CN109534803A - 荷电陶瓷膜及其制备方法 - Google Patents
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Abstract
本发明公开了一种荷电陶瓷膜,其组成包括如下重量份数的组分:堇青石50~70份、碳化硅10~15份、α‑氧化铝3~6份、氧化钕1~3份、氧化钛3~5份、聚乙烯亚胺5~10份、聚乙烯醇20~30份、荷电剂0.1~1份。采用等静压成型法和浸浆法制备上述荷电陶瓷膜。通过各组分比例以及烧结时各阶段的温度控制,并通过加入α‑氧化铝、氧化钕、氧化钛等降低烧结温度,提高堇青石和碳化硅的结合强度,形成双层孔隙结构以获得高强度的支撑体和膜层,制得的荷电陶瓷膜孔隙率可达45%,强度达20MPa。
Description
技术领域
本发明涉及一种陶瓷材料,尤其是涉及一种荷电陶瓷膜,同时涉及其制备方法。
背景技术
陶瓷膜是无机膜中的一种,属于膜分离技术中的固体膜材料,主要以不同规格的氧化铝、氧化锆、氧化钛和氧化硅等无机陶瓷材料作为支撑体,经表面涂膜、高温烧制而成。分离用陶瓷膜通常具有三层结构:支撑体(又称载体层)、过渡层(又称中间层)、膜层(又称分离层),其中支撑层的作用是增加膜的机械强度;中间层的孔径比支撑层的孔径小,其作用是防止膜层制备过程中颗粒向多孔支撑层的渗透;膜层具有分离功能。整个膜的孔径分布由支撑层到膜层逐渐减小,形成不对称的结构分布。根据支撑体的不同,陶瓷膜的构型可分为平板、管式、多通道三种。而陶瓷膜荷电可通过电学相关作用(Donnan排斥、静电排斥、介电效应等)截留粒径较小的粒子或离子,因此对于其分离性能、耐污性能等有重要影响。但是,此类荷电陶瓷膜依然存在成本较高、制备工艺严苛等问题。
发明内容
为解决上述技术问题,本发明提供一种制备成本低、强度高的荷电陶瓷膜。
本发明的技术方案是提供一种荷电陶瓷膜,其组成包括如下重量份数的组分:堇青石50~70份、碳化硅10~15份、α-氧化铝3~6份、氧化钕1~3份、氧化钛3~5份、聚乙烯亚胺5~10份、聚乙烯醇20~30份、荷电剂0.1~1份。
所述堇青石中10~20wt%为纳米堇青石,采用该质量比例纳米堇青石在烧制时颗粒受热迅速快速形成烧结晶粒,同时能够降低烧结温度节省能耗。
所述荷电剂为氧化钇、氧化锆、天然多糖中的一种或多种。
本发明还提供一种荷电陶瓷膜的制备方法,包括如下步骤:
S1.除荷电剂全部制备膜层浆料之外,将上述原料的90wt%(质量百分比)制备陶瓷膜支撑体浆料,10wt%制备膜层浆料;
S2.陶瓷膜支撑体浆料的制备:取堇青石、碳化硅、α-氧化铝、氧化钕、氧化钛按比例混合后投入球磨机中球磨24~30h,后加入聚乙烯亚胺、聚乙烯醇,继续球磨1~4h;
S3.膜层浆料的制备:取堇青石、碳化硅、α-氧化铝、氧化钕、氧化钛、荷电剂按比例混合后投入球磨机中球磨24~30h,后加入聚乙烯亚胺、聚乙烯醇,去离子水,搅拌混合均匀;
S4.利用等静压成型法将步骤S2中的陶瓷膜支撑体浆料制成坯体,坯体自然干燥24~30h;
S5.烧结坯体,烧结参数为以1~3℃/min升温速率升至1100~1250℃保温2~6h,以同样的升温速率升至1450~1600℃,保温1~3h;首先使堇青石在α-氧化铝、氧化钕、氧化钛等烧结助剂作用下形成三维网状孔隙结构,升高温度后发现碳化硅在堇青石形成的网状结构支点形成了新的烧结晶粒,加强了堇青石孔隙结构的强度;同时碳化硅本身其颗粒间形成了新的疏松网状孔隙结构,进一步提高整个坯体强度,此外以一定的升温速率升温能使双层网状孔隙结构均匀,优化孔隙结构;
