CN108705087B - 具有控碳层的金刚石复合片 - Google Patents
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Abstract
本发明公开了一种具有控碳层的金刚石复合片，包括聚晶金刚石工作层、硬质合金基体以及位于二者之间的控碳层，所述控碳层包括镀衣金刚石微粉，或过渡金属、金刚石微粉、和镀衣金刚石微粉中的至少两种，所述镀衣金刚石微粉包括Ti、Cr、W、Ni或Cu镀衣金刚石微粉中的至少一种。通过在聚晶金刚石工作层和硬质合金基体之间增加控碳层来改善PDC的界面性能和表面性能，提高耐热性、耐磨性和抗冲击性能。
Description
技术领域
本发明属于超硬材料技术领域，具体涉及一种具有控碳层的金刚石复合片。
背景技术
聚晶金刚石复合片(PDC)是由聚晶金刚石层与碳化钨(WC)硬质合金基体两部分组成的超硬复合材料，兼具金刚石的硬度、耐磨性及碳化钨的韧性，广泛应用于各类油气钻井的钻头。目前，PDC主要通过聚晶金刚石微粉与碳化钨硬质合金基体在高温高压下直接烧结得到，在烧结过程中，碳化钨硬质合金基体中的钴(Co)熔融，向金刚石微粉中渗透扩散，催化金刚石晶粒之间形成强的d-d键，实现金刚石微粉的粘接。Co上渗会溶解部分金刚石，此时聚晶层碳势较高，碳容易向基体中逆向扩散，使界面处WC-Co体系处于富碳环境中，导致WC晶粒容易沿着001方向择优生长成大颗粒的三棱柱晶体，影响耐热性与冲击韧性。这是因为：1)碳化钨的脆性较大，大尺寸的碳化钨晶粒更容易发生穿晶断裂，形成裂纹源；2)粘接相Co的自由程较大，在烧结后难以停留在韧性较好的α相而回到脆性的ε相，不能有效阻止碳化钨晶粒裂纹的生长；3)Co相对于碳化钨与金刚石而言，热膨胀系数更大，较大的Co自由程导致界面处的热应力不均匀，容易产生裂纹，影响耐热性。此外，聚晶金刚石层与碳化钨硬质合金基体的热膨胀系数及弹性模量等物性参数差异也较大，在冷却过程中硬质合金基体收缩更快，导致界面处存在较大的残余应力，层间附着力和抗冲击性能较差，使聚晶金刚石层在切削过程中易脱落，影响钻头的使用寿命。
为解决这一问题，中国专利申请CN201410292965.2提供一种石油钻探用金刚石复合片，包括由金刚石聚晶层、过渡层和硬质合金基体，该金刚石聚晶层和过渡层中均含有富钴的纳米金属结合剂，以改善界面结合。然而，这种方法易造成金刚石颗粒间的金属钴分布不均，极易因热膨胀系数的差异而形成大量的热残余应力，此外，其过渡层中还包括相对含量较高的WC，WC随Co运输会加速WC晶粒的生长，影响耐热性和抗冲击性能。
发明内容
为了解决上述技术问题，本发明提供一种金刚石复合片，通过在聚晶金刚石工作层和硬质合金基体之间增加控碳层来改善PDC的界面性能和表面性能，提高耐热性、耐磨性和抗冲击性能。
为了实现上述目的，本发明采用以下技术方案：
一种具有控碳层的金刚石复合片，其特征在于，包括聚晶金刚石工作层、硬质合金基体以及位于二者之间的控碳层，所述控碳层包括镀衣金刚石微粉，或过渡金属、金刚石微粉、和镀衣金刚石微粉中的至少两种，所述镀衣金刚石微粉包括Ti、Cr、W、Ni或Cu镀衣金刚石微粉中的至少一种。
优选地，所述过渡金属包括Ti、Zr、Ta、Nb、W、Cr、V和Mn中的至少一种，其中Ti、Zr、Ta、Nb和W容易吸收C，形成相应的碳化物，降低界面C含量，防止WC晶粒的取向性生长；Cr、V、Mn可以降低WC-Co体系对碳的敏感性，减少WC在界面处的偏析。
优选地，所述控碳层掺杂稀土元素，所述稀土元素包括Ce、Nd、Pm和Eu中的至少一种，所述稀土元素能抑制WC随钴输运，降低WC晶粒的生长速度，抑制晶粒长大，同时增加工作层金刚石微粉与粘结剂的结合力，提高工作层的耐磨性和抗冲击性能。
更优选地，所述过渡金属或稀土元素的含量为控碳层总重量的0.1-5％。
优选地，所述聚晶金刚石工作层与控碳层的重量比为1-10:1-2。
优选地，控碳层金刚石微粉的颗粒度大于工作层金刚石微粉的颗粒度。
本发明对所述金刚石复合片的制备方法没有特别的限定，优选地，该制备方法包括以下步骤：
(S1)将工作层金刚石微粉投入金属杯中，压平；
(S2)将控碳层原料投入步骤(1)的工作层上，压平，放入碳化钨基体，盖上金属杯，真空净化，再与叶蜡石和加热组件组装成合成块，用六面顶压机在高温高压下合成，最后经机械加工，得到PDC成品。
本发明的有益效果：
(1)控碳层的金属可以有效控制界面处的游离碳含量，或抑制WC在熔融钴中的溶解度，起到抑制界面晶粒长大的效果，改善的界面有利于提高冲击韧性，同时具有耐热疲劳和热冲击的特性；
(2)控碳层的金属可以与上渗的钴合金化，降低了聚晶层中钴的质量分数，合金化的钴与纯相的钴相比具有更低的热膨胀系数，利于降低复合片使用过程中的热损耗，提高耐磨性；
(3)控碳层优化了钴输运通道，使其更均匀的充满整个聚晶层，改善细粒度微粉不容易粘接的问题，提高了产品合成的成品率；
