CN104072138B - 一种碳化钨-立方氮化硼复合材料及其制备方法 - Google Patents
一种碳化钨-立方氮化硼复合材料及其制备方法 Download PDFInfo
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Abstract
一种碳化钨-立方氮化硼复合材料及其制备方法,涉及材料工程领域,其中碳化钨-立方氮化硼复合材料主要成分包括WC和cBN,在WC表面包覆有Co纳米粒子层,在cBN粉体表面包覆有SiO2纳米层,通过包覆纳米层提高复合材料的硬度、韧性等性能。一种碳化钨-立方氮化硼复合材料的制备方法,采用化学气相沉积法和高温烧结法,首先分别在WC和cBN表面包覆纳米粒子层,然后再高温烧结获得块状材料,制成的碳化钨-立方氮化硼复合材料具有结构热稳定性高,硬度高等特点,可作为高速切削刀具材料或作为钛合金、冷硬铸铁等传统刀具难以处理的特殊材料的加工成型领域,且本发明提供的制备方法简易,成本较低,可实现大规模商业化生产。
Description
技术领域
本发明属于材料工程领域,特别涉及一种高致密度、高性能的高速切削刀具材料以及其粉体的表面处理和制备方法。
背景技术
在机械加工中,切削或磨削加工目前仍是零件最终形成的主要工艺手段。切削加工的主要发展方向之一是高速切削(包括高速软切削、高速硬切削、高速干切削、大进给量切削等)。经历了理论探索、应用探索、初步应用和较成熟应用等四个阶段,高速切削技术已在生产中得到了一定的推广,加工钢件时切削速度最高已达到2000m·min-1,加工铸铁时达到3000m·min-1,加工铝合金则达到7000m·min-1,为普通切削速度的5~10倍。高速切削之所以得到工业界越来越广泛的关注,是因为它相对传统加工具有显著的优越性,如加工时间短(效率高、成本低)、工件表面质量好(表面精度高)、不需要冷却液(绿色加工、不污染环境)并且可以加工淬硬钢等传统加工手段难以处理的特殊材料。
作为高速切削刀具用材料,应具有良好的机械性能和热稳定性,即具有高硬度、抗冲击、耐磨损、抗热疲劳等特性。目前工业界采用的高速切削刀具材料主要有硬质合金、复合氮化硅陶瓷、立方氮化硼和金刚石等。WC和cBN形成的复合材料,将兼具两种材料的优点。超硬cBN相的引入不仅会显著提高WC硬质合金的硬度和耐磨损,其本身在复合材料中作为超硬粒子,引发裂纹偏转从而可以进一步提高材料的韧性,由于具有优异的硬度、耐磨损和韧性的性能组合,WC-cBN复合材料被看作是切割刀具领域最有发展潜力的新一代材料,引起了世界范围内的广泛关注。2007年,西班牙纳瓦拉国立大学的Martínez等人采用热等静压的方法,制备出了不同cBN含量的WC/Co-cBN复合材料。当cBN含量为30vol%时,复合材料硬度达到25Gpa;而当cBN提高到50vol%时,由于所需Co烧结助剂含量的增加导致了cBN向六方氮化硼(hBN)软相的相变,复合材料的硬度反而降低了4GPa(Journal of the American Ceramic Society, 2007, 90, p415-424)。2009年,土耳其Eskisehir Osmangazi大学的Yaman等人采用放电等离子体烧结方法制备了cBN体积含量为25%的WC/6wt%Co-cBN复合材料,虽然韧性最大值达到了12MPam1/2,最大硬度只有21GPa左右(Materials Letters, 2009, 63, p1041-1043),低于Martínez等人的报道值。2012年,波兰华沙工业大学的Rosinski 等人采用脉冲等离子体烧结方法制备了WC/Co-cBN复合材料,立方氮化硼的体积含量为30%,最大硬度为23GPa左右(Journal of Materials Science, 2012, 47, p7064-7071)。2007年,国内武汉理工大学材料复合新技术国家重点实验室的史晓亮等人用化学气相沉积法对cBN进行了表面镀金属钛(Ti)膜预处理后,采用热压烧结方法在温度烧结压力30MPa、1380℃保温60 min的条件下制备了cBN体积分数为30%的WC-10Co-cBN复合材料,材料的相对致密度为94.2%,强度为750MPa(机械工程材料, 2007, 31, p71-73)。除科研院所外,瑞典三特威克公司(全球领先刀具生产商)也在2012年公开了一篇关于WC-cBN复合材料的专利(Method for producing a sintered composite body, Patent WO2012038529A2, Sandvik Intellectual Property Ab.),以钴作为烧结助剂,采用无压烧结方法在1350 °C下制备了WC/Co-cBN复合材料,但得到的复合材料的最大硬度为13GPa。
