CN110681263A - 一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜及其制备方法 - Google Patents
一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种Al2O3‑TiO2梯度多孔结构陶瓷超滤膜及其制备方法，包括陶瓷支撑结构及Al2O3‑TiO2过滤结构，Al2O3‑TiO2过滤结构周围附有若干毛刺，Al2O3‑TiO2过滤结构及其毛刺环绕于陶瓷支撑结构周围，形成多梯度多孔过滤结构。其制备方法为：S1：依次向球磨罐内加入钛粉、明胶、分散剂、去离子水及氧化锆球；S2：放入烘箱内放置1～24小时，温度控制在30～100℃，并球磨24～72小时；S3：坯体的成型：将制备好的陶瓷料浆倒入事先准备好的模具中，并将其放入冻干机内，冻干12～72小时，冻干机的温度控制在‑10℃～‑60℃；S4：烧结工艺：将冻干的坯体放入坩埚内，采用氧化铝粉末进行包覆；S5：将坩埚放入马弗炉内，在500～900℃的温度中恒温烧结1～24小时。本发明的优点是，工艺简单，节约成本，在环保领域应用广泛。
Description
技术领域
本发明属于多孔结构陶瓷超滤膜领域，具体涉及一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜及其制备方法。
背景技术
陶瓷超滤膜是一种利用微孔结构对污染物进行分离的多孔陶瓷材料，由于其优异的力学性能已经广泛应用于环保器械领域。冷冻铸造技术可以通过升华溶剂得到多孔结构坯体，利用放热反应进行烧结可以有效降低陶瓷材料的烧结温度。现有陶瓷超滤膜的成型工艺复杂且陶瓷烧结温度高，导致生产成本一直居高不下，另一方面通过现在制备方法制备的陶瓷超滤膜有闭孔孔隙存在，影响了其在过滤领域的应用。
发明内容
本发明的目的是解决上述问题，提供一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜及其制备方法，解决了现有方法制备的陶瓷超滤膜制备工艺复杂，成本消耗大的问题。
为实现上述目的，本发明提供如下技术方案：
一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜，包括陶瓷支撑结构及Al2O3-TiO2过滤结构，所述Al2O3-TiO2过滤结构周围附有若干毛刺，所述Al2O3-TiO2过滤结构及其毛刺环绕于陶瓷支撑结构周围，形成多梯度多孔过滤结构。
进一步的，所述陶瓷超滤膜的孔径为100nm左右，孔隙率为55％～70％，抗压强度为31～42MPa。
上述Al2O3-TiO2梯度多孔结构陶瓷超滤膜的制备方法，其包括以下步骤：
S1：依次向球磨罐内加入钛粉、明胶、分散剂、去离子水及氧化锆球；
S2：放入烘箱内放置1～24小时，温度控制在30～100℃，并球磨24～72小时；
S3：坯体的成型：将制备好的陶瓷料浆倒入事先准备好的模具中，并将其放入冻干机内，冻干12～72小时，冻干机的温度控制在-10℃～-60℃；
S4：烧结工艺：将冻干的坯体放入坩埚内，采用氧化铝粉末进行包覆；
S5：将坩埚放入马弗炉内，在500～900℃的温度中恒温烧结1～24小时。
进一步的，所述S1中，钛粉的粒度为500目～4000目，钛粉的质量分数为： 5％～50％，明胶的质量分数为：0％～5％，分散剂的质量分数为：0％～5％，其余均为去离子水。
优选的，所述S1中钛粉的粒度为800目～1500目，料浆中钛粉的质量分数为15％～30％，明胶的质量分数为2％～3％，分散剂的质量分数为2％～3％；所述 2中烘箱内放置时间为12～16小时，球磨时间为30～50小时，其余均为去离子水。
进一步的，所述S3中，冻干时间为18～64小时，冻干机温度控制为 -20℃～-50℃。
优选的，所述S3中，冻干时间为30～60小时，冻干机温度控制为-30℃～-45℃。
进一步的，所述S5中，马弗炉温度控制在850℃，保温4～20小时。
优选的，所述S5中，马弗炉温度控制在750℃，保温5～18小时。
优选的，所述S2中，氧化锆球与浆料的体积比为2：1；所述S3中所用的模具为金属模具或聚四氟乙烯模具；所述S4中包覆所用的氧化铝粉末粒度为30 nm～500nm。
与现有技术相比，本发明的有益效果在于：
本发明通过冷冻铸造与反应烧结相结合的方法，使梯度多孔结构陶瓷超滤膜一步成型，其过滤层孔径主要集中于50nm左右，同时陶瓷的烧结温度降低了 500℃～700℃，工艺流程简单，极大节约了成本，解决了现有技术中多孔陶瓷材料一般为闭孔、瓷烧结温度太高、制备工艺复杂，成本消耗大的问题，在环保器械领域有广泛的应用前景。
附图说明
为了更清楚地说明本发明实施例技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明为了更清楚地说明本发明实施例或现有技术中的技术方案，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明陶瓷超滤膜的结构示意图；
