CN106592197A - 一种具有核壳结构的多功能静电纺丝发光纤维的制备方法 - Google Patents
一种具有核壳结构的多功能静电纺丝发光纤维的制备方法 Download PDFInfo
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Abstract
本发明公开了一种具有核壳结构的多功能静电纺丝发光纤维的制备方法，第一步，采用静电纺丝技术制备稀土掺杂的纳米发光纤维；第二步，采用原子层沉积技术ALD在第一步制备的纳米发光纤维表面沉积一层功能无机材料；所述无机材料包括Al2O3、SiO2、TiO2、或Au、Ag。该项技术在保持了静电纺丝纤维的形貌的同时，并简单地实现静电纺丝纤维的核壳结构，赋予了稀土静电纺丝纤维的多种功能，拓宽了其应用范围，为获得同时具有多种功能如光、电、磁、热、声等性质的复合静电纺丝纤维的商品化生产，打下良好的技术基础。
Description
技术领域
本发明涉及具有核壳结构的多功能稀土静电纺丝纳米发光纤维材料的制备方法。
背景技术
静电纺丝技术是一种制备聚合物、无机物、有机物、无机/有机复合纳米纤维的通用技术，但是，通过静电纺丝技术获得核壳结构的纳米纤维较为困难。通常的做法是采用同轴静电纺丝技术，但其缺点是电纺参数不易控制，很难得到核层和壳层尺寸可控，且直径都很均匀的复合纤维。到目前为止，未有文献与专利报道，采用静电纺丝技术+ALD技术获得具有核壳结构的多功能稀土静电纺丝纳米发光纤维材料。
发明内容
本发明提供一种具有核壳结构的多功能静电纺丝发光纤维的制备方法。拓展其应用范围，使之能够应用在发光显示、荧光标记与检测、载药诊疗、太阳能电池等领域。
本项技术第一步采用静电纺丝技术制备稀土掺杂的纳米发光纤维；第二步，采用原子层沉积技术(ALD)在第一步制备的纳米发光纤维表面沉积一层功能无机材料(如Al2O3、SiO2、TiO2、或Au、Ag或其他材料)，获得多功能多用途的稀土纳米发光纤维材料。该项技术在保持了静电纺丝纤维的形貌的同时，并简单地实现静电纺丝纤维的核壳结构，赋予了稀土静电纺丝纤维的多种功能，拓宽了其应用范围，为获得同时具有多种功能如光、电、磁、热、声等性质的复合静电纺丝纤维的商品化，打下良好的技术基础。
本发明具体通过以下技术方案实现：
一种具有核壳结构的多功能静电纺丝发光纤维的制备方法，其特征在于：
第一步，采用静电纺丝技术制备稀土掺杂的纳米发光纤维；所述稀土掺杂的纳米发光纤维包括稀土氧化物、稀土氮化物、稀土氟化物、稀土铝酸盐、稀土钨钼酸盐。
第二步，采用原子层沉积技术ALD在第一步制备的纳米发光纤维表面沉积一层功能无机材料；所述无机材料包括Al2O3、SiO2、TiO2、或Au、Ag。
进一步地，在上述技术方案中，第一步，核壳结构纳米纤维的制备，将Ⅰ、Ⅱ加入到去离子水中溶解至透明澄清的溶液，PVP加入到该混合溶液中，搅拌1-4小时至澄清透明，在10-15kv的电压和10-30cm的接收距离下，进行纺丝，接收8小时以上，获得均匀的前驱体纤维；该前驱体纤维在真空烘箱中80-120℃干燥2-8小时；得到核壳结构纳米纤维；包括Gd2O3：Eu@Al2O3核壳结构纳米纤维。
所述Ⅰ选自Gd(NO3)3、Y(NO3)3、La(NO3)3、Lu(NO3)3；
所述Ⅱ选自Eu(NO3)3、Yb(NO3)3、Er(NO3)3、Tm(NO3)3、Sm(NO3)3、Ho(NO3)3、Nd(NO3)3、Pr(NO3)3、Dy(NO3)3、Ce(NO3)3、Tb(NO3)3。
