CN108911706A - 一种粉煤灰基陶瓷微滤膜的共烧结制备方法 - Google Patents
一种粉煤灰基陶瓷微滤膜的共烧结制备方法 Download PDFInfo
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Abstract
本发明涉及一种低成本粉煤灰基陶瓷膜的共烧结制备方法。通过在粉煤灰晶须中掺杂刚性氧化物晶须，继而在生坯粉煤灰基载体上涂覆氧化铝陶瓷微滤膜，采用共烧结技术，一步烧结制备了粉煤灰基陶瓷微滤膜。刚性晶须的掺杂缓解了粉煤灰载体过度收缩，匹配了顶层氧化铝膜的热力学性质，可以通过共烧结技术一步制备出完整无缺陷的粉煤灰基陶瓷膜。制备粉煤灰基陶瓷微滤膜大幅度降低了陶瓷膜的原料成本和烧结能耗，较文献报道的陶瓷微滤膜的性能更高。
Description
技术领域
本发明涉及一种低成本粉煤灰基陶瓷微滤膜的共烧结制备方法，属于膜材料制备领域。
背景技术
陶瓷膜以其优异的材料性能在很多苛刻的应用体系中表现出有机膜无可比拟的优势，但是陶瓷膜较高的制备成本是一个不可忽视的问题，已成为限制陶瓷膜应用的主要因素，如何降低陶瓷膜的制备成本成为当前陶瓷领域关注的核心问题之一。
共烧结技术是同时从缩短工艺和降低能耗的角度出发，将原来多次的烧结过程简化成一次烧结过程，可以大幅度降低材料的烧结能耗和制备成本，缩短材料的制备周期，已经广泛应用于功能陶瓷元件、氧化物燃料电池以及陶瓷膜的制备过程中，并且在多通道陶瓷微滤膜的制备过程中也得到了良好的应用。不同材料层等进行共烧结时，需要控制不同界面间的反应和界面扩散，需要匹配各介质层的共烧性能，使致密化速率、烧结收缩率及热膨胀速率等参数尽量达到一致，否则容易产生层裂、翘曲和裂纹等缺陷。
Dong等(J Membr Sci,2006,281:592-599)以两种低成本且热力学性质相似的堇青石粉末为原料，通过共烧结技术制备了高性能陶瓷微滤膜，平均孔径分别为1.55μm和2.17μm。Feng等(J Membr Sci,2007,305:20-26)提出共烧结过程除了需要考察两层膜材料在烧结性能上的匹配性及膜层缺陷的控制外，还需要注意共烧结过程与载体间的截面结合强度。Qiu等(J Mater Sci,2009,44:689-699)在此基础上对共烧结理论进行深度分析，对担载膜受限烧结孔结构模型进行了改进和普适性研究，对烧结过程中堆积方式、保温时间以及载体限制作用导致的膜层z方向加速收缩等因素进行了考察，并且采用改进的模型对氧化锆担载膜在1000℃左右烧结后，对孔径分布、孔隙率、膜层厚度等参数进行预测。此外，Qiu等(J Membr Sci,2010,348(1-2):252-259)在此理论基础上，采用氧化钛溶胶和氧化钛晶须配制成制膜液作为过渡层，纯氧化钛溶胶作为顶层分离层，在平均孔径为3μm的载体上采用共烧结工艺一步烧结制备了双层氧化钛超滤膜。
发明内容
本发明的目的是为了改进现有技术的不足而提出一种粉煤灰基陶瓷微滤膜的共烧结制备方法，通过刚性晶须的掺杂，缓解了载体的收缩速率，和分离层膜的收缩速率一致，采用共烧结技术一步制备了高性能粉煤灰基陶瓷微滤膜，大幅度降低了陶瓷膜的烧结能耗和原料成本。
