CN117534449A - 一种铜溜槽用刚玉质浇注料及其制备方法 - Google Patents
一种铜溜槽用刚玉质浇注料及其制备方法 Download PDFInfo
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- CN117534449A CN117534449A CN202410033188.3A CN202410033188A CN117534449A CN 117534449 A CN117534449 A CN 117534449A CN 202410033188 A CN202410033188 A CN 202410033188A CN 117534449 A CN117534449 A CN 117534449A
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- 239000010431 corundum Substances 0.000 title claims abstract description 109
- 229910052593 corundum Inorganic materials 0.000 title claims abstract description 109
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 46
- 239000010949 copper Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical class N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 97
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 29
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 18
- 239000007767 bonding agent Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims description 76
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 11
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- RCOVTJVRTZGSBP-UHFFFAOYSA-N 4-(chloromethyl)benzoyl chloride Chemical compound ClCC1=CC=C(C(Cl)=O)C=C1 RCOVTJVRTZGSBP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000012312 sodium hydride Substances 0.000 claims description 7
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 230000035939 shock Effects 0.000 abstract description 8
- 239000011819 refractory material Substances 0.000 abstract description 5
- 230000003628 erosive effect Effects 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004568 cement Substances 0.000 description 8
- 229910052582 BN Inorganic materials 0.000 description 7