总结国内外的研究现状可以看出,虽然国内外对WC-cBN复合材料进行了研究并取得了初步成果,但仍然存在复合材料致密化困难、硬度和耐磨损性能不足等问题。WC和cBN都属于难烧结材料,其复合材料通常以Co、Ni等为烧结助剂(重量含量通常为6-15wt%左右或更高)在高温下长时间无压或加压烧结才能获得。但Co、Ni等金属本身硬度低,会导致复合材料的硬度特别是红硬性的降低。另外一方面,高含量的金属烧结助剂还会加速cBN向六方氮化硼(hBN)的相变。而hBN是类石墨软相,硬度与石墨相当,因此cBN向hBN的相变也将导致复合材料硬度的降低,另外相变所带来的体积变化同时会导致材料气孔率的增加,也会引发刀具材料硬度和耐磨损性能的降低,从而导致其使用寿命进一步缩短。
发明内容
本发明解决的技术问题:针对上述问题,本发明提供了一种在WC和cBN粉体表面上分别包覆SiO2和Co纳米层以提高其烧结性能,抑制cBN的相变,提高材料硬度的碳化钨-立方氮化硼复合材料及其制备方法。
技术方案:一种碳化钨-立方氮化硼复合材料,主要成分包括WC和cBN,其中在WC表面包覆有Co纳米粒子层,其厚度为60-120 nm,在cBN粉体表面包覆有SiO2纳米层,其厚度为20-100nm,包覆有SiO2纳米层的cBN在复合材料中的体积含量为30-50vol%,WC和cBN粉体的纯度均在95%以上。
作为优选,WC粉体的平均粒径为2μm。
作为优选,cBN粉体的平均粒径为3μm。
一种碳化钨-立方氮化硼复合材料的制备方法,制备步骤如下:
(1)将WC粉体放入化学气相沉积反应室中,抽真空,预热至500-700℃,以二茂钴为原料,蒸发温度为120-150℃,反应室开始旋转,反应时间为18-50min,包覆结束后,停止旋转,并停止原料供应,待冷却至室温,取出;
(2)将cBN粉体放入化学气相沉积反应室中,抽真空,预热500-700℃,以正硅酸乙酯为原料,加热至80-130℃,反应室开始旋转,反应时间为15-50min,包覆结束后,停止旋转,并停止原料供应,待冷却至室温,取出;
(3)将包覆后的WC和cBN粉体混合,其中包覆后的cBN在混合粉体中的重量含量为9%-18%,然后过筛;
(4)将混合过筛好的粉体放入模具,烧结制备块体材料,即碳化钨-立方氮化硼复合材料;
其中,烧结过程中所使用的烧结温度为1200-1500℃,压力为4-8GPa,时间0.5-2h。
作为优选,WC粉体包覆过程在氩气保护气氛中进行,氩气的气体流量为20-50sccm。
作为优选,cBN粉体包覆过程在氩气保护气氛中进行,氩气的气体流量为10-30sccm。
作为优选,上述步骤(1)和步骤(2)反应室的旋转速率为30-60r/min。
作为优选,包覆后的WC和cBN粉体的采用滚筒法混合,混合时间5-10h。
作为优选,混合后的WC和cBN粉体过筛的筛孔的尺寸为100-200目,过筛次数为3次。
有益效果:本发明提供的碳化钨-立方氮化硼复合材料及其制备方法,是采用化学气相沉积法和高温烧结法,首先使用化学气相沉积法,在WC粉体表面包覆Co纳米层,在cBN表面包覆SiO2纳米层,通过在粉体表面包覆和均匀分散,减少软相粒子Co的使用量,提高复合材料的硬度;通过正硅酸乙酯的氧化分解在cBN粉体表面包覆SiO2非晶纳米层,抑制cBN在烧结过程中的相变,提高材料的硬度等力学性能,然后再高温烧结获得块状材料,制成的碳化钨-立方氮化硼复合材料具有结构热稳定性高,硬度高等特点,可作为高速切削刀具材料或作为钛合金、冷硬铸铁等传统刀具难以处理的特殊材料的加工成型领域,而且本发明提供的制备方法简易,成本较低,可实现大规模商业化生产。
附图说明
图1为本发明碳化钨-立方氮化硼复合材料中WC和cBN粉体表面包覆示意图。
具体实施方式