本发明的技术方案为：一种粉煤灰基陶瓷微滤膜的共烧结制备方法，其具体步骤如下：A将分级后的粉煤灰和刚性氧化物晶须按比列混合，然后加入粘结剂，经过混料、炼泥、造粒后，通过干压成型，压出生坯片式粉煤灰-晶须载体；B将一定粒径的氧化铝粉体、分散剂和增稠剂在超声作用下制备出稳定的微滤膜制膜液，将制膜液采用喷枪喷涂在生坯片式粉煤灰-晶须载体上，经过干燥、共烧结过程，得到粉煤灰基陶瓷微滤膜。
优选所述的分级后的粉煤灰为采用100-1000目的筛子进行分离原料粉煤灰。
优选所述的刚性氧化物晶须为自莫来石、氧化铝、碳化硅或氧化硅晶须中的一种或者多种；刚性晶须和粉煤灰采用机械搅拌1-60min；刚性氧化物晶须和粉煤灰的质量比为1:(6-10)。
优选所述的粘结剂为甘油、聚乙烯醇或甲基纤维素中的一种或者多种；其中粘结剂的添加量为占粉煤灰和晶须总质量的2％-10％。
优选压成型的压力为5MPa-30MPa，压制时间为5-60s。
优选所述的氧化铝粉体的粒径在300-1000nm之间；所述的增稠剂为甲基纤维素、聚乙烯醇或聚乙二醇中的一种或者多种；分散剂为硝酸、硫酸或盐酸中的一种；制备的制膜液中氧化铝的质量分数为5％-35％，增稠剂的质量分数控制在5％-20％，分散剂的加入量为控制制膜液的pH值为2-4。
优选采用喷枪在生坯片式粉煤灰-晶须载体上喷涂制膜液的喷涂次数为2-16次，每次喷涂时间为5-10秒。
优选所述的干燥、共烧结过程为：在室温下晾干12-24h，然后在70-120℃的温度下烘干12-24h，共烧结温度控制在900℃-1100℃之间，保温时间为1-5h，升温和降温速率控制在0.5-3℃/min。
本发明制得的粉煤灰基陶瓷微滤膜的膜层厚度为10-100μm,平均孔径为100-300nm,渗透率为400-2500Lm-2h-1bar-1。
有益效果：
本发明通过往粉煤灰基载体中掺杂刚性纤维，缓解了低成本载体和小孔径陶瓷微滤膜在烧结过程中的匹配问题，共烧结制备了低成本粉煤灰基陶瓷微滤膜，大幅度降低了陶瓷膜的原料成本和烧结能耗。
附图说明
图1为实施例3中的粉煤灰基载体收缩速率的调控图；
图2位实施例3中掺杂晶须的粉煤灰基载体的SEM照片；
图3为实施例3中双层粉煤灰-氧化铝微滤膜的断层结构图；
图4为实施例3中粉煤灰基陶瓷微滤膜的表面图；
图5为实施例3中粉煤灰基陶瓷微滤膜孔径分布图。
具体实施方式
实施例1
首先采用100目的筛子对粉煤灰进行分级处理，将分级后的粉煤灰和氧化铝晶须(刚性氧化物晶须和粉煤灰的质量比为1:6)采用搅拌混合1min，在混合后的粉体中加入占粉煤灰和氧化铝晶须总质量为2％的甘油进行混料，炼泥，通过干压成型过程，制备出生坯片式粉煤灰/晶须载体，控制压力在5Mpa，停留时间为60s。其次将平均粒径为300nm的氧化铝粉体、一定量的硫酸，一定量的聚乙烯醇在超声仪的作用下，配制成稳定的制膜液，制备的制膜液中氧化铝的质量分数为5wt.％，增稠剂的质量分数控制在20wt.％，最终制备的制膜液的pH值为2。通过喷枪喷涂法，将制膜液喷涂在生坯片式粉煤灰/晶须载体，涂膜次数为2次，每次喷涂时间为5s。在室温下晾干12h，然后在70℃的温度下烘干12h，共烧结温度控制在900℃，保温时间为5h，升温和降温速率控制在0.5℃/min。制备出的粉煤灰基微滤膜的膜层平均孔径为100nm，膜层厚度为10μm，渗透性能为950Lm-2h-1bar-1。
