CN113943159B - 一种碳化硼复合陶瓷的制备方法 - Google Patents

一种碳化硼复合陶瓷的制备方法 Download PDF

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CN113943159B
CN113943159B CN202111557861.6A CN202111557861A CN113943159B CN 113943159 B CN113943159 B CN 113943159B CN 202111557861 A CN202111557861 A CN 202111557861A CN 113943159 B CN113943159 B CN 113943159B
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王汝江
董世昌
于海培
张怀顺
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Shandong Jinhong New Material Co ltd
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Abstract

本发明公开了一种碳化硼复合陶瓷的制备方法,属于陶瓷制备技术领域,本发明的制备方法包括制备复合粉体,复合粉体改性,造粒,注射成型,真空脱脂,一次烧结,二次烧结;通过本发明的制备方法,能够在获得高密度,高硬度的同时,解决碳化硼陶瓷的高温氧化问题,减少在制备碳化硼陶瓷过程中粉体团聚问题。

Description

一种碳化硼复合陶瓷的制备方法
技术领域
本发明涉及陶瓷制备技术领域,具体涉及一种碳化硼复合陶瓷的制备方法。
背景技术
碳化硼陶瓷是一种仅次于金刚石和立方氮化硼的超硬材料,碳化硼具有超硬、高熔点、低密度等一系列优良的物理化学性能。碳化硼陶瓷的显著特点是非常坚硬,其显微硬度约为50000MPa,仅次于金刚石和立方氮化硼,它的研磨效率可达到金刚石的60-70%,是碳化硅的1倍,是刚玉研磨能力的1-2倍,它耐酸碱性能好,热膨胀系数小,因而它有较好的热稳定性,能吸收热中子,但抗冲击性能差,脆性大。此外,碳化硼在1000℃时能抵抗空气的腐蚀,不过在较高的温度时它在氧化气氛中很容易氧化。
为了获得致密的碳化硼陶瓷,一般采用热压烧结法来制取碳化硼陶瓷。热压烧结的碳化硼陶瓷可以达到理论密度的98%,制备时在真空热压炉或普通热压炉中进行,热压温度为2100℃,压力为80-100MPa,保温数分钟后降温,降温时需要保持压力。但是由于碳化硼陶瓷的抗热震性较差,因此降温要缓慢,而且热压温度不宜过高,到2150℃会出现B4C-C共晶液相,影响碳化硼陶瓷的硬度,但温度过低,就会导致产品密度低,虽然采用碳化硼超细粉原料,可以获得密度和硬度均高的碳化硼陶瓷制品,但是使用碳化硼超细粉原料制备碳化硼陶瓷时会出现团聚问题,而且使用碳化硼超细粉原料并不能解决碳化硼陶瓷的高温氧化问题;因此,研发一种碳化硼陶瓷的制备方法,能够在获得高密度,高硬度的同时,解决碳化硼陶瓷的高温氧化问题,减少在制备碳化硼陶瓷过程中粉体团聚问题,是目前急需解决的问题。
专利CN108821772B公开了一种添加氧化铝粉制备碳化硼铝系复合陶瓷粉的方法,该制备方法如下:先将碳质还原剂破碎成粉料;将破碎好的碳质还原剂粉,硼酸粉和Al2O3粉按一定的配比进行配料、混料、并压制成球团,再将球团进行烘干;将球团放入加热炉内进行高温冶炼制备碳化硼复合陶瓷粗粉;将得到的粗粉破碎并进行分级除杂;得到的渣粉进行回收再利用,碳化硼复合陶瓷精粉用于制作碳化硼复合陶瓷烧结原料;该专利的不足:制备的复合陶瓷材料抗高温氧化性能差。