- 239000011148 porous material Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- -1 aluminum-magnesium-zirconium Chemical compound 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
本发明属于耐火材料技术领域,具体涉及一种铜溜槽用刚玉质浇注料及其制备方法。该浇注料包括以下重量份组分:白刚玉60‑70份;致密刚玉10‑15份;碳化硅5‑10份;改性氮化硼2‑4份;金属硅粉1‑2份;金属铝粉0.1‑0.3份;聚羧酸减水剂0.2‑0.5份;改性结合剂5‑10份;其中改性结合剂由有机改性氮化硼、硅溶胶组成;本发明所制得的浇注料具有良好的抗铜侵蚀性能,结构强度高,热震稳定性良好,用于阳极炉出铜溜槽,使用寿命长。
Description
技术领域
本发明属于耐火材料技术领域,具体涉及一种铜溜槽用刚玉质浇注料及其制备方法。
背景技术
有色金属铜是我们普遍应用的重要金属材料之一,其高温下粘度低、渗透性强;目前,铜冶炼厂阳极铜浇注溜槽大多采用耐火砖和胶泥砌筑,其使用寿命通常较低,所用耐火砖和胶泥气孔率大,金属铜液沿气孔渗入,冷铜残留多,粘结严重,清理时耐火层容易损坏,造成铜及耐火材料的浪费,耐火层脱落的杂质也会影响阳极板的质量;进一步提升铜浇注溜槽用耐火材料的强度、高温体积稳定性、抗热震性、抗渗透性和抗侵蚀性等性能,对于延长铜浇注溜槽的使用寿命而言至关重要。
申请号为202011382392.4的专利公开了一种铜溜槽用铝碳质浇注料,包括以下重量份数:粒度为1.001-4mm的85特级高铝32-36份,粒度为0-1mm的85特级高铝15-20份,粒度为0.089-1mm的90碳化硅5-12份,粒度为0-0.088mm的90碳化硅15-24份,92硅微粉2-6份,Secar-68水泥4-8份,320目的结合粘土8-12份,200目的金属硅粉1-3份,复合防爆材料0.1-0.2份,复合外加剂0.3-0.5份,所提供的浇注料具有良好的抗铜侵蚀性能,结构强度高,热震稳定性良好,抗爆裂性能好,但采用水泥作结合剂,存在用水量大,后期养护复杂,浇注料中温强度偏高等缺陷;申请号为202210717961.9的专利公开了一种阳极炉出铜溜槽用铝镁锆质浇注料及其制备方法,包括的微孔刚玉、氧化镁、氧化锆、氟化铝、氢氧化锆、金属铝、聚羧酸减水剂,在制备过程中采用锆溶胶作结合剂,克服了水泥作为浇注料结合剂存在的缺陷,所制得的浇注料具备低导热、高强度、整体性好、抗热震性能优异和抗熔体渗透能力强的特点,氢氧化锆分解时会留下气孔,导致浇注料各组分之间结合不致密,微孔刚玉的气孔也会影响浇注料的抗渗透性,在高温烧结作用下可能导致其气孔长大并出现裂纹,影响浇注料的综合性能;因此,亟需研制出一种综合性能较好的铜溜槽用浇注料,以延长铜溜槽的使用寿命。
发明内容
本发明的目的在于针对现有技术的不足,提供一种铜溜槽用刚玉质浇注料及其制备方法,本发明所制得的浇注料具有良好的抗铜侵蚀性能,结构强度高,热震稳定性良好,用于阳极炉出铜溜槽,使用寿命长。
本发明为实现上述目的所采取的技术方案为:
一种铜溜槽用刚玉质浇注料,包括以下重量份组分:白刚玉60-70份;致密刚玉10-15份;碳化硅5-10份;改性氮化硼2-4份;金属硅粉1-2份;金属铝粉0.1-0.3份;聚羧酸减水剂0.2-0.5份;改性结合剂5-10份;
进一步地,所述白刚玉中的Al2O3≥98wt%;所述白刚玉包括质量比为2-3:1-2:1-2:1的粒度为3-5mm的颗粒、粒度为1-3mm的颗粒、粒度为0-1mm的颗粒、粒度为325目的细粉。
进一步地,所述致密刚玉中的Al2O3≥98wt%;所述致密刚玉包括质量比为2-4:1-2的粒度为1-3mm的颗粒、粒度为0-1mm的颗粒。
进一步地,所述碳化硅的粒径为0.088mm;所述金属硅粉的粒径为200-325目;所述金属铝粉的粒径为45μm。
进一步地,所述改性结合剂由有机改性氮化硼、硅溶胶组成;所述有机改性氮化硼、硅溶胶的质量比为1:30-40;所述硅溶胶中二氧化硅的质量百分含量为30%-40%。
