CN113914094A - 一种碳酸钙/聚合物纳米纤维复合膜的制备方法 - Google Patents
一种碳酸钙/聚合物纳米纤维复合膜的制备方法 Download PDFInfo
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Abstract
本发明涉及过滤材料制备技术领域，尤其涉及一种碳酸钙/聚合物纳米纤维复合膜的制备方法。共混静电纺丝法制备的有机‑无机杂化纳米纤维膜，力学强度小，不能直接作为污水处理的过滤膜。基于上述问题，本发明提供一种碳酸钙/聚合物纳米纤维复合膜的制备方法，其将静电纺丝与微生物诱导矿化技术相结合，尿素在微生物的新陈代谢作用下分解产生碳酸根离子，碳酸根离子与钙离子发生共沉淀，在相互交错地高分子聚合物纤维丝表面生成碳酸钙结晶体，高分子聚合物纤维丝类似于“钢筋结构”，而碳酸钙结晶体类似于“混凝土”，碳酸钙结晶体的形成显著增强了高分子聚合物纤维膜的力学强度，可使其应用于污水处理中的过滤膜，并产生较好的过滤效果。
Description
技术领域
本发明涉及过滤材料制备技术领域，尤其涉及一种碳酸钙/聚合物纳米纤维复合膜的制备方法。
背景技术
静电纺丝是一种简单、快速、高效的纳米纤维制备方法。其操作方便，装置简单主要由高压电源、带导电喷丝头的贮液装置、收集器组成。其制备的纳米纤维膜，孔隙率高、比表面积大、生物相容性好，被广泛应用在生物组织工程支架，伤口修复、药物控释、催化载体、过滤介质和生物传感器等领域。
微生物诱导矿化技术是一种新颖的无机碳酸盐晶体制备技术，它是指在微生物新陈代谢作用下分解脲素产生碳酸根离子与金属离子结合而形成固态碳酸盐沉淀的过程。它具有环境友好、反应温和等优点，是一种环境友好的绿色碳酸盐晶体制备技术。微生物诱导矿化技术已经广泛应用于岩土加固、土壤修复等领域。
有机-无机杂化静电纺丝纳米纤维膜是以一个尺寸在微米至纳米级的聚合物静电纺丝纳米纤维为基体材料，在其表面、间隙或内部填充包覆数层无机材料而形成的一种复合多相结构的有机-无机杂化材料，属于功能性纳米纤维膜，其在催化、过滤、吸附等领域具有重要的应用。
目前，制备有机-无机杂化纳米纤维膜最常用的方法为共混静电纺丝法，这种方法只是简单的将无机纳米材料与高分子聚合纤维进行复合，无机纳米材料对高分子聚合物纤维的力学性能贡献不大，这种有机-无机杂化纳米纤维膜强度小，不能直接作为污水处理的过滤膜。
发明内容
针对现有技术中存在的问题，本发明要解决的技术问题是：共混静电纺丝法制备的有机-无机杂化纳米纤维膜，力学强度小，不能直接作为污水处理的过滤膜。
本发明解决其技术问题所采用的技术方案是：本发明提供一种碳酸钙/聚合物纳米纤维复合膜的制备方法，包括以下步骤；
(1)将高分子聚合物溶解在有机溶剂中，得到质量浓度为8-12wt％的高分子聚合物溶液，采用静电纺丝技术将聚合物溶液纺成纳米纤维膜；
(2)裁切步骤(1)得到纳米纤维膜，采用抽滤的方式将微生物培养溶液与纳米纤维膜复合，获得负载微生物的纳米纤维膜；
(3)将步骤(2)中负载微生物的纳米纤维膜置于含有钙离子、尿素的水溶液中浸泡，水溶液中钙离子的浓度为1-1000mmol/L，水溶液中尿素的浓度为1-1000mmol/L，在微生物代谢尿素产生碳酸根，钙离子与碳酸根在纳米纤维膜上形成多孔碳酸钙结晶体，反应完成后，去离子水冲洗未结合的碳酸盐晶体，干燥后，即得到碳酸钙/聚合物纳米纤维复合膜。
