CN108425239B - 一种在纤维表面生长复合石墨烯气凝胶的方法 - Google Patents
一种在纤维表面生长复合石墨烯气凝胶的方法 Download PDFInfo
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Abstract
一种在纤维表面生长复合石墨烯气凝胶的方法,本发明涉及一种在纤维表面生长气凝胶的方法。本发明要解决现有纤维表面改性中工艺流程复杂,设备成本较高,比表面积低的问题。方法:一、石墨烯分散液的制备;二、石墨烯水凝胶在纤维表面的生长;三、石墨烯气凝胶负载纤维的制备;四、复合石墨烯气凝胶负载纤维的制备,即完成一种在纤维表面生长复合石墨烯气凝胶的方法。本发明用于一种在纤维表面生长复合石墨烯气凝胶的方法。
Description
技术领域
本发明涉及一种在纤维表面生长气凝胶的方法。
背景技术
化学纤维具有强度高、质轻、易洗快干、弹性好、不怕霉蛀等突出优点,因而在生产生活的各个领域得到了广泛的应用。随着科技的发展,已涌现出性能更加优异的特种合成纤维,如聚苯并咪唑纤维、芳纶、聚苯撑苯并二噁唑纤维等。然而,化学纤维表面较为光滑,功能基团含量较少,具有较高的表面惰性,从而限制了其在某些领域的应用。常用的纤维表面处理方法包括辐射处理、等离子体处理、偶联剂处理、化学处理及超临界处理等,其原理是通过增加纤维表面的粗糙度和功能基团的数量,提高纤维的表面活性。但上述方法的操作工艺复杂,所需设备成本较高,比表面积低,仅为10平方米每克到20平方米每克,从而限制了在纤维表面改性方法的应用。
发明内容
本发明要解决现有纤维表面改性中工艺流程复杂,设备成本较高,比表面积低的问题,而提供一种在纤维表面生长复合石墨烯气凝胶的方法。
一种在纤维表面生长复合石墨烯气凝胶的方法是按以下步骤进行:
一、石墨烯分散液的制备:
将氧化石墨烯加入水中,得到氧化石墨烯分散液,然后向氧化石墨烯分散液中加入还原剂,超声处理1h~2h,得到石墨烯分散液;
所述的氧化石墨烯与还原剂的质量比为1:(0.3~1);所述的氧化石墨烯分散液的浓度为1mg/mL~10mg/mL;
所述的还原剂为抗坏血酸、亚硫酸氢钠、乙二胺、水合肼或碘化氢;
二、石墨烯水凝胶在纤维表面的生长:
将抽提过的纤维或者预处理后的纤维置于超细管状模具中并固定纤维两端,然后将石墨烯分散液注入超细管状模具中,密封,然后在温度为20℃~180℃的条件下,水热还原2h~18h,将水热还原后的纤维水洗涤,得到石墨烯水凝胶负载的纤维;
所述的超细管状模具内径为0.05mm~5mm;
三、石墨烯气凝胶负载纤维的制备:
将石墨烯水凝胶负载的纤维绕卷,干燥生成孔隙结构,得到石墨烯气凝胶负载纤维;
四、复合石墨烯气凝胶负载纤维的制备:
将功能材料配制成功能材料溶液,将石墨烯气凝胶负载纤维浸渍在功能材料溶液中1h~24h,取出后洗涤,得到石墨烯气凝胶复合纤维;
所述的功能材料溶液浓度为0.1g/L~100g/L;
所述的功能材料为金属有机骨架化合物、碳纳米管、小分子染料、金纳米粒子、聚苯胺、氧化硅、二氧化钛、氧化铝、碳化硅或氮化硅。
本发明采用现有公开的方法制备氧化石墨烯,如申请号为201010561022.7的《石墨烯/TiO2基抗近红外/紫外辐射高分子复合薄膜及其制备方法》中记载的制备方法。
本发明的有益效果是:
本发明提供了一种工艺简单,制备高效,成本低廉的在纤维表面生长石墨烯气凝胶的方法。本发明将抽提过的纤维或者预处理后的纤维通过超细管状模具,在注入石墨烯分散液后进行原位水热反应,得到石墨烯水凝胶负载纤维。经由干燥,去除石墨烯水凝胶中的水分,得到石墨烯气凝胶负载纤维。将石墨烯气凝胶负载纤维置于纳米粒子或有机分子的溶液中,利用石墨烯气凝胶的强吸附性制得复合石墨烯气凝胶负载的纤维。本发明涉及的在纤维表面生长复合石墨烯气凝胶的方法工艺简单,成本低廉,可赋予纤维多种功能性,因而可大大拓宽了纤维的应用领域并提升其附加值。
