物包括碳化物(化学计量比和非化学计量比两种)或混合碳化物例如碳化钒钨。还包括不同碳化物的固溶体。
可以使用本领域中已知的方法例如X射线荧光光谱法(XRF)和电子衍射光谱法(EDS)探测本发明材料的详细元素特性。
使用例如用于测量氧化速率的热重分析法(TGA)、用作测量抗磨损性的Paarl花岗岩车削测试(Paarl Granite Turning Test)(PGT)、用作检测所形成化合物的各种相的手段的X射线衍射(XRD)、和测量磨损速率的磨蚀测试，可观测到本发明的PCD材料的性能和力学行为优点例如改善的抗氧化性、改善的抗磨损性和改善的热稳定性。
本发明的PCD材料包含粘结金刚石颗粒的第一区，该第一区典型占该材料的60-98体积％，优选80-95体积％。钒或碳化钒或碳化钒钨在PCD层中优选以PCD材料的1-8质量％，更优选2-6质量％的量存在。
在含有大量金刚石与金刚石粘结的第一区中的金刚石颗粒或晶粒将典型地具有1-50微米的平均颗粒尺寸。本发明特别适用于高等级PCD(即其中金刚石颗粒是细的PCD)且更特别适用于其中金刚石颗粒具有小于20微米尺寸的PCD。
PCD材料优选粘结到基材例如胶结碳化物基材，通常以PCD层形式进行粘结。粘合剂/催化剂的来源将典型是(至少部分)碳化物基材。该碳化物优选为碳化钨形式，所述碳化钨是第二相中钨的来源。
现将通过下面实施例描述本发明。
实施例1
将3质量％碳化钒和2质量％钴粉末的混合物初始球磨1小时以形成均匀混合物。然后逐步将双峰分布的金刚石颗粒(平均颗粒尺寸为2微米和12微米)加入到该混合物中并且将该混合物进一步球磨。总计，将全部混合物球磨4.5小时。扫描电子显微术(SEM)显示所得混合物是均匀的。然后用胶结碳化钨基材承载(back)该混合物，并且在真空炉中处理以除去任何杂质。使初生状态产物经受金刚石处于热力学稳定的高的温度和压力，以产生包含粘结到胶结碳化物基材的PCD层的复合金刚石坯体。
SEM分析(图1)显示PCD层中存在金刚石交互生长。显微照片中的黑色区表示金刚石相，灰色区域表示粘合剂/催化剂钴，以及较亮区表示碳化钨或碳化钒相。灰色区域和较亮区表示第二相并且该第二相散布在金刚石相之间。电子衍射光谱法(EDS)测量样品中存在的元素。EDS分析还显示：较亮区表示粘合剂池中存在钒和/或钨。通过XRF分析进一步证实了烧结坯体中钒的存在。
PCD层的XRD分析未能揭示任何钒-钴金属间化合物，即VCo、V3Co或VCo3。主要观察到，存在于PCD层中的钒以碳化钒或碳化钒钨形式出现。
对该实施例的复合金刚石坯体进行热稳定性测试并且与常规复合金刚石坯体对比，所述常规复合金刚石坯体的PCD层以钴作为第二相。在图2中图解显示，该测试清楚地表明本发明的复合金刚石坯体相对于标准品(常规复合金刚石坯体)的热稳定性改善。
还在抗磨蚀性测试中将该实施例的复合金刚石坯体与标准品对比。将彼此之间的不同仅在于烧结条件的5个坯体变体与标准品对比，由图3中所示可见，所有5个变体显示出比标准品优越的抗磨蚀性。
在抗氧化性测试中将该实施例的复合金刚石坯体与标准品对比，由图4中所示可见，再次证明了优越性。
实施例2
将5质量％金属钒和12微米金刚石颗粒的混合物球磨2小时以形成均匀混合物。扫描电子显微术(SEM)显示所得混合物是均匀的。然后用胶结碳化钨基材承载该混合物，并且在真空炉中处理以除去任何杂质。使初生状态产物经受金刚石处于热力学稳定的高的温度和压力，以获得包含粘结到胶结碳化物基材的PCD层的复合金刚石坯体。
SEM分析(图5)显示PCD层中存在金刚石交互生长即金刚石相。EDS分析显示在散布于金刚石相之间的粘合剂池内存在钒和/或钨。通过XRF分析进一步证实了烧结坯体中钒的存在。
对该实施例的复合金刚石坯体进行抗磨蚀性测试并且与实施例1中描述的标准品对比。该实施例的复合金刚石坯体与标准品相比显示出优越的抗磨蚀性。
还使用XRD分析该实施例的复合金刚石坯体，没有观测到明显的钒-钴金属间化合物，即VCo、V3Co或VCo3。主要观察到，存在于PCD层中的钒以碳化钒或碳化钒钨或类似相形式出现。
分别从图2和4中所示可见，显示出该实施例的复合金刚石坯体显示具有比标准品更大的热稳定性和抗氧化性。

Claims (13)

1.多晶金刚石材料，其包含：粘结的金刚石颗粒的第一相，其中存在金刚石与金刚石粘结；和散布在第一相之间的第二相，该第二相含有金属形式、碳化物形式或碳化钒钨形式的钒、或者这些形式的钒中两种或更多种的混合物，其中钒或碳化钒或碳化钒钨或者这些形式的钒中两种或更多种的混合物具有低于1000ppm的氧含量。
2.根据权利要求1的多晶金刚石材料，其中金属形式或碳化钒形式或碳化钒钨形式的钒在多晶金刚石材料中的总存在量是该材料的1-8质量％。
3.根据权利要求1或2的多晶金刚石材料，其中金属形式或碳化钒形式或碳化钒钨形式的钒在多晶金刚石材料中的总存在量是该材料的2-6质量％。
4.根据权利要求1或2的多晶金刚石材料，其中第二相含有金刚石催化剂。
5.根据权利要求4的多晶金刚石材料，其中金刚石催化剂是钴、铁，镍或含有钴、铁或镍的合金。
6.根据权利要求4的多晶金刚石材料，其中第二相基本上由金刚石催化剂和下列形式的钒构成：金属形式的钒、碳化物形式的钒或碳化钒钨形式的钒、或者这些形式的钒中两种或更多种的混合物。
7.根据权利要求1或2的多晶金刚石材料，其中金刚石颗粒尺寸小于20微米。
8.根据权利要求1或2的多晶金刚石材料，其中金刚石颗粒是单峰的，即该金刚石将具有单一的平均颗粒尺寸。
9.根据权利要求1或2的多晶金刚石材料，其中金刚石颗粒是多峰的，即该金刚石将包含具有多于一种平均颗粒尺寸的颗粒的混合物。
10.根据权利要求1或2的多晶金刚石材料，其包含粘结的金刚石颗粒的第一相，该第一相占该材料的60-98体积％。
11.根据权利要求1或2的多晶金刚石材料，其包含粘结的金刚石颗粒的第一相，该第一相占该材料的80-95体积％。
12.根据权利要求1或2的多晶金刚石材料，其粘结于胶结碳化物基材。
13.根据权利要求12的多晶金刚石材料，其中基材是胶结碳化钨基材。
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