CN106800420B - 一种碳化硅晶须原位复合刚玉高温陶瓷材料及其制备方法 - Google Patents
一种碳化硅晶须原位复合刚玉高温陶瓷材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种碳化硅晶须原位复合刚玉高温陶瓷材料及其制备方法,属于高温陶瓷材料技术领域。本发明中碳化硅晶须原位复合刚玉高温陶瓷材料由复合原料和结合剂制成,所述复合原料由以下重量百分比的原料组成:刚玉粉82%~91.5%、碳化稻壳粉7%~15%、催化剂0.5%~2%、二氧化硅微粉或硅粉0.2%~1%;所述结合剂的质量为所述复合原料总质量的3%~5%。本发明所用原料价格低、来源广,制备工艺简单;所得制品具有抗热震性好、高温强度大、体积稳定性佳等优点,适合推广应用。
Description
技术领域
本发明涉及一种碳化硅晶须原位复合刚玉高温陶瓷材料,属于高温陶瓷材料技术领域。
背景技术
刚玉材料具有耐高温、强度高、硬度大、耐磨损、抗侵蚀性强等优异性能,被誉为“陶瓷王”,已在航空航天、国防军工、冶金、汽车发动机、机械电子等领域得到广泛应用。但其断裂韧性仅为3~4MPa·m1/2,抗热震性较差,在剧烈的热冲击作用下易开裂,限制了其在高温环境下优异性能的发挥和更广泛的应用。近几十年来,国内外科研人员多通过在刚玉材料中添加氧化锆或引入碳化硅晶须对其断裂韧性进行改善,前者通过氧化锆的马氏体相变和微裂纹增韧作用进行改进,后者则是通过在刚玉基体中添加预合成的或引入原位生成的碳化硅晶须,利用晶须拔出、裂纹桥联、偏转或分叉机制吸收外来能量、抵消外加应力进行改进。二者虽可在一定程度上改善刚玉材料的韧性,但因马氏体相变对温度的依赖性较强(升温和降温时分别为1170℃和950℃),高温下将减弱或失去对刚玉材料的增韧作用;预合成的碳化硅晶须多呈团聚状,混料过程中难以均匀分散于刚玉基体中,不能充分发挥其增韧效果,且其位于刚玉颗粒间,使刚玉的扩散传质路径延长,不利于烧结致密化;目前研究的碳化硅晶须原位复合刚玉材料,多以多级配氧化铝颗粒为主要材料,以高纯Si粉、SiO2微纳米粉为硅源,炭黑、石墨或酚醛树脂为碳源,在氩气、氮气、氢气或真空条件下烧制获得,多级配氧化铝颗粒成型后致密度较高,难以为碳化硅晶须的生长发育提供足够的空间,所得碳化硅晶须的长径比较小,对基体材料韧性的贡献有限,且所用原料价格昂贵、工序复杂、制备过程难控制,这些均限制了刚玉制品在工业中的推广应用。
在现有研究中,专利申请公布号为CN101880173A的发明专利,公开了一种碳化硅晶须原位增韧氧化铝陶瓷,专利申请公布号为CN101880163A的发明专利公开了一种碳化硅晶须原位增韧氧化铝陶瓷制造方法,此两项专利均是将四组份助剂MO(M为Mg,Ba,Be,Ca中的一种)–SiO2–C–LxOy(L为过渡金属元素,为Fe,Ni,Cu中的一种)添加到氧化铝粉体中,以酚醛树脂或聚乙烯醇为结合剂,混合机压后制得素坯,将其于250℃热处理20min除去结合剂,再置于真空炉中抽真空4~5Pa后充入氮气进行保护,经1300~1400℃烧成后制得碳化硅晶须原位复合氧化铝陶瓷,该方法存在如下缺陷:1、原料成本高;2、烧制工艺复杂、过程难控制;3、未对制备材料的力学性能及微观结构等作说明,使其推广应用有限。因此,寻找工艺简单、价格低廉的高性能碳化硅晶须原位复合刚玉高温陶瓷材料的有效制备方法,已成为亟待解决的关键性课题。
