CN117383949A - 一种碳纳米纤维增韧耐火材料的制备方法 - Google Patents
一种碳纳米纤维增韧耐火材料的制备方法 Download PDFInfo
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- 239000011819 refractory material Substances 0.000 title claims abstract description 46
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000005011 phenolic resin Substances 0.000 claims abstract description 22
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 31
- 239000010431 corundum Substances 0.000 claims description 31
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011449 brick Substances 0.000 claims description 11
- 229910052849 andalusite Inorganic materials 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 235000012211 aluminium silicate Nutrition 0.000 claims description 8
- 239000004927 clay Substances 0.000 claims description 8
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004576 sand Substances 0.000 claims description 8
- 229910052845 zircon Inorganic materials 0.000 claims description 8
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 7
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 150000003112 potassium compounds Chemical class 0.000 claims description 2
- 150000003388 sodium compounds Chemical class 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- 230000035939 shock Effects 0.000 abstract description 11
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 206010063385 Intellectualisation Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
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- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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Abstract
本发明公开了一种碳纳米纤维增韧耐火材料的制备方法。该耐火材料的组成包括酚醛树脂、固化剂、催化剂，以及耐火材料各组分，按照特定的加料顺序，经混合、压制、高温烧结等步骤制备而成。在高温烧结过程中，酚醛树脂裂解出CH4、C2H2等含碳的气态组分，在催化剂作用下原位以碳纳米纤维的形式形成碳网结构，分布在耐火材料的基体中。这类由原位生成碳纳米纤维增韧的耐火材料，具有轻质、高耐磨、热震稳定性能优异，原料易得，制备方便等特点。
Description
技术领域
本发明属于耐火材料领域，涉及一种碳纳米纤维原位增韧的耐火材料，同时提供这类材料的制备方法。
背景技术
耐火材料是钢铁、化工、建材等高温工业领域重要的基础和支撑材料。而高温工业技术的进步又推动着耐火材料产业的发展。以长寿化、功能化、轻量化、智能化、绿色化等为特征的先进耐火材料已成为耐火材料产业的发展方向和研究热点。