专利CN106854080B公开了一种致密超细晶碳化硼陶瓷材料降低烧结温度的制备方法,选取平均粒度小于20μm的粗碳化硼粉末进行球磨、沉降,得到粒径小于1μm的碳化硼超细粉末;将碳化硼超细粉末与MnNiCoCrFex高熵合金粉末混合进行球磨,得到B4C-MnNiCoCrFex混合粉末;将该混合粉末进行加压烧结,得到烧结温度降低的致密超细晶碳化硼陶瓷材料;该专利的不足:在制备致密超细晶碳化硼陶瓷材料时碳化硼超细粉末易发生团聚。
发明内容
针对现有技术存在的不足,本发明提供了一种碳化硼复合陶瓷的制备方法,能够在获得高密度,高硬度的同时,解决碳化硼陶瓷的高温氧化问题,减少在制备碳化硼陶瓷过程中粉体团聚问题。
为解决以上技术问题,本发明采取的技术方案如下:
一种碳化硼复合陶瓷的制备方法,包括制备复合粉体,复合粉体改性,造粒,注射成型,真空脱脂,一次烧结,二次烧结。
所述制备复合粉体,将碳化硼粉体,氧化锌粉体,二氧化硅粉体,二水硫酸钙粉体,一水硫酸镁粉体混合均匀后置于球磨机中,在球磨前先将球磨罐内抽真空,然后通入纯度为99.6-99.9%的氧气,控制球磨罐内氧气的气体压力为0.04-0.05MPa,球磨过程中控制球磨温度为25-30℃,球料比为5-6:1,转速为280-300rpm,球磨时间为3-4h,球磨结束后得到初级混合粉,然后向初级混合粉表面喷淋活性液,喷淋结束后进行微波震荡,控制微波震荡的强度为80-100W,微波震荡的时间为4-6min,微波震荡结束得到初混料,将初混料置于真空干燥箱中进行真空干燥,控制真空干燥箱的真空度为0.04-0.06MPa,温度为70-80℃,真空干燥时间为1.5-2h,真空干燥结束得到复合粉体。
所述碳化硼粉体的纯度为99-99.5%,粒径为20-40μm。
所述活性液的组成,按重量份计,包括:30-35份无水乙醇,3-4份三乙胺,2-3份脂肪醇聚氧乙烯醚,1-3份聚苯乙烯磺酸钠,1-2份丙烯酰胺。
其中,碳化硼粉体,氧化锌粉体,二氧化硅粉体,二水硫酸钙粉体,一水硫酸镁粉体的质量比为35-40:5-8:7-9:2-3:1-3。
所述初级混合粉与活性液的质量比为1:3-4。
所述复合粉体改性,将复合粉体,黄原胶,硅藻土,纳米氮化硼混合均匀后置于球磨机中,在球磨前先将球磨罐内抽真空,然后通入氮气作为保护气体,控制球磨罐内氮气的气体压力为0.05-0.06MPa,控制球磨温度为40-50℃,球料比为8-10:1,转速为200-250rpm,球磨时间为3-5h,球磨结束得到混合粉体,然后将混合粉体置于γ-射线辐射场中进行辐照,控制吸收剂量为80-100KGy,辐照结束得到改性后的复合粉体。
其中,复合粉体,黄原胶,硅藻土,纳米氮化硼的质量比为25-30:2-3:3-5:1-2。
所述造粒,将改性后的复合粉体置于造粒机中造粒,将造粒机的温度控制在130-140℃,获得粒径为30-50目的圆形粉料。
所述注射成型,将圆形粉料置于注射机料盒中,控制加热温度为150-160℃,通过注射机成型后得到生坯。
所述真空脱脂,将生坯置于真空脱脂炉中,控制真空度为50-60Pa,以1-3℃/min的升温速率升至300-350℃,保温1-2h,得到脱脂后的坯体。
所述一次烧结,将脱脂后的坯体置于真空烧结炉中,以单质硅掩埋后在真空下进行烧结,控制真空度为0.02-0.03MPa,烧结温度为1500-1550℃,烧结时间为1-1.5h,然后自然冷却至室温后得到一次烧结后的复合陶瓷。
