CN114517359A - 基于含铬废革屑水解物-金属有机框架制备柔性电磁屏蔽纳米纤维薄膜的方法 - Google Patents
基于含铬废革屑水解物-金属有机框架制备柔性电磁屏蔽纳米纤维薄膜的方法 Download PDFInfo
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Abstract
本发明公开了一种基于含铬废革屑水解物‑金属有机框架制备柔性电磁屏蔽纳米纤维薄膜的方法。将制革加工过程产生的蓝湿革废革屑经过酸水解得到含铬废革屑水解物,将其与聚丙烯腈和金属有机框架充分混合,然后通过静电纺丝法制备含铬废革屑水解物/聚丙烯腈/金属有机框架纳米纤维薄膜,再将含铬废革屑水解物/聚丙烯腈/金属有机框架纳米纤维薄膜依次置于空气气氛中和氩气气氛中进行预氧化及碳化,碳化后得到柔性电磁屏蔽纳米纤维薄膜。该发明将制革加工过程产生的蓝湿革废革屑回收利用,工艺简单,制得的柔性电磁屏蔽纳米纤维薄膜电导率可以达到100 S/m,最大电磁屏蔽效能可以达到23 dB。
Description
技术领域
本发明属于柔性电子材料领域,具体涉及了制备柔性电磁屏蔽纳米纤维薄膜及其制备方法。
背景技术
随着通信和电子设备的蓬勃发展,电磁波辐射污染会对包括人类在内的生物造成危害,进而备受关注。因此,开发高性能的电磁干扰屏蔽材料成为目前的研究热点之一。金属材料具有良好的导电性、高密度、高刚度等特点,能够有效地反射电磁波,一直是电磁屏蔽的首选材料。然而,金属材料质量重、密度高、易腐蚀,难以满足柔性电子器件等新兴领域日益增长的需求。相比于传统的金属系电磁屏蔽材料,碳基复合材料具有质量轻、耐腐蚀、易加工、导电性高等优点,受到了广泛的关注。
皮革作为一类生物质材料,来源丰富,降解性好,应用广泛。然而,在皮革生产过程中产生了大量的废革屑,难以处理,常用的处理方式是焚烧或填埋,会导致严重的环境问题,且造成大量蛋白质浪费。因此合理处理皮革废革屑十分必要。研究者将废革屑水解得到胶原衍生物,具有良好的亲和性,且含有很多可离子化基团,有利于对其进行交联改性实现功能化。
金属有机框架材料是近十年来发展迅速的一种配位化合物,是指过渡金属离子与有机配体通过自组装形成的具有周期性网络结构的晶体多孔材料,其具有高孔隙率、低密度、大比表面积等优点。此外,金属有机框架高温热解时可以生成金属/多孔碳纳米复合材料,具有良好的磁损耗、介电损耗特性和独特的孔结构,可以通过协同作用、界面极化和多重反射/散射等机制有效衰减入射的电磁波,因此是一种潜在的性能优良的电磁波吸收材料。
静电纺丝作为相对容易的纳米纤维制备方法,具有大规模连续生产纳米纤维的潜力。制成的纳米纤维薄膜具有多孔结构、较高的比表面积。Ji等人以ZIF-8和聚丙烯腈为原料,采用静电纺丝法和高温碳化法相结合,制备了轻质、柔韧的多孔碳包覆金属粒子纳米纤维膜,并将其用作有效的电磁干扰屏蔽材料(Weihua Gu, Jing Lv, Bin Quan, et al.Achieving MOF-derived one-dimensional porous ZnO/C nanofiber with lightweightand enhanced microwave response by an electrospinning method[J]. Journal ofAlloys and Compounds, 2019, 806 (5).)。
本发明公开了一种基于含铬废革屑水解物-金属有机框架制备柔性电磁屏蔽纳米纤维薄膜的方法。将含铬废革屑水解物、聚丙烯腈、金属有机框架充分混合后通过静电纺丝法制备含铬废革屑水解物/聚丙烯腈/金属有机框架纳米纤维薄膜,再将其经过预氧化及碳化获得柔性电磁屏蔽纳米纤维薄膜。该柔性电磁屏蔽纳米纤维薄膜可应用在柔性电子器件上,可以保护电路及设备的正常运行,在柔性电子领域具有广泛的应用。同时,为制革废革屑的资源化利用提供新思路。
发明内容
本发明提供了一种制备柔性电磁屏蔽纳米纤维薄膜的简单方法。以含铬废革屑水解物、聚丙烯腈、金属有机框架为原料,充分混合后通过静电纺丝法制备含铬废革屑水解物/聚丙烯腈/金属有机框架纳米纤维薄膜,再将其经过预氧化及碳化获得柔性电磁屏蔽纳米纤维薄膜。该电磁屏蔽薄膜电导率可达到100 S/m,最大电磁屏蔽效能在10.4 GHz可以达到23 dB。
本发明为解决上述技术问题采用如下技术方案:
基于含铬废革屑水解物-金属有机框架制备柔性电磁屏蔽纳米纤维薄膜的方法,将制革加工过程产生的蓝湿革废革屑经过酸水解得到含铬废革屑水解物,将其与聚丙烯腈和金属有机框架充分混合,然后通过静电纺丝法制备含铬废革屑水解物/聚丙烯腈/金属有机框架纳米纤维薄膜,再将含铬废革屑水解物/聚丙烯腈/金属有机框架纳米纤维薄膜依次置于空气气氛中和氩气气氛中进行预氧化及碳化,碳化后得到柔性电磁屏蔽纳米纤维薄膜。
具体包括以下步骤:
(1)含铬废革屑水解物的制备:
第一次预处理:称取羊皮蓝湿革废革屑25~30 g,然后加入250~300 g的水,12~15g的硫酸,在30~35 ℃水浴中搅拌6~7 h,抽滤收集产物置于冰箱冷藏保存;
第二次预处理:将第一次预处理后收集的产物加入300~350 g的水,16~20 g的硫酸,在30~35 ℃水浴中搅拌6~7 h,抽滤收集产物置于冰箱冷藏保存;
酸解及提取:将第二次预处理后收集的产物加入100~150 g的水,9~12 g的冰乙酸,在70~75 ℃水浴中搅拌6~7 h,得到的含铬废革屑水解液,在含铬废革屑水解液中加入氯化钠盐析,静置收集含铬废革屑水解物将其干燥后备用;
(2)含铬废革屑水解物/聚丙烯腈/金属有机框架纳米纤维薄膜的制备:
将0.06~0.18 g的金属有机框架置于6~8 mL的DMF溶液中超声分散15~20 min,向分散液加入0.2~0.6 g含铬废革屑水解物与0.2~0.6 g的聚丙烯腈,将其置于80~90 ℃的水浴中磁力搅拌充分混合形成均匀的纺丝液,然后进行静电纺丝制得含铬废革屑水解物/聚丙烯腈/金属有机框架纳米纤维薄膜;
(3)柔性电磁屏蔽纳米纤维薄膜的制备:
将含铬废革屑水解物/聚丙烯腈/金属有机框架纳米纤维薄膜置于240~260 ℃的空气气氛下进行预氧化,将预氧化后的纳米纤维薄膜取出置于650~850 ℃的氩气气氛中碳化,得到柔性电磁屏蔽纳米纤维薄膜。
所述金属有机框架为ZIF-67。
所述静电纺丝的纺丝条件为:纺丝液置于10 mL的注射器中,注射器针头为0.4~0.7 mm,接收屏采用铝箔接负极接收,针头与接收屏距离为10~15 cm。
本发明将制革加工过程产生的蓝湿革废革屑回收利用,工艺简单,制得的柔性电磁屏蔽纳米纤维薄膜电导率可以达到100 S/m,最大电磁屏蔽效能可以达到23 dB。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明,但不应该将此理解为本发明上述主题的范围仅限于以下的实施例,凡基于本发明上述内容实现的技术均属于本发明的范围。
实施例1:
(1)含铬废革屑水解物的制备:
第一次预处理:称取羊皮蓝湿革废革屑25 g,然后加入250 g的水,12 g的硫酸,在35 ℃水浴中搅拌6 h,抽滤收集产物置于冰箱冷藏保存。
第二次预处理:将第一次预处理后收集的产物加入350 g的水,16 g的硫酸,在35℃水浴中搅拌6 h,抽滤收集产物置于冰箱冷藏保存。
酸解及提取:将第二次预处理后收集的产物加入100 g的水,12 g的冰乙酸,在75℃水浴中搅拌6 h,得到的含铬废革屑水解液,在含铬废革屑水解液中加入氯化钠盐析,提取沉淀进行干燥得到含铬废革屑水解物。
(2)含铬废革屑水解物/聚丙烯腈/ZIF-67纳米纤维薄膜的制备:
将0.12 g的ZIF-67置于7 mL的DMF溶液中超声分散15 min,向分散液加入0.27 g含铬废革屑水解物与0.57 g的聚丙烯腈置于85 ℃的水浴中磁力搅拌充分混合形成均匀的纺丝液,然后进行静电纺丝制得含铬废革屑水解物/聚丙烯腈/ ZIF-67纳米纤维薄膜。纺丝条件:将纺丝液至于10 mL的注射器中,注射器针头为0.5 mm,静电纺丝过程中喷出流速0.1mL/h,接收屏采用铝箔接负极接收,针头与接收屏距离为15 cm。
(3)柔性电磁屏蔽薄膜的制备
将含铬废革屑水解物/聚丙烯腈/ZIF-67纳米纤维薄膜置于250 ℃的空气气氛下进行预氧化,将预氧化后的纳米纤维薄膜取出置于750 ℃的氩气气氛中碳化得到柔性电磁屏蔽纳米纤维薄膜。
实施例2:
(1)含铬废革屑水解物的制备:
第一次预处理:称取羊皮蓝湿革废革屑30 g,然后加入300 g的水,15 g的硫酸,在35 ℃水浴中搅拌6 h,抽滤收集产物置于冰箱冷藏保存。
第二次预处理:将第一次预处理后收集的产物加入400 g的水,18 g的硫酸,在35℃水浴中搅拌6 h,抽滤收集产物置于冰箱冷藏保存。
