CN116477954B - 一种高温低弹性模量的高强碳化硅耐火材料及制备方法 - Google Patents
一种高温低弹性模量的高强碳化硅耐火材料及制备方法 Download PDFInfo
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- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 94
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000011819 refractory material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001336 alkenes Chemical class 0.000 claims abstract description 16
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 16
- 229910003564 SiAlON Inorganic materials 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 40
- 229910000676 Si alloy Inorganic materials 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 15
- -1 silicon aluminum silicon Chemical compound 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 238000005121 nitriding Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 238000007580 dry-mixing Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000035939 shock Effects 0.000 abstract description 14
- 230000008646 thermal stress Effects 0.000 abstract description 7
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000009977 dual effect Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000010791 quenching Methods 0.000 description 22
- 230000000171 quenching effect Effects 0.000 description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 239000000571 coke Substances 0.000 description 9
- 239000011449 brick Substances 0.000 description 8
- 229910052849 andalusite Inorganic materials 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
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- 239000011863 silicon-based powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- 229920005551 calcium lignosulfonate Polymers 0.000 description 1
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
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- 150000004767 nitrides Chemical class 0.000 description 1
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Abstract
本发明涉及一种高温低弹性模量的高强碳化硅耐火材料，属于耐火材料技术领域。涉及的一种高温低弹性模量的高强碳化硅耐火材料以β‑SiAlON+碳纳米管+BN烯为结合相，碳化硅为主晶相；高温低弹性模量的高强碳化硅耐火材料中β‑SiAlON+碳纳米管+BN烯含量为10%‑30%，碳化硅主晶相的含量为70%‑90%。本发明能满足高温工业对耐火材料高强度和高热震稳定性的双重需求；可以在不降低高温强度的前提下，显著降低服役温度下的弹性模量，降低热应力数值，改善热应力分布，提高服役寿命2倍以上。
Description
技术领域
本发明涉及碳化硅耐火材料，具体涉及一种高温低弹性模量的高强碳化硅耐火材料及制备方法。
背景技术
干熄焦炉是干法熄焦技术的核心装备，干熄炉斜道区耐火材料是影响干熄焦炉寿命和效率的最关键因素，当前主要使用莫来石-红柱石砖和莫来石-碳化硅砖，存在的主要问题是可靠性差、中修周期偏短、一代炉役寿命短、运行和维护成本高；斜道区是干熄炉的关键部位，也是直接影响干熄炉寿命的重要部位；该部位结构复杂，炉内工况变化大，诸多因素影响斜道区支柱耐火材料的使用寿命：（a）在整体结构设计上，斜道区支撑梁必须承受预存段上部直筒部分全部耐火材料的重量，高温荷重必然导致结构强度的逐渐降低；（b）在焦炭自上而下、循环气体自下而上的运动过程中，斜道区支柱的耐火材料承受焦炭的冲击、磨损以及气流和粉尘的剧烈冲刷；（c）斜道区支撑梁下部的温度约为300℃，上部温度约为1000℃，支撑梁的耐火材料由下到上存在近700℃的温度梯度，致使耐火材料内部应力聚集，产生裂纹、变形；(d)耐火材料热震损伤。材料由于温度剧变，急冷急热的条件下产生热应力，在热冲击循环作用下，材料先出现开裂、剥落，然后碎裂或变质，最终整体损伤；(e)化学侵蚀作用。炼焦夹带的有害介质、冷却产生的还原性气体、煤灰粉尘、余热回收工艺制度的变化（喷雾、喷气、渗透等）等也是导致耐火材料侵蚀和损毁的因素。因此该部位需要选用抗热震性、抗磨损性和抗折强度都很高的材料。传统的莫来石-红柱石和莫来石-碳化硅在强度、热震性、耐磨性等使用性能方面已经无法满足长寿干熄炉长期稳定运行的需要，1~2年就需要进行大修。而氮化物结合碳化硅具有强度高，热膨胀系数小，热震性好，抗化学侵蚀性好的一系列优异性能，更适合干熄炉特别是其斜道区苛刻的工况条件。
部分生产企业在斜道区采用传统Si3N4结合SiC和赛隆结合碳化硅耐火材料后，干熄焦炉的寿命和效率相比在斜道区采用莫来石-红柱石和莫来石-碳化硅作为内衬的有了较明显进步；Si3N4结合SiC砖和赛隆结合碳化硅砖的常、高温抗折强度通常是莫来石-红柱石砖和莫来石-碳化硅砖的2倍以上，在高温荷重方面具有明显的优势；虽然Si3N4结合SiC和赛隆结合碳化硅因为具有高导热，低膨胀等特点，不容易在较大砖型内部产生温度梯度和热应力集中，在干熄焦炉斜道区频繁温度波动的条件下，也具有良好的热震稳定性；但随着干熄焦炉的大型化以及超大型化和各相关配套自动化装备以及锅炉的技术进步，焦化行业对斜道区用耐火材料的热震稳定性提出了更高的要求，来匹配各相关设备的长寿命服役周期；传统的氮化硅结合碳化硅和赛隆结合碳化硅等氮化物结合碳化硅耐火材料和莫来石-红柱石以及莫来石-碳化硅相比，弹性模量明显偏大，如果能开发一种既具有高强度，弹性模量又适中的耐火材料应用于干熄炉斜道区，势必会提高该位置的热震稳定性同时满足该位置对高温荷重的要求，提高干熄炉的稳定性和服役寿命。
我国是当前干熄焦技术的最大使用国，对传统Si3N4结合SiC和赛隆结合碳化硅等氮化物结合碳化硅耐火材料进行升级优化，使其更满足干熄炉斜道区对强度和热震稳定性的苛刻要求具有重要的现实意义。
发明内容
本发明的目的是提供一种高温低弹性模量的高强碳化硅耐火材料及制备方法，使其能满足高温工业对耐火材料高强度和高热震稳定性兼顾的需求；例如焦化行业干熄焦炉斜道区特别是“牛腿”、环梁等部位工作衬；旋转焦罐斜锥段和底闸门内衬等。
本发明为完成上述目的采用如下技术方案：
一种高温低弹性模量的高强碳化硅耐火材料，所述的高温低弹性模量的高强碳化硅耐火材料以高硅铝硅合金粉、氧化铝微粉和碳化硅为原料，B4C粉为添加剂；高硅铝硅合金粉氮化反应生成氮化硅和氮化铝，然后氮化铝和氧化铝微粉固溶到由高硅铝硅合金粉氮化生成的氮化硅中生成β-SiAlON；赛隆的形貌为团簇状聚集体，每一个团簇状单体具有“刺猬状”结构；“刺猬状”结构的刺为赛隆，内部基体为赛隆包裹微量未氮化的硅；B4C添加剂转化为具有较高长径比的碳纳米管和具有薄膜状结构的BN烯；所述的高温低弹性模量的高强碳化硅耐火材料以碳化硅为主晶相，以β-SiAlON+碳纳米管+BN烯为结合相；高温低弹性模量的高强碳化硅耐火材料中β-SiAlON+碳纳米管+BN烯结合相的含量为10%-30%，碳化硅主晶相的含量为70%-90%。
高温低弹性模量的高强碳化硅耐火材料的弹性模量在1000℃以上为45-55GPa。