S6.待坯体冷却后,采用浸浆法在坯体表面浸渍步骤S3制备的膜层浆料,室温干燥后烧结,烧结参数为1~3℃/min升温速率升至800℃保温1~2h,以3~6℃/min的升温速率升至1100~1250℃保温2~6h,再以3~6℃/min的升温速率升至1400~1550℃,保温1~3h,冷却;升温至800℃时先除去可挥发的有机物,使膜层初步形成并促使膜层内出现大孔隙结构,然后以较快的升温速率升至较高温度使堇青石快速填充在大孔隙中并相互联结形成网状,由于膜层较薄因此形成的堇青石晶粒填充率高,膜层致密性提高,再次升温促进碳化硅形成第二层孔隙结构进一步提升膜层致密性和膜层强度,提高陶瓷膜的比表面积。
所述荷电陶瓷膜的膜层厚度为5~10μm,膜层过薄时,过滤孔无法有规律地形成,导致孔径均匀度差,过滤精度非常低,而膜层过厚时,虽然能够形成有规律的过滤孔,但是通过扫描电镜观察过滤孔易相互交叠,破坏整体孔隙的结构,同样不利于提高过滤精度,因此该膜层厚度下,过滤孔径能够得到良好控制,有助于提高过滤精度。
所述步骤S3中搅拌的同时进行超声处理,超声频率为50kHz,功率为0.4~0.5w/cm2,超声时间为20~40min,超声处理是浆料混合更加均匀同时提高膜层浆料中颗粒悬浮性能便于浆料附着在坯体表面。
所述步骤S3制备所得的膜层浆料的固体含量分别为40wt%、60wt%、70wt%,用于坯体多次浸渍。
所述步骤S6坯体浸渍膜层浆料的步骤为:
S61.将坯体用固体含量70wt%的膜层浆料浸渍,干燥;重复1~2次;
S62.将坯体用固体含量60wt%的膜层浆料浸渍,干燥;
S63.将坯体用固体含量40wt%的膜层浆料浸渍,干燥。
所述步骤S6中坯体冷却过程为以2~4℃/min的速率冷却,膜层中粒子生长需要一定时间,保持一定的降温速率能够控制粒子粒径,保证膜层均一性良好。
本发明的优点和有益效果:采用堇青石、碳化硅作为荷电陶瓷膜的主要骨架成分,制备时通过球磨作用将颗粒粒径降低同时均匀各组分的颗粒粒径,有利于成型,并在烧结过程中各颗粒的受热面近似,受热程度相近保证升温同步,烧结时各粒子生长速度接近并可控;膜层烧结过程中各组分形成共熔液,其中碳化硅在氧化铝、氧化镁、氧化钕作用下,协助堇青石形成致密膜层并且膜层中出现双层孔隙结构,孔隙率在40%左右,此外氧化铝、氧化镁、氧化钕可降低陶瓷的烧结温度,降低能耗。
具体实施方式
下面结合具体实施方式对本发明作进一步说明。
实施例1
本发明提供一种荷电陶瓷膜,其组成包括如下重量份数的组分:堇青石50份(其中10wt%为纳米堇青石)、碳化硅10份、α-氧化铝3份、氧化钕1份、氧化钛3份、聚乙烯亚胺5份、聚乙烯醇20份、壳聚糖0.1份,膜层厚度为5μm。
上述荷电陶瓷膜的制备方法,包括如下步骤:
S1.除荷电剂全部制备膜层浆料之外,将上述原料的90wt%(质量百分比)制备陶瓷膜支撑体浆料,10wt%制备膜层浆料;
S2.陶瓷膜支撑体浆料的制备:取堇青石、碳化硅、α-氧化铝、氧化钕、氧化钛按比例混合后投入球磨机中球磨24h,后加入聚乙烯亚胺、聚乙烯醇,继续球磨4h;
S3.膜层浆料的制备:取堇青石、碳化硅、α-氧化铝、氧化钕、氧化钛、荷电剂按比例混合后投入球磨机中球磨24h,后加入聚乙烯亚胺、聚乙烯醇,去离子水,采用超声搅拌混合均匀,其中超声频率为50kHz,功率为0.4w/cm2,超声时间为20min;制得的膜层浆料的固体含量分别为40wt%、60wt%、70wt%,用于坯体多次浸渍;
S4.采用冷等静压成型法将步骤S2中的陶瓷膜支撑体浆料在模具中制成坯体,成型压力为6000kgf/cm2,坯体自然干燥24h;
S5.烧结坯体,烧结参数为以1~3℃/min升温速率升至1100~1250℃保温2~6h,以同样的升温速率升至1450~1600℃,保温1~3h;
