CN109652721A - 一种含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金 - Google Patents
一种含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金 Download PDFInfo
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Abstract
为了改善WC‑Co硬质合金的硬度、耐磨性,研制了一种含(W,Ti,Ta)C复式碳化物的WC‑8%Co超细硬质合金。采用WC‑6%Co和WC‑8%Co硬质合金为原料,采用的最佳工艺参数为:烧结温度1390℃。在此烧结温度下制得的硬质合金力学性能最佳,其矫顽磁力为56.98kA·m‑1,硬度为141HRA,抗弯强度为3461MPa。合金内部的晶粒细小,符合超细晶硬质合金的制备要求。所制得的含(W,Ti,Ta)C复式碳化物的WC‑8%Co超细硬质合金,其硬度、致密化程度、抗弯强度都得到大幅提升。本发明能够为制备高性能的WC‑8Co超细硬质合金提供一种新的生产工艺。
Description
所属技术领域
本发明涉及一种硬质合金材料,尤其涉及一种含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金。
背景技术
硬质合金是一种由硬质相(WC、TiC、TaC、VC和Cr,C:等)和粘结相(Co、Ni和Fe)采用粉末冶金工艺生产的具有高硬度和高耐磨性材料,其具有高硬度、高强度、耐腐蚀、耐磨损、高弹性模量、热膨胀系数很低以及化学稳定性很好等特点,在钻具、刀具、耐磨耐腐零部件等方面有广泛应用,有“工业的牙齿”美称。硬质合金属于脆性材料,硬度和强度即耐磨性和韧性之间的矛盾一直是困扰其发展的主要因素。
超细WC-Co类硬质合金是指WC晶粒度≤0.5μm的硬质合金,具有高强度、高硬度、高耐磨性等优良的综合性能,因此广泛的用于工业生产中,尤其是刀具生产中。超细WC-Co类硬质合金在烧结过程中的晶粒长大是制约其能否取得超高力学性能的主要因素。复合碳化物是一种硬质合金行业和其它新材料行业广泛使用的原料,通常由两种或多种碳化物及其它化合物(如氮化物等)固溶而成。添加适量的复合碳化物可以有效抑制WC晶粒在烧结过程中的长大。
发明内容
本发明的目的是为了改善WC-Co硬质合金的硬度、耐磨性,设计了一种含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金。
本发明解决其技术问题所采用的技术方案是:
含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金的制备原料包括:WC-6%Co和WC-8%Co硬质合金。
含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金的制备步骤为:将原料按实验设计方案进行混合,随后加入至ND7-2行星式球磨机进行球磨,球磨介质为无水乙醇,成型剂为固体石蜡,球料比为5:1,球磨时间为60h。待原料均匀混合后,将混合料抽真空加热至其完全干燥,随后进行擦筛。将制得的粉末通过万能试验机下压制成B型样条,压制压力为250MPa,并在1390℃进行压力烧结,压力烧结的烧结压力为4MPa。
含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金的检测步骤为:洛氏硬度采用HR150型洛氏硬度仪,抗弯强度采用三点弯曲试验,钴磁采用ZS型钴磁测量仪,矫顽磁力采用YSK矫顽磁力计,微观组织采用Pect50型扫描电镜,能谱微区成分采用TecN透射电镜下。
所述的含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金,复式碳化物的添加能够增强硬质合金的力学性能。其作用机理为复式碳化物的添加能够有效地抑制合金晶粒在烧结过程中的长大,并且能够细化硬质合金的晶粒,达到提高硬质合金致密度的作用。
所述的含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金,复式碳化物的添加能够提高硬质合金的硬度、抗弯强度和矫顽磁力。
所述的含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金,采用的最佳工艺参数为:烧结温度1390℃。在此烧结温度下制得的硬质合金力学性能最佳,其矫顽磁力为56.98kA·m-1,硬度为141HRA,抗弯强度为3461MPa。合金内部的晶粒细小,符合超细晶硬质合金的制备要求。