实施例2
首先采用1000目的筛子对粉煤灰进行分级处理，将分级后的粉煤灰和碳化硅晶须(刚性氧化物晶须和粉煤灰的质量比为1:10)采用传统搅拌进行混合60min，在混合后的粉体中加入占粉煤灰和氧化铝晶须总质量为10％的聚乙烯醇进行混料，炼泥，通过干压成型过程，制备出生坯片式粉煤灰/晶须载体，控制压力在30Mpa，停留时间为5s。其次将平均粒径为1000nm的氧化铝粉体、一定量的盐酸，一定量的聚乙二醇在超声仪的作用下，配制成稳定的制膜液，制备的制膜液中氧化铝的质量分数为35wt.％，增稠剂的质量分数控制在5wt.％，最终制备的制膜液的pH值为4。通过喷枪喷涂法，将制膜液喷涂在生坯片式粉煤灰/晶须载体，涂膜次数为16次，每次喷涂时间为10s。在室温下晾干24h，然后在120℃的温度下烘干24h，共烧结温度控制在1100℃，保温时间为1h，升温和降温速率控制在3℃/min。制备出的膜层平均孔径为300nm，膜层厚度为100μm，渗透性能为2500Lm-2h-1bar-1。
实施例3
首先采用300目的筛子对粉煤灰进行分级处理，将分级后的粉煤灰和莫来石晶须(刚性氧化物晶须和粉煤灰的质量比为1:8)采用传统搅拌进行混合5min，在混合后的粉体中加入占粉煤灰和氧化铝晶须总质量为4％的聚乙烯醇进行混料，炼泥，通过干压成型过程，制备出生坯片式粉煤灰/晶须载体，控制压力在20Mpa，停留时间为20s。其次将平均粒径为300nm的氧化铝粉体、一定量的硝酸，一定量的甲基纤维素在超声仪的作用下，配制成稳定的制膜液，制备的制膜液中氧化铝的质量分数为20wt.％，增稠剂的质量分数控制在14wt.％，最终制备的制膜液的pH值为2。通过喷枪喷涂法，将制膜液喷涂在生坯片式粉煤灰/晶须载体，涂膜次数为8次，每次喷涂时间为6s。在室温下晾干18h，然后在70℃的温度下烘干18h，共烧结温度控制在1050℃，保温时间为2h，升温和降温速率控制在2℃/min。制备出的膜层平均孔径为100nm，膜层厚度为40μm，渗透性能为450Lm-2h-1bar-1。图1是本实施例中陶瓷载体和微滤膜收缩速率，莫来石晶须的掺杂可以减缓粉煤灰基载体的收缩速率。图2是本实施例中的粉煤灰载体的SEM照片，来表征制备载体的微观形貌。从图中可以看出粉煤灰载体中混有明显的刚性晶须，并且晶须的加入并没有对载体表面的完整性造成影响。图3是本实施例中共烧结制备的粉煤灰基陶瓷微滤膜的膜层结构，其中膜层厚度大约为40-50μm左右。图4本实施例中制备的微滤膜的SEM电镜照片，表面完整没有缺陷。图5本实施例中制备的粉煤灰基陶瓷微滤膜的孔径分布，孔径大约为100nm左右。表1本实施例中制备的微滤膜和文献中性能的比较，由图可知，本方法制备的微微滤(平均孔径为100nm左右)较文献比较渗透性更好，成本更低。
实施例4