发明内容
本发明的目的旨在提供一种碳化硅晶须原位复合刚玉高温陶瓷材料,其具有常温及高温强度大、抗热震性好、荷重软化温度高、体积稳定性佳的特点,综合性能优良。
本发明的另一个目的在于提供一种碳化硅晶须原位复合刚玉高温陶瓷材料的制备方法,该方法成本低、工艺简便易行,利于规模化生产。
为实现上述目的,本发明所采用的技术方案是:
一种碳化硅晶须原位复合刚玉高温陶瓷材料,该碳化硅晶须原位复合刚玉高温陶瓷材料由复合原料和结合剂制成,该复合原料由以下重量百分比的原料组成:刚玉粉82%~91.5%、碳化稻壳粉7%~15%、催化剂0.5%~2%、二氧化硅微粉或硅粉0.2%~1%;上述结合剂的质量为所述复合原料总质量的3%~5%。
上述二氧化硅微粉或硅粉中选择其中一种,重量百分比都为0.2%~1%。
上述刚玉粉为粒径单一尺寸的颗粒,刚玉粉中的Al2O3含量≥99%,粒径在45~88μm内选择。
上述二氧化硅微粉中的SiO2含量≥99.9%,粒径≤5μm。
上述硅粉中的Si含量≥99.9%,粒径≤5μm。
上述催化剂为铁粉、氯化钠、硫酸亚铁、硼酸中的一种或几种。
上述催化剂纯度均≥90%,粒径≤5μm。
上述结合剂为亚硫酸纸浆废液或糊精液。上述亚硫酸纸浆废液浓度为40%~50%。上述糊精液浓度为30%~35%。
上述碳化稻壳粉由包括如下步骤的方法制得:
将稻壳在真空或惰性气氛下经500~700℃碳化0.5~2h,即得碳化稻壳粉。
上述碳化稻壳粉的制备方法优选为:将筛选、清洗后的稻壳干燥后,在真空或惰性气氛下中经500~700℃碳化0.5~2h,冷却后取出,湿磨12h,干燥后过筛,制得碳化稻壳粉。
上述碳化稻壳粉的粒径≤44μm。
上述碳化稻壳粉的化学组成中C与SiO2的质量比为0.63~0.76。
上述碳化硅晶须原位复合刚玉高温陶瓷材料的制备方法,包括:
1)将配方量的复合原料混合,再加入结合剂混合均匀,制成坯料;
2)将步骤1)所得坯料成型制成坯体,干燥后在还原气氛中于1400~1550℃热处理3~6h即得。
上述步骤1)优选操作为:按比例称取复合原料,刚玉粉、碳化稻壳粉、催化剂、二氧化硅微粉或硅粉置于球磨罐中干混90min,再加入液态结合剂混合均匀,制成坯料。
上述步骤2)中,干燥温度为100~120℃,干燥时间8~12h。
上述步骤2)中,成型为通过机压成型,成型的压力为150~200MPa,保压的时间为15~30s。
上述步骤2)中,上述还原气氛是指将坯体密封于石墨粉中形成的气氛。进一步,还原气氛是通过将坯体掩埋于装满石墨的刚玉坩埚中并用刚玉坩埚盖密封,于1400~1550℃热处理过程中获得。
上述步骤2)中,以2~5℃/min的速率升温至1400~1550℃,热处理时间为3~6h。
本发明的有益效果:
本发明中的碳化硅晶须原位复合刚玉高温陶瓷材料具有优异的结构,具体是原位生成的大量晶须状的碳化硅填充于刚玉颗粒形成的骨架中,在受外力或热冲击作用时,这些碳化硅晶须通过晶须拔出、裂纹桥联或偏转等机制抵消外加应力、缓和应力集中,使所得成品具有常温及高温强度大、抗热震性好、荷重软化温度高、体积稳定性佳的优点。
