CN109320224A - 一种高纯度堇青石结合莫来石的材料及其制备方法 - Google Patents

一种高纯度堇青石结合莫来石的材料及其制备方法 Download PDF

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CN109320224A
CN109320224A CN201811258468.5A CN201811258468A CN109320224A CN 109320224 A CN109320224 A CN 109320224A CN 201811258468 A CN201811258468 A CN 201811258468A CN 109320224 A CN109320224 A CN 109320224A
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mullite
synthesis
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cordierite
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张晓峰
孙文礼
李玉强
张瑛
李志军
史永鹏
李凯
李芳�
王倩倩
杨舒琪
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ZIBO INDUSTRIAL CERAMIC REFRACTORY MATERIAL Co Ltd
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Abstract

本发明属于陶瓷新材料技术领域,涉及一种高纯度堇青石结合莫来石的材料及其制备方法。骨料使用合成莫尔柯、基质使用高纯度合成堇青石、使用复合型有机添加剂解决成型性能,无粘土添加。高纯度堇青石本身具备较高的高温抗折强度、较低的热膨胀率、较低的杂质含量;堇青石‑莫来石材料的基质全部采用高纯度堇青石,制作出的堇青石‑莫来石材料具备了高温抗折强度高、热膨胀率低、高温下使用循环次数多、变形小、寿命长的突出优点。

