CN111574226A - 一种高密度低游离硅含量反应烧结碳化硅陶瓷材料的制备方法 - Google Patents
一种高密度低游离硅含量反应烧结碳化硅陶瓷材料的制备方法 Download PDFInfo
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Abstract
本发明提供一种高密度低游离硅含量反应烧结碳化硅陶瓷材料的制备方法,该制备方法包括混料、真空除气、注浆成型、脱模干燥和烧结处理步骤,其中选取合理的原料粒度级配,并采用压力注浆成型,增强了产品素坯的密度;在烧结过程中采用优化的烧结曲线,有机物排除同预烧合二为一,在不影响产品质量的情况下降低烧结成本,减少碳化硅陶瓷素坯在高温排除有机物过程中发生的坯体的变形或开裂问题;使高密度坯体能够在较低温度下充分反应烧结,生成高密度、低游离硅陶瓷制品,保证了碳化硅陶瓷素坯显微结构均匀,大大提高了陶瓷材料的强度及结构稳定性。
Description
技术领域
本发明属于陶瓷材料制备技术领域,具体涉及一种高密度低游离硅含量反应烧结碳化硅陶瓷材料的制备方法。
背景技术
碳化硅陶瓷是一种机械强度高、硬度高、耐高温、耐化学腐蚀、抗氧化和抗热震性优良、导热性良好、低膨胀系数等特点的工业材料,特别是抗氧化性是所有非金属陶瓷中最好的一种,其中反应烧结法制备的碳化硅具有低温和净尺寸的优势,是工业上广泛采用的方法,常被用于电子封装、航空航天、军事、汽车行业等复杂异型件的生产。
反应烧结碳化硅中残留硅的存在不可避免,限制了反应烧结碳化硅的使用温度和使用环境。但是从单方面降低硅的含量并不能提高碳化硅陶瓷的整体性能,如一味的调整原料含量,可造成产品密度的降底,也可能造成产品烧结不透反应不完整。降低硅的含量获得较纯的碳化硅陶瓷,可以改善反应烧结碳化硅的弹性模量、力学性能及耐腐蚀性能,具有重要的理论意义和应用前景。本发明以不同颗粒级配通过低温直接反应的方法制备低残硅量高密度的复杂碳化硅陶瓷材料,使碳化硅陶瓷在传统反应烧结基础上获得组织和性能的改善。
目前,反应烧结碳化硅陶瓷的制备工艺主要有干压成型、挤压成型、注射成型和注浆成型工艺。其中,干压成型工艺是利用压力将制备碳化硅陶瓷的干粉坯料在模型中压成致密体的一种成型方法;挤压成型是将原料搅拌成含有较少水分的泥浆经压力挤出形成简单形状坯体的一种成型方法;注射成型工艺主要包括:配料、混炼(需添加粘结剂、喂料)、注射成型、脱脂及烧结;注浆成型是将所有物料混合搅拌成可以流动的固含量较高的浆液注入石膏模具形成想要的形状成型有一种方法。但是,干压成型工艺制备的碳化硅陶瓷密度虽然高但结构均一性差,无法制成复杂形状的产品,主要以片状板状为主;挤出成型制出的产品虽然密度高于注浆成型,但也无法制做形状复杂的产品,主要以棒状梁状为主;注射成型工艺需要大量的有机粘结剂,陶瓷素坯收缩大,无法制备出高体积分数的碳化硅陶瓷材料,因而也无法实现高性能要求的碳化硅陶瓷材料;现有的注浆成型方法虽然能生产形状复杂的异形件产品,但是产品密度较低,最高只能达到3.06-3.08g/cm3,不能满足高力学性能的要求,不能应用于更高技术要求的领域。
发明内容
为解决现有技术存在的问题,对现有工艺进行进一步优化,本发明提供一种高密度低游离硅含量反应烧结碳化硅陶瓷材料的制备方法,以实现降低陶瓷材料中游离硅含量、提高陶瓷材料密度、结构均一、提高碳化硅陶瓷制品力学性能的发明目的。
为达到上述发明目的,本发明采用以下技术方案:
一种高密度低游离硅含量反应烧结碳化硅陶瓷材料的制备方法,其特征在于,包括混料、真空除气、注浆成型、脱模干燥和烧结处理步骤;
所述混料,原料料浆组成,按重量份数计,包括:
碳黑5-10%、碳化硅微粉60-70%、分散剂1-2%、粘结剂0.2-0.6%、解凝剂0.2-0.6%、纯净水18-25%;
所述碳黑,粒径为20-100nm;优选地,粒径为36-40nm;
所述碳化硅微粉,粒径为3-90um,其中粒径为3-5um的占总重量的20%,粒径为40-46um占总重量的40%,粒径为85-90um占总重量的40%;
所述粘结剂为CMC纤维素钠;
所述分散剂为羧酸制剂;
优选地,分散剂为聚羧酸钠盐分散剂OROTAN 731A;
所述解凝剂为多羧基酸钠盐;
优选地,解凝剂为DOLAPIX PC 67;
所述真空除气,真空度为100Pa以下;处理时间为2-20min;
所述注浆成型,料浆罐内压力达到0.3-0.35MPa;注浆后浆料在模具中自然脱水固化24h成型;
所述脱模干燥,包括先进行低温干燥,再进行高温干燥;所述低温干燥,温度为20-50℃,干燥时间24-30h;所述高温干燥,温度为50-90℃,干燥12-24h;
所述烧结处理,需加入焙烧料,所述焙烧料的组成,按重量份数计,包括金属硅粉18-24份、氮化硼粉0.2-0.5份、碳黑0.2-0.5份、胶水1-3份
优选地,包括金属硅粉20份、氮化硼粉0.3份、碳黑0.5份、胶水2份;
所述金属硅粉,粒度为1-5mm;
所述胶水,成分为PVK90,浓度为20-25%;
所述烧结处理,焙烧料的加入量是素坯重量的30%-50%;
所述烧结处理,包括加热升温过程,所述加热升温,包括从常温到300℃,加热时长为1.5-2个小时,并恒温20-30分钟;从301-600℃加热时长为2.5-3个小时,并恒温30-35分钟;601-800℃加热时长为2-2.5个小时,并恒温1-1.5小时;
优选地,所述加热升温,包括:从常温到300℃,加热时长为1.5个小时,并恒温20分钟;从301-600℃加热时长为2.5个小时,并恒温30分钟;601-800℃加热时长为2个小时,并恒温1小时;
所述烧结处理,还包括在加热升温过程同时进行脱蜡,氮气流速为80-85L/min;
所述烧结处理,还包括真空烧结,真空度维持在3pa以下,温控时长为:801-1100℃加热时长为3个小时,恒温30-40分钟;1101-1400℃加热时长为3.5-4个小时,恒温30-40分钟;1401-1700℃加热时长为4个小时,恒温3-3.5个小时;
优选地,所述真空烧结,温控时长为:801-1100℃加热时长为3个小时,恒温30分钟;1101-1400℃加热时长为3.5个小时,恒温30分钟;1401-1700℃加热时长为4个小时,恒温3个小时;
所述烧结处理,包括停止加热,电炉自然降至室温;
采用本发明的制备方法,选取合理的原料粒度级配,可以使碳化硅颗粒、碳黑颗粒在水中均匀分散,结合压力注浆成型,增强了产品素坯的密度;同时在烧结过程中采用优化的烧结曲线,有机物排除同预烧合二为一,在不影响产品质量的情况下降低烧结成本,减少碳化硅陶瓷素坯在高温排除有机物过程中发生的坯体的变形或开裂问题;使高密度坯体能够在较低温度下充分反应烧结,生成高密度、低游离硅陶瓷制品,保证了碳化硅陶瓷素坯显微结构均匀,大大提高了陶瓷材料的强度及结构稳定性。
采用上述技术方案,本发明的有益效果为:
1、采用本发明碳化硅陶瓷材料制备方法,制备出的反应烧结碳化硅陶瓷材料,密度达到3.13-3.14g/cm3,目前达到国际最高水平,超出了干压成型、挤压成型生产的陶瓷密度,得到较高力学性能的产品;
2、采用本发明碳化硅陶瓷材料制备方法,制备出的反应烧结碳化硅陶瓷材料,游离硅含量仅为4-5%,相比于,现有技术中反应烧结碳化硅制品中游离硅含量8-10%甚至15%以上,游离硅含量大大降低,产品的应用更加广泛;
3、采用本发明碳化硅瓷材料制备方法,采用注浆成型工艺,可以制备复杂异形结构的产品,产品结构均匀;可以得到强度较高、结构均一、使用环境温度更高、不需加工就能达到产品使用要求的性能较好的近“净”尺寸碳化硅陶瓷材料。
4、采用本发明碳化硅陶瓷材料制备方法,制备出的反应烧结碳化硅陶瓷材料,使用环境温度更高,由1380℃提高到1760-1788℃。
5、采用本发明碳化硅陶瓷材料制备方法,生产成本较低,适合批量工业化生产。
具体实施方式:
下面结合具体的实施例,进一步阐述本发明。
实施例1一种高密度低游离硅含量反应烧结碳化硅陶瓷材料的制备方法
所述高密度低游离硅含量的反应烧结碳化硅陶瓷材料的制备方法,包括以下步骤:
1、混料
将碳黑倒入加足水的搅拌罐中进行搅拌,然后依次加入分散剂、粘结剂、解凝剂,搅拌30min后再将碳化硅微粉加入其中,混合均匀,搅拌24h,制得原料料浆;
所述原料料浆,按重量份数计,原材料组成包括:
碳黑9%、碳化硅微粉70%、分散剂1%、粘结剂0.5%、解凝剂0.5%、纯净水19%;
所述碳黑,粒径为36nm;
所述碳化硅微粉,粒径为3-90um,其中粒径为3um的占总重量的20%,粒径为40um占总重量的40%,粒径为90um占总重量的40%;
所述粘结剂为CMC纤维素钠;
所述分散剂为聚羧酸钠盐分散剂OROTAN 731A;
所述解凝剂为多羧基酸钠盐DOLAPIX PC 67;
2、真空除气
将原料料浆抽入真空搅拌罐,在真空环境下搅拌20min,除去料浆中的所有气泡;
所述真空除气,真空度为100Pa;
所述真空除气,处理时间为15min;
3、注浆成型
将经过真空除气后的料浆真空罐升高到2米的高度,向真空搅拌罐中冲入氮气,使罐中压力达到0.3Mpa,开启注浆口,使浆料沿模具壁注入到石膏模具的模腔中,将模具轻微振动排出气泡,石膏微孔模具将浆料中部分水份吸收,浆料在模具中自然脱水干燥成型,经过24小时后得到固化定型的陶瓷坯体;
4、脱模干燥
将陶瓷坯体先在烘干箱中低温干燥24小时,后再把坯体放在高温干燥箱内高温干燥12-24小时,得到有一定强度的陶瓷毛坯,对毛坯按图纸要求进行加工修整,得到符合要求的陶瓷素坯;
所述低温干燥,温度为25℃;所述高温干燥,温度为50℃;
5、烧结处理
将陶瓷素坯称重后放入石墨坩埚中,在坩埚中加入素坯重量30%的焙烧料,把石墨坩埚放入高温真空炉中进行烧结处理,具体包括以下步骤:
1)先配制焙烧料,搅拌混合均匀,将焙烧料烘干备用;
所述焙烧料的组成,按重量份数计,包括金属硅粉20份、氮化硼粉0.3份、碳黑0.5份、胶水2份;
所述金属硅粉,粒度为1-3mm;
所述胶水,成分为PVK90,浓度为20%;
2)把素坯和焙烧料一起放入真空炉中,开启真空泵将气压抽到真空度3Pa,后充入保护气体氮气,至与外界大气压平衡;
3)开启电炉加热按钮对电炉进行加热升温,同时打开脱蜡系统边升温边脱蜡,按流量为80L/min的速度向炉中持续充入氮气,将坯料中的燃烧有机物带走,升温至800℃并保温结束后停止充氮气,完成脱蜡;