本发明选用碳化稻壳粉为原料,极大的降低了制备成本,与此同时,本发明选用单一粒径的刚玉为原料,不仅简化了工艺,同时也为碳化硅晶须的生长发育提供了足够的空间,有利于提高碳化硅晶须的长径比,原位生成的碳化硅晶须克服了添加预制碳化硅晶须导致的混料不均,其均匀分布在刚玉颗粒间的孔隙中,有利于制品整体结构性能的提高。此外,本发明是通过将坯体掩埋于装满石墨的刚玉坩埚中并密封,经1400~1500℃烧制获得成品,该方法工艺简单、成本低廉,适合大规模推广应用。
附图说明
图1为实施例1所得碳化硅晶须原位复合刚玉高温陶瓷材料的SEM图;
图2为实施例2所得碳化硅晶须原位复合刚玉高温陶瓷材料的SEM图。
具体实施方式
下面结合具体实施例对本发明作进一步详细描述。
为避免重复,将本具体实施例中原料作如下统一描述,实施例中不再赘述:
本发明所使用的刚玉粉中的Al2O3含量≥99%,二氧化硅微粉的SiO2含量≥99.9%,粒径≤5μm,硅粉的Si含量≥99.9%,粒径≤5μm,催化剂中,铁粉、氯化钠、硫酸亚铁、硼酸的纯度均≥90%,粒径均≤5μm。
实施例1
本实施例的碳化硅晶须原位复合刚玉高温陶瓷材料由复合原料和结合剂制成,所述复合原料由以下重量百分比的原料组成:刚玉粉82%、碳化稻壳粉15%、二氧化硅微粉1%、铁粉1.5%、硼酸0.5%,刚玉粉的粒径为45μm,碳化稻壳粉化学组成中C与SiO2的质量比为0.67,结合剂为浓度为35%的糊精液,糊精液的重量为复合原料总重量的5%。
本实施例的碳化稻壳粉通过以下方法制得:
将筛选、清洗后的稻壳烘干,置于匣钵内于真空炉中经550℃碳化1.5h,冷却后取出,以水为球磨介质湿磨12h,烘干后过筛,优选粒径≤44μm的碳化稻壳粉。
本实施例的碳化硅晶须原位复合刚玉高温陶瓷材料的制备方法,包括以下步骤:
1)按比例称取刚玉粉、碳化稻壳粉、二氧化硅微粉、铁粉和硼酸置于球磨罐中干混90min,再加入糊精液,混合15min制成坯料;
2)将坯料装入模具中,在液压机上于200MPa压力下保压15s成型,得到坯体;
3)将坯体置于烘箱中于120℃下干燥10h;
4)将干燥后的坯体置于刚玉坩埚中,用石墨将四周掩埋,并用刚玉坩埚盖密封,再以3℃/min的速率升温至1500℃并热处理3h,随炉冷却后即得碳化硅晶须原位复合刚玉高温陶瓷材料。
实施例2
本实施例的碳化硅晶须原位复合刚玉高温陶瓷材料由复合原料和结合剂制成,所述复合原料由以下重量百分比的原料组成:刚玉粉91%、碳化稻壳粉7%、二氧化硅微粉0.5%、硫酸亚铁1%、氯化钠0.5%,刚玉粉的粒径为88μm,碳化稻壳粉化学组成中C与SiO2的质量比为0.63,结合剂为浓度为40%的亚硫酸纸浆废液,亚硫酸纸浆废液的重量为复合原料总重量的4%。
本实施例的碳化稻壳粉通过以下方法制得:
将筛选、清洗后的稻壳烘干,置于匣钵内于真空炉中经700℃碳化0.5h,冷却后取出,以水为球磨介质湿磨12h,烘干后过筛,优选粒径≤44μm的碳化稻壳粉。
本实施例的碳化硅晶须原位复合刚玉高温陶瓷材料的制备方法,采用以下步骤实现:
1)按比例称取刚玉粉、碳化稻壳粉、二氧化硅微粉、硫酸亚铁和氯化钠置于球磨罐中干混90min,再加入亚硫酸纸浆废液,混合15min制成坯料;
2)将坯料装入模具中,在液压机上于150MPa压力下保压30s成型,得到坯体;
3)将坯体置于烘箱中于110℃下干燥10h;
4)将干燥后的坯体置于刚玉坩埚中,用石墨将四周掩埋,并用刚玉坩埚盖密封,再以2℃/min的速率升温至1400℃并热处理6h,随炉冷却后即得碳化硅晶须原位复合刚玉高温陶瓷材料。
