CN110950664A - 一种轻质高强碳化硅节能窑具及其制备方法 - Google Patents
一种轻质高强碳化硅节能窑具及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种轻质高强碳化硅节能窑具及其制备方法,所述轻质高强碳化硅节能窑具的组成中碳化硅含量不低于98%,且内部存在球形气孔,孔隙率为30~55vol%,孔径为5~40μm。
Description
技术领域
本发明涉及一种轻质高强碳化硅节能窑具及其制备方法。
背景技术
窑具广泛应用于日用陶瓷、耐火材料、电陶、磨料等高温行业,包括匣钵、承烧板、支撑梁、立柱等。作为高温行业的基础性材料,窑具质量与性能的好坏对烧成制品的质量、能耗、合格率、等级率、生产成本等起到举足轻重的作用。窑具对材料性能的要求包括:1)高温强度好;2)导热性高,以提高窑具材料的热效;3)良好的抗高温蠕变性与抗热震性;4)轻质,以降低由于窑具蓄热导致的能源消耗;5)厚度薄,以提高窑炉的填装量。碳化硅陶瓷具有高温强度好,耐化学腐蚀性优异,导热率高、热膨胀系数低等特性,故碳化硅窑具具有强度高、重量轻、导热系数大、厚度薄、使用寿命长(一般80~100次)等优点,长期使用几乎不变形,可装填量大,有利于提高产品的合格率和等级率,且节能效果明显,是一种理想的高档窑具。
常用的碳化硅窑具包括氧化物结合碳化硅窑具、氮化硅结合碳化硅(N-SiC)窑具、反应烧结碳化硅(RBSC)窑具、重结晶碳化硅(R-SiC)窑具。氧化物结合碳化硅窑具,高温荷重软化温度低于1200℃,容易发生蠕变而变形,影响使用寿命。N-SiC与RBSC窑具其本质是反应结合的碳化硅窑具,制备过程中容易出现反应不充分,残留单质硅,进而导致高温下强度下降明显,且容易发生氧化现象,因此N-SiC窑具、RBSC窑具的使用温度均低于1350℃。R-SiC是以粗细级配的碳化硅为原料,在惰性气体、2200~2450℃温度下,发生蒸发-凝聚再结晶作用,在粗颗粒接触处发生颗粒共生形成的烧结体。R-SiC作为一种高档窑具材料,国产制品可在1350~1400℃下长期使用,进口产品可长期使用于1500℃。例如,郭玉广等以高纯SiC粉(>99%,粗细级配比为6:4)为主要原料,通过注浆成型、捣打成型、挤出成型和等静压成型,在2450℃下烧成得到高纯R-SiC窑具。R-SiC窑具由于高的纯度且存在一定孔隙率(10~20%),而具有好的高温强度、导热率、抗热震性和抗氧化性。然而,R-SiC窑具制备温度高达2200~2450℃,生产过程中能耗大,成本相对较高;同时R-SiC窑具的孔隙率通常为10~20%,强度为80~100MPa,在满足使用强度要求的条件下,孔隙率难以进一步提升,密度仍然相对较高,节能效果的改善受到限制。
常压固相烧结碳化硅陶瓷(S-SiC)具有高的纯度、好的高温强度、优异的抗氧化性,且具有极佳的耐磨性和良好的热导率,因此,S-SiC也是一种理想的高温结构材料,可用于1600℃的高温环境,然而市场中的S-SiC陶瓷多为致密材料,抗热震相对较差,故较少用作窑具材料。
发明内容
针对传统碳化硅窑具强度(尤其是高温强度)低、密度偏高、节能效果有限等问题,本发明的目的在于提出一种轻质高强碳化硅节能窑具及其制备方法。主要通过在耐高温、高温强度好的常压固相烧结碳化硅陶瓷中引入球形气孔,大幅改善材料的抗热震性并降低材料的密度,显著提升碳化硅窑具材料节能效果。
一种轻质高强碳化硅节能窑具,所述轻质高强碳化硅节能窑具的组成中碳化硅含量不低于98%,且内部存在球形气孔,孔隙率为30~55vol%,孔径为5~40μm。
较佳的,所述轻质高强碳化硅节能窑具的密度为1.4~2.5g/cm3,室温下抗弯强度不低于100MPa,1350℃下抗弯强度不低于80MPa。