所述二次烧结,将一次烧结后的复合陶瓷置于真空烧结炉中,以渗钛助剂掩埋后在真空下进行烧结,控制真空度为0.02-0.03MPa,首先以0.5-1℃/min的升温速度升至500-600℃,在500-600℃下保温2.5-3h,然后以2-3℃/min的升温速度升至1500-1550℃,在1500-1550℃保温1-1.5h,然后自然冷却至室温后得到碳化硼复合陶瓷。
所述渗钛助剂的组成,按重量份计,包括:60-70份钛粉,10-12份氯化铝,5-10份氧化锌,2-5份氧化钙。
与现有技术相比,本发明的有益效果为:
(1)本发明的碳化硼复合陶瓷的制备方法,通过在制备复合粉体步骤中喷淋活性液和微波震荡,以及在复合粉体改姓步骤中将混合粉置于γ-射线辐射场中进行辐照,能够解决在烧结过程中粉体易发生团聚的问题;
(2)本发明的碳化硼复合陶瓷的制备方法,通过在制备复合粉体步骤中喷淋活性液和微波震荡,在复合粉体改姓步骤中将混合粉置于γ-射线辐射场中进行辐照,以及进行二次烧结,能提高碳化硼复合陶瓷的致密度,维氏硬度,弹性模量,抗拉强度,抗弯强度,抗压强度,本发明制备的碳化硼复合陶瓷的密度为3.25-3.29g/cm3,致密度为98.7-99.2%,维氏硬度为26-28GPa,弹性模量为445-451GPa,抗拉强度为317-321MPa,抗弯强度为437-441MPa,抗压强度为1950-2010MPa;
(3)本发明的碳化硼复合陶瓷的制备方法,通过在制备复合粉体步骤中喷淋活性液和微波震荡,在复合粉体改姓步骤中将混合粉置于γ-射线辐射场中进行辐照,以及进行二次烧结,能降低碳化硼复合陶瓷的脆性,提高碳化硼陶瓷的断裂韧性,本发明制备的碳化硼陶瓷的断裂韧性为5.5-5.7 MPa·m1/2
(4)本发明的碳化硼复合陶瓷的制备方法,通过在制备复合粉体步骤中喷淋活性液和微波震荡,在复合粉体改姓步骤中将混合粉置于γ-射线辐射场中进行辐照,以及进行二次烧结,能提高碳化硼复合陶瓷的高温抗氧化性能,按照JC/T 2530-2019标准对本发明制备的碳化硼复合陶瓷的抗氧化性进行测试,将试样放入炉子中,于1400℃中氧化60h后的质量变化为0.25-0.28g/cm3
具体实施方式
为了对本发明的技术特征、目的和效果有更加清楚的理解,现说明本发明的具体实施方式。
实施例1
一种碳化硼复合陶瓷的制备方法,具体为:
1.制备复合粉体:将碳化硼粉体,氧化锌粉体,二氧化硅粉体,二水硫酸钙粉体,一水硫酸镁粉体混合均匀后置于球磨机中,在球磨前先将球磨罐内抽真空,然后通入纯度为99.6%的氧气,控制球磨罐内氧气的气体压力为0.04MPa,球磨过程中控制球磨温度为25℃,球料比为5:1,转速为280rpm,球磨时间为3h,球磨结束后得到初级混合粉,然后向初级混合粉表面喷淋活性液,喷淋结束后进行微波震荡,控制微波震荡的强度为80W,微波震荡的时间为4min,微波震荡结束得到初混料,将初混料置于真空干燥箱中进行真空干燥,控制真空干燥箱的真空度为0.04MPa,温度为70℃,真空干燥时间为1.5h,真空干燥结束得到复合粉体;
所述碳化硼粉体的纯度为99%,粒径为20μm。
所述活性液的组成,按重量份计,包括:30份无水乙醇,3份三乙胺,2份脂肪醇聚氧乙烯醚,1份聚苯乙烯磺酸钠,1份丙烯酰胺。
其中,碳化硼粉体,氧化锌粉体,二氧化硅粉体,二水硫酸钙粉体,一水硫酸镁粉体的质量比为35:5:7:2:1。
所述初级混合粉与活性液的质量比为1:3。
