CN102531603A - 基体粉末系统和复合材料以及由其制成的物品 - Google Patents

基体粉末系统和复合材料以及由其制成的物品 Download PDF

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CN102531603A
CN102531603A CN2011103750415A CN201110375041A CN102531603A CN 102531603 A CN102531603 A CN 102531603A CN 2011103750415 A CN2011103750415 A CN 2011103750415A CN 201110375041 A CN201110375041 A CN 201110375041A CN 102531603 A CN102531603 A CN 102531603A
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matrix
carbide
matrix powder
adhesive
powder
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CN102531603B (zh
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邓欣
D·班纳吉
M·维尔费特
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Kennametal Inc
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Abstract

本发明包括一种含一种或多种多晶碳化物、无粘合剂碳化物、或者它们的组合的基体粉末系统；包含该基体粉末系统和一种金属粘合相的一种复合材料；由该复合材料制造的、用于石油和天然气钻探的钻头尖的一个基体钻尖本体；用于石油和天然气钻探、包括该基体钻尖本体和至少一个切割器的一种钻头尖。该多晶和/或无粘合剂碳化物可以包括：W、Ti、V、Cr、Nb、Mo、Ta、Hf、Zr的碳化物，或者它们的组合。该无粘合剂碳化物具有小于3wt.％的粘合剂并且该无粘合剂和/或多晶碳化物可以具有≤15μm的晶粒大小和≥1900HV(0.5千克力)的硬度。在该基体粉末系统中还可以存在额外的陶瓷组分和/或金属。可替代地，该复合材料可以存在于仅该基体钻尖本体表面的一部分上。

Description

基体粉末系统和复合材料以及由其制成的物品
技术领域
本发明涉及一种基体粉末系统、一种包含该基体粉末系统的复合材料，以及由用于石油和天然气钻探的钻头尖的这样一种复合材料制成的一个基体钻尖本体。更加具体地讲，本发明涉及一种基体粉末系统，该基体粉末系统包括一种或多种多晶碳化物、无粘合剂碳化物，或者它们的组合，所述多晶碳化物和/或无粘合剂碳化物包括W、Ti、V、Cr、Nb、Mo、Ta、Hf、Zr的碳化物，或它们的组合。
背景技术
用于石油和天然气钻探的一种钻地钻头尖1，如图1所示，包括几个被附接在一个钻头尖本体4上的切削元件2。这种类型的钻头尖也可以被称为剪切钻尖、剪切基体本体切割器，或者基体本体钻头尖。钻头尖本体4是由具有硬质基体相的一种复合材料制成的，该硬质基体相包含一种或多种陶瓷组分，例如铸造碳化钨、粗晶碳化钨、附聚物渗碳的碳化钨(agglomerate carburized tungsten carbide)、压碎的烧结碳化钨、碳化钨钴/镍小粒，和/或处于小颗粒形式的其他碳化物类、氮化物类、硼化物类、和/或氧化物类。