具体地，所述高分子聚合物为聚丙烯腈、聚乳酸、聚己内酯、聚氨酯、聚甲基丙烯酸甲酯、聚苯乙烯、聚偏氟乙烯或聚碳酸酯。
具体地，所述有机溶剂为N,N-二甲基甲酰胺、二氯甲烷或丙酮。
具体地，所述纳米纤维膜的厚度为100μm。
具体地，所述静电纺丝的电压为15-20kV，纺丝口至接受器的距离为15-20cm，纺丝口直径为0.6mm。
具体地，所述微生物培养液中的微生物为产脲酶菌。
具体地，所述微生物培养液中微生物浓度以吸光度表示OD＝0.1-1.0。
具体地，所述产脲酶菌为巴氏芽孢杆菌、蜡样芽孢杆菌或赖氨酸芽孢杆菌。
本发明的有益效果是：
(1)本发明将静电纺丝与微生物诱导矿化技术相结合，尿素在微生物的新陈代谢作用下分解产生碳酸根离子，碳酸根离子与钙离子发生共沉淀，在相互交错地高分子聚合物纤维丝表面生成碳酸钙结晶体，高分子聚合物纤维丝类似于“钢筋结构”，而碳酸钙结晶体类似于“混凝土”，碳酸钙结晶体的形成显著增强了高分子聚合物纤维膜的力学强度，可使其应用于污水处理中的过滤膜，并产生较好的过滤效果；
(2)本发明在高分子聚合物纤维丝表面形成生物诱导碳酸钙结晶体是多孔的结构，不仅可以增强纤维膜的力学强度，还可以进一步提高过滤效果。
附图说明
图1：实施例1所获碳酸钙/聚合物纳米纤维复合膜的SEM图。
图2：对比例1所获纤维膜的SEM图。
具体实施方式
现在结合实施例对本发明作进一步详细的说明。
本发明以下实施例中所采用的有机溶剂为N,N-二甲基甲酰胺、二氯甲烷或丙酮。
本发明以下实施例中静电纺丝的电压为15-20kV，纺丝口至接受器的距离为15-20cm，纺丝口直径为0.6mm。
本发明以下实施例中所采用的产脲酶菌为巴氏芽孢杆菌、蜡样芽孢杆菌或赖氨酸芽孢杆菌。
实施例1
碳酸钙/聚合物纳米纤维复合膜的制备方法，按照以下步骤制备；
(1)将重均分子量为150000g/mol的聚丙烯腈溶解在N,N-二甲基甲酰胺有机溶剂中，得到质量浓度为10wt％的高分子聚合物溶液，采用静电纺丝技术将聚合物溶液纺成厚度为100μm的纳米纤维膜；
(2)裁切步骤(1)得到直径为4.0cm的圆形纳米纤维膜，采用抽滤的方式将20mL OD＝1.0的巴氏芽孢杆菌微生物培养溶液与纳米纤维膜复合，获得负载微生物的纳米纤维膜；
(3)将步骤(2)中负载微生物的纳米纤维膜置于30mL含有钙离子、尿素的水溶液中浸泡30min，水溶液中钙离子的浓度为500mmol/L，水溶液中尿素的浓度为500mmol/L，在微生物代谢尿素产生碳酸根，钙离子与碳酸根在纳米纤维膜上形成多孔碳酸钙结晶体，反应完成后，去离子水冲洗未结合的碳酸盐晶体，干燥后，即得到如图1所示的碳酸钙/聚合物纳米纤维复合膜。
实施例2
碳酸钙/聚合物纳米纤维复合膜的制备方法，按照以下步骤制备；
(1)将重均分子量为100000g/mol的聚乳酸溶解在二氯甲烷有机溶剂中，得到质量浓度为8wt％的高分子聚合物溶液，采用静电纺丝技术将聚合物溶液纺成厚度为100μm的纳米纤维膜；
(2)裁切步骤(1)得到直径为4.0cm的圆形纳米纤维膜，采用抽滤的方式将20mL OD＝0.5的蜡样芽孢杆菌微生物培养溶液与纳米纤维膜复合，获得负载微生物的纳米纤维膜；
(3)将步骤(2)中负载微生物的纳米纤维膜置于30mL含有钙离子、尿素的水溶液中浸泡30min，水溶液中钙离子的浓度为1mmol/L，水溶液中尿素的浓度为1mmol/L，在微生物代谢尿素产生碳酸根，钙离子与碳酸根在纳米纤维膜上形成多孔碳酸钙结晶体，反应完成后，去离子水冲洗未结合的碳酸盐晶体，干燥后，即得到碳酸钙/聚合物纳米纤维复合膜。