实施例3
本实施例的碳化硅晶须原位复合刚玉高温陶瓷材料由复合原料和结合剂制成,所述复合原料由以下重量百分比的原料组成:刚玉粉82.5%、碳化稻壳粉15%、硅粉0.5%、硼酸1.5%、氯化钠0.5%,刚玉粉的粒径为45μm,碳化稻壳粉化学组成中C与SiO2的质量比为0.72,结合剂为浓度为50%的亚硫酸纸浆废液,亚硫酸纸浆废液的重量为复合原料总重量的5%。
本实施例的碳化稻壳粉通过以下方法制得:
将筛选、清洗后的稻壳烘干,置于匣钵内于真空炉中经500℃碳化2h,冷却后取出,以水为球磨介质湿磨12h,烘干后过筛,优选粒径≤44μm的碳化稻壳粉。
本实施例的碳化硅晶须原位复合刚玉高温陶瓷材料的制备方法,采用以下步骤实现:
1)按比例称取刚玉粉、碳化稻壳粉、硅粉、硼酸和氯化钠置于球磨罐中干混90min,再加入糊精液,混合15min制成坯料;
2)将坯料装入模具中,在液压机上于180MPa压力下保压25s成型,得到坯体;
3)将坯体置于烘箱中于120℃下干燥8h;
4)将干燥后的坯体置于刚玉坩埚中,用石墨将四周掩埋,并用刚玉坩埚盖密封,再以4℃/min的速率升温至1450℃并热处理5h,随炉冷却后即得碳化硅晶须原位复合刚玉高温陶瓷材料。
实施例4
本实施例的碳化硅晶须原位复合刚玉高温陶瓷材料由复合原料和结合剂制成,所述复合原料由以下重量百分比的原料组成:刚玉粉85%、碳化稻壳粉13%、二氧化硅微粉1%、硫酸亚铁0.5%、硼酸0.5%,刚玉粉的粒径为80μm,碳化稻壳粉化学组成中C与SiO2的质量比为0.76,结合剂为浓度为35%的糊精液,糊精液的重量为复合原料总重量的4%。
本实施例的碳化稻壳粉通过以下方法制得:
将筛选、清洗后的稻壳烘干,置于匣钵内于真空炉中经600℃碳化1h,冷却后取出,以水为球磨介质用球磨机湿磨12h,烘干后过筛,优选粒径≤44μm的碳化稻壳粉。
本实施例的碳化硅晶须原位复合刚玉高温陶瓷材料的制备方法,采用以下步骤实现:
1)按比例称取刚玉粉、碳化稻壳粉、二氧化硅微粉、硫酸亚铁和硼酸置于球磨罐中干混90min,再加入糊精液,混合15min制成坯料;
2)将坯料装入模具中,在液压机上于150MPa压力下保压20s成型,得到坯体;
3)将坯体置于烘箱中于110℃下干燥10h;
4)将干燥后的坯体置于刚玉坩埚中,用石墨将四周掩埋,并用刚玉坩埚盖密封,再以3℃/min的速率升温至1500℃并热处理3h,随炉冷却后即得碳化硅晶须原位复合刚玉高温陶瓷材料。
实施例5
本实施例的碳化硅晶须原位复合刚玉高温陶瓷材料由复合原料和结合剂制成,所述复合原料由以下重量百分比的原料组成:刚玉粉91.5%、碳化稻壳粉7.8%、硅粉0.2%、硼酸0.5%,刚玉粉的粒径为88μm,碳化稻壳粉化学组成中C与SiO2的质量比为0.72,结合剂为浓度为30%的糊精液,糊精液的重量为复合原料总重量的3%。
本实施例的碳化稻壳粉通过以下方法制得:
将筛选、清洗后的稻壳烘干,置于匣钵内于真空炉中经650℃碳化1.5h,冷却后取出,以水为球磨介质用球磨机湿磨12h,烘干后过筛,优选粒径≤44μm的碳化稻壳粉。
本实施例的碳化硅晶须原位复合刚玉高温陶瓷材料的制备方法,采用以下步骤实现:
1)按比例称取刚玉粉、碳化稻壳粉、硅粉和硼酸置于球磨罐中干混90min,再加入糊精液,混合15min制成坯料;