碳复合耐火材料具有优异的热震稳定性和抗渣侵蚀性能而被广泛用作裂解炉、转炉、电炉、钢包等化工、冶金用的炉衬材料，但单纯降低传统碳复合耐火材料中的鳞片石墨含量，会导致材料的韧性降低、热震稳定性能变差。而碳纳米纤维作为一种新型纳米碳源具有非常优异的力学性能，将其部分或全部取代鳞片石墨引入到低碳碳复合耐火材料中，有望解决材料韧性低、热震稳定性差的问题。
申请人长期从事耐火材料的研发与生产，针对一些耐火衬里使用周期短、耐材消耗大等缺点，优选特级钒土、碳化硅、电熔白刚玉、红柱石等为原料，经高压成形、高温烧成等制造工艺，制造出主晶相为莫来石的硅莫红砖高性能耐磨耐火材料。在此基础上，为了进一步提高耐火材料的热震稳定性和抗渣侵蚀性能，采用碳纳米纤维原位增韧耐火材料的技术，研究并开发轻质、高耐磨、热震稳定性能优异的耐火材料，以扩大其应用范围。
发明内容
本发明提供了一种碳纳米纤维增韧耐火材料的制备方法。碳纳米纤维是由酚醛树脂催化剂、耐火材料各组分，在高温烧结过程中，酚醛树脂裂解出CH4、C2H2等含碳的气态组分，在催化剂作用下将其以碳纳米纤维的形式形成碳网结构，原位分布在耐火材料的基体中，从而大大提高耐火材料的热震稳定性和抗渣侵蚀性能，同时也大大降低了原有耐火材料的密度，为开发轻质、高耐磨、热震稳定性能优异的耐火材料提供了一种有效的方法。
具体是这样实施的：一种碳纳米纤维增韧耐火材料的制备方法，其特征在于，（1）该碳纳米纤维增韧耐火材料中各组分及质量百分比含量为：
酚醛树脂 10％～15％
固化剂 0.7％～1.6％
催化剂 0.3％～0.8％
无水乙醇 3％～5％
电熔白刚玉 直径0～0 .044mm 14％～19％
电熔白刚玉 直径0～1mm 19％～22％
电熔白刚玉 直径1～3mm 12％～20％
煅烧α-氧化铝微粉 直径0～2mm 12％～15％
高岭土 直径0～4mm 5％～7％
锆英砂 直径1～3mm 3％～5％
焦宝石 直径0～2mm 3％～5％
红柱石微粉 直径0～2mm 2％～3％；
所述催化剂为钾化合物、钠化合物其中的一种，优选KCl、NaCl；
所述固化剂为苯胺或六次甲基四胺或三聚氰胺等，优选六次甲基四胺；
（2）该碳纳米纤维增韧耐火材料的制备方法包括以下步骤：
步骤1，酚醛树脂预混料的制作：将酚醛树脂、催化剂、无水乙醇、直径为0～0.044mm的电熔白刚玉、固化剂混合均匀；步骤2，将步骤1配制的酚醛树脂预混料与其余原料混合均匀；步骤3，将混合均匀的原料压制成耐火材料砖坯；步骤4，将砖坯烧结成耐火材料制品。
进一步地，步骤1中，先将无水乙醇、催化剂、直径为0～0 .044mm电熔白刚玉混合均匀，然后再加酚醛树脂和固化剂混合均匀。
进一步地，步骤3中，采用2500吨全自动压机将耐火材料泥料压制成耐火材料砖坯。
进一步地，步骤4中，耐火材料砖坯在隧道窑中烧结，烧结温度为1500℃-1600℃。
本发明与现有技术相比具有下述明显优点：
通常碳复合耐火材料中的碳来源于鳞片石墨，对材料的韧性降低、热震稳定性能不利。为了改善含碳功能耐火材料服役功能和寿命，减少碳含量，特别是降低非晶态碳含量，本申请采用酚醛树脂，在催化剂作用下原位形成晶态碳纤维。这类碳纳米纤维增韧耐火材料，具有轻质、高耐磨、热震稳定性能优异，制备原料易得，制备方便等特点。
下面通过实施例进一步说明本发明，但本发明不限于此。
具体实施方式
实施例1
碳纳米纤维增韧耐火材料的各组分及质量百分比含量为：酚醛树脂为 10％，固化剂六次甲基四胺为0.7％，催化剂KCl为0.3％，无水乙醇为3％，电熔白刚玉（直径为0～0.044mm）为19％，电熔白刚玉（直径为0～1mm）为19％，电熔白刚玉（直径为1～3mm）为20％，煅烧α-氧化铝微粉（直径0～2mm）为12％，高岭土（直径0～4mm）为7％，锆英砂（直径1～3mm）为3％，焦宝石（直径0～2mm）为3％，红柱石微粉（直径0～2mm）为2％。
碳纳米纤维增韧耐火材料的制备方法，具体步骤如下：
步骤1，将无水乙醇、催化剂、电熔白刚玉（直径为0～0 .044mm）混合均匀，然后加酚醛树脂和固化剂混合均匀。
步骤2，将步骤1配制的酚醛树脂预混料与其余原料混合均匀；
步骤3，采用2500吨全自动压机，将混合均匀的原料压制成耐火材料砖坯；
步骤4，将砖坯在隧道窑中于1500℃-1600℃烧结成耐火材料制品，其制品性能指标见表1。
实施例2
碳纳米纤维增韧耐火材料的各组分及质量百分比含量为：酚醛树脂为 12％，固化剂苯胺为1.2％，催化剂NaCl为0.8％，无水乙醇为5％，电熔白刚玉（直径为0～0 .044mm）为18％，电熔白刚玉（直径为0～1mm）为19％，电熔白刚玉（直径为1～3mm）为16％，煅烧α-氧化铝微粉（直径0～2mm）为12％，高岭土（直径0～4mm）为6％，锆英砂（直径1～3mm）为4％，焦宝石（直径0～2mm）为4％，红柱石微粉（直径0～2mm）为2％。