进一步地,所述有机改性氮化硼的制备方法为:将羟基化氮化硼加入到甲苯中,分散均匀后,滴加3-氨基丙基三甲氧基硅烷,滴毕,氮气保护下,升温至50-60℃,反应4-6h,冷却后,离心,沉淀物干燥后得到有机改性氮化硼;所述羟基化氮化硼、3-氨基丙基三甲氧基硅烷的质量比为1:0.3-0.4。
进一步地,所述改性氮化硼的制备方法为:
S1、将有机改性氮化硼分散到无水二氯甲烷中,氮气保护下,滴加4-氯甲基苯甲酰氯,滴毕,升温至30-40℃,反应2-4h,冷却后,离心后收集沉淀,并用无水二氯甲烷洗涤,干燥后得到氯化改性氮化硼;所述有机改性氮化硼、4-氯甲基苯甲酰氯的质量比为1:0.4-0.5;
S2、将聚乙二醇单甲醚、氢化钠加入到无水四氢呋喃中,氮气保护,升温至30-40℃,反应3-4h,再加入氯化改性氮化硼的无水四氢呋喃分散液,继续反应4-6h,冷却后,离心后收集沉淀,并依次用无水四氢呋喃、乙醇洗涤,干燥得到改性氮化硼;所述氯化改性氮化硼、聚乙二醇单甲醚、氢化钠的质量比为1:0.8-1:0.2-0.4。
本发明还提供了一种铜溜槽用刚玉质浇注料的制备方法,包括如下步骤:按组分配比,将白刚玉、致密刚玉、碳化硅、改性氮化硼、金属硅粉、金属铝粉、聚羧酸减水剂混合均匀,再加入改性结合剂,搅拌均匀,得到刚玉质浇注料。
本发明具有如下有益效果:
本发明将羟基化氮化硼与3-氨基丙基三甲氧基硅烷反应,得到了表面接枝3-氨基丙基三甲氧基硅烷分子结构的有机改性氮化硼,有机改性氮化硼与硅溶胶复配成改性结合剂,有机改性氮化硼能够促进硅溶胶中网状结构的形成,有效促进硅溶胶的凝胶过程,提升浇注料的致密性;本发明对有机改性氮化硼进一步改性,依次与4-氯甲基苯甲酰氯、聚乙二醇单甲醚反应,得到了表面接枝非离子表面活性剂聚乙二醇单甲醚分子结构的改性氮化硼,所制得的改性氮化硼具有良好的分散、流动性,能更好地分散至浇注料中,进而与碳化硅协同作用,降低高温下白刚玉、致密刚玉组分的粘结性,防止金属铜液粘结,还能够与减水剂协同作用,降低了浇注料各组分之间的阻力,增加了浇注料的流动性,使各组分能充分混合均匀,发挥其作用,从而制得了综合性能较好的浇注料。
本发明以高温耐火材料白刚玉作为浇注料的主要成分,致密刚玉、碳化硅、改性氮化硼作为辅助成分,并以由有机改性氮化硼、硅溶胶组成的改性结合剂,代替水泥作结合剂,所制得的浇注料具有良好的抗铜侵蚀性能,结构强度高,热震稳定性良好,用于阳极炉出铜溜槽,使用寿命长。
具体实施方式
下面将结合本申请实施例,对本申请实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本申请一部分实施例,而不是全部的实施例。基于本申请中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本申请保护的范围。
下列所有实施例及对比例中所有化学试剂均为普通市售,3-氨基丙基三甲氧基硅烷CAS号13822-56-5;氢氧化钠CAS号1310-73-2;4-氯甲基苯甲酰氯CAS号876-08-4;聚乙二醇单甲醚CAS号9004-74-4(相对分子质量为1000);氢化钠CAS号7646-69-7;甲苯CAS号108-88-3;二氯甲烷CAS号75-09-2;四氢呋喃CAS号109-99-9;乙醇CAS号64-17-5。
实施例1
一种铜溜槽用刚玉质浇注料,包括以下重量份组分:白刚玉70份;致密刚玉15份;碳化硅10份;改性氮化硼4份;金属硅粉2份;金属铝粉0.3份;聚羧酸减水剂0.5份;改性结合剂10份。
其中白刚玉中的Al2O3≥98wt%;白刚玉包括质量比为3:2:2:1的粒度为3-5mm的颗粒、粒度为1-3mm的颗粒、粒度为0-1mm的颗粒、粒度为325目的细粉;致密刚玉中的Al2O3≥98wt%;致密刚玉包括质量比为2:1的粒度为1-3mm的颗粒、粒度为0-1mm的颗粒;碳化硅的粒径为0.088mm;金属硅粉的粒径为325目;金属铝粉的粒径为45μm;改性结合剂由有机改性氮化硼、硅溶胶组成;有机改性氮化硼、硅溶胶的质量比为1:40;硅溶胶中二氧化硅的质量百分含量为40%;按质量配比,将有机改性氮化硼均匀分散到硅溶胶中,得到改性结合剂。