较佳的,所述轻质高强碳化硅节能窑具为坩埚、匣钵、辊棒、或硼板。
另一方面,本发明提供了一种如上述轻质高强碳化硅节能窑具的制备方法,包括:
(1)将SiC粉体、硼源、碳源和球形有机造孔剂混合后并压制成型,得到素坯;
(2)将所得素坯在1750~2200℃下烧结,得到所述轻质高强碳化硅节能窑具;
所述球形有机造孔剂选自聚乙烯、聚苯乙烯、聚乙二醇、淀粉中的至少一种;所述球形有机造孔剂的体积为SiC粉体体积的45~130vol%。
较佳的,所述硼源为碳化硼粉或/和硼粉;所述硼源的质量为SiC粉体质量的0.1~1.5wt%。
较佳的,所述碳源为无机碳源或/和有机碳源,所述无机碳源为碳粉,所述有机碳源为碳有机前驱体;所述碳源的质量为SiC粉体质量的0.5~10wt%。
较佳的,所述SiC粉体的中位粒径为0.1~20μm;所述球形有机造孔剂的中位粒径为5~50μm。
较佳的,所述压制成型的方法为干压成型、挤出成型、注浆成型、或凝胶注模成型。
较佳的,在烧结之前,将所得素坯进行脱粘处理,所述脱粘在真空中进行,温度为150~600℃,时间为1~3小时。本发明中,脱粘工艺需根据TG/TGA曲线确定,受球形造孔剂种类与添加量影响,脱粘过程中的保温温度点等都是特需控制的要点。
较佳的,所述烧结的时间为0.5~3小时;所述烧结的气氛为惰性气氛,优选为氩气。
有益效果:
(1)本发明所述的轻质高强碳化硅节能窑具具有质量轻、密度低的特点,其中含有孔隙率为30~55%的球形气孔,密度仅为1.4~2.5g/cm3,有利于大幅度降低由于窑具蓄热导致的无效能源消耗;
(2)本发明所述的轻质高强碳化硅节能窑具具有强度高的特点,室温抗弯强度不低于100MPa,高温(1350℃)抗弯强度不低于80MPa,从而可减小节能窑具材料的厚度,进而提升窑炉的填装量。其中,窑具包括匣钵、承烧板、支撑梁、立柱等,种类很多,形状尺寸千差万别,本发明主要是针对窑具材料体系进行保护,不是针对特定窑具产品。
附图说明
图1为实施例1得到的轻质高强碳化硅节能窑具的微观结构照片;
图2为实施例1得到的轻质高强碳化硅节能窑具的微观结构照片。
具体实施方式
以下通过下述实施方式进一步说明本发明,应理解,下述实施方式仅用于说明本发明,而非限制本发明。
在本公开中,提供了一种性能优异的含球形气孔的常压固相烧结碳化硅节能窑具及其制备方法,主要是通过球形气孔的引入可显著改善陶瓷材料的抗热震性,得到具有轻质、高强、节能效果好的S-SiC节能窑具。该轻质高强碳化硅节能窑具包括但不限于坩埚、匣钵、辊棒、硼板。
本发明中,轻质高强碳化硅节能窑具的组成中碳化硅含量不低于98%,内部存在球形气孔,孔隙率为30~55%,孔径为5~40μm。轻质高强碳化硅节能窑具具有密度低的特点(1.4~2.5g/cm3),其还具有优异的力学强度,室温(25℃)抗弯强度不低于100MPa,高温(1350℃)抗弯强度不低于80MPa。
在本发明一实施方式中,选用球形有机造孔剂,并采用常压固相烧结工艺以制备轻质高强碳化硅节能窑。而且,本发明还可通过球形有机造孔剂的粒径与添加量的改变来进行调控轻质高强碳化硅节能窑的孔径与孔隙率。以下示例性地说明轻质高强碳化硅节能窑的制备方法。
将碳化硅粉体、硼源(碳化硼粉或/和硼粉))、碳源(碳粉或/和碳有机前驱体)、球形有机造孔剂依次倒入混料机充分混合,得到混合粉体。其中,球形有机造孔剂选自聚乙烯、聚苯乙烯、聚乙二醇、淀粉等。球形有机造孔剂的体积为SiC粉体体积的45~130vol%,所述的轻质高强碳化硅节能窑具的孔径通过球形有机造孔剂的粒径调控,孔隙率通过球形有机造孔剂的体积调控。若是球形有机造孔剂加入量过少,碳化硅窑具密度较大,气孔率偏低,降低节能效果。若是球形有机造孔剂加入量过多,窑具孔隙率偏高,强度过低。而且,加入高达45-130vol%的球形造孔剂的引入,存在与碳化硅粉体共分散的问题,本发明是通过分散剂对球形造孔剂的表面改性,并配合特殊分散设备,在工艺参数优化的基础上实现的。