为了进一步理解本发明,下面结合实施例对本发明优选实施方案进行描述,但是应当理解,这些描述只是为进一步说明本发明的特征和优点,而不是对本发明权利要求的限制。
根据本发明提供的碳化钨-立方氮化硼复合材料的制备方法制备型碳化钨-立方氮化硼复合材料,材料选用纯度大于95%以上粉体材料和纯度大于98%以上的金属有机原料,其中WC粉体的平均粒径为2μm,cBN粉体的平均粒径为3μm,所有材料在进行化学气相沉积处理之前,已在真空中除气除湿,然后按照本发明提供的制备方法进行制备。
实施例1
根据本发明提供的碳化钨-立方氮化硼复合材料的制备方法制备型碳化钨-立方氮化硼复合材料,步骤如下:
(1)将WC粉体放入化学气相沉积反应室中,抽真空至5Pa,预热至500℃,以二茂钴为原料,蒸发温度为120℃,反应室开始旋转,旋转速率为30r/min,氩气气体流量为20sccm,通过二茂钴的热分解在WC粉体表面包覆Co纳米粒子层,反应时间为20min,包覆结束后,停止旋转,并停止原料供应,待冷却至室温,取出;
(2)将cBN粉体放入化学气相沉积反应室中,抽真空至5Pa,预热500℃,以正硅酸乙酯为原料,加热至80℃,反应室开始旋转,旋转速率为30r/min,氩气气体流量为10sccm,通过正硅酸乙酯的氧化热分解在WC粉体表面包覆SiO2纳米层,反应时间为20min,包覆结束后,停止旋转,并停止原料供应,待冷却至室温,取出;
采用FESEM和TEM相结合的方法测定粉体表面纳米粒子层的粒度及厚度,SiO2纳米层的厚度为20nm,WC粉体表面Co的粒径为20nm,厚度为60nm;
(3)将9.1g包覆后的WC粉体和0.9g包覆后的cBN粉体采用滚筒法(干法)混合5h,然后过100目筛3次;
(4)将混合过筛好的粉体放入模具,烧结制备块体材料,烧结过程中所使用的烧结温度为1200℃,压力为4GPa,时间2h;
烧结后cBN相的体积含量为30%,制成的样品直径为30mm,厚度为5mm。
实施例2
根据本发明提供的碳化钨-立方氮化硼复合材料的制备方法制备型碳化钨-立方氮化硼复合材料,步骤如下:
(1)将WC粉体放入化学气相沉积反应室中,抽真空至10Pa,预热至500℃,以二茂钴为原料,蒸发温度为130℃,反应室开始旋转,旋转速率为45r/min,氩气气体流量为30sccm,通过二茂钴的热分解在WC粉体表面包覆Co纳米粒子层,反应时间为18min,包覆结束后,停止旋转,并停止原料供应,待冷却至室温,取出;
(2)将cBN粉体放入化学气相沉积反应室中,抽真空至10Pa,预热500℃,以正硅酸乙酯为原料,加热至120℃,反应室开始旋转,旋转速率为50r/min,氩气气体流量为20sccm,通过正硅酸乙酯的氧化热分解在cBN粉体表面包覆SiO2纳米层,反应时间为15min,包覆结束后,停止旋转,并停止原料供应,待冷却至室温,取出;
采用FESEM和TEM相结合的方法测定粉体表面纳米粒子层的粒度及厚度,SiO2纳米层的厚度为20nm,WC粉体表面Co的粒径为20nm,厚度为60nm;
(4)将8.9g包覆后的WC粉体和1.1g 包覆后的cBN粉体采用滚筒法(干法)混合10h,然后过200目筛3次;
(5)将混合过筛好的粉体放入模具,烧结制备块体材料,烧结过程中所使用的烧结温度为1300℃,压力为6GPa,时间1.5h;
烧结后cBN相的体积含量为35%,制成的样品直径为30mm,厚度为5mm。
实施例3
根据本发明提供的碳化钨-立方氮化硼复合材料的制备方法制备型碳化钨-立方氮化硼复合材料,步骤如下:
(1)将WC粉体放入化学气相沉积反应室中,抽真空至20Pa,预热至500℃,以二茂钴为原料,蒸发温度为140℃,反应室开始旋转,旋转速率为60r/min,氩气气体流量为40sccm,通过二茂钴的热分解在WC粉体表面包覆Co纳米粒子层,反应时间为50min,包覆结束后,停止旋转,并停止原料供应,待冷却冷至室温,取出;
(2)将cBN粉体放入化学气相沉积反应室中,抽真空至20Pa,预热500℃,以正硅酸乙酯为原料,加热至90℃,反应室开始旋转,旋转速率为40r/min,氩气气体流量为30sccm,通过正硅酸乙酯的氧化热分解在cBN粉体表面包覆SiO2纳米层,反应时间为50min,包覆结束后,停止旋转,并停止原料供应,待冷却冷至室温,取出;
