CN113385052B - 氧化铝基陶瓷平板膜 - Google Patents
氧化铝基陶瓷平板膜 Download PDFInfo
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 13
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开一种低成本氧化铝基陶瓷平板膜的制备方法,所述陶瓷平板膜包括支撑体和膜层两部分,所述支撑体采用挤出成型的方法制备,所述膜层采用喷涂法涂覆在支撑体生坯外表面,所述支撑体生坯和膜层共同干燥后,采用“支撑体+膜层”一步共烧结工艺制得陶瓷平板膜。该法缩短了陶瓷平板膜的制备周期,减少了烧结次数,在时间和能源耗用方面节省了大量成本。本发明通过支撑体和膜层间的颗粒级配,减小两者在高温烧结时产生的收缩率差异,制得的陶瓷平板膜表面平整,无裂纹,孔径分布集中,具有良好的热稳定性、化学稳定性和力学性能。
Description
技术领域
本发明属于陶瓷过滤膜技术领域,还涉及氧化铝基陶瓷平板膜的制备方法。
背景技术
陶瓷膜由于其优异的热稳定性、化学稳定性和高渗透性而受到越来越多的关注,尤其在除浊、油-水分离及其他重要工业应用中表现出优异的性能。通常,陶瓷膜由陶瓷支撑体、孔径较小的至少一层过渡层以及承担分离功能的分离层构成。因此,陶瓷膜的制造需要多次重复“涂覆-干燥-烧结”工艺,这导致烧结能耗成本增加,生产周期延长,并限制了其应用范围。为了尽量缩短陶瓷膜制造工艺,人们做了共烧结的研究。例如:用共烧结工艺制备出了氧化铝中空纤维膜,双层氧化铝膜,氧化铝-氧化锆陶瓷膜,堇青石微滤膜和氧化钛超滤膜。这些研究表明,通过调整烧结温度,膜厚度和有机/无机添加剂,可将共烧结工艺应用在刚性支撑体上制备双层膜结构。然而,关于生坯载体和膜层的共烧结过程的报道很少。陶瓷膜支撑体的壁厚一般为1-3mm,比膜层的厚度大得多,并且共烧结过程中支撑体的收缩张力差与膜的厚度成正比。因此,通过共烧结工艺制备“载体+层”比制备“层+层”更困难。
发明内容
为克服现有技术的不足,本发明提供一种氧化铝基陶瓷平板膜,其采用特定的原料配方,使得可以实现支撑体生坯与分离膜层的一次烧结。所得陶瓷平板膜的膜表面平整,无裂纹,孔径分布集中,具有良好的热稳定性、化学稳定性和力学性能。
根据本发明的氧化铝基陶瓷平板膜,包括支撑体以及包覆在支撑体外表面的分离膜层两部分。其中,用于支撑体的氧化铝的平均粒径与用于分离膜层的氧化铝的平均粒径之比在2.5-15之间,优选在4-10之间,更优选在5-8之间,并且,所述支撑体中包含堇青石相。
在本发明的具体实施方式中,支撑体中堇青石相的含量在2-10%之间,典型的在3-8%之间。该堇青石相的存在,可以有效降低支撑体烧结中的收缩率,避免在与分离膜层共烧时的支撑体的开裂。
在本发明的一种具体实施方式中,用于形成支撑体的原料以重量计包含类球形氧化铝粉100份、水洗高岭土2-10份和煅烧滑石0.5-5份。在该实施例中,水洗高岭土和煅烧滑石有助于形成堇青石相。
通常,在支撑体配方中引入其他功能性助剂,例如造孔剂;粘结剂、润滑剂、增塑剂和烧结助剂。适用的造孔剂包括但不限于淀粉,适用的粘结剂包括但不限于羧甲基纤维素钠、聚乙烯醇、羟丙基甲基纤维素、甲基纤维素中的一种或多种;适用的润滑剂包括但不限于甘油;适用的增塑剂包括但不限于聚氧化乙烯;适用的烧结助剂优选纳米二氧化钛。
在本发明的一种优选实施方式中,支撑体原料组成为:每100份类球形氧化铝粉加入2~6份淀粉、2~8份粘结剂、2~10份水洗高岭土、0.5~5份煅烧滑石、0.2~1份纳米二氧化钛、0.5~2份甘油、15~25份固含量0.3%的聚氧化乙烯(PEO)溶液。