在可选的实施方式中,碳源的质量可为SiC粉体质量的0.5~10wt%。硼源的质量可为SiC粉体质量的0.1~1.5wt%。碳有机前驱体选自酚醛树脂、蔗糖、沥青、果糖等中的至少一种。SiC粉体的中位粒径可为0.1~20μm。球形有机造孔剂的中位粒径可为5~50μm。
在可选的实施方式中,上述混合粉体中还可加入粘结剂,一般占碳化硅粉体质量的1~10wt%。其中,粘结剂可为聚乙烯醇、羟甲基纤维素、糊精、聚乙烯醇缩丁醛等中的至少一种。
将混合粉体进行压制成型工序,得到素坯。其中,压制成型的方法包括但不限于干压成型、挤出成型、注浆成型、或凝胶注模成型等。优选地,加入45-130vol%的球形造孔剂后,由于有机造孔剂在成型过程中发生明显的弹性变形,坯体成型工艺控制不好,易开裂。对此,本发明人通过优化成型过程中的压力大小与加压速率等成型参数解决的。
在可选的实施方式中,干压成型的压力可为20~200MPa。干压成型的时间可为1~30分钟。
在可选的实施方式中,挤出成型包括:(1)将混合粉体(或称复合粉体)、粘结剂(例如,聚乙烯醇、羟甲基纤维素、糊精、聚乙烯醇缩丁醛等)和溶剂(例如,水、乙醇、丁醇等)混合,得到泥料。优选,在泥料中还加入占SiC粉体质量0.1~2wt%的分散剂(例如,四甲基氢氧化铵、聚乙烯亚胺、聚丙烯酸铵、氨水等)。(2)将所得泥料进行挤出成型,制备得到素坯。
在可选的实施方式中,注浆成型包括:(1)将混合粉体(或称复合粉体)、占SiC粉体质量0.1~2wt%的分散剂(例如,四甲基氢氧化铵、聚乙烯亚胺、聚丙烯酸铵、氨水等)和溶剂(例如,水、乙醇、丁醇等)混合,得到稳定的浆料。(2)将浆料置于石膏模具中注浆成型。(3)最后再经脱模和干燥,得到素坯。
在可选的实施方式中,凝胶注模成型包括:(1)将混合粉体(或称复合粉体)、占SiC粉体质量0.1~2wt%的分散剂(例如,四甲基氢氧化铵、聚乙烯亚胺、聚丙烯酸铵、氨水等)和含有丙烯酰胺、亚甲基双丙烯酰胺的溶剂(例如,水、乙醇、丁醇等)混合,得到稳定的浆料。(2)然后在浆料中加入引发剂(例如,过硫酸铵、过硫酸钾、偶氮[2-(2-咪唑啉-2-基)]丙烷盐酸,等)和催化剂(例如,四甲基乙二胺等)后快速浇注于模具中。(3)最后再经脱模和干燥,得到素坯。
将素坯经高温烧结,得到轻质高强碳化硅节能窑具。其中,烧结的温度可为1750~2200℃。烧结的时间可为0.5~3小时。烧结的气氛可为惰性气氛,例如氩气等。在高温烧结之前,将素坯进行脱粘处理。而且,45~130vol%的球形造孔剂引入后,脱粘处理阶段也要进行特殊控制,否则易开裂。其中,脱粘处理在真空中进行,温度可为150~600℃,时间可为1~3小时。
在本发明中,按照GB/T 25995-2010方法测试所得轻质高强碳化硅节能窑具的孔隙率。按照GB/T 21650.1-2008方法测试所得轻质高强碳化硅节能窑具的抗弯强度。按照GB/T25995-2010方法测试所得轻质高强碳化硅节能窑具的密度。
下面进一步例举实施例以详细说明本发明。同样应理解,以下实施例只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制,本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例,即本领域技术人员可以通过本文的说明做合适的范围内选择,而并非要限定于下文示例的具体数值。