一种铜溜槽用刚玉质浇注料的制备方法,包括如下步骤:按组分配比,将白刚玉、致密刚玉、碳化硅、改性氮化硼、金属硅粉、金属铝粉、聚羧酸减水剂混合均匀,再加入改性结合剂,搅拌均匀,得到刚玉质浇注料。
有机改性氮化硼的制备方法为:将羟基化氮化硼加入到甲苯中,分散均匀后,滴加3-氨基丙基三甲氧基硅烷,滴毕,氮气保护下,升温至60℃,反应6h,冷却后,离心,沉淀物干燥后得到有机改性氮化硼;羟基化氮化硼、3-氨基丙基三甲氧基硅烷的质量比为1:0.4;甲苯的用量为羟基化氮化硼质量的20倍。
羟基化氮化硼的制备方法为:将纳米氮化硼分散在5mol/L氢氧化钠水溶液中,加入到水热釜中,120℃下反应20h,反应完成后,自然冷却至室温,离心后收集沉淀,并用去离子水洗涤至中性,干燥后得到羟基化氮化硼;其中氮化硼、氢氧化钠的质量比为1:20。
改性氮化硼的制备方法为:
S1、将有机改性氮化硼分散到无水二氯甲烷中,氮气保护下,滴加4-氯甲基苯甲酰氯,滴毕,升温至40℃,反应4h,冷却后,离心后收集沉淀,并用无水二氯甲烷洗涤,干燥后得到氯化改性氮化硼;有机改性氮化硼、4-氯甲基苯甲酰氯的质量比为1:0.5;无水二氯甲烷的用量为有机改性氮化硼质量的25倍;
S2、将聚乙二醇单甲醚、氢化钠加入到无水四氢呋喃中,氮气保护,升温至40℃,反应4h,再加入氯化改性氮化硼的无水四氢呋喃分散液,继续反应6h,冷却后,离心后收集沉淀,并依次用无水四氢呋喃、乙醇洗涤,干燥得到改性氮化硼;氯化改性氮化硼、聚乙二醇单甲醚、氢化钠的质量比为1:1:0.4;无水四氢呋喃用量为聚乙二醇单甲醚质量的10倍;氯化改性氮化硼的无水四氢呋喃分散液中氯化改性氮化硼、无水四氢呋喃的质量比为1:15。
实施例2
一种铜溜槽用刚玉质浇注料,包括以下重量份组分:白刚玉60份;致密刚玉10份;碳化硅5份;改性氮化硼2份;金属硅粉1份;金属铝粉0.1份;聚羧酸减水剂0.2份;改性结合剂5份。
其中白刚玉中的Al2O3≥98wt%;白刚玉包括质量比为2:1:1:1的粒度为3-5mm的颗粒、粒度为1-3mm的颗粒、粒度为0-1mm的颗粒、粒度为325目的细粉;致密刚玉中的Al2O3≥98wt%;致密刚玉包括质量比为4:1的粒度为1-3mm的颗粒、粒度为0-1mm的颗粒;碳化硅的粒径为0.088mm;金属硅粉的粒径为200目;金属铝粉的粒径为45μm;改性结合剂由有机改性氮化硼、硅溶胶组成;有机改性氮化硼、硅溶胶的质量比为1:30;硅溶胶中二氧化硅的质量百分含量为30%;按质量配比,将有机改性氮化硼均匀分散到硅溶胶中,得到改性结合剂。
一种铜溜槽用刚玉质浇注料的制备方法,包括如下步骤:按组分配比,将白刚玉、致密刚玉、碳化硅、改性氮化硼、金属硅粉、金属铝粉、聚羧酸减水剂混合均匀,再加入改性结合剂,搅拌均匀,得到刚玉质浇注料。
有机改性氮化硼、改性氮化硼的制备方法与实施例1相同。
实施例3
一种铜溜槽用刚玉质浇注料,包括以下重量份组分:白刚玉70份;致密刚玉13份;碳化硅8份;改性氮化硼3份;金属硅粉1份;金属铝粉0.2份;聚羧酸减水剂0.3份;改性结合剂8份。
其中白刚玉中的Al2O3≥98wt%;白刚玉包括质量比为3:1:2:1的粒度为3-5mm的颗粒、粒度为1-3mm的颗粒、粒度为0-1mm的颗粒、粒度为325目的细粉;致密刚玉中的Al2O3≥98wt%;致密刚玉包括质量比为3:2的粒度为1-3mm的颗粒、粒度为0-1mm的颗粒;碳化硅的粒径为0.088mm;金属硅粉的粒径为325目;金属铝粉的粒径为45μm;改性结合剂由有机改性氮化硼、硅溶胶组成;有机改性氮化硼、硅溶胶的质量比为1:35;硅溶胶中二氧化硅的质量百分含量为40%;按质量配比,将有机改性氮化硼均匀分散到硅溶胶中,得到改性结合剂。
一种铜溜槽用刚玉质浇注料的制备方法,包括如下步骤:按组分配比,将白刚玉、致密刚玉、碳化硅、改性氮化硼、金属硅粉、金属铝粉、聚羧酸减水剂混合均匀,再加入改性结合剂,搅拌均匀,得到刚玉质浇注料。
有机改性氮化硼、改性氮化硼的制备方法与实施例1相同。
对比例1
一种铜溜槽用刚玉质浇注料,包括以下重量份组分:白刚玉70份;致密刚玉15份;碳化硅10份;氮化硼4份;金属硅粉2份;金属铝粉0.3份;聚羧酸减水剂0.5份;改性结合剂10份;