这些切削元件2最常见地是通过与该钻头尖本体材料进行钎焊或者一种机械/冶金粘合而附接到该钻头尖本体4的烧结碳化物基体上的分离的金刚石或多晶金刚石复合材料。
通常，该基体材料钻头尖本体是使用一种熔渗工艺制造的，该熔渗工艺使用一种金属粘合相来粘合这些小的基体颗粒。在该熔渗工艺中，将一种基体粉末倾倒入一个模具中。然后该将会变成该复合材料的金属粘合相的熔渗金属于被放在该基体粉末的顶部件上。当装载该模具之后，在该模具上放置一个顶部件并且在一个加热炉内将该模具加热到在该金属粘合相的熔点之上但是在该基体粉末的陶瓷组分的熔点之下的一个温度。该金属粘合相熔化并且熔渗该基体粉末。在冷却并且凝固后，该金属粘合相将该基体粉末粘合在一起从而形成一种固体复合材料。一个钢质柄在凝固之后被粘结到该钻头尖本体4上亦或在加热之前被放入该模具中，这样使得该熔渗金属将该柄粘合到了钻头尖本体4上。在凝固之后使用钎焊或者另一种合适的附接方法将这些切割器2附接到钻头尖本体4上，以便将它们固定在由该模具在钻头尖本体4内形成的多个凹槽或凹陷内。
授予Liang等人的美国专利号7,475,743说明了一种钻地的钻头尖，该钻头尖具有一个基体钻尖本体，该基体钻尖本体包含烧结碳化钨和铸造碳化钨并且它是使用熔渗方法制造的。在Liang的专利中，这些切削元件是在已经使用该熔渗方法制造了该基体钻尖本体之后钎焊到该基体钻尖本体上的。Deng等人的美国专利申请公开号2008/0206585说明了具有一种基体钻尖本体的一种钻头尖，该基体钻尖本体包含碳化物类、硼化物类、氮化物类，和/或氧化物类并且它是使用熔渗方法制造的。
在用于制造该基体材料钻头尖本体的熔渗工艺过程中，温度达到约1200℃。因此，对于该基体组分，即，这些碳化物而言，必须具有良好的热稳定性，使得它们在制造过程中不会破裂。
在操作过程中，此类钻地钻头尖本体经受到大量的腐蚀和冲击。虽然由金刚石或多晶金刚石复合材料制成的这些切割器2，在工使用中具有高的硬度和良好的耐腐蚀性，但是目前所使用的这些钻头尖本体4是较少耐腐蚀的。其结果是，对于该钻头尖的寿命而言的限制因素是对钻头尖本体4的劣化。
因此，对于钻头尖本体4而言，需要包含一个基体粉末系统的一种复合材料，该基体粉末系统具有更好的热稳定性以忍受该制造工艺以及更高的硬度和更好的耐腐蚀性，以便与这些切割器2的硬度和耐腐蚀性更紧密地相匹配。
发明内容
本发明是针对用于制造陶瓷金属复合材料的一种基体粉末系统以及由其制成的复合材料。该基体粉末系统包括一种或多种多晶碳化物、无粘合剂碳化钨，或者它们的组合。这些多晶和/或无粘合剂碳化物包括W、Ti、V、Cr、Nb、Mo、Ta、Hf、Zr的碳化物，或者它们的组合。该基体粉末系统还可以包含除了多晶碳化物和/或无粘合剂碳化物之外的额外的陶瓷相和/或金属。该陶瓷金属复合材料包括本发明的基体粉末系统和一种金属粘合相。
本发明还是针对由这种复合材料制造的、用于钻地的钻头尖的一种基体钻尖本体。可替代地，该基体钻尖本体可以具有一种复合材料，该复合材料在仅其表面的一部分上包括多晶碳化物和/或无粘合剂碳化物基体粉末系统。
本发明还是针对用于石油和天然气钻探的一种钻头尖，该钻头尖包括由这种复合材料制造的一个钻头尖本体以及至少一个切割器。
附图说明
图1是根据本发明的钻头尖的一个实施方案的等角视图；
图2A和图2B是熔渗有一种铜合金的无粘合剂碳化钨的显微照片；并且
图2C和图2D是熔渗有一种铜合金的碳化钨-钴小粒的显微照片。
具体实施方式