本发明中,分离膜层主要由氧化铝粉形成,其他成分为常用助剂。在一种典型实施方式中,每100份氧化铝粉引入0.3-1份分散剂、5-10份烧结助剂、20-50份粘结剂和1-5份消泡剂。其中,分散剂可以为聚丙烯酸铵溶液、聚丙烯酸溶液、聚丙烯酰胺溶液、聚丙烯酸钠溶液中的一种或多种;烧结助剂为硅溶胶、纳米二氧化钛、纳米二氧化锆、纳米氧化锌、水洗高岭土、煅烧滑石中的两种或多种;粘结剂优选为固含量30%的聚乙烯醇溶液,粘度1500~2500mPa.s;陶瓷消泡剂为聚醚类消泡剂。
分离膜层通过浸渍或喷涂的方式涂覆在支撑体生坯上,优选以喷涂的方式,这可以更精确地控制分离膜层的厚度,可以将厚度控制得更薄。具体制备方法包括下述步骤:
(1)陶瓷平板支撑体的制备
将平均粒径3~50μm的类球形氧化铝粉与淀粉、粘结剂、水洗高岭土、煅烧滑石、纳米二氧化钛在混料机中混合成粉料;将甘油、固含量0.3%的PEO(聚氧化乙烯)溶液搅拌混合均匀,并在陶瓷泥料捏合机中,加入到混合好的粉料中,捏合练泥;再经过泥料陈腐,真空练泥,挤出成型,湿坯干燥等工序,获得待涂膜的支撑体生坯。
(2)膜层浆料的制备
先将分散剂加入水中,搅拌分散5min;再加入平均粒径0.3~3μm的氧化铝粉和烧结助剂,搅拌分散20min;然后加入粘结剂和陶瓷消泡剂,搅拌分散5min;最后将上述浆料转入球磨罐中,球磨分散2h,即得涂膜浆料;所述涂膜浆料的粘度为50~100mPa.s。
(3)喷涂工艺制备分离膜层
将上述陶瓷平板支撑体生坯置于烘箱中80℃干燥2h以上备用;将上述涂膜浆料真空除泡后备用;在喷涂间中,通过喷枪将除泡后的浆料均匀的涂覆在热的支撑体生坯外表面,得到外表膜层均匀的陶瓷平板膜,60℃干燥后放入窑炉中烧结1300~1400℃,保温2h,即可制得平均孔径0.05~0.5μm的陶瓷平板膜。
本发明与现有技术相比,有益效果在于:
(1)本发明采用“支撑体+膜层”一步共烧工艺制备陶瓷平板膜,缩短了陶瓷平板膜的制备周期,减少了烧结次数,在时间和能源耗用方面节省了大量成本。
(2)本发明在选取支撑体和膜层用氧化铝粉体时,支撑体用氧化铝的平均粒径与膜层用氧化铝的平均粒径之间的比值≤15,可减小两者在高温烧结时产生的收缩率差异,避免膜层开裂。
(3)本发明在支撑体中引入生高岭土和煅烧滑石,在高温烧结过程中生成热膨胀系数低的堇青石相,降低支撑体高温烧结时的收缩率,减小支撑体与膜层在高温烧结时产生的收缩率差异,避免膜层开裂。
(4)本发明在膜层浆料中引入硅溶胶、二氧化钛等纳米粉体做为烧结助剂,可有效避免膜层在干燥和煅烧过程中开裂。
附图说明
图1-1是实施例1制备的氧化铝陶瓷平板膜膜层表面的SEM图。
图1-2是实施例1制备的氧化铝陶瓷平板膜膜层截面的SEM图。
图1-3为实施例1制备的氧化铝陶瓷平板膜的孔径分布图。
图1-4为实施例1制备的氧化铝陶瓷平板膜的XRD图谱。
图2-1是实施例2制备的氧化铝陶瓷平板膜膜层表面的SEM图。
图2-2是实施例2制备的氧化铝陶瓷平板膜膜层截面的SEM图。
图2-3为实施例2制备的氧化铝陶瓷平板膜的孔径分布图。
图2-4为实施例2制备的氧化铝陶瓷平板膜的XRD图谱。
图3-1是比较例1制备的氧化铝陶瓷平板膜膜层表面的SEM图。
图3-2是比较例1制备的氧化铝陶瓷平板膜膜层截面的SEM图。
图3-3为比较例1制备的氧化铝陶瓷平板膜的孔径分布图。
图3-4为比较例1制备的氧化铝陶瓷平板膜的XRD图谱。
图4-1是比较例2制备的氧化铝陶瓷平板膜膜层表面的SEM图。
图4-2是比较例2制备的氧化铝陶瓷平板膜膜层截面的SEM图。
图4-3为比较例2制备的氧化铝陶瓷平板膜的孔径分布图。
图4-4为比较例2制备的氧化铝陶瓷平板膜的XRD图谱。
图5-1是比较例3制备的氧化铝陶瓷平板膜膜层表面的SEM图。
图5-2是比较例3制备的氧化铝陶瓷平板膜膜层截面的SEM图。
图5-3为比较例3制备的氧化铝陶瓷平板膜的孔径分布图。
图5-4为比较例3制备的氧化铝陶瓷平板膜的XRD图谱。
具体实施方式
下述实施例是对于本发明内容的进一步说明以作为对本发明技术内容的阐释,但本发明的实质内容并不仅限于下述实施例所述,本领域的普通技术人员可以且应当知晓任何基于本发明实质精神的简单变化或替换均应属于本发明所要求的保护范围。