采用FESEM和TEM相结合的方法测定粉体表面纳米粒子层的粒度及厚度,SiO2纳米层的厚度为50nm,WC粉体表面Co的粒径为40nm,厚度为120nm。
(4)将8.7g包覆后的WC粉体和1.3g 包覆后的cBN粉体采用滚筒法(干法)混合10h,然后过200目筛3次;
(5)将混合过筛好的粉体放入模具,烧结制备块体材料,烧结过程中所使用的烧结温度为1400℃,压力为5GPa,时间0.5h;
烧结后cBN相的体积含量为40%,制成的样品直径为30mm,厚度为5mm。
实施例4
根据本发明提供的碳化钨-立方氮化硼复合材料的制备方法制备型碳化钨-立方氮化硼复合材料,步骤如下:
(1)将WC粉体放入化学气相沉积反应室中,抽真空至15Pa,预热至500℃,以二茂钴为原料,蒸发温度为150℃,反应室开始旋转,旋转速率为35r/min,氩气气体流量为40sccm,通过二茂钴的热分解在WC粉体表面包覆Co纳米粒子层,反应时间为40min,包覆结束后,停止旋转,并停止原料供应,待冷却至室温,取出;
(2)将cBN粉体放入化学气相沉积反应室中,抽真空至15Pa,预热500℃,以正硅酸乙酯为原料,加热至130℃,反应室开始旋转,旋转速率为35r/min,氩气气体流量为25sccm,通过正硅酸乙酯的氧化热分解在WC粉体表面包覆Co纳米粒子层,反应时间为40min,包覆结束后,停止旋转,并停止原料供应,待冷却冷至室温,取出;
采用FESEM和TEM相结合的方法测定粉体表面纳米粒子层的粒度及厚度,SiO2纳米层的厚度为100nm,WC粉体表面Co的粒径为40nm,厚度为120nm。
(4)将8.5g包覆后的WC粉体和1.5g包覆后的cBN粉体采用滚筒法(干法)混合6h,然后过100目筛3次;
(5)将混合过筛好的粉体放入模具,烧结制备块体材料,烧结过程中所使用的烧结温度为1400℃,压力为5GPa,时间1.5h;
烧结后cBN相的体积含量为45%,制成的样品直径为30mm,厚度为5mm。
实施例5
根据本发明提供的碳化钨-立方氮化硼复合材料的制备方法制备型碳化钨-立方氮化硼复合材料,步骤如下:
(1)将WC粉体放入化学气相沉积反应室中,抽真空至10Pa,预热至500℃,以二茂钴为原料,蒸发温度为150℃,反应室开始旋转,旋转速率为60r/min,氩气气体流量为25sccm,通过二茂钴的热分解在WC粉体表面包覆Co纳米粒子层,反应时间为20min,包覆结束后,停止旋转,并停止原料供应,待冷却至室温,取出;
(2)将cBN粉体放入化学气相沉积反应室中,抽真空至20Pa,预热500℃,以正硅酸乙酯为原料,加热至130℃,反应室开始旋转,旋转速率为60r/min,氩气气体流量为25sccm,通过正硅酸乙酯的氧化热分解在WC粉体表面包覆Co纳米粒子层,反应时间为25min,包覆结束后,停止旋转,并停止原料供应,待冷却至室温,取出;
采用FESEM和TEM相结合的方法测定粉体表面纳米粒子层的粒度及厚度,SiO2纳米层的厚度为40nm,WC粉体表面Co的粒径为30nm,厚度为60nm。
(4)将8.2g包覆后的WC粉体和1.8g 包覆后的cBN粉体采用滚筒法(干法)混合10h,然后过100目筛3次;
(5)将混合过筛好的粉体放入模具,烧结制备块体材料,烧结过程中所使用的烧结温度为1500℃,压力为8GPa,时间0.5h;
烧结后,cBN相的体积含量为50%,制成的样品直径为30mm,厚度为5mm。
将上述具体实施方式制成的样品采用维氏硬度压痕法测试WC-cBN复合材料的硬度和断裂韧性,拉伸法测试材料的强度,结果如下:
表1 WC-cBN复合材料的致密度、硬度、韧性和强度等。
由表可知,本发明新型WC-cBN复合材料具有较高的硬度、韧性和强度,随着包覆后cBN相的体积含量由30%增加到50%,WC-cBN复合材料的致密度呈起伏变化趋势,经历两次起伏,在包覆后cBN相的体积含量达到45%时,致密度最高;复合材料的硬度指标随着包覆后cBN相的体积含量的增加呈现先上升再下降的趋势,在包覆后cBN相的体积含量达到45%时,硬度最高;复合材料的韧性与硬度指标的变化趋势相近,在包覆后cBN相的体积含量达到40%时,韧性最好;复合材料的强度指标的变化趋势与致密度呈现相同的变化趋势,在包覆后cBN相的体积含量达到45%时,强度最高。