酸解及提取:将第二次预处理后收集的产物加入120 g的水,15 g的冰乙酸,在75℃水浴中搅拌6 h,得到的含铬废革屑水解液,在含铬废革屑水解液中加入氯化钠盐析,提取沉淀进行干燥得到含铬废革屑水解物。
(2)含铬废革屑水解物/聚丙烯腈/ZIF-67纳米纤维薄膜的制备:
将0.15 g的ZIF-67置于8 mL的DMF溶液中超声分散20 min,向分散液加入0.4 g含铬废革屑水解物与0.4 g的聚丙烯腈置于90 ℃的水浴中磁力搅拌充分混合形成均匀的纺丝液,然后进行静电纺丝制得含铬废革屑水解物/聚丙烯腈/ ZIF-67纳米纤维薄膜。纺丝条件:将纺丝液至于10 mL的注射器中,注射器针头为0.5 mm,静电纺丝过程中喷出流速0.1mL/h,接收屏采用铝箔接负极接收,针头与接收屏距离为15 cm。
(3)柔性电磁屏蔽薄膜的制备
将含铬废革屑水解物/聚丙烯腈/ZIF-67纳米纤维薄膜置于260 ℃的空气气氛下进行预氧化,将预氧化后的纳米纤维薄膜取出置于850 ℃的氩气气氛中碳化得到柔性电磁屏蔽纳米纤维薄膜。
以上实施例仅用于对本发明的发明内容作进一步的详细描述,但不应该将此理解为本发明上述主题的范围仅限于上述实施例。在不脱离本发明上述技术思想情况下,根据本领域普通的技术知识和常用手段,做出的各种替换和变更,均应包括在本发明应保护的范围内。
Claims (4)
1.基于含铬废革屑水解物-金属有机框架制备柔性电磁屏蔽纳米纤维薄膜的方法,其特征在于,将制革加工过程产生的蓝湿革废革屑经过酸水解得到含铬废革屑水解物,将其与聚丙烯腈和金属有机框架充分混合,然后通过静电纺丝法制备含铬废革屑水解物/聚丙烯腈/金属有机框架纳米纤维薄膜,再将含铬废革屑水解物/聚丙烯腈/金属有机框架纳米纤维薄膜依次置于空气气氛中和氩气气氛中进行预氧化及碳化,碳化后得到柔性电磁屏蔽纳米纤维薄膜。
2.根据权利要求1所述的基于含铬废革屑水解物-金属有机框架制备柔性电磁屏蔽纳米纤维薄膜的方法,其特征在于:
具体包括以下步骤:
(1)含铬废革屑水解物的制备:
第一次预处理:称取羊皮蓝湿革废革屑25~30 g,然后加入250~300 g的水,12~15 g的硫酸,在30~35 ℃水浴中搅拌6~7 h,抽滤收集产物置于冰箱冷藏保存;
第二次预处理:将第一次预处理后收集的产物加入300~350 g的水,16~20 g的硫酸,在30~35 ℃水浴中搅拌6~7 h,抽滤收集产物置于冰箱冷藏保存;
酸解及提取:将第二次预处理后收集的产物加入100~150 g的水,9~12 g的冰乙酸,在70~75 ℃水浴中搅拌6~7 h,得到的含铬废革屑水解液,在含铬废革屑水解液中加入氯化钠盐析,静置收集含铬废革屑水解物将其干燥后备用;
(2)含铬废革屑水解物/聚丙烯腈/金属有机框架纳米纤维薄膜的制备:
将0.06~0.18 g的金属有机框架置于6~8 mL的DMF溶液中超声分散15~20 min,向分散液加入0.2~0.6 g含铬废革屑水解物与0.2~0.6 g的聚丙烯腈,将其置于80~90 ℃的水浴中磁力搅拌充分混合形成均匀的纺丝液,然后进行静电纺丝制得含铬废革屑水解物/聚丙烯腈/金属有机框架纳米纤维薄膜;
(3)柔性电磁屏蔽纳米纤维薄膜的制备:
将含铬废革屑水解物/聚丙烯腈/金属有机框架纳米纤维薄膜置于240~260 ℃的空气气氛下进行预氧化,将预氧化后的纳米纤维薄膜取出置于650~850 ℃的氩气气氛中碳化,得到柔性电磁屏蔽纳米纤维薄膜。
3.根据权利要求2所述的基于含铬废革屑水解物-金属有机框架制备柔性电磁屏蔽纳米纤维薄膜的方法,其特征在于:所述金属有机框架为ZIF-67。
4.根据权利要求3所述的基于含铬废革屑水解物-金属有机框架制备柔性电磁屏蔽纳米纤维薄膜的方法,其特征在于:
所述静电纺丝的纺丝条件为:纺丝液置于10 mL的注射器中,注射器针头为0.4~0.7mm,接收屏采用铝箔接负极接收,针头与接收屏距离为10~15 cm。
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CN110137461A (zh) * | 2019-05-10 | 2019-08-16 | 陕西科技大学 | 锂离子电池用mof衍生的钴氧化物碳纳米纤维柔性电极材料及其制备方法 |
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