2.复合粉体改性:将复合粉体,黄原胶,硅藻土,纳米氮化硼混合均匀后置于球磨机中,在球磨前先将球磨罐内抽真空,然后通入氮气作为保护气体,控制球磨罐内氮气的气体压力为0.05MPa,控制球磨温度为40℃,球料比为8:1,转速为200rpm,球磨时间为3h,球磨结束得到混合粉体,然后将混合粉体置于γ-射线辐射场中进行辐照,控制吸收剂量为80KGy,辐照结束得到改性后的复合粉体;
其中,复合粉体,黄原胶,硅藻土,纳米氮化硼的质量比为25:2:3:1。
3.造粒:将改性后的复合粉体置于造粒机中造粒,将造粒机的温度控制在130℃,获得粒径为30目的圆形粉料。
4.注射成型:将圆形粉料置于注射机料盒中,控制加热温度为150℃,通过注射机成型后得到生坯。
5.真空脱脂:将生坯置于真空脱脂炉中,控制真空度为50Pa,以1℃/min的升温速率升至300℃,保温1h,得到脱脂后的坯体。
6.一次烧结:将脱脂后的坯体置于真空烧结炉中,以单质硅掩埋后在真空下进行烧结,控制真空度为0.02MPa,烧结温度为1500℃,烧结时间为1h,然后自然冷却至室温后得到一次烧结后的复合陶瓷。
7.二次烧结:将一次烧结后的复合陶瓷置于真空烧结炉中,以渗钛助剂掩埋后在真空下进行烧结,控制真空度为0.02MPa,首先以0.5℃/min的升温速度升至500℃,在500℃下保温2.5h,然后以2℃/min的升温速度升至1500℃,在1500℃保温1h,然后自然冷却至室温后得到碳化硼复合陶瓷;
所述渗钛助剂的组成,按重量份计,包括:60份钛粉,10份氯化铝,5份氧化锌,2份氧化钙。
本实施例的制备过程中未出现粉体团聚问题。
实施例2
一种碳化硼复合陶瓷的制备方法,具体为:
1.制备复合粉体:将碳化硼粉体,氧化锌粉体,二氧化硅粉体,二水硫酸钙粉体,一水硫酸镁粉体混合均匀后置于球磨机中,在球磨前先将球磨罐内抽真空,然后通入纯度为99.8%的氧气,控制球磨罐内氧气的气体压力为0.04MPa,球磨过程中控制球磨温度为27℃,球料比为5:1,转速为290rpm,球磨时间为3.5h,球磨结束后得到初级混合粉,然后向初级混合粉表面喷淋活性液,喷淋结束后进行微波震荡,控制微波震荡的强度为90W,微波震荡的时间为5min,微波震荡结束得到初混料,将初混料置于真空干燥箱中进行真空干燥,控制真空干燥箱的真空度为0.05MPa,温度为75℃,真空干燥时间为1.7h,真空干燥结束得到复合粉体;
所述碳化硼粉体的纯度为99.2%,粒径为30μm。
所述活性液的组成,按重量份计,包括:32份无水乙醇,3份三乙胺,2份脂肪醇聚氧乙烯醚,3份聚苯乙烯磺酸钠,2份丙烯酰胺。
其中,碳化硼粉体,氧化锌粉体,二氧化硅粉体,二水硫酸钙粉体,一水硫酸镁粉体的质量比为37:7:8:2:3。
所述初级混合粉与活性液的质量比为1:3.5。
2.复合粉体改性:将复合粉体,黄原胶,硅藻土,纳米氮化硼混合均匀后置于球磨机中,在球磨前先将球磨罐内抽真空,然后通入氮气作为保护气体,控制球磨罐内氮气的气体压力为0.05MPa,控制球磨温度为45℃,球料比为9:1,转速为220rpm,球磨时间为4h,球磨结束得到混合粉体,然后将混合粉体置于γ-射线辐射场中进行辐照,控制吸收剂量为90KGy,辐照结束得到改性后的复合粉体。
其中,复合粉体,黄原胶,硅藻土,纳米氮化硼的质量比为27:2:4:1。
3.造粒:将改性后的复合粉体置于造粒机中造粒,将造粒机的温度控制在135℃,获得粒径为40目的圆形粉料。
4.注射成型:将圆形粉料置于注射机料盒中,控制加热温度为155℃,通过注射机成型后得到生坯。
5.真空脱脂:将生坯置于真空脱脂炉中,控制真空度为55Pa,以2℃/min的升温速率升至320℃,保温1.5h,得到脱脂后的坯体。