本发明是包括一种或多种多晶碳化物、无粘合剂碳化钨，或者它们的组合的一种基体粉末系统。这些多晶和/或无粘合剂碳化物包括W、Ti、V、Cr、Nb、Mo、Ta、Hf、Zr的碳化物，或者它们的组合。该多晶碳化物由多个包含在一个单个颗粒中的晶粒组成。在该多晶碳化物中没有粘合剂。无粘合剂碳化物具有0至3wt.％的金属粘合剂。在多晶碳化物或无粘合剂碳化物内的这些碳化物的晶粒大小是≤15μm，，优选的是≤1μm，并且更加优选的是0.2μm至0.6μm。
与传统上用于石油和天然气钻探的钻头尖的复合基体钻尖本体中的铸造碳化物、粗晶碳化物、烧结碳化物或者附聚物渗碳的碳化物相比，多晶碳化物和无粘合剂碳化物更硬。由于硬度通常与耐腐蚀性相关，因而与传统上用于石油和天然气钻探的钻头尖的基体钻尖本体中的这些碳化物相比，这些多晶碳化物和无粘合剂碳化物同样具有改进的耐腐蚀性。此外，与传统上用于石油和天然气钻探的钻头尖的基体本体中的这些碳化物相比，这些多晶碳化物和/或无粘合剂碳化物在制造的过程中使用一种熔渗工艺而具有更好的热稳定性。因此，根据本发明，为了改进该基体钻尖本体的耐腐蚀性，该基体粉末系统包括一种或多种多晶碳化物和/或无粘合剂碳化物。
该无粘合剂碳化物包含小于3wt.％的金属粘合剂，该金属粘合剂是选自但不限于：从W、Mo、Co、Ni、Ti、Cr、V、Fe、以及Mn。优选地，该粘合剂相是小于0.5wt.％，并且更优选地是小于0.2wt.％。
这些多晶碳化物和/或无粘合剂碳化物是处于一种粉末的形式，该粉末可以是任何形状，包括但不限于：球状的、立方体的、椭圆的、似立方体的、或者不规则的，并且可以是处于0.005mm(0.000197英寸，2500目)与1.19mm(0.047英寸，16目)之间，优选的是0.02mm至0.42mm，并且更优选的是0.044mm至0.25mm。可以使用任意组合了多种形状和/或多种尺寸的碳化物粉末。
此类多晶碳化物和/或无粘合剂碳化物可以是使用多种工艺制造的，包括但不限于对以下各项进行快速全方向压实(ROC)、硬的热等静压压制(硬HIP)、微波烧结、等离子烧结、以及热压制：1)一种金属粉末和碳粉末混合物，2)一种金属碳化物粉末，或者3)一种金属碳化物粉末和金属粘合剂混合物。可以将产生的多晶碳化物和/或无粘合剂碳化物压碎以便获得该更细颗粒的碳化物材料。
多晶碳化钨和/或无粘合剂碳化钨因其高硬度特别适合在该基体粉末系统中使用。多晶碳化钨是由其中一个颗粒内有多个晶粒的纯碳化钨所组成的。在多晶碳化钨中没有粘合剂并且碳化钨是唯一的相。无粘合剂碳化钨具有0至3wt.％的金属粘合剂和/或高达10wt.％的碳化二钨(W2C)。通过引用结合在此的美国专利申请号12/700,991中说明了一种这样的无粘合剂碳化钨。总体上，无粘合剂碳化钨不是单相的，除了在它的0wt.％的金属粘合剂或W2C的极端情况下。在本发明中所使用的多晶碳化钨和/或无粘合剂碳化钨可以具有1900HV(0.5千克力)或更大的硬度，这远远超过表1中所示的传统上在基体钻尖本体中使用的这些碳化钨的硬度。
表1
 基体粉末组分   硬度HV(0.5千克力)
 无粘合剂碳化钨，RT500压碎的   2941±208
 压碎的铸造碳化钨   1943±236
 球状的铸造碳化钨   2498±118
除了一种或多种多晶碳化物和/或无粘合剂碳化物之外，该基体粉末系统可以包括含碳化物类、氮化物类、硼化物类、和/或氧化物类的一种额外的陶瓷组分。这些额外的陶瓷粉末包括，但不限于：作为用于复合基体钻尖本体的基体粉末使用的碳化物、氮化物、硼化物、或氧化物的粉末。此类粉末包括：铸造碳化钨，粗晶碳化钨，烧结碳化钨，附聚物渗碳的碳化钨，Cr、Ta、Mo、V、Zr、Hf、Ti、和/或Nb的碳化物，和/或难熔的金属硼化物。该额外的陶瓷组分可以由占该基体粉末系统的0至90wt.％。
