CN113636852B - 球壳-海绵结构六铝酸钙-镁铝尖晶石复相材料的制备方法 - Google Patents

球壳-海绵结构六铝酸钙-镁铝尖晶石复相材料的制备方法 Download PDF

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CN113636852B
CN113636852B CN202111110575.5A CN202111110575A CN113636852B CN 113636852 B CN113636852 B CN 113636852B CN 202111110575 A CN202111110575 A CN 202111110575A CN 113636852 B CN113636852 B CN 113636852B
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calcium hexaluminate
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范沐旭
武刚
李森寅
冯志源
王晗
侯晓静
赵志龙
李坤鹏
张涛
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Sinosteel Luoyang Institute of Refractories Research Co Ltd
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Abstract

本发明属于耐火材料领域,涉及一种球壳‑海绵结构六铝酸钙‑镁铝尖晶石复相材料的制备方法。涉及的一种球壳‑海绵结构六铝酸钙‑镁铝尖晶石复相材料的制备方法以重质六铝酸钙颗粒、六铝酸钙细粉、氧化铝微粉、电熔氧化镁为起始物料;加入结合剂,经轮碾机混合,机压成型,坯体经干燥后,在高温窑炉或电炉中进行烧成,在小于1100℃的温度下电熔氧化镁表面和氧化铝微粉产生固相反应形成镁铝尖晶石壳,同时在1100~1200℃还原气氛下保温3~6h,随后恢复氧化气氛,最高烧成温度为1600℃~1750℃。本发明大大改善了六铝酸钙‑镁铝尖晶石复相材料的热震稳定性,使得六铝酸钙材料能够在在高碱侵蚀、高热震条件下使用。