所述的含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金,复式碳化物在烧结过程中的存在方式是溶解在粘结相中,所以需要制定一个非常严格的复式碳化物的添加量。
本发明的有益效果是:
采用WC-6%Co和WC-8%Co硬质合金为原料,经过配料、球磨、干燥、制粒、成形、烧结工艺成功制备了具有优异力学性能的含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金。其中,复式碳化物的加入能够有效抑制WC晶粒的长大,这也是WC-8Co超细硬质合金力学性能得到大幅提升的根本。所制得的含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金,其硬度、致密化程度、抗弯强度都得到大幅提升。本发明能够为制备高性能的WC-8Co超细硬质合金提供一种新的生产工艺。
具体实施方式
实施案例1:
含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金的制备原料包括:WC-6%Co和WC-8%Co硬质合金。含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金的制备步骤为:将原料按实验设计方案进行混合,随后加入至ND7-2行星式球磨机进行球磨,球磨介质为无水乙醇,成型剂为固体石蜡,球料比为5:1,球磨时间为60h。待原料均匀混合后,将混合料抽真空加热至其完全干燥,随后进行擦筛。将制得的粉末通过万能试验机下压制成B型样条,压制压力为250MPa,并在1390℃进行压力烧结,压力烧结的烧结压力为4MPa。含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金的检测步骤为:洛氏硬度采用HR150型洛氏硬度仪,抗弯强度采用三点弯曲试验,钴磁采用ZS型钴磁测量仪,矫顽磁力采用YSK矫顽磁力计,微观组织采用Pect50型扫描电镜,能谱微区成分采用TecN透射电镜下。
实施案例2:
在Co含量相同的情况下,YG8和YG6的硬度和抗弯强度变化的趋势相同,都是随着复式碳化物含量的增加,合金的硬度随着增加,但是抗弯强度呈减小的趋势。复式碳化物是一种脆硬相,使合金的硬度增加;同时Co对复式碳化物的润湿性比对WC的润湿性差,更易形成具有严重缺陷的孔隙,故降低合金的抗弯强度。Co含量从4%增加到7%后,合金的硬度降低但是抗弯强度增加。粘结相Co增加,使WC晶粒的邻接度下降,合金抗弯强度增加;金属Co的硬度远低于WC的硬度,合金硬度降低。
实施案例3:
在Co含量一定的情况下,矫顽磁力随着复式碳化物含量的增加而降低;相对磁饱和随着复式碳化物含量的增加,变化趋势不明显。当复式碳化物含量相同,YG6对应的矫顽磁力比YG8大。YG6合金的磁饱和强度理论值为11.7,YG8合金的磁饱和强度理论值为14.9,相对磁饱和值处于正常的两相区,硬质合金没有明显的脱碳现象。硬质合金的矫顽磁力主要受合金Co含量和碳化物粒度的影响。在硬质相粒度相同的情况下,Co含量越少,粘结相的平均自由程越小,合金的矫顽磁力越大。合金Co含量相同的情况下,硬质相越细,粘结相的平均自由程越小,合金的矫顽磁力越大。
实施案例4:
在复式碳化物含量相同的情况下,WC晶粒大小变化不大。YG8比YG6抗弯强度高,Co含量由4%增加到7%,增大了粘结相的平均自由程,Co对WC颗粒有更好的润湿,在合金破断的过程中,粘结相能够吸收大量的能量而阻止裂纹扩展,没有粘结相包裹的或粘结相层较薄的部位都会成为薄弱环节。复式碳化物从1%增加到3%,加入复式碳化物更多,碳化物颗粒更粗大。Co含量相同的情况下,复式碳化物的增多,矫顽磁力是下降的趋势,碳化物晶粒在增大。
实施案例5:
加入了少量抑制剂的硬质合金性能相对更优。加入适量的抑制剂可以抑制液相烧结过程中的连续长大,得到晶粒细小并且分布比较均匀的超细晶硬质合金,硬质合金的矫顽磁力、硬度和抗弯强度都与硬质相的颗粒大小有着密切的联系,在工艺相同,Co含量一致的情况下,细晶硬质合金的力学性能更好。
实施案例6:
Co相保留下了部分高温时的流动性状态,以粘结相填充到了WC晶粒之间。抑制剂抑制晶粒长大主要有吸附说,偏析说,溶解说。当抑制剂在WC-Co中添加过量或者分散不好时,WC/Co相界纳米偏析膜被发现;或是抑制剂优先在粘结相中溶解,抑制剂元素降低W和C在粘结相中的溶解度,抑制了晶粒长大。