脱腊系统由引风机、真空球阀,烟气管道组成,开启引风机、真空球阀,使燃烧的有机物形成的烟气由炉内经烟管、真空球阀、引风机排出炉内;
所述加热升温,升温过程如下:从常温到300℃,加热时长为1.5个小时,并恒温20分钟;从301-600℃加热时长为2.5个小时,并恒温30分钟;601-800℃加热时长为2个小时,并恒温1小时;
4)打开真空系统对电炉抽真空后进行真空烧结;
所述真空烧结是真空度维持在3pa以下,温控时长为:801-1100℃加热时长为3个小时,恒温30分钟;1101-1400℃加热时长为3.5个小时,恒温30分钟;1401-1700℃加热时长为4个小时,恒温3个小时;
5)停止加热,电炉自然降温,降至室温时打开炉门取出陶瓷制品,对表面进行清理后得到反应烧结碳化硅陶瓷材料。
实施例2一种高密度低游离硅含量反应烧结碳化硅陶瓷材料的制备方法
所述高密度低游离硅含量的反应烧结碳化硅陶瓷材料的制备方法,包括以下步骤:
1、混料
将碳黑倒入加足水的搅拌罐中进行搅拌,然后依次加入分散剂、粘结剂、解凝剂,搅拌30min后再将碳化硅微粉加入其中,混合均匀,搅拌24h,制得原料料浆;
所述原料料浆,按重量份数计,原材料组成包括:
碳黑8%、碳化硅微粉65%、分散剂2%、粘结剂0.5%、解凝剂0.5%、纯净水24%;
所述碳黑,粒径为40nm;
所述碳化硅微粉,粒径为3-90um,其中粒径为5um的占总重量的20%,粒径为45um占总重量的40%,粒径为90um占总重量的40%;
所述粘结剂为CMC纤维素钠;
所述分散剂为聚羧酸钠盐分散剂OROTAN 731A;
所述解凝剂为多羧基酸钠盐DOLAPIX PC 67;
2、真空除气
将原料料浆抽入真空搅拌罐,在真空环境下搅拌20min,除去料浆中的所有气泡;
所述真空除气,真空度为120Pa;
所述真空除气,处理时间为5min;
3、注浆成型
将经过真空除气后的料浆真空罐升高到2米的高度,向真空搅拌罐中冲入氮气,使罐中压力达到0.35Mpa,开启注浆口,使浆料沿模具壁注入到石膏模具的模腔中,将模具轻微振动排出气泡,石膏微孔模具将浆料中部分水份吸收,浆料在模具中自然脱水干燥成型,经过24小时后得到固化定型的陶瓷坯体;
4、脱模干燥
将陶瓷坯体先在烘干箱中低温干燥24小时,后再把坯体放在高温干燥箱内高温干燥12小时,得到有一定强度的陶瓷毛坯,对毛坯按图纸要求进行加工修整,得到符合要求的陶瓷素坯;
所述低温干燥,温度为50℃;所述高温干燥,温度为90℃;
5、烧结处理
将陶瓷素坯称重后放入石墨坩埚中,在坩埚中加入素坯重量50%的焙烧料,把石墨坩埚放入高温真空炉中进行烧结处理,具体包括以下步骤:
1)先配制焙烧料,搅拌混合均匀,将焙烧料烘干备用;
所述焙烧料的组成,按重量份数计,包括金属硅粉22份、氮化硼粉0.5份、碳黑0.2份、胶水3份;
所述金属硅粉,粒度为4-5mm;
所述胶水,成分为PVK90,浓度为25%;
2)把素坯和焙烧料一起放入真空炉中,开启真空泵将气压抽到真空度3Pa,后充入保护气体氮气,至与外界大气压平衡;
3)开启电炉加热按钮对电炉进行加热升温,同时打开脱蜡系统边升温边脱蜡,按流量为85L/min的速度向炉中持续充入氮气,将坯料中的燃烧有机物带走,升温至800℃并保温结束后停止充氮气,完成脱蜡;
脱腊系统由引风机、真空球阀,烟气管道组成,开启引风机、真空球阀,使燃烧的有机物形成的烟气由炉内经烟管、真空球阀、引风机排出炉内;