制备方法同实施例1，其制品性能指标见表1。
实施例3
碳纳米纤维增韧耐火材料的各组分及质量百分比含量为：酚醛树脂为 12％，固化剂六次甲基四胺为1.6％，催化剂KCl为0.4％，无水乙醇为4％，电熔白刚玉（直径为0～0.044mm）为16％，电熔白刚玉（直径为0～1mm）为20％，电熔白刚玉（直径为1～3mm）为17％，煅烧α-氧化铝微粉（直径0～2mm）为13％，高岭土（直径0～4mm）为5％，锆英砂（直径1～3mm）为4％，焦宝石（直径0～2mm）为4％，红柱石微粉（直径0～2mm）为3％。
制备方法同实施例1，其制品性能指标见表1。
实施例4
碳纳米纤维增韧耐火材料的各组分及质量百分比含量为：酚醛树脂为 12％，固化剂三聚氰胺为1.5％，催化剂NaCl为0.5％，无水乙醇为5％，电熔白刚玉（直径为0～0.044mm）为18％，电熔白刚玉（直径为0～1mm）为20％，电熔白刚玉（直径为1～3mm）为12％，煅烧α-氧化铝微粉（直径0～2mm）为14％，高岭土（直径0～4mm）为6％，锆英砂（直径1～3mm）为4％，焦宝石（直径0～2mm）为4％，红柱石微粉（直径0～2mm）为3％。
制备方法同实施例1，其制品性能指标见表1。
实施例5
碳纳米纤维增韧耐火材料的各组分及质量百分比含量为：酚醛树脂为 15％，固化剂六次甲基四胺为1.4％，催化剂KCl为0.6％，无水乙醇为3％，电熔白刚玉（直径为0～0.044mm）为14％，电熔白刚玉（直径为0～1mm）为22％，电熔白刚玉（直径为1～3mm）为12％，煅烧α-氧化铝微粉（直径0～2mm）为15％，高岭土（直径0～4mm）为5％，锆英砂（直径1～3mm）为5％，焦宝石（直径0～2mm）为5％，红柱石微粉（直径0～2mm）为2％。
制备方法同实施例1，其制品性能指标见表1。
对照例
无碳纳米纤维增韧耐火材料的各组分及质量百分比含量为：羧甲基纤维素钠为15％，水为5％，电熔白刚玉（直径为0～0 .044mm）为18％，电熔白刚玉（直径为0～1mm）为15％，电熔白刚玉（直径为1～3mm）为15％，煅烧α-氧化铝微粉（直径0～2mm）为15％，高岭土（直径0～4mm）为6％，锆英砂（直径1～3mm）为4％，焦宝石（直径0～2mm）为4％，红柱石微粉（直径0～2mm）为3％。
无碳纳米纤维增韧耐火材料的制备方法，具体步骤如下：
步骤1，将水、羧甲基纤维素钠、电熔白刚玉（直径为0～0 .044mm）混合均匀。其余步骤同实施例1，其制品性能指标见表1。
表1制品性能指标
| 技术指标 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 对照例 |
| 耐火度，℃ | 1800 | 1850 | 1830 | 1780 | 1800 | 1500 |
| 体积密度，g/cm3 | 1.83 | 1.95 | 1.91 | 2.00 | 1.88 | 2.68 |
| 常温耐压强度，MPa | 105 | 100 | 108 | 110 | 106 | 70 |
| 热震稳定性，1100℃ | ≥30 | ≥30 | ≥30 | ≥30 | ≥30 | ≥20 |
Claims (6)
1.一种碳纳米纤维增韧耐火材料的制备方法，其特征在于，（1）该碳纳米纤维增韧耐火材料中各组分及质量百分比含量为：
酚醛树脂 10％～15％
固化剂 0.7％～1.6％
催化剂 0.3％～0.8％
无水乙醇 3％～5％
电熔白刚玉 直径0～0 .044mm 14％～19％
电熔白刚玉 直径0～1mm 19％～22％
电熔白刚玉 直径1～3mm 12％～20％
煅烧α-氧化铝微粉 直径0～2mm 12％～15％
高岭土 直径0～4mm 5％～7％
锆英砂 直径1～3mm 3％～5％
焦宝石 直径0～2mm 3％～5％
红柱石微粉 直径0～2mm 2％～3％；
所述催化剂为钾化合物、钠化合物其中的一种；
所述固化剂为苯胺或六次甲基四胺或三聚氰胺；
（2）该碳纳米纤维增韧耐火材料的制备方法包括以下步骤：
步骤1，酚醛树脂预混料的制作：将酚醛树脂、催化剂、无水乙醇、直径为0～0 .044mm的电熔白刚玉、固化剂混合均匀；步骤2，将步骤1配制的酚醛树脂预混料与其余原料混合均匀；步骤3，将混合均匀的原料压制成耐火材料砖坯；步骤4，将砖坯烧结成耐火材料制品。
2.根据权利要求1所述的一种碳纳米纤维增韧耐火材料的制备方法，其特征在于：催化剂为KCl或NaCl。