实施例1
将0.5μm SiC粉体、占碳化硅粉体质量0.5wt%的碳化硼粉与占碳化硅粉体质量1wt%的碳粉、占碳化硅粉体体积100vol%的15μm聚苯乙烯球,在搅拌桶中均匀混合,得到复合粉体。之后,加入占碳化硅粉体质量1wt%的羟甲基纤维素作为粘结剂,干压成型(200MPa,1分钟),得到板状生坯。最后,将板状生坯在150℃下,真空中脱粘,而后放入石墨炉中,Ar气氛下,升温至2100℃烧2h,得到轻质高强碳化硅节能窑具(硼板),其结构与性能数据如表1;微观结构照片如图1和图2,球形气孔分布均匀。
实施例2
将0.1μm SiC粉体、占碳化硅粉体质量1.5wt%的硼粉与占碳化硅粉体质量10wt%的碳粉、占碳化硅粉体体积45vol%的5μm淀粉球,在搅拌桶中均匀混合,得到复合粉体。之后,向复合粉体中加入占碳化硅粉体质量10wt%的聚乙烯醇作为粘结剂,干压成型(20MPa,30分钟),得到坩埚状生坯。最后,将坩埚状生坯在650℃下,真空中脱粘,而后放入石墨炉中,Ar气氛下,升温至1750℃烧结0.5h,得到轻质高强碳化硅节能窑具(坩埚),其碳化硅含量为98%,密度为2.5g/cm3,孔隙率为30%,孔径为5μm,常温三点抗弯强度为150MPa,1350℃三点抗弯强度为135MPa。
实施例3
将20μm SiC粉体、占碳化硅粉体质量0.1wt%的碳化硼粉与占碳化硅粉体质量0.5wt%的碳粉、占碳化硅粉体体积130vol%的50μm聚乙烯球,在搅拌桶中均匀混合,得到复合粉体。接着,以四甲基氢氧化铵为分散剂,将复合粉体加入水溶液中搅拌,得到稳定的浆料。之后将浆料浇注到特定形状的石膏模具中,注浆成型,经脱模、干燥后,得到匣钵状生坯。最后,将匣钵状生坯在350℃下,真空中脱粘,而后放入石墨炉中,Ar气氛下,升温至2200℃烧结3h,得到轻质高强碳化硅节能窑具(匣钵),其碳化硅含量为98.5%,密度为1.4g/cm3,孔隙率为55%,孔径为40μm,常温三点抗弯强度为100MPa,1350℃三点抗弯强度为80MPa。
实施例4
将10μm SiC粉体、占碳化硅粉体质量0.8wt%的碳化硼粉与占碳化硅粉体质量6wt%的碳粉、占碳化硅粉体体积110vol%的40μm聚乙二醇球,在搅拌桶中均匀混合,得到复合粉体。接着,以四甲基氢氧化铵为分散剂,将复合粉体加入到含有丙烯酰胺、亚甲基双丙烯酰胺的水溶液中搅拌,得到稳定浆料。之后,向浆料中加入引发剂过硫酸铵与催化剂四甲基乙二胺,迅速浇注于板状模具中,凝胶注模成型,经脱模、干燥后,得到生坯。最后,将板状生坯在450℃下,真空中脱粘,而后放入石墨炉中,Ar气氛下,升温至2100℃烧结1.5h,得到轻质高强碳化硅节能窑具(硼板),其碳化硅含量为99.3%,密度为1.61g/cm3,孔隙率为50%,孔径为30μm,常温三点抗弯强度为110MPa,1350℃三点抗弯强度为95MPa。
实施例5
将5μm SiC粉体、占碳化硅粉体质量1.2wt%的碳化硼粉与占碳化硅粉体质量3wt%的碳粉、占碳化硅粉体体积80vol%的10μm聚苯乙烯球,在搅拌桶中均匀混合,得到复合粉体。接着,依次加入占碳化硅粉体质量3wt%的羟甲基纤维素、占碳化硅粉体质量5wt%的甘油、占碳化硅粉体质量25wt%的水,在混炼机中充分混炼,得到泥料。之后,泥料经挤出成型、干燥后,得到管状生坯。最后,将管状生坯在550℃下,真空中脱粘,而后放入石墨炉中,Ar气氛下,升温至2050℃烧结1h,得到轻质高强碳化硅节能窑具(辊棒),其碳化硅含量为98.7%,密度为1.85g/cm3,孔隙率为42%,孔径为30μm,常温三点抗弯强度为130MPa,1350℃三点抗弯强度为118MPa。
对比例1