实施例1
(1)陶瓷平板支撑体的制备
取平均粒径16.47μm的类球形氧化铝粉1000g、淀粉20g、羟丙基甲基纤维素20g、水洗高岭土30g、煅烧滑石10g、纳米二氧化钛3g,在混料机中混合成粉料;取甘油10g、固含量0.3%的PEO(聚氧化乙烯)溶液200g搅拌混合均匀,并在陶瓷泥料捏合机中,加入到混合好的粉料中,捏合练泥;再经泥料陈腐(湿度≥70%,温度25℃~30℃,时间24~48h),真空练泥(真空度≤-0.092MPa),挤出成型,湿坯干燥(微波干燥定型后,烘箱中70~80℃干燥10h以上),即可获得待涂膜的支撑体生坯。
(2)膜层浆料的制备
先取分散剂聚丙烯酰胺5g加入到800g水中,搅拌分散5min;再加入平均粒径2.159μm的氧化铝粉1000g、硅溶胶60g、纳米二氧化钛20g,搅拌分散20min;然后加入固含量30%的聚乙烯醇溶液400g和陶瓷消泡剂20g,搅拌分散5min;最后将上述浆料转入球磨罐中,球磨分散2h,即得涂膜浆料;所述涂膜浆料的粘度为70.6mPa.s。
(3)喷涂工艺制备分离膜层
将上述陶瓷平板支撑体生坯置于烘箱中80℃干燥2h备用;将上述涂膜浆料真空除泡后备用(真空度≤-0.092MPa);在喷涂间中,通过喷枪将除泡后的浆料均匀的涂覆在热的支撑体生坯外表面,得到外表膜层均匀的陶瓷平板膜,喷涂后的陶瓷平板膜在烘箱中60℃干燥2h,最后放入窑炉中1400℃烧结,保温2h,即可制得平均孔径0.21μm的陶瓷平板膜。
图1-1是所得陶瓷平板膜膜层表面的SEM图,由图可见,成品的分离膜层质量优良,没有任何裂纹。图1-2是所得平板膜的横断面的SEM图,图中清晰示出支撑体层和分离膜层,支撑体层和分离膜层结合良好,未出现任何裂痕。图1-3是本实施例产品的孔径分布图,图中显示孔径在0.12-0.33μm之间,孔径分布非常均匀。图1-4为本实施例所得氧化铝陶瓷平板膜的XRD图谱,图中显示最终烧成的产品中包含有堇青石相,含量为2.19%。
实施例2
(1)陶瓷平板支撑体的制备
取平均粒径6.38μm的类球形氧化铝粉1000g、淀粉40g、羧甲基纤维素钠40g、水洗高岭土50g、煅烧滑石30g、纳米二氧化钛2g,在混料机中混合成粉料;取甘油16g、固含量0.3%的PEO(聚氧化乙烯)溶液220g搅拌混合均匀,并在陶瓷泥料捏合机中,加入到混合好的粉料中,捏合练泥;再经泥料陈腐(湿度≥70%,温度25℃~30℃,时间24~48h),真空练泥(真空度≤-0.092MPa),挤出成型,湿坯干燥(微波干燥定型后,烘箱中70~80℃干燥10h以上),即可获得待涂膜的支撑体生坯。
(2)膜层浆料的制备
先取分散剂聚丙烯酸3g加入到900g水中,搅拌分散5min;再加入平均粒径1.033μm的氧化铝粉1000g、硅溶胶80g、水洗高岭土5g,搅拌分散20min;然后加入固含量30%的聚乙烯醇溶液350g和陶瓷消泡剂15g,搅拌分散5min;最后将上述浆料转入球磨罐中,球磨分散2h,即得涂膜浆料;所述涂膜浆料的粘度为52.6mPa.s。
(3)喷涂工艺制备分离膜层
将上述陶瓷平板支撑体生坯置于烘箱中80℃干燥2h备用;将上述涂膜浆料真空除泡后备用(真空度≤-0.092MPa);在喷涂间中,通过喷枪将除泡后的浆料均匀的涂覆在热的支撑体生坯外表面,得到外表膜层均匀的陶瓷平板膜,喷涂后的陶瓷平板膜在烘箱中60℃干燥2h,最后放入窑炉中1350℃烧结,保温2h,即可制得平均孔径0.10μm的陶瓷平板膜。
图2-1是所得陶瓷平板膜膜层表面的SEM图,由图可见,成品的分离膜层质量优良,没有任何裂纹。图2-2是所得平板膜的横断面的SEM图,图中清晰示出支撑体层和分离膜层,支撑体层和分离膜层结合良好,未出现任何裂痕。2-3是本实施例产品的孔径分布图,图中显示孔径在0.07-0.14μm之间,孔径分布非常均匀。图1-4为本实施例所得氧化铝陶瓷平板膜的XRD图谱,图中显示最终烧成的产品中包含有堇青石相,含量为6.82%。