6.一次烧结:将脱脂后的坯体置于真空烧结炉中,以单质硅掩埋后在真空下进行烧结,控制真空度为0.02MPa,烧结温度为1520℃,烧结时间为1.2h,然后自然冷却至室温后得到一次烧结后的复合陶瓷。
7.二次烧结:将一次烧结后的复合陶瓷置于真空烧结炉中,以渗钛助剂掩埋后在真空下进行烧结,控制真空度为0.02MPa,首先以0.7℃/min的升温速度升至550℃,在550℃下保温2.7h,然后以2.5℃/min的升温速度升至1520℃,在1520℃保温1.2h,然后自然冷却至室温后得到碳化硼复合陶瓷。
所述渗钛助剂的组成,按重量份计,包括:65份钛粉,11份氯化铝,8份氧化锌,3份氧化钙。
本实施例的制备过程中未出现粉体团聚问题。
实施例3
一种碳化硼复合陶瓷的制备方法,具体为:
1.制备复合粉体:将碳化硼粉体,氧化锌粉体,二氧化硅粉体,二水硫酸钙粉体,一水硫酸镁粉体混合均匀后置于球磨机中,在球磨前先将球磨罐内抽真空,然后通入纯度为99.9%的氧气,控制球磨罐内氧气的气体压力为0.05MPa,球磨过程中控制球磨温度为30℃,球料比为6:1,转速为300rpm,球磨时间为4h,球磨结束后得到初级混合粉,然后向初级混合粉表面喷淋活性液,喷淋结束后进行微波震荡,控制微波震荡的强度为100W,微波震荡的时间为6min,微波震荡结束得到初混料,将初混料置于真空干燥箱中进行真空干燥,控制真空干燥箱的真空度为0.06MPa,温度为80℃,真空干燥时间为2h,真空干燥结束得到复合粉体;
所述碳化硼粉体的纯度为99.5%,粒径为40μm。
所述活性液的组成,按重量份计,包括:35份无水乙醇,4份三乙胺,3份脂肪醇聚氧乙烯醚,3份聚苯乙烯磺酸钠,2份丙烯酰胺。
其中,碳化硼粉体,氧化锌粉体,二氧化硅粉体,二水硫酸钙粉体,一水硫酸镁粉体的质量比为40:8:9:3:3。
所述初级混合粉与活性液的质量比为1:4。
2.复合粉体改性:将复合粉体,黄原胶,硅藻土,纳米氮化硼混合均匀后置于球磨机中,在球磨前先将球磨罐内抽真空,然后通入氮气作为保护气体,控制球磨罐内氮气的气体压力为0.06MPa,控制球磨温度为50℃,球料比为10:1,转速为250rpm,球磨时间为5h,球磨结束得到混合粉体,然后将混合粉体置于γ-射线辐射场中进行辐照,控制吸收剂量为100KGy,辐照结束得到改性后的复合粉体。
其中,复合粉体,黄原胶,硅藻土,纳米氮化硼的质量比为30:3:5:2。
3.造粒:将改性后的复合粉体置于造粒机中造粒,将造粒机的温度控制在140℃,获得粒径为50目的圆形粉料。
4.注射成型:将圆形粉料置于注射机料盒中,控制加热温度为160℃,通过注射机成型后得到生坯。
5.真空脱脂:将生坯置于真空脱脂炉中,控制真空度为60Pa,以3℃/min的升温速率升至350℃,保温2h,得到脱脂后的坯体。
6.一次烧结:将脱脂后的坯体置于真空烧结炉中,以单质硅掩埋后在真空下进行烧结,控制真空度为0.03MPa,烧结温度为1550℃,烧结时间为1.5h,然后自然冷却至室温后得到一次烧结后的复合陶瓷。
7.二次烧结:将一次烧结后的复合陶瓷置于真空烧结炉中,以渗钛助剂掩埋后在真空下进行烧结,控制真空度为0.03MPa,首先以1℃/min的升温速度升至600℃,在600℃下保温3h,然后以3℃/min的升温速度升至1550℃,在1550℃保温1.5h,然后自然冷却至室温后得到碳化硼复合陶瓷。
所述渗钛助剂的组成,按重量份计,包括:70份钛粉,12份氯化铝,10份氧化锌,5份氧化钙。
本实施例的制备过程中未出现粉体团聚问题。
对比例1
采用实施例1所述的碳化硼复合陶瓷的制备方法,其不同之处在于:第1步制备复合粉体步骤中省略喷淋活性液和微波震荡,即将第1步的初级混合粉作为复合粉体用于第2步复合粉体改性。