任选地，在该基体粉末系统中，还可以包括作为金属粉末引入的一种金属。这种金属粉末可以是Ni、Fe、Cu、Mn、P、Cr、Co、Si、B、Zn、Sn、或者它们的合金。该金属可以占该基体粉末系统的0至15wt.％组成，并且是存在为增强该复合材料的金属粘合相与存在于该复合材料的基体相内的陶瓷的粘合。
本发明还包括一种复合材料，该复合材料包括：(i)该基体粉末系统以及(ii)一个金属粘合相。该金属粘合相，当在此以及以下说明的熔渗过程中融化时，将该基体粉末系统的这些颗粒粘合在一起。该金属粘合相包括以下物质的一种或多种：Cu、Ni、Mn、Fe、Co、Al、Cr、Zn、Sn、Ag、B、Pb、Si、P、Ti、以及Mg。Cu-Ni-Mn合金(如美国专利号5,589,268,5,733,649，和5,733,664中说明的，它们通过引用结合在此)，尤其是基本上不含锌和锡的合金(如通过引用结合在此的美国专利申请公开号2008/0206585中说明的)特别适合作为有待用于石油和天然气钻探的钻头尖的基体钻尖本体的复合材料的金属粘合相。该金属粘合相另外可以是可热处理的以便在凝固后改变该复合材料的机械特性(如在先前所引用的美国专利申请公开号2008/0206585中所说明的)。
图1示出了具有本发明的复合材料的钻头尖本体4的钻头尖1的一个实施方案。要形成这种具有本发明的复合材料的钻头尖本体4的钻头尖1，可以使用一种熔渗工艺。将包括多晶碳化物粉末和/或无粘合剂碳化物粉末的系统以及，任选地，一种或多种额外的陶瓷粉末和/或金属粉末的基体粉末系统倾倒入一个模具内。然后该将会变成复合材料的金属粘合相的熔渗金属被放在该基体粉末系统的顶部。该金属粘合相总体上是一种金属合金，如上所述，并且可以是处于一种粉末的形式或者处于大约6.3mm(0.25英寸)至12.7mm(0.5英寸)的更大片的形式。在将其装载之后，在该模具上放置一个顶部件并且在一个加热炉内将该模具加热到在该金属粘合相的熔点之上但是在该基体粉末系统的陶瓷组分的熔点之下的一个温度。该金属粘合相熔化并且熔渗该基体粉末系统，由此形成一个钻头尖本体。在冷却和凝固之后，该熔渗金属与该基体粉末系统粘合在一起。一个钢质柄在凝固之后被粘合在该钻头尖本体上亦或在加热之前被放入模具中，这样使得该熔渗金属将该柄粘合到钻头尖本体上。这些多晶金刚石切割器2是在凝固之后使用钎焊或者另一种适合的附接方法来附接到该基体钻尖本体上的，以便将它们固定在由该模具在该基体钻尖本体内形成的多个凹槽或凹陷内。
该基体粉末系统占该复合材料的5wt.％至95wt.％、优选的是20wt.％至85wt.％、并且更加优选的是45wt.％至80wt.％。
用于本发明中的多晶碳化物和无粘合剂碳化物具有比用于钻头尖本体的、使用该熔渗工艺制造的传统碳化物更高的热稳定性。这是通过图2A至图2D所示的显微照片来展示的，其中可以看到在该熔渗工艺后碳化钨-钴小球被该熔渗金属渗透并且被分解成多个更小的片，而该熔渗金属没有渗透保持完整的这些无粘合剂碳化钨颗粒。
为了展示通过本发明而实现的耐腐蚀性的改进，使用该熔渗工艺制造了用于基体钻尖本体的一种对比的、传统复合材料。该基体粉末系统是0.125mm至0.177mm(0.0049英寸至0.0070英寸，80目至120目)的压碎的铸造碳化钨，并且该金属粘合相是53％Cu-24％Mn-15％Ni-8％Zn合金(按重量计)。除了在该基体粉末系统中无粘合剂碳化钨代替了该压碎的铸造碳化钨以外，以同一种方式来制造一种本发明的复合材料。对于对比的复合材料而言，腐蚀体积损失(这应该被最小化)是0.18cm3，而对于该本发明的复合材料而言仅是0.10cm3。
