CN111778436B - 一种冷压-热压烧结制备wc-y2o3无粘结相硬质合金的方法 - Google Patents
一种冷压-热压烧结制备wc-y2o3无粘结相硬质合金的方法 Download PDFInfo
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Abstract
本发明涉及无粘结相硬质合金的制备技术领域,尤其涉及一种冷压‑热压烧结制备WC‑Y2O3无粘结相硬质合金的方法。本发明的方法包括以下步骤:将WC粉体和Y2O3粉体进行球磨混合,得到WC‑Y2O3粉体;向所述WC‑Y2O3粉体中加入饱和草酸溶液至完全润湿,将润湿后的WC‑Y2O3粉体进行冷压烧结,得到烧结体;所述冷压烧结的压力为200~400MPa;所述冷压烧结的升温程序为:先升温至100~150℃保温1h,继续升温至200~300℃保温1~2h;将所述烧结体进行热压烧结,得到WC‑Y2O3无粘结相硬质合金。本发明能显著降低无粘结相WC基硬质合金的烧结温度,同时提高合金的致密度和综合力学性能。
Description
技术领域
本发明涉及无粘结相硬质合金的制备技术领域,尤其涉及一种冷压-热压烧结制备WC-Y2O3无粘结相硬质合金的方法。
背景技术
碳化钨(WC)基硬质合金由于具有高强度、硬度以及高杨氏模量,广泛应用于切削刀具、模具以及耐磨、耐高压零件等。纯WC具有较高的熔点(2785℃),故烧结温度高、烧结致密化困难且烧结体断裂韧性差,人们通常所采用的方法是加入钴(Co)、镍(Ni)等金属粘结相制备出WC-M(金属相)硬质合金。但在高速、高效干切削的苛刻工况下这些金属粘结相比WC硬质相更加容易被氧化、腐蚀和磨损失效,限制了其在钛合金、高温合金等难加工材料领域的应用。在高温下,WC-M硬质合金模具中的金属相不仅易于氧化且容易向玻璃产品扩散,成为高精密光学玻璃模具制造亟需突破的材料瓶颈。此外,金属粘结相Co、Ni等随着刀具、零部件磨损以粉尘、蒸汽等形式进入环境对工人健康产生极大威慑。因此,发展具有高硬度高断裂韧性的“双高”力学性能,且又具有比传统WC-M(金属相)合金更加优异的耐磨性、抗腐蚀与抗高温氧化性能的WC无粘结相硬质合金的制备技术和方法,对工量刃具技术的发展与绿色制造具有非常重要的意义。
无粘结相WC基硬质合金具有比传统硬质合金更优异的耐磨性、抗腐蚀和抗高温氧化性,目前已成为国际硬质合金领域的研究热点与发展方向。然而由于WC熔点高达2785℃,无粘结相WC基硬质合金烧结温度高,制备的材料致密性差,综合力学性能不佳,影响使用。虽然放电等离子(SPS)烧结技术能极大地降低烧结温度,制备得到无粘结相WC基硬质合金综合性能较优,但设备昂贵,制备成本高,烧结尺寸受到限制,因此极大地限制了无粘结相WC基硬质合金的工业推广与应用。
发明内容
本发明的目的在于提供一种冷压-热压烧结制备WC-Y2O3无粘结相硬质合金的方法,能显著降低无粘结WC基硬质合金的烧结温度,同时提高合金的致密度和综合力学性能,且成本低廉。
为了实现上述发明目的,本发明提供以下技术方案:
本发明提供了一种冷压-热压烧结制备WC-Y2O3无粘结相硬质合金的方法,包括以下步骤:
将WC粉体和Y2O3粉体进行球磨混合,得到WC-Y2O3粉体;
向所述WC-Y2O3粉体中加入饱和草酸溶液至完全润湿,将润湿后的WC-Y2O3粉体进行冷压烧结,得到烧结体;所述冷压烧结的压力为200~400MPa;所述冷压烧结的升温程序为:先升温至100~150℃保温1h,继续升温至200~300℃保温1~2h;