首先采用300目的筛子对粉煤灰进行分级处理，将分级后的粉煤灰和氧化硅晶须(刚性氧化物晶须和粉煤灰的质量比为1:8)采用传统搅拌进行混合5min，在混合后的粉体中加入占粉煤灰和氧化铝晶须总质量为4％的甘油进行混料，炼泥，通过干压成型法，制备出生坯片式粉煤灰/晶须载体，控制压力在20Mpa，停留时间为20s。其次将平均粒径为300nm的氧化铝粉体、一定量的硝酸，一定量的甲基纤维素在超声仪的作用下，配制成稳定的制膜液，制备的制膜液中氧化铝的质量分数为20wt.％，增稠剂的质量分数控制在14wt.％，最终制备的制膜液的pH值为2。通过喷枪喷涂法，将制膜液喷涂在生坯片式粉煤灰/晶须载体，涂膜次数为8次，每次喷涂时间为6s。在室温下晾干18h，然后在70℃的温度下烘干18h，共烧结温度控制在1050℃，保温时间为2h，升温和降温速率控制在2℃/min。制备出的膜层平均孔径为100nm，膜层厚度为40μm，渗透性能为400Lm-2h-1bar-1。
表1是在实施例3中的制备的微滤膜和文献比较，由表可知，本方法制备的微滤膜(平均孔径为100nm左右)较文献比较渗透性更好，成本更低
表1实施例3制备的微滤膜性能和文献比较(孔径的单位：nm,渗透性能单位:Lm-2h-1bar-1)
Claims (9)
1.一种粉煤灰基陶瓷微滤膜的共烧结制备方法，其具体步骤如下：A将分级后的粉煤灰和刚性氧化物晶须按比列混合，然后加入粘结剂，经过混料、炼泥、造粒后，通过干压成型法，压出生坯片式粉煤灰-晶须载体；B将一定粒径的氧化铝粉体、分散剂和增稠剂在超声作用下制得微滤膜制膜液，将微滤膜制膜液采用喷枪喷涂在生坯片式粉煤灰-晶须载体上，经过干燥、共烧结过程，得到粉煤灰基陶瓷微滤膜。
2.根据权利要求1所述的共烧结制备方法，其特征在于：所述的分级后的粉煤灰为采用100-1000目的筛子进行分离原料粉煤灰。
3.根据权利要求1所述的共烧结制备方法，其特征在于：所述的刚性氧化物晶须为自莫来石、氧化铝、碳化硅或氧化硅晶须中的一种或者多种；刚性晶须和粉煤灰采用机械搅拌1-60min；刚性氧化物晶须和粉煤灰的质量比为1:(6-10)。
4.根据权利要求1所述的共烧结制备方法，其特征在于：所述的粘结剂为甘油、聚乙烯醇或甲基纤维素中的一种或者多种；其中粘结剂的添加质量为占粉煤灰和晶须总质量的2％-10％。
5.根据权利要求1所述的共烧结制备方法，其特征在于：干压成型过程中的压力为5MPa-30MPa，压制时间为5-60s。
6.根据权利要求1所述的共烧结制备方法，其特征在于：所述的氧化铝粉体的粒径在300-1000nm之间；所述的增稠剂为甲基纤维素、聚乙烯醇或聚乙二醇中的一种或者多种；分散剂为硝酸、硫酸或盐酸中的一种；制备的微滤膜制膜液中氧化铝的质量分数为5％-35％，增稠剂的质量分数控制在5％-20％，分散剂的加入量为控制膜液的pH值为2-4。
7.根据权利要求1所述的共烧结制备方法，其特征在于：采用喷枪在生坯片式粉煤灰-晶须载体上喷涂制膜液的喷涂次数为2-16次，每次喷涂时间为5-10秒。
8.根据权利要求1所述的共烧结制备方法，其特征在于：所述的干燥、共烧结过程为：在室温下晾干12-24h，然后在70-120℃的温度下烘干12-24h，共烧结温度控制在900℃-1100℃之间，保温时间为1-5h，升温和降温速率控制在0.5-3℃/min。
9.根据权利要求1所述的共烧结制备方法，其特征在于：制得的粉煤灰基陶瓷微滤膜的膜层厚度为10-100μm,平均孔径为100-300nm,渗透率为400-2500Lm-2h-1bar-1。
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