实施例3
碳酸钙/聚合物纳米纤维复合膜的制备方法，按照以下步骤制备；
(1)将重均分子量为100000g/mol聚苯乙烯溶解在N,N-二甲基甲酰胺有机溶剂中，得到质量浓度为12wt％的高分子聚合物溶液，采用静电纺丝技术将聚合物溶液纺成厚度为100μm的纳米纤维膜；
(2)裁切步骤(1)得到直径为4.0cm的圆形纳米纤维膜，采用抽滤的方式将20mL OD＝0.1的赖氨酸芽孢杆菌微生物培养溶液与纳米纤维膜复合，获得负载微生物的纳米纤维膜；
(3)将步骤(2)中负载微生物的纳米纤维膜置于30mL含有钙离子、尿素的水溶液中浸泡30min，水溶液中钙离子的浓度为1000mmol/L，水溶液中尿素的浓度为1000mmol/L，在微生物代谢尿素产生碳酸根，钙离子与碳酸根在纳米纤维膜上形成多孔碳酸钙结晶体，反应完成后，去离子水冲洗未结合的碳酸盐晶体，干燥后，即得到碳酸钙/聚合物纳米纤维复合膜。
实施例4
碳酸钙/聚合物纳米纤维复合膜的制备方法，按照以下步骤制备；
(1)将重均分子量为100000g/mol聚偏氟乙烯溶解在N,N-二甲基甲酰胺与丙酮按照体积比8:2混合的有机溶剂中，得到质量浓度为9wt％的高分子聚合物溶液，采用静电纺丝技术将聚合物溶液纺成厚度为100μm的纳米纤维膜；
(2)裁切步骤(1)得到直径为4.0cm的圆形纳米纤维膜，采用抽滤的方式将20mL，OD＝0.5的微生物培养溶液与纳米纤维膜复合，获得负载微生物的纳米纤维膜；
(3)将步骤(2)中负载微生物的纳米纤维膜置于30mL含有钙离子、尿素的水溶液中浸泡30min，水溶液中钙离子的浓度为800mmol/L，水溶液中尿素的浓度为800mmol/L，在微生物代谢尿素产生碳酸根，钙离子与碳酸根在纳米纤维膜上形成多孔碳酸钙结晶体，反应完成后，去离子水冲洗未结合的碳酸盐晶体，干燥后，即得到碳酸钙/聚合物纳米纤维复合膜。
实施例5
碳酸钙/聚合物纳米纤维复合膜的制备方法，按照以下步骤制备；
(1)将重均分子量为100000g/mol聚甲基丙烯酸甲酯溶解在N,N-二甲基甲酰胺中，得到质量浓度为10wt％的高分子聚合物溶液，采用静电纺丝技术将聚合物溶液纺成厚度为100μm的纳米纤维膜；
(2)裁切步骤(1)得到直径为4.0cm的圆形纳米纤维膜，采用抽滤的方式将20mL OD＝1.0的微生物培养溶液与纳米纤维膜复合，获得负载微生物的纳米纤维膜；
(3)将步骤(2)中负载微生物的纳米纤维膜置于30mL含有钙离子、尿素的水溶液中浸泡30min，水溶液中钙离子的浓度为600mmol/L，水溶液中尿素的浓度为600mmol/L，在微生物代谢尿素产生碳酸根，钙离子与碳酸根在纳米纤维膜上形成多孔碳酸钙结晶体，反应完成后，去离子水冲洗未结合的碳酸盐晶体，干燥后，即得到碳酸钙/聚合物纳米纤维复合膜。
实施例6同实施例1，不同之处在于，实施例6采用的高分子聚合物为重均分子量为150000g/mol的聚已内酯。
实施例7同实施例1，不同之处在于，实施例7采用的高分子聚合物为重均分子量为150000g/mol的聚氨酯。
实施例8同实施例1，不同之处在于，实施例8采用的高分子聚合物为重均分子量为150000g/mol的聚碳酸酯。
实施例9同实施例1，不同之处在于，实施例9采用的高分子聚合物为重均分子量为150000g/mol的聚甲基丙烯酸甲酯。