将所述烧结体进行热压烧结,得到WC-Y2O3无粘结相硬质合金。
优选的,所述WC-Y2O3粉体和饱和草酸溶液的固液比为10g:(1~1.5)mL。
优选的,所述Y2O3粉体的质量占WC粉体和Y2O3粉体总质量的1~3%。
优选的,所述WC粉体的平均晶粒尺寸为200nm~400nm。
优选的,所述Y2O3粉体的平均晶粒尺寸为50nm~200nm。
优选的,所述热压烧结的升温程序为:在150℃保温20min,然后升温至250℃保温20min,继续升温至800℃保温60min,最后升温至1400~1650℃保温90min。
优选的,所述热压烧结的压力为40MPa。
优选的,所述冷压烧结和热压烧结过程中各所述升温的速率独立为10~15℃/min。
优选的,所述球磨混合的条件包括:球料质量比为(5~15):1,球磨介质为无水乙醇,球磨转速为200~250r/min,球磨时间为6~12h。
优选的,所述球磨混合后还包括对球磨后的物料进行干燥,所述干燥为真空干燥。
本发明提供了一种冷压-热压烧结制备WC-Y2O3无粘结相硬质合金的方法,包括以下步骤:将WC粉体和Y2O3粉体进行球磨混合,得到WC-Y2O3粉体;向所述WC-Y2O3粉体中加入饱和草酸溶液至完全润湿,将润湿后的WC-Y2O3粉体进行冷压烧结,得到烧结体;所述冷压烧结的压力为200~400MPa;所述冷压烧结的升温程序为:先升温至100~150℃保温1h,继续升温至200~300℃保温1~2h;将所述烧结体进行热压烧结,得到WC-Y2O3无粘结相硬质合金。
本发明将WC粉体和Y2O3粉体进行球磨混合,使得Y2O3粉体在WC粉体中充分分散开来;然后向得到的WC-Y2O3粉体中加入饱和草酸溶液至完全润湿,Y2O3本身微溶于草酸溶液,在冷压烧结的压力和温度作用下,Y2O3开始先发生部分溶解,随着温度的升高,草酸溶液蒸发,Y2O3会析出,正是由于微量Y2O3在草酸溶液中的溶解-析出,使得WC-Y2O3粉体间隙处达到过饱和状态,并使颗粒接触区的化学势高于晶体,此时溶解的原子或离子簇将在晶体处析出,从而促进WC-Y2O3的致密化,使WC-Y2O3无粘结相硬质合金在较低的温度下(100℃~300℃)获得相对密度达70%以上的烧结体,进而极大地降低了后续传统烧结工艺(热压烧结)制备无粘结相WC基硬质合金的烧结温度,且得到的WC-Y2O3无粘结相硬质合金致密性高,综合性能优异。实施例的结果表明,采用本发明的方法,可将传统热压烧结的温度降至1650℃以下,且制备的无粘结相WC基硬质合金的致密性高,为97.87~100%,硬度为2357~2500HV30,断裂韧性为8.2~9.3MPa·m1/2,综合性能优异。
附图说明
图1为实施例1球磨前后物料的SEM形貌图;
图2为实施例1冷压烧结后所得烧结体的SEM断口形貌图;
图3为实施例1制备的WC-1wt.%Y2O3无粘结相硬质合金的SEM断口形貌图;
图4为实施例2制备的WC-2wt.%Y2O3无粘结相硬质合金的SEM断口形貌图;
图5为实施例3制备的WC-3wt.%Y2O3无粘结相硬质合金的SEM断口形貌图;
图6为实施例4制备的WC-3wt.%Y2O3无粘结相硬质合金的SEM断口形貌图;
图7为对比例制备的WC-2wt.%Y2O3无粘结相硬质合金的SEM断口形貌图。
具体实施方式
本发明提供了一种冷压-热压烧结制备WC-Y2O3无粘结相硬质合金的方法,包括以下步骤:
将WC粉体和Y2O3粉体进行球磨混合,得到WC-Y2O3粉体;
向所述WC-Y2O3粉体中加入饱和草酸溶液至完全润湿,将润湿后的WC-Y2O3粉体进行冷压烧结,得到烧结体;所述冷压烧结的压力为200~400MPa;所述冷压烧结的升温程序为:先升温至100~150℃保温1h,继续升温至200~300℃保温1~2h;
将所述烧结体进行热压烧结,得到WC-Y2O3无粘结相硬质合金。
在本发明中,未经特殊说明,所用原料均为本领域熟知的市售商品。
本发明将WC粉体和Y2O3粉体进行球磨混合,得到WC-Y2O3粉体。在本发明中,所述WC粉体的平均晶粒尺寸优选为200nm~400nm,更优选为200~300nm,在本发明的实施例中,具体为200nm。在本发明中,所述Y2O3粉体的平均晶粒尺寸优选为50nm~200nm,更优选为100~150nm,在本发明的实施例中,具体为50nm。在本发明中,所述Y2O3粉体的质量优选占WC粉体和Y2O3粉体总质量的1~3%,更优选为1.5~2.5%。
在本发明中,所述球磨混合的条件优选包括:球料质量比为(5~15):1,球磨介质为无水乙醇,球磨转速为200~250r/min,球磨时间为6~12h。进一步的,所述球料质量比更优选为10:1,球磨转速更优选为210~230r/min,球磨时间更优选为8~10h。在本发明中,所述球磨混合过程中,本发明优选每5分钟换向一次。为了避免球磨过程中产生杂质,本发明优选采用硬质合金球磨罐和磨球。所述球磨混合后,本发明优选还包括对球磨后的物料进行干燥,所述干燥优选为真空干燥,所述真空干燥的温度优选为60℃,所述真空干燥的时间优选为24h。本发明利用球磨使得Y2O3粉体在WC粉体中充分分散开来。
得到WC-Y2O3粉体后,本发明向所述WC-Y2O3粉体中加入饱和草酸溶液至完全润湿,将润湿后的WC-Y2O3粉体进行冷压烧结,得到烧结体。
在本发明中,使所述WC-Y2O3粉体完全润湿采用的饱和草酸溶液的用量优选满足:WC-Y2O3粉体和饱和草酸溶液的固液比为10g:(1~1.5)mL,更优选为10g:1mL。
在本发明中,所述冷压烧结的压力为200~400MPa,优选为250~350MPa;所述冷压烧结的升温程序优选为:先升温至100~150℃保温1h,继续升温至200~300℃保温1~2h;更优选:先升温至150℃保温1h,然后继续升温至250℃保温2h。本发明优选自室温开始升温。在本发明中,冷压烧结过程中各所述升温的速率独立地优选为10~15℃/min。本发明优选将WC-Y2O3粉体置于金属模具中,在金属模具外圈安装加热圈,然后金属模具上压头施加压力,将加热圈按上述升温程序进行升温进行所述冷压烧结。
本发明向得到的WC-Y2O3粉体中加入饱和草酸溶液至完全润湿,Y2O3本身微溶于草酸溶液,在冷压烧结的压力和温度作用下,Y2O3开始先发生部分溶解,随着温度的升高,草酸溶液蒸发,Y2O3会析出,正是由于微量Y2O3在草酸溶液中的溶解-析出,使得WC-Y2O3粉体间隙处达到过饱和状态,并使颗粒接触区的化学势高于晶体,此时溶解的原子或离子簇将在晶体处析出,从而促进WC-Y2O3的致密化,使WC-Y2O3无粘结相硬质合金在较低的温度下(100℃~300℃)获得相对密度达70%以上的烧结体,进而极大地降低了后续传统烧结工艺(热压烧结)制备无粘结相WC基硬质合金的烧结温度,且得到的WC-Y2O3无粘结相硬质合金致密性高,综合性能优异。