进一步地，在上述技术方案中，Ⅰ：Ⅱ：去离子水：PVP加入量比为0.3-0.9g：0.015-0.045g：15-30ml：1.0-5.0g。
进一步地，在上述技术方案中，第二步：纳米纤维的包覆，将第一步制备的前驱体纳米纤维转移至ALD反应室内，采用烷基金属化合物或和挥发性的无机盐作为前驱体，水作为氧化剂，沉积温度100-250℃，前驱体吸附时间为10ms-50s，N2清洗时间为10ms-100s，水吸附时间为30ms-50s，氮气清洗时间为50ms-50ms；将最后制备的样品转入马弗炉中进行煅烧，升温速率1-10℃/min，加热至500-1000℃，并在此温度下保温2-6小时，获得核壳结构发光纳米纤维。
进一步地，在上述技术方案中，所述前驱体为三甲基铝TMA或二乙基锌或TiCl4。
进一步地，在上述技术方案中，使用高纯度的氩气作为运载气体，流量为100ml/min。
附图说明
图1为本发明静电纺丝技术+ALD技术获得核壳结构稀土纳米发光纤维的工艺示意图；
图2为实施例2中静电纺丝技术+ALD技术获得的核壳结构Gd2O3:Eu3+@ZnO复合纤维的TEM图和EDS谱；
图3为实施例1中静电纺丝技术+ALD技术获得的核壳结构的Gd2O3:Eu3+@Al2O3复合纤维的TEM图和EDS谱；
图4实施例3中静电纺丝技术+ALD技术获得的核壳结构的Gd2O3:Eu3+@TiO2复合纤维的TEM图。
具体实施方式
实施例1
Gd2O3：Eu@Al2O3核壳结构纳米纤维的制备
第一步：静电纺丝法制备Gd2O3：Eu前驱体纳米纤维
0.3gGd(NO3)3、0.015gEu(NO3)3加入到15ml去离子水中溶解至透明澄清的溶液，1.0gPVP加入到该混合溶液中，搅拌4个小时至澄清透明，在15kv的电压和20cm的接收距离下，进行纺丝，接收8小时以上，获得均匀的前驱体纤维。该前驱体纤维在真空烘箱中80℃干燥4小时。
第二步：Gd2O3：Eu纳米纤维的包覆
将第一步制备的前驱体纳米纤维转移至的ALD反应室内，采用三甲基铝(TMA)作为铝前驱体，水作为氧化剂，沉积温度150℃，三甲基铝吸附时间为1s，N2清洗时间为15s，水吸附时间为1s，氮气清洗时间为15s。将最后制备的样品转入马弗炉中进行煅烧，升温速率1℃/min，加热至800℃，并在此温度下保温3小时，获得Gd2O3：Eu@Al2O3核壳结构发光纳米纤维。
实施例2
Gd2O3：Eu@ZnO核壳结构纳米纤维的制备
第一步：静电纺丝法制备Gd2O3：Eu前驱体纳米纤维
0.3gGd(NO3)3、0.015gEu(NO3)3加入到15ml去离子水中溶解至透明澄清的溶液，1.0gPVP加入到该混合溶液中，搅拌4个小时至澄清透明，在15kv的电压和20cm的接收距离下，进行纺丝，接收8小时以上，获得均匀的前驱体纤维。该前驱体纤维在真空烘箱中80℃干燥4小时。
第二步：Gd2O3：Eu纳米纤维的包覆
将第一步制备的前驱体纳米纤维转移至的ALD反应室内，以二乙基锌和水为前驱体源，载气和吹扫气体为氮气。在制备氧化锌薄膜的过程中，首先通入前驱体二乙基锌，锌源在基片表面吸附并与基片表面附着的羟基反应，锌源的通入时间为30ms；之后通入吹扫气体，清除腔内的残余气体，吹扫时间为10s；最后通入前驱体源H2O(g)，通入时间为30ms，让水分子与衬底表面吸附的二乙基锌完成反应。实验过程中衬底的温度保持在150℃。将最后制备的样品转入马弗炉中进行煅烧，升温速率1℃/min，加热至700℃，并在此温度下保温3小时，获得Gd2O3：Eu@ZnO核壳结构发光纳米纤维。
实施例3
Gd2O3：Eu@TiO2核壳结构纳米纤维的制备
第一步：静电纺丝法制备Gd2O3：Eu前驱体纳米纤维