S6.以2~4℃/min的速率冷却坯体后,采用浸浆法在坯体表面浸渍步骤S3制备的膜层浆料,具体过程为用固体含量70wt%的膜层浆料浸渍0.5h,干燥,重复1次;再用固体含量60wt%的膜层浆料浸渍0.5h,干燥,最后用固体含量40wt%的膜层浆料浸渍0.5h,干燥;重复浸渍浓度较高的膜层浆料使坯体表面初步充分吸附膜层材料,干燥后采用再次浸渍浓度稍低的膜层浆料,利用坯体表面膜层材料浓度较低与膜层浆料形成浓度差以及坯体表面的微孔结构使膜层浆料进一步吸附至坯体表面,填充膜层缺陷处,增加坯体表面膜层的完整度和均一度;
S7.室温下干燥后烧结,烧结参数为1~3℃/min升温速率升至800℃保温1~2h,以3~6℃/min的升温速率升至1100~1250℃保温2~6h,再以3~6℃/min的升温速率升至1400~1550℃,保温1~3h,冷却。
制得的荷电陶瓷膜孔隙率为45%,强度为18MPa,平均孔径为50nm,纯水通量为100L/(m2·h)。
实施例2
本发明提供一种荷电陶瓷膜,其组成包括如下重量份数的组分:堇青石70份(其中20wt%为纳米堇青石)、碳化硅15份、α-氧化铝6份、氧化钕3份、氧化钛5份、聚乙烯亚胺10份、聚乙烯醇30份、酵母葡聚糖1份,膜层厚度为8μm。
上述荷电陶瓷膜的制备方法,包括如下步骤:
S1.除荷电剂全部制备膜层浆料之外,将上述原料的90wt%(质量百分比)制备陶瓷膜支撑体浆料,10wt%制备膜层浆料;
S2.陶瓷膜支撑体浆料的制备:取堇青石、碳化硅、α-氧化铝、氧化钕、氧化钛按比例混合后投入球磨机中球磨30h,后加入聚乙烯亚胺、聚乙烯醇,继续球磨1h;
S3.膜层浆料的制备:取堇青石、碳化硅、α-氧化铝、氧化钕、氧化钛、荷电剂按比例混合后投入球磨机中球磨30h,后加入聚乙烯亚胺、聚乙烯醇,去离子水,采用超声搅拌混合均匀,其中超声频率为50kHz,功率为0.5w/cm2,超声时间为40min;制得的膜层浆料的固体含量分别为40wt%、60wt%、70wt%,用于坯体多次浸渍;
S4.采用冷等静压成型法将步骤S2中的陶瓷膜支撑体浆料在模具中制成坯体,成型压力为6000kgf/cm2,坯体自然干燥30h;
S5.烧结坯体,烧结参数为以1~3℃/min升温速率升至1100~1250℃保温2~6h,以同样的升温速率升至1450~1600℃,保温1~3h;
S6.以2~4℃/min的速率冷却坯体后,采用浸浆法在坯体表面浸渍步骤S3制备的膜层浆料,具体过程为用固体含量70wt%的膜层浆料浸渍0.1h,干燥,重复1次;再用固体含量60wt%的膜层浆料浸渍0.1h,干燥,最后用固体含量40wt%的膜层浆料浸渍0.1h,干燥;重复浸渍浓度较高的膜层浆料使坯体表面初步充分吸附膜层材料,干燥后采用再次浸渍浓度稍低的膜层浆料,利用坯体表面膜层材料浓度较低与膜层浆料形成浓度差以及坯体表面的微孔结构使膜层浆料进一步吸附至坯体表面,填充膜层缺陷处,增加坯体表面膜层的完整度和均一度;
S7.室温下干燥后烧结,烧结参数为1~3℃/min升温速率升至800℃保温1~2h,以3~6℃/min的升温速率升至1100~1250℃保温2~6h,再以3~6℃/min的升温速率升至1400~1550℃,保温1~3h,冷却。
制得的荷电陶瓷膜孔隙率为40%,强度为20MPa,平均孔径为80nm,纯水通量为150L/(m2·h)。
实施例3
本发明提供一种荷电陶瓷膜,其组成包括如下重量份数的组分:堇青石60份(其中15wt%为纳米堇青石)、碳化硅12份、α-氧化铝5份、氧化钕2份、氧化钛4份、聚乙烯亚胺8份、聚乙烯醇25份、氧化锆0.5份,膜层厚度为3μm。
上述荷电陶瓷膜的制备方法,包括如下步骤:
S1.除荷电剂全部制备膜层浆料之外,将上述原料的90wt%(质量百分比)制备陶瓷膜支撑体浆料,10wt%制备膜层浆料;