图2为本发明Al2O3-TiO2过滤结构的结构示意图；
图3为本发明梯度多孔陶瓷的截面图；
图4为本发明梯度多孔陶瓷的SEM形貌图；
图中：1-陶瓷支撑结构，2-Al2O3-TiO2过滤结构，3-毛刺。
具体实施方式
为了使本领域技术人员更好地理解本发明的技术方案能予以实施，下面结合具体实施例对本发明作进一步说明，但所举实施例只作为对本发明的说明，不作为对本发明的限定。
如图1-4所示的一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜，包括陶瓷支撑结构1及Al2O3-TiO2过滤结构2，所述Al2O3-TiO2过滤结构2周围附有若干毛刺3，所述Al2O3-TiO2过滤结构2及其毛刺3环绕于陶瓷支撑结构1周围，形成多梯度多孔过滤结构。所述陶瓷超滤膜的孔径为100nm左右，孔隙率为55％～70％，抗压强度为31～42MPa。
上述Al2O3-TiO2梯度多孔结构陶瓷超滤膜的制备方法，其具体按照以下步骤实施：
S1：依次向球磨罐内加入500目～4000目钛粉(质量分数为5％～50％)、明胶(质量分数为0％～5％)、分散剂(0％～5％)、去离子水(40％～95％)、氧化锆球；
S2：放入烘箱内放置1～24小时，温度控制在30～100℃，并球磨24～72小时；
S3：坯体的成型：将制备好的陶瓷料浆倒入事先准备好的模具中，并将其放入冻干机内，冻干12～72小时，冻干机的温度控制在-10℃～-60℃；
S4：烧结工艺：将冻干的坯体放入坩埚内，采用粒度为10nm～2000nm的氧化铝粉末进行包覆；
S5：将坩埚放入马弗炉内，在500～900℃的温度中恒温烧结1～24小时。
优选的，所述S2中，氧化锆球与浆料的体积比为2：1；所述S3中所用的模具为金属模具或聚四氟乙烯模具；所述S4中包覆所用的氧化铝粉末粒度为30 nm～500nm。
本实施方法使梯度多孔结构陶瓷超滤膜一步成型，其孔径主要集中于100nm 左右，同时陶瓷的烧结温度降低了500℃～700℃，极大节约了成本，在环保器械领域有广泛的应用前景。
实施例1：
一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜的制备方法，其具体按照以下步骤实施：
S1：依次向球磨罐内加入500目～1000目钛粉(质量分数为50％)、明胶 (质量分数为2％)、分散剂(质量分数为3％)、去离子水45％、氧化锆球；
S2：放入烘箱内放置1～24小时，温度控制在30～100℃，并球磨24～72小时；
S3：坯体的成型：将制备好的陶瓷料浆倒入事先准备好的模具中，并将其放入冻干机内，冻干12～72小时，冻干机的温度控制在-10℃～-60℃；
S4：烧结工艺：将冻干的坯体放入坩埚内，采用粒度为200nm的氧化铝粉末进行包覆；
S5：将坩埚放入马弗炉内，在500～900℃的温度中恒温烧结1～24小时。
本实施例得到的陶瓷超滤膜过滤层孔径主要集中于100nm左右，孔隙率为 55％～70％，抗压强度为31～42MPa。
实施例2：
一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜的制备方法，其具体按照以下步骤实施：
S1：依次向球磨罐内加入1500目钛粉(质量分数为5％)、明胶(质量分数为5％)、分散剂(质量分数为5％)、去离子水85％、氧化锆球；
S2：放入烘箱内放置12小时，温度控制在50℃，并球磨72小时；
S3：坯体的成型：将制备好的陶瓷料浆倒入事先准备好的模具中，并将其放入冻干机内，冻干72小时，冻干机的温度控制在-10℃；
S4：烧结工艺：将冻干的坯体放入坩埚内，采用粒度为100nm的氧化铝粉末进行包覆；
S5：将坩埚放入马弗炉内，在900℃的温度中恒温烧结24小时。
本实施例得到的氧化钛多孔陶瓷孔隙率为65％～80％，抗压强度为25～40 MPa。
本实施例得到的陶瓷超滤膜过滤层孔径主要集中于80nm左右，孔隙率为 65％～80％，抗压强度为28～43MPa。
实施例3：
一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜的制备方法，其具体按照以下步骤实施：
S1：依次向球磨罐内加入1000目钛粉(质量分数为15％)、明胶(质量分数为1％)、分散剂(质量分数为4％)、去离子水80％、氧化锆球；
S2：放入烘箱内放置12小时，温度控制在50℃，并球磨72小时；
S3：坯体的成型：将制备好的陶瓷料浆倒入事先准备好的模具中，并将其放入冻干机内，冻干72小时，冻干机的温度控制在-10℃；
S4：烧结工艺：将冻干的坯体放入坩埚内，采用粒度为50nm的氧化铝粉末进行包覆；
S5：将坩埚放入马弗炉内，在800℃的温度中恒温烧结24小时。
本实施例得到的陶瓷超滤膜过滤层孔径主要集中于40nm左右，孔隙率为 15％～30％，抗压强度为20～35MPa。
实施例4：
一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜的制备方法，其具体按照以下步骤实施：