本对比例在烧结过程中出现了粉体团聚问题。
对比例2
采用实施例1所述的碳化硼复合陶瓷的制备方法,其不同之处在于:第2步复合粉体改性中省略将混合粉置于γ-射线辐射场中进行辐照,即将第2步的混合粉体作为改性后的复合粉体用于第3步造粒。
本对比例在烧结过程中出现了粉体团聚问题。
对比例3
采用实施例1所述的碳化硼复合陶瓷的制备方法,其不同之处在于:省略第7步二次烧结步骤。
本对比例在烧结过程中出现了粉体团聚问题。
对实施例1-3和对比例1-3制备的碳化硼复合陶瓷的密度,致密度,维氏硬度,弹性模量,抗拉强度,抗弯强度,抗压强度,断裂韧性进行检测,检测结果如下所示:
Figure 350423DEST_PATH_IMAGE001
按照JC/T 2530-2019标准对实施例1-3和对比例1-3制备的碳化硼复合陶瓷的抗氧化性进行测试,将试样放入炉子中,于1400℃中氧化60h,测质量变化,测试结果如下:
Figure 276791DEST_PATH_IMAGE002
除非另有说明,本发明中所采用的百分数均为质量百分数。
最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。

Claims (2)

1.一种碳化硼复合陶瓷的制备方法,其特征在于,包括制备复合粉体,复合粉体改性,造粒,注射成型,真空脱脂,一次烧结,二次烧结;
所述制备复合粉体,将碳化硼粉体,氧化锌粉体,二氧化硅粉体,二水硫酸钙粉体,一水硫酸镁粉体混合均匀后置于球磨机中进行球磨,球磨结束后得到初级混合粉,然后向初级混合粉表面喷淋活性液,喷淋结束后进行微波震荡,微波震荡结束得到初混料,将初混料置于真空干燥箱中进行真空干燥,真空干燥结束得到复合粉体;
其中,碳化硼粉体,氧化锌粉体,二氧化硅粉体,二水硫酸钙粉体,一水硫酸镁粉体的质量比为35-40:5-8:7-9:2-3:1-3;
所述初级混合粉与活性液的质量比为1:3-4;
所述活性液的组成,按重量份计,包括:30-35份无水乙醇,3-4份三乙胺,2-3份脂肪醇聚氧乙烯醚,1-3份聚苯乙烯磺酸钠,1-2份丙烯酰胺;
所述复合粉体改性,将复合粉体,黄原胶,硅藻土,纳米氮化硼混合均匀后置于球磨机中,在球磨前先将球磨罐内抽真空,然后通入氮气作为保护气体后进行球磨,球磨结束得到混合粉体,然后将混合粉体置于γ-射线辐射场中进行辐照,控制吸收剂量为80-100KGy,辐照结束得到改性后的复合粉体;
其中,复合粉体,黄原胶,硅藻土,纳米氮化硼的质量比为25-30:2-3:3-5:1-2;
所述造粒,将改性后的复合粉体置于造粒机中造粒,将造粒机的温度控制在130-140℃,获得粒径为30-50目的圆形粉料;
所述一次烧结,将脱脂后的坯体置于真空烧结炉中,以单质硅掩埋后在真空下进行烧结,控制真空度为0.02-0.03MPa,烧结温度为1500-1550℃,烧结时间为1-1.5h,然后自然冷却至室温后得到一次烧结后的复合陶瓷;
所述二次烧结,将一次烧结后的复合陶瓷置于真空烧结炉中,以渗钛助剂掩埋后在真空下进行烧结,烧结结束后自然冷却至室温后得到碳化硼复合陶瓷;
所述渗钛助剂的组成,按重量份计,包括:60-70份钛粉,10-12份氯化铝,5-10份氧化锌,2-5份氧化钙。
2.根据权利要求1所述的碳化硼复合陶瓷的制备方法,其特征在于,所述注射成型,将圆形粉料置于注射机料盒中,控制加热温度为150-160℃,通过注射机成型后得到生坯。
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