S2.陶瓷膜支撑体浆料的制备:取堇青石、碳化硅、α-氧化铝、氧化钕、氧化钛按比例混合后投入球磨机中球磨28h,后加入聚乙烯亚胺、聚乙烯醇,继续球磨2h;
S3.膜层浆料的制备:取堇青石、碳化硅、α-氧化铝、氧化钕、氧化钛、荷电剂按比例混合后投入球磨机中球磨24h,后加入聚乙烯亚胺、聚乙烯醇,去离子水,采用超声搅拌混合均匀,其中超声频率为50kHz,功率为0.5w/cm2,超声时间为30min;制得的膜层浆料的固体含量分别为40wt%、60wt%、70wt%,用于坯体多次浸渍;
S4.采用冷等静压成型法将步骤S2中的陶瓷膜支撑体浆料在模具中制成坯体,成型压力为6000kgf/cm2,坯体自然干燥28h;
S5.烧结坯体,烧结参数为以1~3℃/min升温速率升至1100~1250℃保温2~6h,以同样的升温速率升至1450~1600℃,保温1~3h;
S6.以2~4℃/min的速率冷却坯体后,采用浸浆法在坯体表面浸渍步骤S3制备的膜层浆料,具体过程为用固体含量70wt%的膜层浆料浸渍0.2h,干燥,重复1次;再用固体含量60wt%的膜层浆料浸渍0.2h,干燥,最后用固体含量40wt%的膜层浆料浸渍0.2h,干燥;重复浸渍浓度较高的膜层浆料使坯体表面初步充分吸附膜层材料,干燥后采用再次浸渍浓度稍低的膜层浆料,利用坯体表面膜层材料浓度较低与膜层浆料形成浓度差以及坯体表面的微孔结构使膜层浆料进一步吸附至坯体表面,填充膜层缺陷处,增加坯体表面膜层的完整度和均一度;
S7.室温下干燥后烧结,烧结参数为1~3℃/min升温速率升至800℃保温1~2h,以3~6℃/min的升温速率升至1100~1250℃保温2~6h,再以3~6℃/min的升温速率升至1400~1550℃,保温1~3h,冷却。
制得的荷电陶瓷膜孔隙率为40%,强度为19MPa,平均孔径为70nm,纯水通量为120L/(m2·h)。
实施例4
本发明提供一种荷电陶瓷膜,其组成包括如下重量份数的组分:堇青石55份(其中10wt%为纳米堇青石)、碳化硅14份、α-氧化铝4份、氧化钕2份、氧化钛5份、聚乙烯亚胺10份、聚乙烯醇25份、氧化锡0.8份,膜层厚度为5μm。
上述荷电陶瓷膜的制备方法,包括如下步骤:
S1.除荷电剂全部制备膜层浆料之外,将上述原料的90wt%(质量百分比)制备陶瓷膜支撑体浆料,10wt%制备膜层浆料;
S2.陶瓷膜支撑体浆料的制备:取堇青石、碳化硅、α-氧化铝、氧化钕、氧化钛按比例混合后投入球磨机中球磨24h,后加入聚乙烯亚胺、聚乙烯醇,继续球磨3h;
S3.膜层浆料的制备:取堇青石、碳化硅、α-氧化铝、氧化钕、氧化钛、荷电剂按比例混合后投入球磨机中球磨24h,后加入聚乙烯亚胺、聚乙烯醇,去离子水,采用超声搅拌混合均匀,其中超声频率为50kHz,功率为0.4w/cm2,超声时间为40min;制得的膜层浆料的固体含量分别为40wt%、60wt%、70wt%,用于坯体多次浸渍;
S4.采用冷等静压成型法将步骤S2中的陶瓷膜支撑体浆料在模具中制成坯体,成型压力为6000kgf/cm2,坯体自然干燥24h;
S5.烧结坯体,烧结参数为以1~3℃/min升温速率升至1100~1250℃保温2~6h,以同样的升温速率升至1450~1600℃,保温1~3h;
S6.以2~4℃/min的速率冷却坯体后,采用浸浆法在坯体表面浸渍步骤S3制备的膜层浆料,具体过程为用固体含量70wt%的膜层浆料浸渍0.1h,干燥,重复2次;再用固体含量60wt%的膜层浆料浸渍0.1h,干燥,最后用固体含量40wt%的膜层浆料浸渍0.1h,干燥;重复浸渍浓度较高的膜层浆料使坯体表面初步充分吸附膜层材料,干燥后采用再次浸渍浓度稍低的膜层浆料,利用坯体表面膜层材料浓度较低与膜层浆料形成浓度差以及坯体表面的微孔结构使膜层浆料进一步吸附至坯体表面,填充膜层缺陷处,增加坯体表面膜层的完整度和均一度;