实施例10同实施例1，不同之处在于，实施例10采用的高分子聚合物为重均分子量为150000g/mol的聚苯乙烯。
实施例11同实施例1，不同之处在于，实施例11采用的高分子聚合物为重均分子量为150000g/mol的聚偏氟乙烯。
对比例1同实施例1，不同之处在于，对比例1在步骤(1)得到的高分子聚合物溶液中加入纳米碳酸钙，纳米碳酸钙的加入量为高分子聚合物质量的200％，搅拌均匀后，然后采用静电纺丝技术将混合物溶液纺成如图2所示的纤维膜。
性能测试：
对本发明实施例1-11以及对比例1所获纤维膜，进行相关性能测试：
力学性能测试：拉伸强度和断裂伸长率：使用微机控制电子万能测试机测试纤维膜的拉伸性能，按照GB/T13022塑料薄膜拉伸性能方法标准。
过滤效率：按照依据GB/T2626-2006检测滤芯膜的过滤效率并测试阻力压降。
污水处理效率：将本发明制得的直径为4.0cm的圆形碳酸钙/聚合物纳米纤维复合膜，放入污水处理装置，分别使用有机物污水、含氮污染物污水和含汞污水，水温度为25℃，首先采用BOD测试仪测定初始BOD，采用总氮测试仪测试总氮浓度，采用ICP-OES测试仪测试总汞浓度，然后测一次过滤后对应污染物浓度。
具体测试结果见表1：
表1
以上述依据本发明的理想实施例为启示，通过上述的说明内容，相关工作人员完全可以在不偏离本项发明技术思想的范围内，进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容，必须要根据权利要求范围来确定其技术性范围。
Claims (7)
1.一种碳酸钙/聚合物纳米纤维复合膜的制备方法，其特征在于，包括以下步骤；
（1）将高分子聚合物溶解在有机溶剂中，得到质量浓度为8-12wt%的高分子聚合物溶液，采用静电纺丝技术将聚合物溶液纺成纳米纤维膜；
（2）裁切步骤（1）得到纳米纤维膜，采用抽滤的方式将微生物培养溶液与纳米纤维膜复合，获得负载微生物的纳米纤维膜；
（3）将步骤（2）中负载微生物的纳米纤维膜置于含有钙离子、尿素的水溶液中浸泡，水溶液中钙离子的浓度为1-1000mmol/L，水溶液中尿素的浓度为1-1000mmol/L，反应完成后，去离子水冲洗未结合的碳酸盐晶体，干燥后，即得到碳酸钙/聚合物纳米纤维复合膜。
2.根据权利要求1所述的一种碳酸钙/聚合物纳米纤维复合膜的制备方法，其特征在于，所述高分子聚合物为聚丙烯腈、聚乳酸、聚己内酯、聚氨酯、聚甲基丙烯酸甲酯、聚苯乙烯、聚偏氟乙烯或聚碳酸酯。
3.根据权利要求1所述的一种碳酸钙/聚合物复合纳米纤维膜的制备方法，其特征在于，所述有机溶剂为N,N-二甲基甲酰胺、二氯甲烷或丙酮。
4.根据权利要求1所述的一种碳酸钙/聚合物纳米纤维复合膜的制备方法，其特征在于，所述静电纺丝的电压为15-20 kV，纺丝口至接受器的距离为15-20 cm，纺丝口直径为0.6mm。
5.根据权利要求1所述的一种碳酸钙/聚合物纳米纤维复合膜的制备方法，其特征在于，所述微生物培养液中的微生物为产脲酶菌。
6.根据权利要求5所述的一种碳酸钙/聚合物纳米纤维复合膜的制备方法，其特征在于，所述微生物培养液中微生物浓度以吸光度表示OD=0.1-1.0。
7.根据权利要求5所述的一种碳酸钙/聚合物纳米纤维复合膜的制备方法，其特征在于，所述产脲酶菌为巴氏芽孢杆菌、蜡样芽孢杆菌或赖氨酸芽孢杆菌。
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