将0.5μm SiC粉体、占碳化硅粉体质量0.5wt%的碳化硼粉与占碳化硅粉体质量1wt%的碳粉、占碳化硅粉体体积30vol%的15μm聚苯乙烯球,在搅拌桶中均匀混合,得到复合粉体。之后,加入占碳化硅粉体质量1wt%的羟甲基纤维素作为粘结剂,干压成型(200MPa,1分钟),得到板状生坯。最后,将板状生坯在150℃下,真空中脱粘,而后放入石墨炉中,Ar气氛下,升温至2100℃烧2h,得到轻质高强碳化硅节能窑具(硼板),其结构与性能数据列如表1。
对比例2
将0.5μm SiC粉体、占碳化硅粉体质量0.5wt%的碳化硼粉与占碳化硅粉体质量1wt%的碳粉、占碳化硅粉体体积180vol%的15μm聚苯乙烯球,在搅拌桶中均匀混合,得到复合粉体。之后,加入占碳化硅粉体质量1wt%的羟甲基纤维素作为粘结剂,干压成型(200MPa,1分钟),得到板状生坯。最后,将板状生坯在150℃下,真空中脱粘,而后放入石墨炉中,Ar气氛下,升温至2100℃烧2h,得到轻质高强碳化硅节能窑具(硼板),其结构与性能数据列如表1。
表1为实施例1-5和对比例1-2所得轻质高强碳化硅节能窑具的组成及性能数据:
Claims (10)
1.一种轻质高强碳化硅节能窑具,其特征在于,所述轻质高强碳化硅节能窑具的组成中碳化硅含量不低于98%,且内部存在球形气孔,孔隙率为30~55vol%,孔径为5~40μm。
2.根据权利要求1所述的轻质高强碳化硅节能窑具,其特征在于,所述轻质高强碳化硅节能窑具的密度为1.4~2.5g/cm3,室温下抗弯强度不低于100MPa,1350℃下抗弯强度不低于80MPa。
3.根据权利要求1或2所述的轻质高强碳化硅节能窑具,其特征在于,所述轻质高强碳化硅节能窑具为坩埚、匣钵、辊棒、或硼板。
4.一种如权利要求1-3中任一项所述轻质高强碳化硅节能窑具的制备方法,其特征在于,包括:
(1)将SiC粉体、硼源、碳源和球形有机造孔剂混合后并压制成型,得到素坯;
(2)将所得素坯在1750~2200℃下烧结,得到所述轻质高强碳化硅节能窑具;
所述球形有机造孔剂选自聚乙烯、聚苯乙烯、聚乙二醇、淀粉中的至少一种;所述球形有机造孔剂的体积为SiC粉体体积的45~130 vol%。
5.根据权利要求4所述的制备方法,其特征在于,所述硼源为碳化硼粉或/和硼粉;所述硼源的质量为SiC粉体质量的0.1~1.5 wt%。
6.根据权利要求4或5所述的制备方法,其特征在于,所述碳源为无机碳源或/和有机碳源,所述无机碳源为碳粉,所述有机碳源为碳有机前驱体;所述碳源的质量为SiC粉体质量的0.5~10 wt%。
7.根据权利要求4-6中任一项所述的制备方法,其特征在于,所述SiC粉体的中位粒径为0.1~20μm;所述球形有机造孔剂的中位粒径为5~50μm。
8.根据权利要求4-7中任一项所述的制备方法,其特征在于,所述压制成型的方法为干压成型、挤出成型、注浆成型、或凝胶注模成型。
9.根据权利要求4-8中任一项所述的制备方法,其特征在于,在烧结之前,将所得素坯进行脱粘处理,所述脱粘处理在真空中进行,温度为150~600℃,时间为1~3小时。
10.根据权利要求4-9中任一项所述的制备方法,其特征在于,所述烧结的时间为0.5~3小时;所述烧结的气氛为惰性气氛,优选为氩气。
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CN115716754A (zh) * | 2022-11-17 | 2023-02-28 | 浙江百岸科技有限公司 | 一种氮氧传感器陶瓷芯片高温烧结用承烧板的制备方法 |
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