(4)微粉的金属镀衣提前形成了金属膜，使得钴扩散过程中更容易浸润并包裹住微粉，有利于d-d键的催化生长，使得晶粒之间连接更加牢固。
附图说明
图1是本发明实施例1-3和对比例1的PDC的VTL测试照片；
图2是本发明实施例1-3和对比例1的PDC界面微观形貌图。
具体实施方式
下面结合具体实施例对本发明进行详细的说明。
实施例1
一种金刚石复合片，包括聚晶金刚石工作层、硬质合金基体以及位于二者之间的控碳层，所述控碳层为Ti镀衣金刚石微粉。
该金刚石复合片的制备方法包括以下步骤：
将0.8g工作层金刚石微粉投入金属杯中，压平，投入0.8g Ti镀衣金刚石微粉，压平，放入碳化钨基体，盖上另外两个金属杯，真空净化后与叶蜡石和加热组件组装成合成块，用六面顶压机在高温高压下合成，经过机械加工，得到PDC1613。
实施例2
按实施例1的方法制备金刚石复合片，不同的是，控碳层采用W镀衣金刚石微粉与Cr复配，其中Cr含量占控碳层总重量的0.8％。
实施例3
按实施例1的方法制备金刚石复合片，不同的是，控碳层采用金刚石微粉与Cr和Ti复配，其中Cr和Ti的含量分别占控碳层总重量的1％和2％。
对比例1
按实施例1的方法制备金刚石复合片，区别在于，不含控碳层。
测试例
本测试例用于说明PDC的性能。
(1)耐磨性
将PDC制成车刀，用VTL车床车削
的花岗岩圆柱环端面，纵向进刀0.25mm，转速100r/min，横向进刀5.08mm，分别纪录切削20、40和60刀后的磨口面积，所得结果如表1所示。相应的VTL测试照片详见图1，其中，图1a-1c是实施例1的PDC分别切削20、40和60刀后的照片，图1d-1f是实施例2的PDC分别切削20、40和60刀后的照片，图1g-1i是实施例3的PDC分别切削20、40和60刀后的照片，图1j-1l是对比例1的PDC分别切削20、40和60刀后的照片。
表1实施例1-3和对比例1的PCD切削20、40和60刀后的磨口面积(mm2)
| 实施例1 | 实施例2 | 实施例3 | 对比例1 | |
| 20P | 1.57 | 1.46 | 1.43 | 1.69 |
| 40P | 2.13 | 2.15 | 2.10 | 4.38 |
| 60P | 2.69 | 2.56 | 3.29 | 6.75 |
(2)界面形貌与工作层中的Co含量
取PDC断面，采用ZEISS ULTRA-55场发射扫描电镜观察界面微观形貌，实施例1-3和对比例1的PDC界面微观形貌依次如图2a-2d所示。在垂直于工作层外表面的方向取7个测试点，各测试点到工作层外表面的距离呈等差数列分布，进行EDS分析，记录相应的Co含量，所得结果如表2所示。
表2
由以上结果可知，不含控碳层的PDC片耐磨性不佳，界面处WC晶粒尺寸较大，分布不均匀，且部分晶粒异常长大；添加控碳层后，界面处的WC晶粒明显细化，尺寸分布均匀，界面结合更为紧密，而且工作层Co含量更低，波动更小，产品稳定性好，产品耐磨性明显提高。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，本领域的技术人员在本发明的技术构思范围内进行的多种等同替代或简单变型方式，均属于本发明的保护范围。
Claims (5)
1.一种具有控碳层的金刚石复合片，其特征在于，所述金刚石复合片为聚晶金刚石工作层、硬质合金基体以及位于二者之间的控碳层形成的复合层，所述控碳层包括镀衣金刚石微粉，或过渡金属、金刚石微粉、和镀衣金刚石微粉中的至少两种，所述镀衣金刚石微粉包括Ti、Cr、W、Ni或Cu镀衣金刚石微粉中的至少一种；所述过渡金属的含量为控碳层总重量的0.1-5%；
所述过渡金属包括Ti、Zr、Ta、Nb、W、Cr、V和Mn中的至少一种。
2.根据权利要求1所述的金刚石复合片，其特征在于，所述控碳层掺杂稀土元素，所述稀土元素包括Ce、Nd、Pm和Eu中的至少一种。
3.根据权利要求2所述的金刚石复合片，其特征在于，所述稀土元素的含量为控碳层总重量的0.1-5%。
4.根据权利要求1所述的金刚石复合片，其特征在于，所述聚晶金刚石工作层与控碳层的重量比为1-10:1-2。
5.根据权利要求1所述的金刚石复合片，其特征在于，控碳层金刚石微粉的颗粒度大于工作层金刚石微粉的颗粒度。
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| CN114260453A (zh) * | 2021-12-24 | 2022-04-01 | 郑州新亚复合超硬材料有限公司 | 一种高性能金刚石复合片及其制造工艺 |
| CN115740457A (zh) * | 2022-11-24 | 2023-03-07 | 吉林大学 | 一种钒增强聚晶金刚石复合片及其制备方法 |
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