所述加热升温,升温过程如下:从常温到300℃,加热时长为2个小时,并恒温30分钟;从301-600℃加热时长为3个小时,并恒温30分钟;601-800℃加热时长为2个小时,并恒温1.5小时;
4)打开真空系统对电炉抽真空后进行真空烧结;
所述真空烧结是真空度维持在3pa以下,温控时长为:801-1100℃加热时长为3个小时,恒温40分钟;1101-1400℃加热时长为4个小时,恒温30分钟;1401-1700℃加热时长为4个小时,恒温3.5个小时;
5)停止加热,电炉自然降温,降至室温时打开炉门取出陶瓷制品,对表面进行清理后得到反应烧结碳化硅陶瓷材料。
采用实施例1-2的制备方法制备的碳化硅陶瓷,分别对其进行检测,结果如下:
最后应说明的是:以上所述仅为本发明的优选实施例,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 (10)
1.一种高密度低游离硅含量反应烧结碳化硅陶瓷材料的制备方法,其特征在于,包括混料、真空除气、注浆成型、脱模干燥和烧结处理步骤。
2.根据权利要求1所述的制备方法,其特征在于,所述混料,原料料浆组成,按重量份数计,包括:
碳黑5-10%、碳化硅微粉60-70%、分散剂1-2%、粘结剂0.2-0.6%、解凝剂0.2-0.6%、纯净水18-25%;
所述碳黑,粒径为20-100nm;
所述碳化硅微粉,粒径为3-90um,其中粒径为3-5um的占总重量的20%,粒径为40-46um占总重量的40%,粒径为85-90um占总重量的40%。
3.根据权利要求1所述的制备方法,其特征在于,所述烧结处理,需加入焙烧料,所述焙烧料的组成,按重量份数计,包括金属硅粉18-24份、氮化硼粉0.2-0.5份、碳黑0.2-0.5份、胶水1-3份;
所述金属硅粉,粒度为1-5mm;
所述胶水,成分为PVK90,浓度为20-25%。
4.根据权利要求1所述的制备方法,其特征在于,所述烧结处理,包括加热升温过程,所述加热升温,包括:从常温到300℃,加热时长为1.5-2个小时,并恒温20-30分钟;从301-600℃加热时长为2.5-3个小时,并恒温30-35分钟;601-800℃加热时长为2-2.5个小时,并恒温1-1.5小时。
5.根据权利要求1所述的制备方法,其特征在于,所述烧结处理,还包括真空烧结,真空度维持在3pa以下,温控时长为:801-1100℃加热时长为3个小时,恒温30-40分钟;1101-1400℃加热时长为3.5-4个小时,恒温30-40分钟;1401-1700℃加热时长为4个小时,恒温3-3.5个小时。
6.根据权利要求1所述的制备方法,其特征在于,所述烧结处理,还包括在加热升温过程同时进行脱蜡,氮气流速为80-85L/min。
7.根据权利要求1所述的制备方法,其特征在于,所述注浆成型,料浆罐内压力达到0.3-0.35MPa。
8.根据权利要求1所述的制备方法,其特征在于,所述脱模干燥,包括先进行低温干燥,再进行高温干燥;所述低温干燥,温度为20-50℃;所述高温干燥,温度为50-90℃。
9.根据权利要求1所述的制备方法,其特征在于,所述真空除气,真空度为100Pa以下。
10.根据权利要求1所述的制备方法,其特征在于,所述烧结处理,焙烧料的加入量是素坯重量的30%-50%。
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