实施案例7:
抑制剂元素主要存在方式是溶解在粘结相中,VC,Cr3C2与Co具有较低的共晶温度,抑制剂往往是比WC优先溶解于液态Co中,阻止了WC晶粒的长大,抑制机理更符合溶解说。抑制晶粒的长大实质就是降低晶粒长大驱动力。复式碳化物中的部分抑制剂元素也是要溶解与Co中,以提高合金的热稳定性抗氧化性等。由于加入了复式碳化物,Co的润湿性比WC颗粒差很多,在液相烧结中易形成孔洞,复式碳化物在提高性能的同时以一种脆硬相存在于相与相之间,阻碍液相Co的填充,使硬质合金强度下降。
Claims (4)
1.一种含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金的制备原料包括:WC-6%Co和WC-8%Co硬质合金。
2.根据权利要求1所述的含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金,其特征是含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金的制备步骤为:将原料按实验设计方案进行混合,随后加入至ND7-2行星式球磨机进行球磨,球磨介质为无水乙醇,成型剂为固体石蜡,球料比为5:1,球磨时间为60h,待原料均匀混合后,将混合料抽真空加热至其完全干燥,随后进行擦筛,将制得的粉末通过万能试验机下压制成B型样条(长20mm×宽6.5mm×高5.25mm),压制压力为250MPa,并在1390℃进行压力烧结,压力烧结的烧结压力为4Mpa。
3.根据权利要求1所述的含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金,其特征是含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金的检测步骤为:洛氏硬度采用HR150型洛氏硬度仪,抗弯强度采用三点弯曲试验,钴磁采用ZS型钴磁测量仪,矫顽磁力采用YSK矫顽磁力计,微观组织采用Pect50型扫描电镜,能谱微区成分采用TecN透射电镜下。
4.根据权利要求1所述的含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金,其特征是所述的含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金,复式碳化物的添加能够增强硬质合金的力学性能,其作用机理为复式碳化物的添加能够有效地抑制合金晶粒在烧结过程中的长大,并且能够细化硬质合金的晶粒,达到提高硬质合金致密度的作用,所述的含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金,复式碳化物的添加能够提高硬质合金的硬度、抗弯强度和矫顽磁力,所述的含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金,采用的最佳工艺参数为:烧结温度1390℃,在此烧结温度下制得的硬质合金力学性能最佳,其矫顽磁力为56.98kA·m-1,硬度为141HRA,抗弯强度为3461MPa,合金内部的晶粒细小,符合超细晶硬质合金的制备要求,所述的含(W,Ti,Ta)C复式碳化物的WC-8%Co超细硬质合金,复式碳化物在烧结过程中的存在方式是溶解在粘结相中,所以需要制定一个非常严格的复式碳化物的添加量。
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CN115728195A (zh) * | 2022-11-21 | 2023-03-03 | 湖南博云东方粉末冶金有限公司 | 一种超细wc的晶粒间接评价方法 |
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CN114574727A (zh) * | 2022-03-09 | 2022-06-03 | 自贡中兴耐磨新材料有限公司 | 铬钒钨复式碳化物强韧化WC-Ni硬质合金的制备方法 |
CN115728195A (zh) * | 2022-11-21 | 2023-03-03 | 湖南博云东方粉末冶金有限公司 | 一种超细wc的晶粒间接评价方法 |
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