CN110436901A - 一种SiC-AlN固溶体结合Al2O3-C复合滑板及其制备方法 - Google Patents

一种SiC-AlN固溶体结合Al2O3-C复合滑板及其制备方法 Download PDF

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CN110436901A
CN110436901A CN201910678127.1A CN201910678127A CN110436901A CN 110436901 A CN110436901 A CN 110436901A CN 201910678127 A CN201910678127 A CN 201910678127A CN 110436901 A CN110436901 A CN 110436901A
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solid solution
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aln solid
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李勇
马晨红
李宏宇
薛文东
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University of Science and Technology Beijing USTB
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Abstract

本发明涉及一种SiC‑AlN固溶体结合Al2O3‑C复合滑板及其制备方法，属于耐火材料领域。该滑板的原料组成为60‑90wt.％的刚玉、1‑20wt.％的α‑Al2O3微粉、1‑15wt.％的金属铝、1‑15wt.％的硅、0‑5％wt.％的炭粉，外加2‑7wt.％的酚醛树脂为结合剂。生产时按配比将原料混合均匀，经混炼得到泥料，压制成型，在120℃‑400℃下干燥5‑30h后于400‑660℃氮气气氛下保温1‑10h，最后于1450‑1700℃氮气气氛下烧成。该产品利用Al、Si、C及N2之间的反应在Al2O3基体中原位合成SiC‑AlN固溶体增强相，具有优良的性能：显气孔率5‑20％、体积密度3.00‑3.40g/cm3、常温耐压强度100‑400MPa。本发明产品烧成时无需超高温和高压，大大降低了将SiC‑AlN固溶体应用于耐火材料的成本，适合工业化生产。本发明产品综合了金属、非氧化物和氧化物的优点，具有良好的抗热震性、抗侵蚀性及高温稳定性。