3.根据权利要求1所述的一种碳纳米纤维增韧耐火材料的制备方法，其特征在于：固化剂为六次甲基四胺。
4. 根据权利要求1所述的一种碳纳米纤维增韧耐火材料的制备方法，其特征在于：步骤1中，先将无水乙醇、催化剂、直径为0～0 .044mm电熔白刚玉混合均匀，然后再加酚醛树脂和固化剂混合均匀。
5.根据权利要求1所述的一种碳纳米纤维增韧耐火材料的制备方法，其特征在于：步骤3中，采用2500吨全自动压机将耐火材料泥料压制成耐火材料砖坯。
6.根据权利要求1所述的一种碳纳米纤维增韧耐火材料的制备方法，其特征在于：步骤4中，耐火材料砖坯在隧道窑中烧结，烧结温度为1500℃-1600℃。
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Citations (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0758632A1 (en) * | 1995-03-03 | 1997-02-19 | Kyushu Refractories Co., Ltd. | Unshaped refractories and gunning refractories prepared therefrom |
| CN101254911A (zh) * | 2007-12-14 | 2008-09-03 | 内蒙古科技大学 | 以酚醛树脂做碳源制备碳纳米管及碳纳米纤维的方法 |
| CN101269980A (zh) * | 2007-12-14 | 2008-09-24 | 内蒙古科技大学 | 粗大碳纳米管及碳纳米纤维在碳复合耐火材料中的生成方法 |
| RU2007122623A (ru) * | 2005-04-19 | 2009-05-27 | Кросаки Харима Корпорейшн (Jp) | Огнеупор, способ его производства и исходный материал для огнеупора |
| CN103086731A (zh) * | 2011-10-28 | 2013-05-08 | 中国科学院上海硅酸盐研究所 | 高强度纤维增强陶瓷基复合材料的微区原位反应制备方法 |
| CN103184465A (zh) * | 2011-12-29 | 2013-07-03 | 北京有色金属研究总院 | 一种纳米碳化硅材料的电化学制备方法 |
| CN103833387A (zh) * | 2012-12-04 | 2014-06-04 | 江苏顺星耐火科技有限公司 | 高耐磨硅莫红砖及其制备工艺 |
| CN105801153A (zh) * | 2016-03-21 | 2016-07-27 | 大连理工大学 | 一种原位生长碳化硅纳米纤维协同碳纤维共增陶瓷基复合材料的制备方法 |
| CN106316447A (zh) * | 2016-07-28 | 2017-01-11 | 马琰珂 | 一种稻壳基多孔碳化硅陶瓷材料及其制备方法 |
| CN106336228A (zh) * | 2016-08-21 | 2017-01-18 | 长兴盟友耐火材料有限公司 | 一种复合纤维增韧耐火材料及其制备工艺 |
| CN106810285A (zh) * | 2017-01-14 | 2017-06-09 | 中国矿业大学(北京) | 一种原位生成碳纤维增韧氧化铝陶瓷的制备方法 |
| CN107500794A (zh) * | 2017-06-24 | 2017-12-22 | 河南工业大学 | 一种原位生成碳化硅纤维结合碳化硅耐磨材料及其制备方法 |
| CN107511149A (zh) * | 2017-09-05 | 2017-12-26 | 江西师范大学 | 一种Ag‑碳纳米纤维复合材料及其制备方法和应用 |
| CN108727043A (zh) * | 2018-06-11 | 2018-11-02 | 武汉科技大学 | 一种具有多维增强的低碳铝碳质耐火材料及其制备方法 |
| CN110330319A (zh) * | 2019-07-13 | 2019-10-15 | 南昌航空大学 | 一种低碳超低碳的铝碳烧成耐火材料及其制备方法 |
| CN110330320A (zh) * | 2019-07-13 | 2019-10-15 | 南昌航空大学 | 一种低碳超低碳的铝碳化硅碳耐火材料及其制备方法 |
| CN110483053A (zh) * | 2019-09-25 | 2019-11-22 | 哈尔滨工业大学 | 一种用于高温吸波的SiC纳米线/SiC多孔陶瓷的制备方法 |