Description

一种高纯度堇青石结合莫来石的材料及其制备方法
技术领域
本发明属于陶瓷新材料技术领域,涉及一种高纯度堇青石结合莫来石的材料及其制备方法。
背景技术
现代陶瓷的生产离不开窑具材料,堇青石-莫来石质耐火材料有低的热膨胀率和良好的抗热震性,广泛应用于现代陶瓷业。理想的堇青石-莫来石窑具应具备:高温使用循环次数多而不开裂、变形量小或不变形的优点。
国内通常的堇青石-莫来石质耐火材料制品以莫来石为骨料,以粘土粉、滑石粉、纯度不高的堇青石粉、氧化铝粉等为基质,基质烧成后形成莫来石以提高高温强度(高温抗折强度)、形成原位堇青石以降低热膨胀率。采用注浆成型、机压成型或挤出成型。
基质由于添加粘土,存在较多杂质的原因,烧成后实际上形成了莫来石、堇青石、玻璃相、尖晶石等为主要的矿物相。基质莫来石相含量高,材料的高温抗折强度高,热膨胀率也高,抗热冲击性能下降;基质莫来石相含量低,材料的高温抗折强度低,热膨胀率低,抗热冲击性能好,但由于玻璃相的存在,高温使用时易弯曲变形。很难制作出具备高温强度和热膨胀率俱佳的、实用效果理想的堇青石-莫来石窑具材料。
中国专利申请201110321507.3(CN 102503459 A)公开了一种陶瓷窑用高级堇青石-莫来石质耐火材料及其生产工艺,其制造方法为:1.2-0.5mm莫洛凯特20-40%,0.5-0.088mm莫洛凯特10-25%,0.5-0.088mm合成堇青石0-15%,<0.088mm合成堇青石10-35%,<0.088mm合成莫来石0-20%,镁砂微粉1-3%,氧化铝微粉2-8%,硅灰3-10%,煅烧高岭土微粉0-15%,外加第三代减水剂0.01-0.1%,外加水4-8%。该发明使用莫洛凯特和合成堇青石合成莫来石,同时使用镁砂微粉、硅灰和氧化铝微粉,在烧成过程中仍有堇青石相原位合成,且使用煅烧高岭土,易引进杂质,造成堇青石反应难控制和高温性能降低,使用寿命缩短。
中国专利申请201610053165.4(CN 105669244 A)公开了一种高抗热振性堇青石-莫来石窑具材料,其制造方法为:使用堇青石熟料、堇青石-莫来石窑具废料、漂珠、滑石、氧化铝和粘土及黏土熟料,使用黄糊精作为结合剂,混料、困料后成型烧成制得。其制造方法大量使用粘土,原位合成堇青石基质,同样会影响高温性能及使用寿命。
发明内容
本发明的目的在于提供一种高纯度堇青石结合莫来石的材料及其制备方法。骨料使用合成莫尔柯、基质使用高纯度合成堇青石、使用复合型有机添加剂解决成型性能,无粘土添加。高纯度堇青石本身具备较高的高温抗折强度、较低的热膨胀率、较低的杂质含量;堇青石-莫来石材料的基质全部采用高纯度堇青石,制作出的堇青石-莫来石材料具备了高温抗折强度高、热膨胀率低、高温下使用循环次数多、变形小、寿命长的突出优点。
为解决上述技术问题,本发明采用的技术方案如下:
一种高纯度堇青石结合莫来石的材料,由如下种类、粒度规格及重量百分含量的原料组成:
合成莫尔柯 0.1~1mm 30~60%
合成堇青石 ≤0.045mm 40~70%
复合型有机添加剂 0.1~5%。
进一步地,其化学组成成分为:Al2O3=34~40%,SiO2=50~58%,MgO=4~10%,Fe2O3=0.01~0.5%,TiO2=0.01~0.5%,CaO=0.01~0.5%,K2O=0.01~1%,Na2O=0.01~0.5%。
进一步地,所述合成堇青石的化学组成成分为:Al2O3=32~37%,SiO2=49~53%,MgO=11~14%,其他杂质含量≤0.5%。
进一步地,所述合成莫尔柯的化学组成成分为:Al2O3=38~42%,SiO2=54~58%,K2O=1~3%,其他杂质含量≤3%。
进一步地,所述合成莫尔柯的物理性能为:气孔率≤8%,体积密度≥2.0g/cm3
进一步地,所述复合型有机添加剂为木质素磺酸镁原液、羧甲基纤维素溶液、聚乙烯醇溶液、聚丙烯酸铵、硬脂酸中的两种或两种以上的混合物。
一种如上述所述的高纯度堇青石结合莫来石的材料的制备方法,包含以下步骤:
(1)混料:将合成莫尔柯、复合型有机添加剂加入混料机中,加入适量的水并搅拌均匀,将合成堇青石细粉加入混料机中,混合均匀,根据加水量的不同得到浇注泥料或机压泥料;
(2)困料:机压泥料放入密封编织袋中困料24h以上,浇注泥料在搅拌罐中困料24h以上;
(3)成型:采用机压成型或浇注成型;
(4)烘干:将成型的砖坯放入烘干箱中干燥,干燥温度为70~150℃,保温24h及以上;
(5)烧成:烧成温度为1250℃~1400℃,保温6h及以上。
进一步地,采用机压成型所制得的高纯度堇青石结合莫来石的材料,物理性能为:气孔率=20~28%,体积密度=1.8~2.2g/cm3,常温耐压强度≥85MPa,常温抗折强度≥15MPa,1250℃抗折强度≥25MPa,1000℃热膨胀率≤0.25%。
进一步地,采用浇注成型所制得的高纯度堇青石结合莫来石的材料,物理性能为:气孔率=24~30%,体积密度=1.6~2.0g/cm3,常温耐压强度≥60MPa,常温抗折强度≥15MPa,1250℃抗折强度≥22MPa,1000℃热膨胀率≤0.25%。
本发明相对于现有技术具有以下优点:
(1)仅使用高纯度合成堇青石和合成莫尔柯,性能稳定可控,杂质含量低,烧成收缩小产品合格率高;