得到烧结体后,本发明将所述烧结体进行热压烧结,得到WC-Y2O3无粘结相硬质合金。在本发明中,所述热压烧结的升温程序优选为:在150℃保温20min,然后升温至250℃保温20min,继续升温至800℃保温60min,最后升温至1400~1650℃保温90min;所述热压烧结的压力优选为40MPa。本发明优选将所述烧结体置于石墨模具中进行热压烧结。本发明所述热压烧结过程中残余的草酸溶液进一步分解析出,WC晶粒进一步重排,有效降低空隙和晶界,从而进一步提高烧结体的致密性。本发明优选自室温开始升温。在本发明中,热压烧结过程中各所述升温的速率独立地优选为10~15℃/min。
下面结合实施例对本发明提供的冷压-热压烧结制备WC-Y2O3无粘结相硬质合金的方法进行详细的说明,但是不能把它们理解为对本发明保护范围的限定。
实施例1
1、球磨混合
将平均晶粒尺寸分别为200nm和50nm的WC粉体和Y2O3粉体按一定的质量分数进行球磨混合,氧化钇质量分数为1%,采用硬质合金球磨罐和磨球,球磨工艺如下:球料质量比为10:1,球磨介质为无水乙醇,球磨转速为200r/min,每5分钟换向一次,球磨时间为12h,球磨结束后,将粉体放在真空干燥箱内60℃干燥24h,得到WC-1wt.%Y2O3粉体。球磨前后的粉体形貌如图1所示,其中,a为Y2O3粉体,b为WC粉体,c为球磨后的WC-1wt.%Y2O3粉体,由图1可知,粉体混合均匀,未见Y2O3粉体的局部富集。
2、冷压烧结
称取30gWC-1wt.%Y2O3粉体,滴加饱和草酸溶液3mL至粉体完全湿润,然后将润湿后的粉体置于直径为20mm的金属模具中,金属模具外圈装加热圈,然后金属模具上压头施加压力400MPa,加热圈升温至150℃,保温1h,继续升温至250℃,保温2h,升温速率为10℃/min,得到烧结体。
图2为烧结体试样断口形貌,从图中可以看出,虽然只有250℃的烧结温度,但在400MPa的高压以及饱和草酸溶液存在的环境中,碳化钨晶粒间出现了扩散现象,经测定,试样致密性达到了70%。
3、热压烧结
将冷压烧结制备得到的烧结体装入石墨模具中进行热压烧结,烧结压力为40MPa,升温速率为10℃/min,烧结过程中,在150℃保温20min,250℃保温20min,800℃度保温60min,1600℃保温90min,制备得到掺杂质量分数为1%的Y2O3的无粘结相碳化钨基硬质合金。
测定试样相对密度为97.87%,硬度为2399HV30,断裂韧性为8.2MPa·m1/2。图3显示了本实施例制备的质量分数为1%的Y2O3的无粘结相碳化钨基硬质合金断口形貌,WC晶粒结合紧密,局部区域存在孔隙。
实施例2
1、球磨混合
将平均晶粒尺寸分别为200nm和50nm的WC粉体和Y2O3粉体按一定的质量分数进行球磨混合,氧化钇质量分数为2%,采用硬质合金球磨罐和磨球,球磨工艺如下:球料质量比为10:1,球磨介质为无水乙醇,球磨转速为200r/min,每5分钟换向一次,球磨时间为12h,球磨结束后,将粉体放在真空干燥箱内60℃干燥24h,得到WC-2wt.%Y2O3粉体。
2、冷压烧结
称取30g球磨混合制备得到的WC-2wt.%Y2O3粉体,滴加饱和草酸溶液3mL至粉体完全湿润,然后将润湿的粉体置于直径为20mm的金属模具中,金属模具外圈装加热圈,然后金属模具上压头施加压力400MPa,加热圈升温至150℃,保温1h,继续升温至250℃,保温2h,升温速率为10℃/min,得到烧结体。测定烧结体致密性,相对密度为73%。