| KR102224146B1 (ko) * | 2020-02-04 | 2021-03-05 | 한국해양대학교 산학협력단 | 탄소나노튜브-탄소나노섬유 복합체의 제조방법 및 이에 의해 제조되는 탄소나노튜브-탄소나노섬유 복합체 |
| CN112811917A (zh) * | 2021-01-08 | 2021-05-18 | 武汉科技大学 | 一种晶须增强轻量化铝碳质耐火材料及其制备方法 |
| CN113173795A (zh) * | 2021-06-09 | 2021-07-27 | 江苏君耀耐磨耐火材料有限公司 | 硫磺回收酸性气焚烧炉用铬刚玉砖及其制备工艺 |
| CN113354423A (zh) * | 2021-05-17 | 2021-09-07 | 江苏苏嘉集团新材料有限公司 | 一种碳复合耐火材料配方及制备方法 |
| CN113999023A (zh) * | 2021-09-28 | 2022-02-01 | 赛文斯新型材料(无锡)有限公司 | 用于塞棒的纳米耐火材料制备方法 |
| CN114956844A (zh) * | 2022-06-14 | 2022-08-30 | 张美红 | 一种三维碳纤维增韧陶瓷基复合材料及其制备方法 |
| CN116287833A (zh) * | 2023-03-14 | 2023-06-23 | 河南科技大学 | 原位自生二维碳化物弥散强韧化钼合金的制备方法 |
| CN116463523A (zh) * | 2023-03-14 | 2023-07-21 | 河南科技大学 | 原位自生纳米氧化物碳化物协同增韧细晶钼合金及其制备方法 |
| CN116573922A (zh) * | 2023-03-31 | 2023-08-11 | 武汉钢铁有限公司 | 一种纳米碳纤维增强的低碳镁碳耐火材料及其制备方法 |
-
2023
- 2023-11-10 CN CN202311494144.2A patent/CN117383949B/zh active Active
Patent Citations (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0758632A1 (en) * | 1995-03-03 | 1997-02-19 | Kyushu Refractories Co., Ltd. | Unshaped refractories and gunning refractories prepared therefrom |
| RU2007122623A (ru) * | 2005-04-19 | 2009-05-27 | Кросаки Харима Корпорейшн (Jp) | Огнеупор, способ его производства и исходный материал для огнеупора |
| CN101254911A (zh) * | 2007-12-14 | 2008-09-03 | 内蒙古科技大学 | 以酚醛树脂做碳源制备碳纳米管及碳纳米纤维的方法 |
| CN101269980A (zh) * | 2007-12-14 | 2008-09-24 | 内蒙古科技大学 | 粗大碳纳米管及碳纳米纤维在碳复合耐火材料中的生成方法 |
| CN103086731A (zh) * | 2011-10-28 | 2013-05-08 | 中国科学院上海硅酸盐研究所 | 高强度纤维增强陶瓷基复合材料的微区原位反应制备方法 |
| CN103184465A (zh) * | 2011-12-29 | 2013-07-03 | 北京有色金属研究总院 | 一种纳米碳化硅材料的电化学制备方法 |
| CN103833387A (zh) * | 2012-12-04 | 2014-06-04 | 江苏顺星耐火科技有限公司 | 高耐磨硅莫红砖及其制备工艺 |
| CN105801153A (zh) * | 2016-03-21 | 2016-07-27 | 大连理工大学 | 一种原位生长碳化硅纳米纤维协同碳纤维共增陶瓷基复合材料的制备方法 |
| CN106316447A (zh) * | 2016-07-28 | 2017-01-11 | 马琰珂 | 一种稻壳基多孔碳化硅陶瓷材料及其制备方法 |
| CN106336228A (zh) * | 2016-08-21 | 2017-01-18 | 长兴盟友耐火材料有限公司 | 一种复合纤维增韧耐火材料及其制备工艺 |