Description

一种SiC-AlN固溶体结合Al2O3-C复合滑板及其制备方法
技术领域
本发明涉及一种炼钢连铸用滑板，尤其涉及一种洁净钢、低碳钢连铸用的SiC-AlN固溶体结合的Al2O3-C复合滑板及其制备方法，属于耐火材料领域。
背景技术
滑板砖是滑动水口的关键组成部分，是直接控制钢水、决定滑动水口功能的部件。其在使用过程中需要长时期承受高温钢液的化学侵蚀和物理冲刷，激烈和瞬变的热冲击及机械磨损作用，使用条件极为苛刻，其安全性和长寿化是连铸生产正常运行的关键因素之一。因此滑板砖必须具有高强度、耐磨损、耐侵蚀和热震稳定性好等特性。
目前国内主要使用铝碳质和铝锆碳质滑板砖，它们基本能满足普通钢连铸的需求，但其使用次数仍较国外有一定的差距，且应用于洁净钢、高品质钢等的连铸生产时，还存在许多缺陷，如高温下不耐冲刷等。
金属-非氧化物-氧化物复合耐火材料综合了金属、非氧化物以及氧化物的各项优良特征，具有优良的高温强度、抗热震、抗侵蚀和抗氧化等性能，且满足洁净钢、超低碳钢等冶炼要求，是新一代的优质高效耐火材料的核心。利用金属相与环境气氛及材料高温下发生反应在氧化物基体中原位合成性能优异、多元化、复杂化的非氧化物结合相，可提高材料的高温强度和抗热震、抗侵蚀性等。
AlN和SiC均是重要的纤锌矿型共价化合物，是结构应用的重要先进陶瓷材料。氮化铝与纤锌矿2H-SiC同构并且具有紧密匹配的晶格参数(2H-SiC：a＝3.0763，c＝5.048；AlN：a＝3.1114，c＝4.9792A)。同时，Si和C及Al和N具有相似的电负性，复合Hume-Rothery法则。人们在SiC-AlN复相陶瓷的研究中发现，二者在较宽的组成及温度范围内可形成固溶体，且随着固溶体的形成，材料的烧结活性、显微结构、力学性能、抗氧化性及耐腐蚀性均得到较大程度的改善和提高,即具有更好的综合性能，是Al2O3-C材料良好的非氧化物结合相。
在上述背景下，本发明以金属-非氧化物-氧化物复合理论为基础，在Al2O3-C材料中添加金属铝、硅粉为原料，并控制升温机制在氮气气氛下烧成。利用高温下金属Al、Si、C与N2之间的反应原位合成SiC-AlN固溶体增强相，制备出一种性能优异的无需超高温高压的SiC-AlN固溶体结合Al2O3-C复合滑板。
发明内容
本发明旨在制备出一种无需超高温高压处理的SiC-AlN固溶体结合Al2O3-C复合滑板，其既克服了现有滑板材料中单一添加金属铝易生成AlN、Al4C3等易水化产物使得制品不能长期存放从而影响其工业化的缺陷；又克服了单一添加Si合成SiC易氧化的问题；同时本产品生产工序简单，通过升温机制的控制实现了SiC-AlN固溶体的低温常压合成，产品具有优良的高温强度、抗热震、抗侵蚀和抗氧化等性能，寿命长，满足洁净钢连铸需要。
本发明的技术方案：
一种SiC-AlN固溶体结合Al2O3-C复合滑板，按重量百分比计，原料组成为60-90％的刚玉、0-20％的α-Al2O3微粉、1-15％的金属Al、1-15％的Si、0-5％的碳粉，外加2-7％的酚醛树脂为结合剂。
所述刚玉有3-1mm、1-0.1mm、0.1-0mm三种粒度，所述α-Al2O3微粉为0.1-0mm，所述金属Al和Si的粒度为0.1-0mm。
如上所述SiC-AlN固溶体结合Al2O3-C复合滑板的生产方法，按配比称取各种原料混合均匀，经混炼得到泥料，压制成型，在120℃-400℃下干燥5-30h后于400-660℃氮气气氛下保温1-10h，于1450-1700℃氮气气氛下烧成，经加箍、磨制、涂布即制成本发明产品。
本发明的积极效果：
1、本发明利用金属过渡塑性相工艺，通过控制升温机制制备了SiC-AlN固溶体结合Al2O3-C复合滑板。滑板不含易水化的AlN、Al4C3，或易氧化的SiC等单一相，而是合成了综合性能更加优异的SiC-AlN固溶体增强相，能满足洁净钢生产要求。
2、本发明产品无需超高温高压条件，无需浸油工序，大大降低了SiC-AlN固溶体的合成成本。
3、本发明所得产品为金属、非氧化物和氧化物结合的复合滑板，其中游离态的金属Al、Si发挥塑性相作用，改善材料的韧性和抗热震性能；SiC-AlN固溶体非氧化物作为增强相，改善材料的高温强度，且提高抗氧化性及耐侵蚀性。
4、由于试样内部不存在单一的AlN或Al4C3相，使得滑板具有良好的抗水化性能，便于滑板产品的长期存放及工业化应用。
5、本发明产品具有优良的物理性能指标。显气孔率3-10％、体积密度3.00-3.40g/cm3、常温耐压强度100-400MPa。
6、本发明的滑板产品能满足高品质钢、高洁净钢等高效连铸要求，且以较低的成本引入性能优异的SiC-AlN固溶体增强相，具有较好的市场潜力，适宜于产业化应用，可获得较好的经济、社会收益。
具体实施方式
实施例1：一种SiC-AlN固溶体结合Al2O3-C复合滑板制备方法，按重量百分比计，原料组成为：88％的刚玉、8％的活性氧化铝、2％的金属铝粉，2％的硅粉，外加3.5％的热固性酚醛树脂。
生产时，先按配比称取各种原料，将粉料和骨料混合均匀，经混炼得到泥料，然后经摩擦压力机压制成型，在120-400℃下干燥12h，500-600℃氮气气氛下保温4h，最后于1550-1650℃氮气气氛下烧成。再经加箍、磨制、涂布即制成本发明产品。
所述粉料为粒度小于325目的金属Al粉、Si粉、α-Al2O3粉及部分刚玉，所述骨料为粒度为3-1mm、1-0.1mm的刚玉；上述刚玉分为板状刚玉和白刚玉。
所得产品的性能指标为：显气孔率14.6％，体积密度3.23g/cm3，常温耐压强度201MPa，其抗热震性、抗侵蚀性、抗氧化性及抗水化性均较好。
实施例2：生产工艺和实施例1相同，不同之处在于：
按重量百分比计，原料组成为：84％的刚玉、8％的活性氧化铝、4％的金属铝粉，4％的硅粉，外加3.5％的热固性酚醛树脂。所得产品的性能指标为：显气孔率16.8％，体积密度3.14g/cm3，常温耐压强度217MPa，其抗热震性、抗侵蚀性、抗氧化性及抗水化性均较好。
实施例3：生产工艺和实施例1相同，不同之处在于：
按重量百分比计，原料组成为：80％的刚玉、8％的活性氧化铝、6％的金属铝粉，6％的硅粉，外加3.5％的热固性酚醛树脂。所得产品的性能指标为：显气孔率15.6％，体积密度3.14g/cm3，常温耐压强度187MPa，其抗热震性、抗侵蚀性、抗氧化性及抗水化性均较好。
实施例4：生产工艺和实施例1相同，不同之处在于：
按重量百分比计，原料组成为：78％的刚玉、8％的活性氧化铝、8％的金属铝粉，8％的硅粉，外加3.5％的热固性酚醛树脂。所得产品的性能指标为：显气孔率17.4％，体积密度3.04g/cm3，常温耐压强度116MPa，其抗热震性、抗侵蚀性、抗氧化性及抗水化性均较好。

Claims (3)

1.一种SiC-AlN固溶体结合Al2O3-C复合滑板，其特征在于：按重量百分比计，原料组成为60-90％的刚玉、1-20％的α-Al2O3微粉、1-15％的金属Al、1-15％的Si、0-5％的碳粉，外加2-7％的酚醛树脂为结合剂。
2.根据权利要求1所述的SiC-AlN固溶体结合Al2O3-C复合滑板，其特征在于：所述刚玉有3-1mm、1-0.1mm、0.1-0mm三种粒度，所述α-Al2O3微粉为0.1-0mm，所述金属Al和Si的粒度为0.1-0mm。
3.权利要求1或2所述的SiC-AlN固溶体结合Al2O3-C复合滑板的制备方法，其特征在于：按配比称取各种原料混合均匀，经混炼得到泥料，压制成型，在120℃-400℃下干燥5-30h后于400-660℃氮气气氛下保温1-10h，最后于1450-1700℃氮气气氛下烧成，再经加箍、磨制、涂布即制成本发明产品。
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