此外，在模制过程中，在将该基体粉末系统放入模具之前，可以将一种浆料(包括一种或多种多晶碳化物粉末和/或无粘合剂碳化物粉末以及一种有机粘合剂，如矿物油)涂敷到该模具的内部。这层浆料可以覆盖该模具的整个内部表面或者可以被涂敷在与该基体钻尖本体的表面上需要额外耐腐蚀性的多个区域相对应的多个分离的区域中。然后将用于该基体钻尖本体整体的基体粉末系统倾倒入顶部为这种浆料的模具内，并且该过程如上所述的进行。该有机粘合剂在加热过程中被烧掉。用于该基体钻尖本体整体的基体粉末系统可以是一种传统的组合物或者可以是先前所述的组合物。在凝固后，在该基体钻尖本体的表面上与该模具中浆料所处的区域相对应的这些区域将会包含该多晶碳化钨和/或无粘合剂碳化钨，使得在这些区域内的耐腐蚀性不同于与模具内没有涂敷该浆料的区域相对应的周围表面。
该浆料可以包括一种或多种多晶碳化物粉末和/或无粘合剂碳化物粉末，并且可以与用于该基体钻尖本体(该基体钻尖本体同样包含了如上所述的多晶碳化物和/或无粘合剂碳化物)的整体的一种基体粉末系统一同使用，以便形成一个基体钻尖本体。在这种情况下，在该基体钻尖本体的表面上与模具内放置浆料的区域相对应的这些区域可以被制造成具有与周围区域以及该基体钻尖本体整体不同类型和/或量值的多晶碳化物和/或无粘合剂碳化物。
该浆料还可以包括具有一种或多种碳化物、氮化物、硼化物，或氧化物的粉末的一种额外的陶瓷相，包括但不限于传统上用作钻头尖的复合基体钻尖本体的那些基体粉末。这些包括：铸造碳化物，粗晶碳化物，烧结碳化物，附聚物渗碳碳化物，Cr、Ta、Mo、V、Zr、Hf、Ti，和/或Nb的碳化物，以及/或者难熔的金属硼化物。
可替代地，在模制过程中，在将该基体粉末系统放入模具内之前，可以在模具的底部放置一种面层粉末(face powder)，该面层粉末包含一种或多种多晶碳化物粉末和/或无粘合剂碳化物粉末。这一层面层粉末可以覆盖该模具的底部表面，或者可以仅覆盖该模具底部与该基体钻尖本体的表面上需要额外耐腐蚀性的多个区域相对应的多个分离的区域。然后将用于该基体钻尖本体整体的基体粉末系统倾倒入该顶部为该面层粉末的模具中，并且该过程如上所述的来进行。用于该基体钻尖本体整体的基体粉末系统可以是一种传统的组合物或者可以是先前所述的组合物。在凝固后，在该基体钻尖本体的表面上与模具内该面层粉末所处的区域相对应的这些区域将会包含多晶碳化物和/或无粘合剂碳化物，使得在这些区域内的耐腐蚀性不同于与模具内没有涂敷该面层粉末的区域相对应的周围表面的耐腐蚀性。
该面层粉末还可以包括一种或多种碳化物、氮化物、硼化物、或氧化物粉末的一种额外的陶瓷相，包括但不限于在用于钻头尖的复合基体本体中传统用作基体粉末的那些粉末。这些包括：铸造碳化物，粗晶碳化物，烧结碳化物，附聚物渗碳碳化物，Cr、Ta、Mo、V、Zr、Hf、Ti、和/或Nb的碳化物，以及/或者难熔的金属硼化物。
在模具中面层粉末以总体上比浆料更厚的层来涂敷，从而在完成的基体钻尖本体上形成一个总体上更厚的表面层。由面层粉末或浆料形成的这些表面层总体上还具有比该基体钻尖本体的其他部分更小的强度，因为它们总体上被组成为提供最大的腐蚀保护。因此，通过使用浆料或面层粉末，该基体钻尖本体的表面或者其表面的一部分可以由一种更加耐腐蚀的复合材料制成，同时该本体可以由具有更大强度的一种复合材料制成。
尽管基于当前认为是最实际的并且优选的实施方案而出于说明的目的已经对本发明进行了详细的说明，应该理解，这样的细节仅仅是为了该目的，并且本发明不限于所披露的实施方案，而是正相反，本发明旨在涵盖在所附权利要求的精神和范围内的多种修改和等效安排。例如，应当理解，本发明考虑了(在可能的程度上)任何实施方案的一个或多个特征可以与任何其他实施方案的一个或多个特征相结合。