高温低弹性模量的高强碳化硅耐火材料反应和结合相的生成是在1200-1300℃，氮气气氛下实现的。
高温低弹性模量的高强碳化硅耐火材料以β-SiAlON+碳纳米管+BN烯为结合相，碳化硅为主晶相。
高温低弹性模量的高强碳化硅耐火材料中赛隆结合相的形貌为团簇状聚集体，每一个团簇状单体为“刺猬状”结构；“刺猬状”结构的刺为赛隆，内部基体为赛隆包裹微量未氮化的硅。微量未氮化的硅的量<1%。
β-SiAlON+碳纳米管+BN烯的含量为10%-30%，碳化硅主晶相的含量为70%-90%；
所述的原料中各组分的质量含量为：高硅铝硅合金粉的质量含量为13%-20%，氧化铝微粉的质量含量为2%-5%，碳化硅的质量含量为65-80%，B4C粉添加剂外加的质量含量为+0.1%-+0.9%。高硅铝硅合金粉的粒度为200目-325目，其中硅的质量含量为60%-80%，其余为铝。
一种高温低弹性模量的高强碳化硅耐火材料的制备方法为：第一步把高硅铝硅合金粉和B4C粉添加剂干混15-30分钟，待混炼均匀后，加入3%-5%酚醛树脂湿混5-10分钟，然后在60℃烘干造粒备用得到造粒料；第二步：先把碳化硅颗粒混练均匀，再外加原料总量1-3%的结合剂、外加原料总量0.5~3.5%的溶剂混练均匀，使结合剂在碳化硅颗粒表面形成均匀的薄膜，然后加入预先混好的造粒料和碳化硅细粉混合均匀，然后压制试样，将烘干后的试样装入烧结炉中，在0.1Mpa氮气气氛下，分段升温至1200℃～1300℃，并在此温度下保温6h～10h，得到高温低弹性模量的高强碳化硅耐火材料。
为更好的适应干熄焦炉斜道区温差变化大、磨损大的使用环境，满足其对耐火材料热震性能提出的更高的需求同时兼顾材料的高强度，本发明在赛隆结合碳化硅耐火材料的基础上，通过将硅粉和铝粉单独引入，物理混合再氮化的方式优化为高硅铝硅合金粉的氮化方式，提高了硅粉和铝粉单独引入，物理混合再氮化过程的反应活性，降低了局部氮化区域金属的熔点，改变了氮化、固溶反应历程，最终改变了赛隆的显微结构。同时添加少量的B4C粉添加剂，并且通过高硅铝硅合金粉和B4C粉添加剂先干混，待均匀后再通过酚醛树脂湿混并烘干造粒的方式得到造粒料，然后把碳化硅颗粒混练均匀，再外加原料总量1-3%的结合剂、外加原料总量0.5~3.5%的溶剂混练均匀，使结合剂在碳化硅颗粒表面形成均匀的薄膜，然后加入预先混好的造粒料和碳化硅细粉混合均匀，然后压制试样，将烘干后的试样装入烧结炉中，在0.1Mpa氮气气氛下，分段升温至1200℃～1300℃，并在此温度下保温6h～10h，得到高温低弹性模量的高强碳化硅耐火材料，制备了具有特殊显微结构的新型碳化硅耐火材料。造粒料中酚醛树脂碳化产生的高活性碳、B4C粉添加剂可以充当高硅铝硅合金的稀释剂，避免在化学层面充分混合的高硅铝硅合金的熔点过度降低，影响氮化，将高硅铝硅合金氮化单元分割成无限多和无限小的单元，既利用其熔点低、高活性带来的反应温度的降低，又避免大面积熔硅造成反应通道过早被堵塞，造成“流硅”，影响材料高温性能。此外，造粒料中酚醛树脂碳化产生的碳源和高硅铝硅合金的强还原性叠加氮气营造的微区气氛，为B4C粉添加剂最终转化为碳纳米管和BN烯提供了气氛保障。
该材料相比普通的赛隆结合碳化硅，最显著的特征为高温低弹性模量，特别是温度大于1000℃后，弹性模量从室温的200GPa左右迅速降为50Gpa左右，但高温抗折强度不降低。通过ANSYS软件对干熄焦炉斜道区建模分析，在不改变宏观结构设计的前提下，通过降低碳化硅材料的高温弹性模量可以将该位置的热应力降低50%，从而提高该位置的服役稳定性。
采用该方法制备的高温低弹性模量的高强碳化硅耐火材料，应用于焦化行业干熄焦炉斜道区特别是“牛腿”、环梁等部位工作衬；旋转焦罐斜锥段和底闸门内衬等，可以在不降低高温强度的前提下，显著降低服役温度下的弹性模量，降低热应力数值，改善热应力分布，提高服役寿命2倍以上；
本发明提出的高温低弹性模量的高强碳化硅耐火材料，在服役温度下高温抗折强度高，通过特定的赛隆结合相的“刺猬状”结构实现赛隆陶瓷相和过渡塑性相硅的包裹结构；赛隆提供良好的高温强度，内部包裹的微量硅提供较低的弹性模量和塑性变形机制】添加剂B4C转化的具有较高长径比的碳纳米管和BN烯可以显著降低材料的弹性模量，并且可以提供滑移增韧机制，改善材料的抗热震性，提高服役寿命；
本发明提到的一种高温低弹性模量的高强碳化硅耐火材料，能满足高温工业对耐火材料高强度和高热震稳定性的双重需求；可以应用在包括但不限于以下应用领域：焦化行业干熄焦炉斜道区特别是“牛腿”、环梁等部位工作衬；旋转焦罐斜锥段和底闸门内衬等。
附图说明
图1-1为低倍下普通赛隆结合碳化硅的显微结构。
图1-2为高倍下普通赛隆结合碳化硅的显微结构。
图2-1为低倍下高温低弹性模量赛隆结合碳化硅中赛隆结合相的形貌.