(2)使用的高纯度合成堇青石相组成为堇青石相及少量玻璃相,不含其它杂相,并且杂质成分低,作为基质,能够保证产品的高强度、低热膨胀率、高抗热振性及长寿命;
(3)基质全部采用高纯度堇青石,制作出的堇青石-莫来石材料具备了高温抗折强度高、热膨胀率低、高温下使用循环次数多、变形小、寿命长的突出优点;
(4)骨料使用合成莫尔柯,热膨胀率低,无方石英相,抗热震性能好;
(5)使用复合型有机添加剂解决成型性能,不使用粘土,避免粘土引进杂质影响高温性能,避免因粘土质量波动带来产品性能不稳定,也避免了对环境的过度破坏;
(6)使用远红外干燥箱进行干燥,干燥效率高,干燥均匀性好,减少产品干燥时形成的变形和开裂;
(7)配方简单,所需原料种类少,更有利于生产操作和大规模生产。
具体实施方式
下面对本发明作进一步说明。
机压成型:
原料:0.044mm高纯度合成堇青石、0.1~1mm合成莫尔柯、木质素磺酸镁原液、羧甲基纤维素溶液、聚乙烯醇溶液;
制备方法:
(1)混料:将合成莫尔柯、复合型有机添加剂加入混料机中,加入适量的水并搅拌均匀,将合成堇青石细粉加入混料机中,混合均匀,得到机压泥料;
(2)困料:机压泥料放入密封编织袋中困料24h以上;
(3)成型:采用机压成型;
(4)烘干:将成型的砖坯放入远红外干燥箱中干燥,干燥温度为120℃,保温24h;
(5)烧成:烧成温度为1350℃,保温6h。
表一机压成型配料表
表二机压成型产品物理性能检测数据
实施例1 实施例2 实施例3 实施例4 实施例5 实施例6 实施例7
常温耐压强度/MPa 85.1 89.5 97.6 95.5 116.6 102 85.3
显气孔率/% 21.69 23.33 22.01 23.96 25.52 26.91 25.31
体积密度/g/cm<sup>3</sup> 2.11 2.03 1.95 1.95 1.93 1.91 1.82
1000℃热膨胀率/% 0.18 0.18 0.19 0.19 0.20 0.21 0.21
常温抗折强度/MPa 16.2 18.8 17.5 17.4 19.7 18.5 16.3
1250℃抗折强度/MPa 27.6 26.5 27.6 29.6 31.4 28.7 25.2
表三机压成型产品化学成分检测数据(%)
Si0<sub>2</sub> Al<sub>2</sub>0<sub>3</sub> Mg0 Fe<sub>2</sub>0<sub>3</sub> Ti0<sub>2</sub> Ca0 K<sub>2</sub>0 Na<sub>2</sub>0
实施例1 53.35 35.23 9.01 0.2 0.23 0.28 0.39 0.18
实施例2 53.77 35.48 8.38 0.23 0.27 0.27 0.44 0.18
实施例3 53.99 35.84 7.75 0.26 0.31 0.28 0.51 0.21
实施例4 54.96 36.98 6.24 0.26 0.32 0.26 0.65 0.24
实施例5 54.92 37.15 6.2 0.26 0.32 0.27 0.63 0.24
实施例6 55.1 36.75 6.3 0.35 0.32 0.29 0.65 0.21
实施例7 55.18 36.75 5.25 0.38 0.35 0.33 0.76 0.22
浇注成型:
原料:0.044mm高纯度合成堇青石、0.1~1mm合成莫尔柯、聚丙烯酸铵、聚乙烯醇溶液;
制备方法:
(1)混料:将合成莫尔柯、复合型有机添加剂加入混料机中,加入适量的水并搅拌均匀,将合成堇青石细粉加入混料机中,混合均匀,得到浇注泥料;
(2)困料:浇注泥料在搅拌罐中困料24h;
(3)成型:采用浇注成型;
(4)烘干:将成型的砖坯放入远红外干燥箱中干燥,干燥温度为120℃,保温24h;
(5)烧成:烧成温度为1350℃,保温6h。
表四浇注成型配料表
原料% 规格 实施例8 实施例9 实施例10 实施例11 实施例12 实施例13 实施例14
合成莫尔柯 1-0.1mm 30 35 40 45 50 55 60
合成堇青石 0.044mm 70 65 60 55 50 45 40
聚乙烯醇溶液 6% 1 1 1 1 1 1 1
聚丙烯酸铵 0.5 0.5 0.5 0.5 0.5 0.5 0.5
15.1 13.4 11.3 11 10.4 9.6 9.2
表五浇注成型产品物理性能检测数据
实施例8 实施例9 实施例10 实施例11 实施例12 实施例13 实施例14
常温耐压强度/MPa 60.5 63.7 71.8 70.2 72.3 72.2 68.4
显气孔率/% 26.6 27.9 28.3 27.1 27.4 26.35 26.05
体积密度/g/cm<sup>3</sup> 1.69 1.81 1.77 1.8 1.8 1.84 1.88
1000℃热膨胀率/% 0.17 0.7 0.18 0.19 0.19 0.2 0.21
常温抗折强度/MPa 16.4 15.6 16.9 16.8 17.5 15.6 15.5
1250℃抗折强度/MPa 22.6 23.3 23.6 24.5 28.2 26.8 25.2
表六浇注成型产品化学成分检测数据(%)