其中白刚玉中的Al2O3≥98wt%;白刚玉包括质量比为3:2:2:1的粒度为3-5mm的颗粒、粒度为1-3mm的颗粒、粒度为0-1mm的颗粒、粒度为325目的细粉;致密刚玉中的Al2O3≥98wt%;致密刚玉包括质量比为2:1的粒度为1-3mm的颗粒、粒度为0-1mm的颗粒;碳化硅的粒径为0.088mm;金属硅粉的粒径为325目;金属铝粉的粒径为45μm;改性结合剂由有机改性氮化硼、硅溶胶组成;有机改性氮化硼、硅溶胶的质量比为1:40;硅溶胶中二氧化硅的质量百分含量为40%;按质量配比,将有机改性氮化硼均匀分散到硅溶胶中,得到改性结合剂。
一种铜溜槽用刚玉质浇注料的制备方法,包括如下步骤:按组分配比,将白刚玉、致密刚玉、碳化硅、氮化硼、金属硅粉、金属铝粉、聚羧酸减水剂混合均匀,再加入改性结合剂,搅拌均匀,得到刚玉质浇注料。
有机改性氮化硼的制备方法与实施例1相同。
对比例2
一种铜溜槽用刚玉质浇注料,包括以下重量份组分:白刚玉70份;致密刚玉15份;碳化硅10份;改性氮化硼4份;金属硅粉2份;金属铝粉0.3份;聚羧酸减水剂0.5份;硅溶胶10份;
其中白刚玉中的Al2O3≥98wt%;白刚玉包括质量比为3:2:2:1的粒度为3-5mm的颗粒、粒度为1-3mm的颗粒、粒度为0-1mm的颗粒、粒度为325目的细粉;致密刚玉中的Al2O3≥98wt%;致密刚玉包括质量比为2:1的粒度为1-3mm的颗粒、粒度为0-1mm的颗粒;碳化硅的粒径为0.088mm;金属硅粉的粒径为325目;金属铝粉的粒径为45μm。
一种铜溜槽用刚玉质浇注料的制备方法,包括如下步骤:按组分配比,将白刚玉、致密刚玉、碳化硅、改性氮化硼、金属硅粉、金属铝粉、聚羧酸减水剂混合均匀,再加入硅溶胶,搅拌均匀,得到刚玉质浇注料。
改性氮化硼的制备方法与实施例1相同。
对比例3
一种铜溜槽用刚玉质浇注料,包括以下重量份组分:白刚玉70份;致密刚玉15份;碳化硅10份;氮化硼4份;金属硅粉2份;金属铝粉0.3份;聚羧酸减水剂0.5份;铝酸盐水泥10份;
其中白刚玉中的Al2O3≥98wt%;白刚玉包括质量比为3:2:2:1的粒度为3-5mm的颗粒、粒度为1-3mm的颗粒、粒度为0-1mm的颗粒、粒度为325目的细粉;致密刚玉中的Al2O3≥98wt%;致密刚玉包括质量比为2:1的粒度为1-3mm的颗粒、粒度为0-1mm的颗粒;碳化硅的粒径为0.088mm;金属硅粉的粒径为325目;金属铝粉的粒径为45μm。
一种铜溜槽用刚玉质浇注料的制备方法,包括如下步骤:按组分配比,将白刚玉、致密刚玉、碳化硅、氮化硼、金属硅粉、金属铝粉、聚羧酸减水剂混合均匀,再加入铝酸盐水泥,搅拌均匀,得到刚玉质浇注料。
相关测试
将实施例1-3和对比例1-3的浇注料进行性能测试,其中显气孔率(1250℃×3h)和体积密度(1250℃×3h)参照YB/T5200-1993测试;耐压强度(110℃×24h)和抗折强度(110℃×24h)参照YB/T5201-1993测试;热震稳定性(1100℃水冷)参照YB/T376.1-1995测试;并将浇注料用于铜溜槽,计算平均使用寿命;测试结果如表1所示。
表1浇注料的性能测试结果
样品 | 显气孔率(%) | 体积密度(g/cm3) | 耐压强度(MPa) | 抗折强度(MPa) | 热震稳定性(次) | 使用寿命(d) |
实施例1 | 11.2 | 3.10 | 78.5 | 10.6 | 60 | 280 |
实施例2 | 11.9 | 3.05 | 76.8 | 10.2 | 55 | 270 |
实施例3 | 11.6 | 3.08 | 77.4 | 10.4 | 60 | 276 |
对比例1 | 14.9 | 2.50 | 60.2 | 7.0 | 45 | 225 |
对比例2 | 15.8 | 2.42 | 57.3 | 6.4 | 40 | 211 |
对比例3 | 18.5 | 2.35 | 51.6 | 5.8 | 30 | 180 |