图2-2为高倍下高温低弹性模量赛隆结合碳化硅中赛隆结合相的形貌。
图3-1为高温低弹性模量赛隆结合碳化硅中分布的具有较高长径比的碳纳米管。
图3-2为高温低弹性模量赛隆结合碳化硅中分布的薄膜状BN烯。
实施方式
结合具体实施例对本发明加以详细说明：
实施例
高温低弹性模量的高强碳化硅耐火材料最终组成为：碳化硅比例为70%，β-SiAlON+碳纳米管+BN烯比例为30%。作为原料引入的高硅铝硅合金粉引入量为20%，Al2O3微粉（D50=1μm）的引入量5%，240目SiC细粉的引入量为5%，0.1-1.43mmSiC颗粒的引入量为70%。B4C粉的引入量为+0.9%，结合剂为水溶性氨基树脂，制品的显气孔率为17.0%，体积密度为2.59g/cm3，1300℃高温抗折强度为45.0Mpa，1000℃弹性模量为55GPa。
实施例
高温低弹性模量的高强碳化硅耐火材料最终组成为：碳化硅比例为80%，β-SiAlON+碳纳米管+BN烯比例为20%。作为原料引入的高硅铝硅合金粉引入量为18%，Al2O3微粉（D50=1μm）的引入量3%， 240目SiC细粉的引入量为4%，0.1-1.43mmSiC颗粒的引入量为75%，B4C粉的引入量为+0.5%，结合剂为酚醛树脂，制品的显气孔率为15.0%，体积密度为2.65g/cm3，1200℃高温抗折强度为60.0Mpa，1200℃弹性模量为48GPa。
实施例
高温低弹性模量的高强碳化硅耐火材料最终组成为：碳化硅比例90%，β-SiAlON+碳纳米管+BN烯比例为10%。作为原料引入的高硅铝硅合金粉引入量为13%，Al2O3微粉（D50=1μm）的引入量2%， 240目SiC细粉的引入量为15%，0.1-1.43mmSiC颗粒的引入量为70%，B4C粉的添加剂引入量为+0.1%，结合剂为糊精和木质素磺酸钙，制品的显气孔率为14.0%，体积密度为2.70g/cm3，1400℃高温抗折强度50.0Mpa，1400℃弹性模量为45GPa。
Claims (6)
1.一种高温低弹性模量的高强碳化硅耐火材料，其特征在于：所述的高温低弹性模量的高强碳化硅耐火材料以高硅铝硅合金粉、氧化铝微粉和碳化硅为原料，B4C粉为添加剂；高硅铝硅合金粉氮化反应生成氮化硅和氮化铝，然后氮化铝和氧化铝微粉固溶到由高硅铝硅合金粉氮化生成的氮化硅中生成β-SiAlON；赛隆的形貌为团簇状聚集体，每一个团簇状单体具有“刺猬状”结构；“刺猬状”结构的刺为赛隆，内部基体为赛隆包裹微量未氮化的硅；B4C添加剂转化为具有较高长径比的碳纳米管和具有薄膜状结构的BN烯；所述的高温低弹性模量的高强碳化硅耐火材料以碳化硅为主晶相，以β-SiAlON+碳纳米管+BN烯为结合相；高温低弹性模量的高强碳化硅耐火材料中β-SiAlON+碳纳米管+BN烯结合相的含量为10%-30%，碳化硅主晶相的含量为70%-90%。
2.如权利要求1所述的一种高温低弹性模量的高强碳化硅耐火材料，其特征在于：高温低弹性模量的高强碳化硅耐火材料的弹性模量在1000℃以上为45-55GPa。
3.如权利要求1所述的一种高温低弹性模量的高强碳化硅耐火材料，其特征在于：高温低弹性模量的高强碳化硅耐火材料反应和结合相的生成是在1200-1300℃，氮气气氛下实现的。
4.如权利要求1所述的一种高温低弹性模量的高强碳化硅耐火材料，其特征在于：微量未氮化的硅的量<1%。
5.如权利要求1所述的一种高温低弹性模量的高强碳化硅耐火材料，其特征在于：所述的原料中各组分的质量含量为：高硅铝硅合金粉的质量含量为13%-20%，氧化铝微粉的质量含量为2%-5%，碳化硅的质量含量为65-80%，所述原料中各组分的质量百分比之和为100%；B4C粉添加剂外加的质量含量为+0.1%-+0.9%；高硅铝硅合金粉的粒度为200目-325目，其中硅的质量含量为60%-80%，其余为铝。