Claims (20)

1.一种基体粉末系统，用于制造一种陶瓷基体复合材料，该基体粉末系统包括一种或多种多晶碳化物、无粘合剂碳化物、或者它们的一种组合。
2.如权利要求1所述的基体粉末系统，其中该多晶碳化物，如果存在的话，包括W、Ti、V、Cr、Nb、Mo、Ta、Hf、Zr的碳化物、或者它们的一种组合，并且该无粘合剂碳化物，如果存在的话，包括W、Ti、V、Cr、Nb、Mo、Ta、Hf、Zr的碳化物、或者它们的一种组合。
3.如权利要求1所述的基体粉末系统，其中该无粘合剂碳化物，如果存在的话，包括小于3wt.％的金属粘合剂。
4.如权利要求1所述的基体粉末系统，其中该多晶碳化物，如果存在的话，具有15μm或更小的晶粒大小，并且该无粘合剂碳化物，如果存在的话，具有15μm或更小的晶粒大小。
5.如权利要求1所述的基体粉末系统，其中该多晶碳化物，如果存在的话，包含钨，并且具有1900HV(0.5千克力)或更大的硬度，并且该无粘合剂碳化物，如果存在的话，包含钨，并且具有1900HV(0.5千克力)或更大的硬度。
6.如权利要求1所述的基体粉末系统，其中该无粘合剂碳化物，如果存在的话，包含钨，并且是包括高达10wt.％的碳化二钨的一种两相碳化物。
7.如权利要求1所述的基体粉末系统，其中这些多晶碳化物，如果存在的话，具有0.005mm至1.19mm的颗粒大小，并且这些无粘合剂碳化物，如果存在的话，具有0.005mm至1.19mm的颗粒大小。
8.如权利要求1所述的基体粉末系统，进一步包括选自下组的一种或多种额外的陶瓷相，该组由以下各项组成：碳化物类、氮化物类、硼化物类、或氧化物类。
9.如权利要求8所述的基体粉末系统，其中该额外的陶瓷相是W、Cr、Ta、Mo、V、Zr、Hf、Ti、以及Nb的一种或多种碳化物。
10.如权利要求8所述的基体粉末系统，其中该额外的陶瓷相是该基体粉末系统的0至90wt.％。
11.如权利要求1所述的基体粉末系统，进一步包括一种或多种金属。
12.如权利要求11所述的基体粉末系统，其中该金属是Ni、Fe、Cu、Mn、P、Cr、Co、Si、B、Zn、Sn、或者它们的合金。
13.如权利要求11所述的基体粉末系统，其中该金属是该基体粉末系统的0至15wt.％。
14.一种陶瓷金属复合材料，包括：
根据权利要求1所述的基体粉末系统；以及
一种金属粘合相。
15.如权利要求14所述的复合材料，其中该基体粉末系统占该复合材料的5wt.％至95wt.％。
16.如权利要求14所述的复合材料，其中该金属粘合相包括选自Cu、Ni、Mn、Fe、Co、Al、Cr、Zn、Sn、Ag、B、Pb、S i、P、Ti、以及Mg的组中的一种或多种。
17.一种用于石油和天然气钻探的钻头尖的基体钻尖本体，包括权利要求14所述的复合材料。
18.一种用于石油和天然气钻探的钻头尖的基体钻尖本体，其中其表面的至少一部分包括一种复合材料，该复合材料包括：
根据权利要求1所述的一种基体粉末系统；以及
一种金属粘合相。
19.一种用于石油和天然气钻探的钻头尖的基体钻尖本体，其中该基体钻尖本体的整体和其表面的至少一部分包括：
一种根据权利要求1所述的基体粉末系统；以及
一种金属粘合相。
20.一种用于石油和天然气钻探的钻头尖，包括由权利要求14所述的复合材料组成的一种基体钻尖本体以及用于接合一种结构的至少一个切削元件。
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