Description

球壳-海绵结构六铝酸钙-镁铝尖晶石复相材料的制备方法
技术领域
本发明属于耐火材料领域,具体涉及一种球壳-海绵结构六铝酸钙-镁铝尖晶石复相材料的制备方法。
背景技术
六铝酸钙(CaAl12O19,简写为CA6,矿物名称:黑铝钙石)是 CaO-Al2O3系中Al2O3含量最高的铝酸钙相,其理论密度为 3.38g/cm3,熔点高达1875℃。六铝酸钙具有一系列的优良性能:与含氧化铁的熔渣形成固溶体的范围大,在碱性环境中有足够强的抗化学侵蚀能力,在还原气氛中高度稳定,主要结晶区大,在几种多元系统中有较低的溶解性。
六铝酸钙还原气氛下的高稳定性决定了其适用于有还原气氛的热工窑炉炉衬,碱蒸气环境中抗侵蚀能力强决定了其适用于碱蒸气环境下使用的耐火材料,与熔融金属及熔渣的润湿性低决定了其可作为金属冶炼用耐火材料。
虽然有关六铝酸钙的研究及专利众多,但多集中在利用原位反应膨胀制备轻质隔热材料、轻质骨料、轻质制品等方面;对于高热震稳定性的六铝酸钙-镁铝尖晶石复相材料研究较少,六铝酸钙和镁铝尖晶石由于热膨胀系数较高,热震稳定性不如常规的刚玉-莫来石、堇青石-莫来石等材料,但是六铝酸钙却有着从低温到高温,极其优良的抗碱侵蚀能力。
发明内容
本发明的目的是提出一种球壳-海绵结构六铝酸钙-镁铝尖晶石复相材料的制备方法,通过引入球壳-海绵结构,改善六铝酸钙-镁铝尖晶石复相材料热震稳定性。
本发明的目的是通过以下技术方案实现的:
一种球壳-海绵结构六铝酸钙-镁铝尖晶石复相材料的制备方法,六铝酸钙-镁铝尖晶石复相材料以重质六铝酸钙颗粒、六铝酸钙细粉、氧化铝微粉、电熔氧化镁为起始物料;起始物料的质量百分比为:重质六铝酸钙颗粒55-75%;六铝酸钙细粉10-30%,氧化铝微粉3-24%;电熔氧化镁1-8%;外加2-3%的结合剂,经轮碾机混合,机压成型,坯体经干燥后,在高温窑炉或电炉中进行烧成,在小于1100℃的温度下电熔氧化镁表面和氧化铝微粉产生固相反应形成镁铝尖晶石壳,同时在1100~1200℃还原气氛下保温3~6h,还原气氛下镁蒸气极易从电熔氧化镁未反应的中心区域以气相的形式挥发,从而形成球壳-海绵结构的镁铝尖晶石;随后恢复氧化气氛,最高烧成温度为1600℃~1750℃。
所述的重质六铝酸钙颗粒粒度为5-0.088mm。
所述的六铝酸钙细粉粒度为≤0.088mm。
所述的氧化铝微粉中位径≤5μm。
所述的电熔氧化镁既能够以细颗粒的形式,也能够以细粉的形式引入,粒度范围在0.5~0.074mm。
所述结合剂为纸浆溶液、糊精溶液、水性树脂溶液的一种或几种的复合。
本发明提出的一种球壳-海绵结构六铝酸钙-镁铝尖晶石复相材料的制备方法,与现有技术相比,利用1100℃之前电熔氧化镁表面和氧化铝微粉产生固相反应形成镁铝尖晶石壳,同时利用1100~1200℃还原气氛下镁蒸气极易从电熔氧化镁未反应的中心区域以气相的形式挥发,从而形成球壳-海绵结构镁铝尖晶石;利用上述原理和烧成条件,能够制备具有球壳-海绵结构的六铝酸钙-镁铝尖晶石复相材料;由于生成了球壳-海绵结构,在热震过程中,球壳-海绵结构能够在不牺牲材料强度的情况下,通过吸收微裂纹应力,大大改善六铝酸钙-镁铝尖晶石复相材料的热震稳定性,使得六铝酸钙材料能够在在高碱侵蚀、高热震条件下使用。
附图说明
图1为实施例三制得的具有球壳-海绵结构的六铝酸钙-镁铝尖晶石复相材料显微结构图(放大300倍);
图2为实施例三制得的具有球壳-海绵结构的六铝酸钙-镁铝尖晶石复相材料显微结构图(放大1000倍)。
具体实施方式
为了充分说明本发明的特点,现对本发明举例加以说明,但本发明的具体实施方式不局限于以下实例,可以在允许范围内根据实际情况进行适当的方案调整:
实施例一:各组份配比为(质量百分数):5-0.088mm重质六铝酸钙颗粒70%,六铝酸钙细粉26%,氧化铝微粉3%,0.5-0.1mm电熔氧化镁颗粒1%。
实施例一中先将2.8%的纸浆溶液加入颗粒部分,用轮碾机混合均匀,再将使用V型混料机混合好的细粉部分加入轮碾机,搅拌5~10分钟后出料,使用振动加压成型,经过110℃干燥。经过1100℃还原气氛保温6h,随后恢复氧化气氛,1750℃保温8h烧成,制得具有球壳-海绵结构的六铝酸钙-镁铝尖晶石复相材料。常温耐压强度为152MPa。按照DIN 51068:2008标准,1100℃水冷热震次数能够达到21次。
对比例一:各组份配比为(质量百分数):5-0.088mm重质六铝酸钙颗粒70%,六铝酸钙细粉26%,0.5-0.1mm电熔镁铝尖晶石颗粒4%,其中电熔镁铝尖晶石细粉中MgO含量为25%。
对比例一中先将2.8%的纸浆溶液加入颗粒部分,用轮碾机混合均匀,再将使用V型混料机混合好的细粉部分加入轮碾机,搅拌5~10分钟后出料,使用振动加压成型,经过110℃干燥。经过1100℃还原气氛保温6h,随后恢复氧化气氛,1750℃保温8h烧成,制得六铝酸钙-镁铝尖晶石复相材料。常温耐压强度为138MPa。按照DIN 51068:2008标准,1100℃水冷热震次数仅为7次。
实施例二:各组份配比为(质量百分数):5-0.088mm重质六铝酸钙颗粒60%,六铝酸钙细粉16%,氧化铝微粉18%,0.2-0.1mm电熔氧化镁颗粒6%。
实施例二中先将3%的水性树脂溶液加入颗粒部分,用轮碾机混合均匀,再将使用V型混料机混合好的细粉部分加入轮碾机,搅拌5~10分钟后出料,使用摩擦压砖机成型,经过110℃干燥。经过1200℃还原气氛保温3h,随后恢复氧化气氛,经过1650℃窑保温8h烧成,制得具有球壳-海绵结构的六铝酸钙-镁铝尖晶石复相材料。常温耐压强度为120MPa。按照DIN51068:2008标准,1100℃水冷热震次数能够达到25次。
对比例二:各组份配比为(质量百分数):5-0.088mm重质六铝酸钙颗粒60%,六铝酸钙细粉16%,氧化铝微粉18%,0.2-0.1mm电熔镁铝尖晶石颗粒6%。
对比例二中先将3%的水性树脂溶液加入颗粒部分,用轮碾机混合均匀,再将使用V型混料机混合好的细粉部分加入轮碾机,搅拌5~10分钟后出料,使用摩擦压砖机成型,经过110℃干燥。经过1200℃氧化气氛保温3h,1650℃窑保温8h烧成,制得六铝酸钙-镁铝尖晶石复相材料。常温耐压强度为106MPa。按照DIN 51068:2008标准,1100℃水冷热震次数仅为8次。
实施例三:各组份配比为(质量百分数):5-0.088mm重质六铝酸钙颗粒70%,六铝酸钙细粉18%,氧化铝微粉9%,0.1-0.074mm电熔氧化镁细粉3%。
实施例三中先将1%糊精溶液和1%水性树脂溶液加入颗粒部分,用轮碾机混合均匀,再将使用V型混料机混合好的细粉部分加入轮碾机,搅拌5~10分钟后出料,使用振动加压成型,经过110℃干燥。经过1150℃还原气氛保温4h,随后恢复氧化气氛,1600℃保温8h烧成,制得具有球壳-海绵结构的六铝酸钙-镁铝尖晶石复相材料。常温耐压强度为83MPa。按照DIN 51068:2008标准,1100℃水冷热震次数能够达到28次。
从图1、图2给出的断口显微形貌图,可以看到引入0.1-0.074mm电熔氧化镁,能够形成球壳-海绵结构镁铝尖晶石,大大提高了六铝酸钙-镁铝尖晶石材料热震稳定性。
对比例三:各组份配比为(质量百分数):5-0.088mm重质六铝酸钙颗粒70%,六铝酸钙细粉18%,氧化铝微粉9%,0.1-0.074mm电熔氧化镁细粉3%。
对比例三中先将1%糊精溶液和1%水性树脂溶液加入颗粒部分,用轮碾机混合均匀,再将使用V型混料机混合好的细粉部分加入轮碾机,搅拌5~10分钟后出料,使用振动加压成型,经过110℃干燥。经过1300℃还原气氛保温4h,随后恢复氧化气氛,1600℃保温8h烧成,制得六铝酸钙-镁铝尖晶石复相材料。常温耐压强度为79MPa。按照DIN 51068:2008标准,1100℃水冷热震次数仅为9次。
Figure DEST_PATH_IMAGE001