3、热压烧结
将冷压烧结制备得到的烧结体装入石墨模具中进行热压烧结,烧结温度为1600℃,烧结压力为40MPa,升温速率为10℃/min,烧结过程中,在150℃保温20min,250℃保温20min,800℃度保温60min,1600℃保温90min,制备得到掺杂质量分数为2%的Y2O3的无粘结相碳化钨基硬质合金。
测定试样相对密度为99.96%,硬度为2500HV30,断裂韧性为9.1MPa·m1/2。图4显示了本实施例所制备的质量分数为2%的Y2O3的无粘结相碳化钨基硬质合金断口形貌,WC晶粒紧密结合,基本上不存在孔隙,接近全致密状态。
实施例3
1、球磨混合
将平均晶粒尺寸分别为200nm和50nm的WC粉体和Y2O3粉体按一定的质量分数进行球磨混合,氧化钇质量分数为3%,采用硬质合金球磨罐和磨球,球磨工艺如下:球料质量比为10:1,球磨介质为无水乙醇,球磨转速为200r/min,每5分钟换向一次,球磨时间为12h,球磨结束后,将粉体放在真空干燥箱内60℃干燥24h,得到WC-3wt.%Y2O3粉体。
2、冷压烧结
称取30g球磨混合制备得到的WC-3wt.%Y2O3粉体,滴加饱和草酸溶液3mL至粉体完全湿润,然后将润湿后的粉体置于直径为20mm的金属模具中,金属模具外圈装加热圈,然后金属模具上压头施加压力400MPa,加热圈升温至150℃,保温1h,继续升温至250℃,保温2h,升温速率为10℃/min,得到烧结体。测定烧结体的致密性,相对密度为73%。
3、热压烧结
将冷压烧结制备得到的烧结体装入石墨模具中进行热压烧结,烧结压力为40MPa,升温速率为10℃/min,烧结过程中,在150℃保温20min,250℃保温20min,800℃度保温60min,1600℃保温90min,制备得到掺杂质量分数为3%的Y2O3的无粘结相碳化钨基硬质合金。
测定试样相对密度为99.87%,硬度为2357HV30,断裂韧性为8.8MPa·m1/2。图5显示了本实施例的所制备的质量分数为3%的Y2O3的无粘结相碳化钨基硬质合金断口形貌,WC晶粒紧密结合,只有少量的孔隙存在。
实施例4
1、球磨混合
将平均晶粒尺寸分别为200nm和50nm的WC粉体和Y2O3粉体按一定的质量分数进行球磨混合,氧化钇质量分数为3%,采用硬质合金球磨罐和磨球,球磨工艺如下:球料质量比为10:1,球磨介质为无水乙醇,球磨转速为200r/min,每5分钟换向一次,球磨时间为12h,球磨结束后,将粉体放在真空干燥箱内60℃干燥24h,得到WC-3wt.%Y2O3粉体。
2、冷压烧结
称取30g球磨混合制备得到的WC-3wt.%Y2O3粉体,滴加饱和草酸溶液3mL至粉体完全湿润,然后将润湿后的粉体置于直径为20mm的金属模具中,金属模具外圈装加热圈,然后金属模具上压头施加压力400MPa,加热圈升温至150℃,保温1h,继续升温至250℃,保温2h,升温速率为10℃/min,得到烧结体。测定烧结体的致密性,相对密度为73%。
3、热压烧结
将冷压烧结制备得到的烧结体装入石墨模具中进行热压烧结,烧结压力为40MPa,升温速率为10℃/min,烧结过程中,在150℃保温20min,250℃保温20min,800℃度保温60min,1650℃保温90min,制备得到掺杂质量分数为3%的Y2O3的无粘结相碳化钨基硬质合金。