比较例1
采用实施例1基本相同的原料和操作步骤,不同之处是,支撑体用氧化铝粉的平均粒径是21.47μm,分离膜层氧化铝粉的平均粒径是1.033μm。二者粒径比为20.78。
图3-1是本比较例所得陶瓷平板膜膜层表面的SEM图,由图可见,成品的分离膜层质量较差,表面存在裂纹。图3-2是所得平板膜的横断面的SEM图,图中清晰示出支撑体层和分离膜层,支撑体层和分离膜层结合良好。图3-3是本比较例产品的孔径分布图,图中显示孔径在0.15-0.55μm之间,孔径分布不均一。图3-4为本比较例所得氧化铝陶瓷平板膜的XRD图谱,图中显示最终烧成的产品中包含有堇青石相,含量为2.63%。
比较例2
采用实施例1基本相同的原料和操作步骤,不同之处是,支撑体原料中缺少水洗高岭土。
图4-1是本比较例所得陶瓷平板膜膜层表面的SEM图,由图可见,成品的分离膜层质量较差,表面存在裂纹。图4-2是所得平板膜的横断面的SEM图,图中清晰示出支撑体层和分离膜层,支撑体层和分离膜层结合良好。图4-3是本比较例产品的孔径分布图,图中显示孔径在0.14-0.65μm之间,孔径分布很宽。图4-4为本比较例所得氧化铝陶瓷平板膜的XRD图谱,图中显示最终烧成的产品中只包含氧化铝相,不包含堇青石相。
比较例3
采用实施例1基本相同的原料和操作步骤,不同之处是,支撑体原料中缺少煅烧滑石。
图5-1是本比较例所得陶瓷平板膜膜层表面的SEM图,由图可见,成品的分离膜层质量较差,表面存在裂纹。图5-2是所得平板膜的横断面的SEM图,图中清晰示出支撑体层和分离膜层,支撑体层和分离膜层结合良好。图5-3是本比较例产品的孔径分布图,图中显示孔径在0.12-0.58μm之间,孔径分布很宽。图5-4为本比较例所得氧化铝陶瓷平板膜的XRD图谱,图中显示最终烧成的产品中只包含氧化铝相,不包含堇青石相。
Claims (6)
1.一种氧化铝基陶瓷平板膜,由支撑体和涂覆在该支撑体外表面的分离膜层构成,其特征在于,用于支撑体的氧化铝的平均粒径与用于分离膜层的氧化铝的平均粒径之比在2.5-15之间,并且,所述支撑体中包含堇青石相,
用于形成支撑体的原料以重量计包含:类球形氧化铝粉,100;水洗高岭土,2-10;煅烧滑石,0.5-5;纳米二氧化钛,0.2~1;
用于形成分离膜层的原料以重量计包含:氧化铝粉,100;分散剂,0.3~1;
烧结助剂,5~10;粘结剂,20~50;陶瓷消泡剂,1~5,其中,所述烧结助剂包含硅溶胶和纳米二氧化钛,或包含硅溶胶和水洗高岭土,
所述氧化铝基陶瓷平板膜是通过将支撑体生坯上直接喷涂分离膜层浆料,干燥后一次性烧结得到。
2.根据权利要求1所述的氧化铝基陶瓷平板膜,其中,所述支撑体中堇青石相的含量在2-10%之间。
3.根据权利要求1所述的氧化铝基陶瓷平板膜,其中,用于形成支撑体的原料以重量计还包含:
淀粉,2~6;
粘结剂,2~8;
甘油,0.5~2;
固含量0.3%的聚氧化乙烯溶液,15%~25。
4.根据权利要求3所述的氧化铝基陶瓷平板膜,其中,所述粘结剂为羧甲基纤维素钠、聚乙烯醇、羟丙基甲基纤维素、甲基纤维素中的一种或多种。
5.根据权利要求1所述的氧化铝基陶瓷平板膜,其中,所述分散剂为聚丙烯酸铵溶液、聚丙烯酸溶液、聚丙烯酰胺溶液、聚丙烯酸钠溶液中的一种或多种。
6.根据权利要求1所述的氧化铝基陶瓷平板膜,其中,用于支撑体的氧化铝的平均粒径为3~50μm,用于分离膜层的氧化铝的平均粒径为0.3~3μm。
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CN111545078A (zh) * | 2020-05-15 | 2020-08-18 | 洛阳中超新材料股份有限公司 | 平板陶瓷膜及其制备方法 |
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