| CN106810285A (zh) * | 2017-01-14 | 2017-06-09 | 中国矿业大学(北京) | 一种原位生成碳纤维增韧氧化铝陶瓷的制备方法 |
| CN107500794A (zh) * | 2017-06-24 | 2017-12-22 | 河南工业大学 | 一种原位生成碳化硅纤维结合碳化硅耐磨材料及其制备方法 |
| CN107511149A (zh) * | 2017-09-05 | 2017-12-26 | 江西师范大学 | 一种Ag‑碳纳米纤维复合材料及其制备方法和应用 |
| CN108727043A (zh) * | 2018-06-11 | 2018-11-02 | 武汉科技大学 | 一种具有多维增强的低碳铝碳质耐火材料及其制备方法 |
| CN110330319A (zh) * | 2019-07-13 | 2019-10-15 | 南昌航空大学 | 一种低碳超低碳的铝碳烧成耐火材料及其制备方法 |
| CN110330320A (zh) * | 2019-07-13 | 2019-10-15 | 南昌航空大学 | 一种低碳超低碳的铝碳化硅碳耐火材料及其制备方法 |
| CN110483053A (zh) * | 2019-09-25 | 2019-11-22 | 哈尔滨工业大学 | 一种用于高温吸波的SiC纳米线/SiC多孔陶瓷的制备方法 |
| KR102224146B1 (ko) * | 2020-02-04 | 2021-03-05 | 한국해양대학교 산학협력단 | 탄소나노튜브-탄소나노섬유 복합체의 제조방법 및 이에 의해 제조되는 탄소나노튜브-탄소나노섬유 복합체 |
| CN112811917A (zh) * | 2021-01-08 | 2021-05-18 | 武汉科技大学 | 一种晶须增强轻量化铝碳质耐火材料及其制备方法 |
| CN113354423A (zh) * | 2021-05-17 | 2021-09-07 | 江苏苏嘉集团新材料有限公司 | 一种碳复合耐火材料配方及制备方法 |
| CN113173795A (zh) * | 2021-06-09 | 2021-07-27 | 江苏君耀耐磨耐火材料有限公司 | 硫磺回收酸性气焚烧炉用铬刚玉砖及其制备工艺 |
| CN113999023A (zh) * | 2021-09-28 | 2022-02-01 | 赛文斯新型材料(无锡)有限公司 | 用于塞棒的纳米耐火材料制备方法 |
| CN114956844A (zh) * | 2022-06-14 | 2022-08-30 | 张美红 | 一种三维碳纤维增韧陶瓷基复合材料及其制备方法 |
| CN116287833A (zh) * | 2023-03-14 | 2023-06-23 | 河南科技大学 | 原位自生二维碳化物弥散强韧化钼合金的制备方法 |
| CN116463523A (zh) * | 2023-03-14 | 2023-07-21 | 河南科技大学 | 原位自生纳米氧化物碳化物协同增韧细晶钼合金及其制备方法 |
| CN116573922A (zh) * | 2023-03-31 | 2023-08-11 | 武汉钢铁有限公司 | 一种纳米碳纤维增强的低碳镁碳耐火材料及其制备方法 |
Non-Patent Citations (5)
| Title |
|---|
| CHEN, YQ: "Influence of bonding carbon on low carbon Al2O3-C refractory composites", CERAMICS INTERNATIONAL, vol. 43, no. 17, 1 December 2017 (2017-12-01) * |
| 丁冬海;杨少雨;肖国庆;: "含碳耐火材料酚醛树脂结合剂的研究现状与展望", 材料导报, no. 11, 10 June 2017 (2017-06-10) * |
| 吴小贤;李红霞;刘国齐;杨文刚;马天飞;: "KCl对酚醛树脂炭化生长碳纤维的影响", 耐火材料, no. 01, 15 February 2015 (2015-02-15) * |
| 李红霞;: "耐火材料发展概述", 无机材料学报, no. 02, 11 February 2018 (2018-02-11) * |
| 王军凯;邓先功;张海军;李发亮;宋健波;田亮;张少伟;: "碳纳米管增强碳复合耐火材料的研究进展", 耐火材料, no. 02, 15 April 2016 (2016-04-15) * |
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