测定试样相对密度为100%,硬度为2460HV30,断裂韧性为9.3MPa·m1/2。图6显示了本实施例的所制备的质量分数为3%的Y2O3的无粘结相碳化钨基硬质合金断口形貌,WC晶粒紧密结合,未见孔隙存在。
对比例
1、球磨混合
将平均晶粒尺寸分别为200nm和50nm的WC粉体和Y2O3粉体按一定的质量分数进行球磨混合,氧化钇质量分数为2%,采用硬质合金球磨罐和磨球,球磨工艺如下:球料质量比为10:1,球磨介质为无水乙醇,球磨转速为200r/min,每5分钟换向一次,球磨时间为12h,球磨结束后,将粉体放在真空干燥箱内60℃干燥24h,得到WC-2wt.%Y2O3粉体。
2、热压烧结
称取30g球磨混合制备得到的WC-2wt.%Y2O3粉体,然后将粉体置于直径为20mm的金属模具中,金属模具上压头施加压力400MPa,保持10min,脱模,将压制成型的WC-2wt.%Y2O3块体装入石墨模具中进行热压烧结,烧结压力为40MPa,升温速率为10℃/min,烧结过程中,在150℃保温20min,250℃保温20min,在800℃度保温60min,1600℃保温90min,制备得到掺杂质量分数为2%的Y2O3的无粘结相碳化钨基硬质合金。
测定试样相对密度为96.65%,硬度为2156HV30,断裂韧性为8.2MPa·m1/2。图7显示了本对比例的所制备的质量分数为2%的Y2O3的无粘结相碳化钨基硬质合金断口形貌,有些WC晶粒间没有得到较好地结合,存在较多的孔隙。
由以上实施例可知,本发明提供了一种冷压-热压烧结制备WC-Y2O3无粘结相硬质合金的方法,能显著降低无粘结WC基硬质合金的烧结温度,同时提高合金的致密度和综合力学性能,且成本低廉。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (4)
1.一种冷压-热压烧结制备WC-Y2O3无粘结相硬质合金的方法,包括以下步骤:
将WC粉体和Y2O3粉体进行球磨混合,得到WC-Y2O3粉体;
向所述WC-Y2O3粉体中加入饱和草酸溶液至完全润湿,将润湿后的WC-Y2O3粉体进行冷压烧结,得到烧结体;所述冷压烧结的压力为200~400MPa;所述冷压烧结的升温程序为:先升温至100~150℃保温1h,继续升温至200~300℃保温1~2h;
将所述烧结体进行热压烧结,得到WC-Y2O3无粘结相硬质合金;
所述热压烧结的升温程序为:在150℃保温20min,然后升温至250℃保温20min,继续升温至800℃保温60min,最后升温至1400~1650℃保温90min;所述热压烧结的压力为40MPa;
所述WC-Y2O3粉体和饱和草酸溶液的固液比为10g:(1~1.5)mL;
所述Y2O3粉体的质量占WC粉体和Y2O3粉体总质量的1~3%;
所述冷压烧结和热压烧结过程中各所述升温的速率独立为10~15℃/min;
所述球磨混合的条件包括:球料质量比为(5~15):1,球磨介质为无水乙醇,球磨转速为200~250r/min,球磨时间为6~12h。
2.根据权利要求1所述的方法,其特征在于,所述WC粉体的平均晶粒尺寸为200nm~400nm。
3.根据权利要求1所述的方法,其特征在于,所述Y2O3粉体的平均晶粒尺寸为50nm~200nm。
4.根据权利要求1所述的方法,其特征在于,所述球磨混合后还包括对球磨后的物料进行干燥,所述干燥为真空干燥。
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