S7.室温下干燥后烧结,烧结参数为1~3℃/min升温速率升至800℃保温1~2h,以3~6℃/min的升温速率升至1100~1250℃保温2~6h,再以3~6℃/min的升温速率升至1400~1550℃,保温1~3h,冷却。
制得的荷电陶瓷膜孔隙率为38%,强度为20MPa,平均孔径为60nm,纯水通量为130L/(m2·h)。
本发明实施例涉及到的材料、试剂和实验设备,如无特别说明,均为符合陶瓷材料领域的市售产品。
以上所述,仅为本发明的优选实施例,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明的核心技术的前提下,还可以做出改进和润饰,这些改进和润饰也应属于本发明的专利保护范围。与本发明的权利要求书相当的含义和范围内的任何改变,都应认为是包括在权利要求书的范围内。
Claims (9)
1.一种荷电陶瓷膜,其组成包括如下重量份数的组分:堇青石50~70份、碳化硅10~15份、α-氧化铝3~6份、氧化钕1~3份、氧化钛3~5份、聚乙烯亚胺5~10份、聚乙烯醇20~30份、荷电剂0.1~1份。
2.根据权利要求1所述的荷电陶瓷膜,其特征在于,所述堇青石中10~20wt%为纳米堇青石。
3.根据权利要求1所述的荷电陶瓷膜,其特征在于,所述荷电剂为氧化钇、氧化锆或天然多糖中的一种或多种。
4.权利要求1所述的荷电陶瓷膜的制备方法,包括如下步骤:
S1.除荷电剂全部制备膜层浆料之外,将上述原料的90wt%(质量百分比)制备陶瓷膜支撑体浆料,10wt%制备膜层浆料;
S2.陶瓷膜支撑体浆料的制备:取堇青石、碳化硅、α-氧化铝、氧化钕、氧化钛按比例混合后投入球磨机中球磨24~30h,后加入聚乙烯亚胺、聚乙烯醇,继续球磨1~4h;
S3.膜层浆料的制备:取堇青石、碳化硅、α-氧化铝、氧化钕、氧化钛、荷电剂按比例混合后投入球磨机中球磨24~30h,后加入聚乙烯亚胺、聚乙烯醇,去离子水,搅拌混合均匀;
S4.利用等静压成型法将步骤S2中的陶瓷膜支撑体浆料制成坯体,坯体自然干燥24~30h;
S5.烧结坯体,烧结参数为以1~3℃/min升温速率升至1100~1250℃保温2~6h,以同样的升温速率升至1450~1600℃,保温1~3h;
S6.待坯体冷却后,采用浸浆法在坯体表面浸渍步骤S3制备的膜层浆料,室温干燥后烧结,烧结参数为1~3℃/min升温速率升至800℃保温1~2h,以3~6℃/min的升温速率升至1100~1250℃保温2~6h,再以3~6℃/min的升温速率升至1400~1550℃,保温1~3h,冷却。
5.根据权利要求4所述的荷电陶瓷膜的制备方法,其特征在于,所述荷电陶瓷膜的膜层厚度为5~10μm。
6.根据权利要求4所述的荷电陶瓷膜的制备方法,其特征在于,所述步骤S3中搅拌的同时进行超声处理,超声频率为50kHz,功率为0.4~0.5w/cm2,超声时间为20~40min。
7.根据权利要求4所述的荷电陶瓷膜的制备方法,其特征在于,所述步骤S3制备所得的膜层浆料的固体含量分别为40wt%、60wt%、70wt%,用于坯体多次浸渍。
8.根据权利要求7所述的荷电陶瓷膜的制备方法,其特征在于,所述步骤S6坯体浸渍膜层浆料的步骤为:
S61.将坯体用固体含量70wt%的膜层浆料浸渍,干燥;重复1~2次;
S62.将坯体用固体含量60wt%的膜层浆料浸渍,干燥;
S63.将坯体用固体含量40wt%的膜层浆料浸渍,干燥。
9.根据权利要求4所述的荷电陶瓷膜的制备方法,其特征在于,所述步骤S6中坯体冷却过程为以2~4℃/min的速率冷却。
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