由表1结果可知,实施例1-3所制得的浇注料具有较低的显气孔率,较高的体积密度、强度及热震稳定性,使用寿命长,其综合性能优异;与对比例1-3相比,本发明实施例1中加入改性氮化硼、改性结合剂,其中,改性氮化硼表面接枝的非离子表面活性剂聚乙二醇单甲醚分子结构,增强了改性氮化硼的分散、流动性,使改性氮化硼能更好地分散至浇注料中,进而与碳化硅协同作用,降低高温下白刚玉、致密刚玉组分的粘结性,防止金属铜液粘结,还能够与减水剂协同作用,降低了浇注料各组分之间的阻力,增加了浇注料的流动性;改性结合剂中的有机改性氮化硼表面接枝的3-氨基丙基三甲氧基硅烷分子结构,能够促进硅溶胶中网状结构的形成,有效促进硅溶胶的凝胶过程,有机改性氮化硼也能够有效填充浇注料的孔隙,提升浇注料的致密性。
需要说明的是,在本文中,诸如术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含,从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素,而且还包括没有明确列出的其他要素,或者是还包括为这种过程、方法、物品或者设备所固有的要素;尽管已经示出和描述了本申请的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本申请的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本申请的范围由所附权利要求及其等同物限定。
Claims (8)
1.一种铜溜槽用刚玉质浇注料,其特征在于,包括以下重量份组分:白刚玉60-70份;致密刚玉10-15份;碳化硅5-10份;改性氮化硼2-4份;金属硅粉1-2份;金属铝粉0.1-0.3份;聚羧酸减水剂0.2-0.5份;改性结合剂5-10份;所述改性结合剂由有机改性氮化硼、硅溶胶组成;所述有机改性氮化硼、硅溶胶的质量比为1:30-40;
所述改性氮化硼的制备方法为:
S1、将有机改性氮化硼分散到无水二氯甲烷中,氮气保护下,滴加4-氯甲基苯甲酰氯,滴毕,升温至30-40℃,反应2-4h,冷却后,离心后收集沉淀,并用无水二氯甲烷洗涤,干燥后得到氯化改性氮化硼;
S2、将聚乙二醇单甲醚、氢化钠加入到无水四氢呋喃中,氮气保护,升温至30-40℃,反应3-4h,再加入氯化改性氮化硼的无水四氢呋喃分散液,继续反应4-6h,冷却后,离心后收集沉淀,并依次用无水四氢呋喃、乙醇洗涤,干燥得到改性氮化硼。
2.根据权利要求1所述的一种铜溜槽用刚玉质浇注料,其特征在于,所述有机改性氮化硼的制备方法为:将羟基化氮化硼加入到甲苯中,分散均匀后,滴加3-氨基丙基三甲氧基硅烷,滴毕,氮气保护下,升温至50-60℃,反应4-6h,冷却后,离心,沉淀物干燥后得到有机改性氮化硼。
3.根据权利要求2所述的一种铜溜槽用刚玉质浇注料,其特征在于,所述羟基化氮化硼、3-氨基丙基三甲氧基硅烷的质量比为1:0.3-0.4;所述硅溶胶中二氧化硅的质量百分含量为30%-40%。
4.根据权利要求1所述的一种铜溜槽用刚玉质浇注料,其特征在于,步骤S1中所述有机改性氮化硼、4-氯甲基苯甲酰氯的质量比为1:0.4-0.5;步骤S2中所述氯化改性氮化硼、聚乙二醇单甲醚、氢化钠的质量比为1:0.8-1:0.2-0.4。
5.根据权利要求1所述的一种铜溜槽用刚玉质浇注料,其特征在于,所述白刚玉中的Al2O3≥98wt%;所述白刚玉包括质量比为2-3:1-2:1-2:1的粒度为3-5mm的颗粒、粒度为1-3mm的颗粒、粒度为0-1mm的颗粒、粒度为325目的细粉。
6.根据权利要求1所述的一种铜溜槽用刚玉质浇注料,其特征在于,所述致密刚玉中的Al2O3≥98wt%;所述致密刚玉包括质量比为2-4:1-2的粒度为1-3mm的颗粒、粒度为0-1mm的颗粒。
7.根据权利要求1所述的一种铜溜槽用刚玉质浇注料,其特征在于,所述碳化硅的粒径为0.088mm;所述金属硅粉的粒径为200-325目;所述金属铝粉的粒径为45μm。
8.根据权利要求1-7任一项所述的一种铜溜槽用刚玉质浇注料的制备方法,其特征在于,包括如下步骤:按组分配比,将白刚玉、致密刚玉、碳化硅、改性氮化硼、金属硅粉、金属铝粉、聚羧酸减水剂混合均匀,再加入改性结合剂,搅拌均匀,得到刚玉质浇注料。
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