6.制备权利要求1-5中任一所述一种高温低弹性模量的高强碳化硅耐火材料的制备方法为：第一步把高硅铝硅合金粉和B4C粉添加剂干混15-30分钟，待混炼均匀后，加入3%-5%酚醛树脂湿混5-10分钟，然后在60℃烘干造粒备用得到造粒料；第二步：先把碳化硅颗粒混练均匀，再外加原料总量1-3%的结合剂、外加原料总量0.5~3.5%的溶剂混练均匀，使结合剂在碳化硅颗粒表面形成均匀的薄膜，然后加入预先混好的造粒料和碳化硅细粉混合均匀，然后压制试样，将烘干后的试样装入烧结炉中，在0.1Mpa氮气气氛下，分段升温至1200℃～1300℃，并在此温度下保温6h～10h，得到高温低弹性模量的高强碳化硅耐火材料。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050625A (zh) * | 2010-10-28 | 2011-05-11 | 中钢集团洛阳耐火材料研究院有限公司 | 一种赛隆-石墨复合碳化硅材料及其制备方法 |
| CN104926324A (zh) * | 2015-05-28 | 2015-09-23 | 武汉科技大学 | 一种原位生成片状赛隆增强铝碳耐火材料及其制备方法 |
| WO2016037730A1 (de) * | 2014-09-11 | 2016-03-17 | Refratechnik Holding Gmbh | Versatz für ein aus reaktiongebundenem siliziumcarbid gebranntes erzeugnis und verwendung des versatzes sowie feuerfestes erzeugnis aus dem versatz |
| CN110204339A (zh) * | 2019-07-05 | 2019-09-06 | 唐山时创高温材料股份有限公司 | 一种金属自结合碳化硅砖生产工艺 |
| CN115536397A (zh) * | 2022-10-30 | 2022-12-30 | 中钢集团洛阳耐火材料研究院有限公司 | 一种用于埋碳气氛的自修复碳化硅耐火材料 |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050625A (zh) * | 2010-10-28 | 2011-05-11 | 中钢集团洛阳耐火材料研究院有限公司 | 一种赛隆-石墨复合碳化硅材料及其制备方法 |
| WO2016037730A1 (de) * | 2014-09-11 | 2016-03-17 | Refratechnik Holding Gmbh | Versatz für ein aus reaktiongebundenem siliziumcarbid gebranntes erzeugnis und verwendung des versatzes sowie feuerfestes erzeugnis aus dem versatz |
| CN104926324A (zh) * | 2015-05-28 | 2015-09-23 | 武汉科技大学 | 一种原位生成片状赛隆增强铝碳耐火材料及其制备方法 |
| CN110204339A (zh) * | 2019-07-05 | 2019-09-06 | 唐山时创高温材料股份有限公司 | 一种金属自结合碳化硅砖生产工艺 |
| CN115536397A (zh) * | 2022-10-30 | 2022-12-30 | 中钢集团洛阳耐火材料研究院有限公司 | 一种用于埋碳气氛的自修复碳化硅耐火材料 |
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