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (8)
1.一种碳化钨-立方氮化硼复合材料的制备方法,其特征在于,复合材料主要成分包括WC和cBN,其中在WC表面包覆有Co纳米粒子层,其厚度为60-120 nm,在cBN粉体表面包覆有SiO2纳米层,其厚度为20-100nm,包覆有SiO2纳米层的cBN在复合材料中的体积含量为30-50vol%,WC和cBN粉体的纯度均在95%以上,复合材料的制备步骤如下:
(1)将WC粉体放入化学气相沉积反应室中,抽真空,预热至500-700℃,以二茂钴为原料,蒸发温度为120-150℃,反应室开始旋转,反应时间为18-50min,包覆结束后,停止旋转,并停止原料供应,待冷却至室温,取出;
(2)将cBN粉体放入化学气相沉积反应室中,抽真空,预热500-700℃,以正硅酸乙酯为原料,加热至80-130℃,反应室开始旋转,反应时间为15-50min,包覆结束后,停止旋转,并停止原料供应,待冷却至室温,取出;
(3)将包覆后的WC和cBN粉体混合,其中包覆后的cBN在混合粉体中的重量含量为9%-18%,然后过筛;
(4)将混合过筛好的粉体放入模具,烧结制备块体材料,即碳化钨-立方氮化硼复合材料;
其中,烧结过程中所使用的烧结温度为1200-1500℃,压力为4-8GPa,时间为0.5-2h。
2.根据权利要求1所述的碳化钨-立方氮化硼复合材料的制备方法,其特征在于,WC粉体包覆过程在氩气保护气氛中进行,氩气的气体流量为20-50sccm。
3.根据权利要求1所述的碳化钨-立方氮化硼复合材料的制备方法,其特征在于,cBN粉体包覆过程在氩气保护气氛中进行,氩气的气体流量为10-30sccm。
4.根据权利要求1所述的碳化钨-立方氮化硼复合材料的制备方法,其特征在于,步骤(1)和步骤(2)反应室旋转速率为30-60r/min。
5.根据权利要求1所述的碳化钨-立方氮化硼复合材料的制备方法,其特征在于,包覆后的WC和cBN粉体采用滚筒法混合,混合时间5-10h。
6.根据权利要求1所述的碳化钨-立方氮化硼复合材料的制备方法,其特征在于,混合后的WC和cBN粉体过筛的筛孔的尺寸为100-200目,过筛次数为3次。
7.根据权利要求1所述的碳化钨-立方氮化硼复合材料,其特征在于:WC粉体的平均粒径为2μm。
8.根据权利要求1所述的碳化钨-立方氮化硼复合材料,其特征在于:cBN粉体的平均粒径为3μm。
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- 2015-06-30 NZ NZ727432A patent/NZ727432A/en not_active IP Right Cessation
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- 2015-06-30 WO PCT/CN2015/082923 patent/WO2015192815A1/zh active Application Filing
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- 2015-06-30 US US15/318,379 patent/US10259751B2/en not_active Expired - Fee Related
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WO2015192815A1 (zh) | 2015-12-23 |
AU2015276668B2 (en) | 2018-02-01 |
US10259751B2 (en) | 2019-04-16 |
AU2015276668A1 (en) | 2017-01-05 |
US20170121230A1 (en) | 2017-05-04 |
CN104072138A (zh) | 2014-10-01 |
NZ727432A (en) | 2017-12-22 |
SG11201610563PA (en) | 2017-02-27 |
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