Claims (9)

1.一种高纯度堇青石结合莫来石的材料,其特征在于,由如下种类、粒度规格及重量百分含量的原料组成:
合成莫尔柯 1~0.1mm 30~60%
合成堇青石 ≤0.045mm 40~70%
复合型有机添加剂 0.1~5%。
2.根据权利要求1所述的高纯度堇青石结合莫来石的材料,其特征在于,其化学组成成分为:Al2O3=34~40%,SiO2=50~58%,MgO=4~10%,Fe2O3=0.01~0.5%,TiO2=0.01~0.5%,CaO=0.01~0.5%,K2O=0.01~1%,Na2O=0.01~0.5%。
3.根据权利要求1所述的高纯度堇青石结合莫来石的材料,其特征在于,所述合成堇青石的化学组成成分为:Al2O3=32~37%,SiO2=49~53%,MgO=11~14%,其他杂质含量≤0.5%。
4.根据权利要求1所述的高纯度堇青石结合莫来石的材料,其特征在于,所述合成莫尔柯的化学组成成分为:Al2O3=38~42%,SiO2=54~58%,K2O=1~3%,其他杂质含量≤3%。
5.根据权利要求1或3所述的高纯度堇青石结合莫来石的材料,其特征在于,所述合成莫尔柯的物理性能为:气孔率≤8%,体积密度≥2.0g/cm3
6.根据权利要求1所述的高纯度堇青石结合莫来石的材料,其特征在于,所述复合型有机添加剂为木质素磺酸镁原液、羧甲基纤维素溶液、聚乙烯醇溶液、聚丙烯酸铵、硬脂酸中的两种或两种以上的混合物。
7.一种如权利要求1-6任意一项所述的高纯度堇青石结合莫来石的材料的制备方法,其特征在于,包含以下步骤:
(1)混料:将合成莫尔柯、复合型有机添加剂加入混料机中,加入适量的水并搅拌均匀,将合成堇青石细粉加入混料机中,混合均匀,根据加水量的不同得到浇注泥料或机压泥料;
(2)困料:机压泥料放入密封编织袋中困料24h及以上,浇注泥料在搅拌罐中困料24h及以上;
(3)成型:采用机压成型或浇注成型;
(4)烘干:将成型的砖坯放入烘干箱中干燥,干燥温度为70~150℃,保温24h及以上;
(5)烧成:烧成温度为1250℃~1400℃,保温6h及以上。
8.根据权利要求7所述的制备方法,其特征在于,采用机压成型所制得的高纯度堇青石结合莫来石的材料,物理性能为:气孔率=20~28%,体积密度=1.8~2.2g/cm3,常温耐压强度≥85MPa,常温抗折强度≥15MPa,1250℃抗折强度≥25MPa,1000℃热膨胀率≤0.25%。
9.根据权利要求7所述的制备方法,其特征在于,采用浇注成型所制得的高纯度堇青石结合莫来石的材料,物理性能为:气孔率=24~30%,体积密度=1.6~2.0g/cm3,常温耐压强度≥60MPa,常温抗折强度≥15MPa,1250℃抗折强度≥22MPa,1000℃热膨胀率≤0.25%。
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