Claims (5)

1.一种球壳-海绵结构六铝酸钙-镁铝尖晶石复相材料的制备方法,其特征在于:六铝酸钙-镁铝尖晶石复相材料以重质六铝酸钙颗粒、六铝酸钙细粉、氧化铝微粉、电熔氧化镁为起始物料;起始物料的质量百分比为:重质六铝酸钙颗粒55-75%;六铝酸钙细粉10-30%,氧化铝微粉3-24%;电熔氧化镁1-8%;外加2-3%的结合剂,经轮碾机混合,机压成型,坯体经干燥后,在高温窑炉或电炉中进行烧成,在小于1100℃的温度下电熔氧化镁表面和氧化铝微粉产生固相反应形成镁铝尖晶石壳,同时在1100~1200℃还原气氛下保温3~6h,还原气氛下镁蒸气极易从电熔氧化镁未反应的中心区域以气相的形式挥发,从而形成球壳-海绵镁铝尖晶石;随后恢复氧化气氛,最高烧成温度为1600℃~1750℃。
2.如权利要求1所述的一种球壳-海绵结构六铝酸钙-镁铝尖晶石复相材料的制备方法,其特征在于:所述的重质六铝酸钙颗粒粒度为0.088-5mm。
3.如权利要求1所述的一种球壳-海绵结构六铝酸钙-镁铝尖晶石复相材料的制备方法,其特征在于:所述的六铝酸钙细粉粒度为≤0.088mm。
4.如权利要求1所述的一种球壳-海绵结构六铝酸钙-镁铝尖晶石复相材料的制备方法,其特征在于:所述的氧化铝微粉中位径≤5μm。
5.如权利要求1所述的一种球壳-海绵结构六铝酸钙-镁铝尖晶石复相材料的制备方法,其特征在于:所述的电熔氧化镁既能够以细颗粒的形式,也能够以细粉的形式引入,粒度范围在0.074~0.5mm。
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