S1：依次向球磨罐内加入2000目钛粉(质量分数为25％)、明胶(质量分数为5％)、分散剂(质量分数为1％)、去离子水69％、氧化锆球；
S2：放入烘箱内放置12小时，温度控制在50℃，并球磨72小时；
S3：坯体的成型：将制备好的陶瓷料浆倒入事先准备好的模具中，并将其放入冻干机内，冻干72小时，冻干机的温度控制在-10℃；
S4：烧结工艺：将冻干的坯体放入坩埚内，采用粒度为20nm的氧化铝粉末进行包覆；
S5：将坩埚放入马弗炉内，在700℃的温度中恒温烧结24小时。
本实施例得到的陶瓷超滤膜过滤层孔径主要集中于10nm左右，孔隙率为 65％～80％，抗压强度为20～30MPa。
本发明通过冷冻铸造与反应烧结相结合的方法，使梯度多孔结构陶瓷超滤膜一步成型，其过滤层孔径主要集中于50nm左右，同时陶瓷的烧结温度降低了 500℃～700℃，工艺流程简单，极大节约了成本，解决了现有技术中多孔陶瓷材料一般为闭孔、瓷烧结温度太高、制备工艺复杂，成本消耗大的问题，在环保器械领域有广泛的应用前景。
本发明中未做详细描述的内容均为现有技术。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (10)
1.一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜，其特征在于，包括陶瓷支撑结构(1)及Al2O3-TiO2过滤结构(2)，所述Al2O3-TiO2过滤结构(2)周围附有若干毛刺(3)，所述Al2O3-TiO2过滤结构(2)及其毛刺(3)环绕于陶瓷支撑结构(1)周围，形成多梯度多孔过滤结构。
2.根据权利要求1所述的一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜，其特征在于，所述陶瓷超滤膜的孔径为100nm左右，孔隙率为55％～70％，抗压强度为31～42MPa。
3.根据权利要求1所述的一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜的制备方法，其特征在于，其包括以下步骤：
S1：依次向球磨罐内加入钛粉、明胶、分散剂、去离子水及氧化锆球；
S2：放入烘箱内放置1～24小时，温度控制在30～100℃，并球磨24～72小时；
S3：坯体的成型：将制备好的陶瓷料浆倒入事先准备好的模具中，并将其放入冻干机内，冻干12～72小时，冻干机的温度控制在-10℃～-60℃；
S4：烧结工艺：将冻干的坯体放入坩埚内，采用氧化铝粉末进行包覆；
S5：将坩埚放入马弗炉内，在500～900℃的温度中恒温烧结1～24小时。
4.根据权利要求3所述的一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜的制备方法，其特征在于，所述S1中，钛粉的粒度为500目～4000目，钛粉的质量分数为：5％～50％，明胶的质量分数为：0％～5％，分散剂的质量分数为：0％～5％，其余均为去离子水。
5.根据权利要求3所述的一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜的制备方法，其特征在于，所述S1中钛粉的粒度为800目～1500目，料浆中钛粉的质量分数为15％～30％，明胶的质量分数为2％～3％，分散剂的质量分数为2％～3％；所述2中烘箱内放置时间为12～16小时，球磨时间为30～50小时，其余均为去离子水。
6.根据权利要求3所述的一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜的制备方法，其特征在于，所述S3中，冻干时间为18～64小时，冻干机温度控制为-20℃～-50℃。
7.根据权利要求3所述的一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜的制备方法，其特征在于，所述S3中，冻干时间为30～60小时，冻干机温度控制为-30℃～-45℃。
8.根据权利要求3所述的一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜的制备方法，其特征在于，所述S5中，马弗炉温度控制在850℃，保温4～20小时。
9.根据权利要求3所述的一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜的制备方法，其特征在于，所述S5中，马弗炉温度控制在750℃，保温5～18小时。
10.根据权利要求3至9任一项所述的一种Al2O3-TiO2梯度多孔结构陶瓷超滤膜的制备方法，其特征在于，所述S2中，氧化锆球与浆料的体积比为2：1；所述S3中所用的模具为金属模具或聚四氟乙烯模具；所述S4中包覆所用的氧化铝粉末粒度为30nm～500nm。
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