0.3gGd(NO3)3、0.015gEu(NO3)3加入到15ml去离子水中溶解至透明澄清的溶液，1.0gPVP加入到该混合溶液中，搅拌4个小时至澄清透明，在15kv的电压和20cm的接收距离下，进行纺丝，接收8小时以上，获得均匀的前驱体纤维。该前驱体纤维在真空烘箱中80℃干燥4小时。
第二步：Gd2O3：Eu纳米纤维的包覆
将第一步制备的前驱体纳米纤维转移至的ALD反应室内，用TiCl4和H2O作为Ti和O的前驱体源，使用高纯度的氩气作为运载气体，流量为100ml/min。TiO2薄膜的ALD脉冲沉积顺序为250ms/250ms(TiCl4/H2O)。氮吹时间为10s，沉积温度为150℃，沉积结束后，将最后制备的样品转入马弗炉中进行煅烧，升温速率1℃/min，加热至500℃，并在此温度下保温3小时，获得Gd2O3：Eu@TiO2核壳结构纳米发光纤维。
实施例4
采用Y(NO3)3替代Gd(NO3)3，其余与实施例1相同。
实施例5
采用Yb(NO3)3替代Eu(NO3)3、其余与实施例2相同。
实施例6
采用Y(NO3)3替代Gd(NO3)3，Tb(NO3)3替代Eu(NO3)3、其余与实施例3相同。
Claims (6)
1.一种具有核壳结构的多功能静电纺丝发光纤维的制备方法，其特征在于：
第一步，采用静电纺丝技术制备稀土掺杂的纳米发光纤维；
第二步，采用原子层沉积技术ALD在第一步制备的纳米发光纤维表面沉积一层功能无机材料；所述无机材料包括Al2O3、SiO2、TiO2、或Au、Ag。
2.根据权利要求1所述具有核壳结构的多功能静电纺丝发光纤维的制备方法，其特征在于：第一步，核壳结构纳米纤维的制备，将Ⅰ、Ⅱ加入到去离子水中溶解至透明澄清的溶液，PVP加入到该混合溶液中，搅拌1-4小时至澄清透明，在10-15kv的电压和10-30cm的接收距离下，进行纺丝，接收8小时以上，获得均匀的前驱体纤维；该前驱体纤维在真空烘箱中80-120℃干燥2-8小时；
所述Ⅰ选自Gd(NO3)3、Y(NO3)3、La(NO3)3、Lu(NO3)3；
所述Ⅱ选自Eu(NO3)3、Yb(NO3)3、Er(NO3)3、Tm(NO3)3、Sm(NO3)3、Ho(NO3)3、Nd(NO3)3、Pr(NO3)3、Dy(NO3)3、Ce(NO3)3、Tb(NO3)3。
3.根据权利要求1所述具有核壳结构的多功能静电纺丝发光纤维的制备方法，其特征在于Ⅰ：Ⅱ：去离子水：PVP加入量比为0.3-0.9g：0.015-0.045g：15-30ml：1.0-5.0g。
4.根据权利要求1所述具有核壳结构的多功能静电纺丝发光纤维的制备方法，其特征在于：
第二步：纳米纤维的包覆
将第一步制备的前驱体纳米纤维转移至ALD反应室内，
采用烷基金属化合物或和挥发性的无机盐作为前驱体，水作为氧化剂，沉积温度100-250℃，前驱体吸附时间为10ms-50s，N2清洗时间为10ms-100s，水吸附时间为30ms-50s，氮气清洗时间为50ms-50ms；
将最后制备的样品转入马弗炉中进行煅烧，升温速率1-10℃/min，加热至500-1000℃，并在此温度下保温2-6小时，获得核壳结构发光纳米纤维。
5.根据权利要求4所述具有核壳结构的多功能静电纺丝发光纤维的制备方法，其特征在于：所述前驱体为三甲基铝TMA或二乙基锌或TiCl4。
6.根据权利要求4所述具有核壳结构的多功能静电纺丝发光纤维的制备方法，其特征在于：使用高纯度的氩气作为运载气体，流量为100ml/min。
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