2)将坯料装入模具中,在液压机上于180MPa压力下保压20s成型,得到坯体;
3)将坯体置于烘箱中于100℃下干燥12h;
4)将干燥后的坯体置于刚玉坩埚中,用石墨将四周掩埋,并用刚玉坩埚盖密封,再以5℃/min的速率升温至1550℃并热处理3h,随炉冷却后即得碳化硅晶须原位复合刚玉高温陶瓷材料。
试验例1
本试验例检测各实施例所得碳化硅晶须原位复合刚玉高温陶瓷材料的常温耐压强度、高温抗折强度、残余强度保持率、荷重软化温度及其结束点温度对应的形变率,结果如表1所示。
表1各实施例碳化硅晶须原位复合刚玉高温陶瓷材料的性能检测结果
由表1的试验结果可知,本发明的碳化硅晶须原位复合刚玉高温陶瓷材料,其常温机械强度高,对应耐压强度为79~122MPa;高温力学性能佳,1400℃时的高温抗折强度为10~18MPa;抗热震性好,1100℃热震温差下风冷3次后的残余强度保持率达77%~92%;荷重软化温度高,0.2MPa载荷下试样软化温度(由膨胀最大值压缩变形为原始高度的0.6%时对应的温度)高于1693℃;体积稳定性佳,荷重软化实验结束点温度对应形变率为0.31%~0.6%;该碳化硅晶须原位复合刚玉高温陶瓷材料兼具常温及高温强度大、抗热震性好、荷重软化温度高、体积稳定性佳的特点,适合工业化推广应用。
试验例2
实施例1所得碳化硅晶须原位复合刚玉高温陶瓷材料的SEM图如图1所示,实施例2所得碳化硅晶须原位复合刚玉高温陶瓷材料的SEM图如图2所示。
由图1和图2可知,原位生成的大量晶须状的碳化硅填充于刚玉颗粒形成的骨架中,试样受外力或热冲击时,这些碳化硅晶须通过晶须拔出、裂纹桥联或偏转等机制抵消外加应力、缓和应力集中,使制品具有较高的常温机械性能、高温力学性能和抗热震性。
Claims (4)
1.一种碳化硅晶须原位复合刚玉高温陶瓷材料的制备方法,所述碳化硅晶须原位复合刚玉高温陶瓷材料由复合原料和结合剂制成,所述复合原料由以下重量百分比的原料组成:刚玉粉82%~91.5%、碳化稻壳粉7%~15%、催化剂0.5%~2%、二氧化硅微粉或硅粉0.2%~1%;所述结合剂为亚硫酸纸浆废液或糊精液,所述结合剂的质量为所述复合原料总质量的3%~5%;所述催化剂为铁粉、氯化钠、硫酸亚铁、硼酸中的一种或几种;其特征在于,包括以下步骤:
1)将配方量的复合原料混合均匀,再加入结合剂混合均匀,制成坯料;
2)将步骤1)所得坯料成型制成坯体,干燥后在还原气氛中以2~5℃/min的速率升温至1400~1550℃热处理3~6h即得;
其中,所述碳化稻壳粉由包括如下步骤的方法制得:将稻壳在真空或惰性气氛下经500~700℃碳化0.5~2h,即得碳化稻壳粉,所述碳化稻壳粉中含有质量比为0.63~0.76的C与SiO2。
2.根据权利要求1所述的制备方法,其特征在于,步骤2)中,所述成型为机压成型,成型的压力为150~200MPa,保压的时间为15~30s。
3.根据权利要求1所述的制备方法,其特征在于,步骤2)中,所述在还原气氛是指将坯体密封于石墨粉中形成的气氛。
4.根据权利要求1所述的制备方法,其特征在于,步骤2)中,所述干燥温度为100~120℃,干燥时间8~12h。
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