由于纤维是一种极细的材料,而通常情况下石墨烯气凝胶为三维体型材料,要想使石墨烯气凝胶均匀负载到纤维表面,并控制负载到纤维表面石墨烯气凝胶的厚度,本发明采用长径比极高的超细毛细管为模具,使石墨烯气凝胶在模具中定向生长,均匀地负载到纤维表面。通过BET测试本发明制备的石墨烯气凝胶复合纤维比表面积为100平方米每克~300平方米每克,大大提高了纤维的吸附性能。本发明制备的石墨烯气凝胶复合纤维单丝拉伸强度为4.8Gpa~5.1Gpa。
本发明用于一种在纤维表面生长复合石墨烯气凝胶的方法。
附图说明
图1为实施例一制备的石墨烯气凝胶复合纤维的SEM图。
具体实施方式
具体实施方式一:本实施方式的一种在纤维表面生长复合石墨烯气凝胶的方法是按以下步骤进行:
一、石墨烯分散液的制备:
将氧化石墨烯加入水中,得到氧化石墨烯分散液,然后向氧化石墨烯分散液中加入还原剂,超声处理1h~2h,得到石墨烯分散液;
所述的氧化石墨烯与还原剂的质量比为1:(0.3~1);所述的氧化石墨烯分散液的浓度为1mg/mL~10mg/mL;
所述的还原剂为抗坏血酸、亚硫酸氢钠、乙二胺、水合肼或碘化氢;
二、石墨烯水凝胶在纤维表面的生长:
将抽提过的纤维或者预处理后的纤维置于超细管状模具中并固定纤维两端,然后将石墨烯分散液注入超细管状模具中,密封,然后在温度为20℃~180℃的条件下,水热还原2h~18h,将水热还原后的纤维水洗涤,得到石墨烯水凝胶负载的纤维;
所述的超细管状模具内径为0.05mm~5mm;
三、石墨烯气凝胶负载纤维的制备:
将石墨烯水凝胶负载的纤维绕卷,干燥生成孔隙结构,得到石墨烯气凝胶负载纤维;
四、复合石墨烯气凝胶负载纤维的制备:
将功能材料配制成功能材料溶液,将石墨烯气凝胶负载纤维浸渍在功能材料溶液中1h~24h,取出后洗涤,得到石墨烯气凝胶复合纤维;
所述的功能材料溶液浓度为0.1g/L~100g/L;
所述的功能材料为金属有机骨架化合物、碳纳米管、小分子染料、金纳米粒子、聚苯胺、氧化硅、二氧化钛、氧化铝、碳化硅或氮化硅。
石墨烯气凝胶是一种高强度的凝胶态物质,是一种多孔,高弹性的三维纳米碳材料。由于其超高的孔隙率和比表面积,石墨烯气凝胶具有超强的吸附性能,将其引入至纤维表面可显著改善纤维表面性质并赋予其功能性。与此同时,位于纤维表面的石墨烯气凝胶还可通过吸附不同的有机分子或者纳米粒子赋予纤维多种功能,实现其应用。
本具体实施方式的有益效果是:本具体实施方式提供了一种工艺简单,制备高效,成本低廉的在纤维表面生长石墨烯气凝胶的方法。本具体实施方式将预处理后纤维通过超细管状模具,在注入石墨烯分散液后进行原位水热反应,得到石墨烯水凝胶负载纤维。经由干燥,去除石墨烯水凝胶中的水分,得到石墨烯气凝胶负载纤维。将石墨烯气凝胶负载纤维置于纳米粒子或有机分子的溶液中,利用石墨烯气凝胶的强吸附性制得复合石墨烯气凝胶负载的纤维。本具体实施方式涉及的在纤维表面生长复合石墨烯气凝胶的方法工艺简单,成本低廉,可赋予纤维多种功能性,因而可大大拓宽了纤维的应用领域并提升其附加值。
由于纤维是一种极细的材料,而通常情况下石墨烯气凝胶为三维体型材料,要想使石墨烯气凝胶均匀负载到纤维表面,并控制负载到纤维表面石墨烯气凝胶的厚度,本具体实施方式采用长径比极高的超细毛细管为模具,使石墨烯气凝胶在模具中定向生长,均匀地负载到纤维表面。通过BET测试本具体实施方式制备的石墨烯气凝胶复合纤维比表面积为100平方米每克~300平方米每克,大大提高了纤维的吸附性能。本具体实施方式制备的石墨烯气凝胶复合纤维单丝拉伸强度为4.8Gpa~5.1Gpa。
本具体实施方式步骤二中超细管状模具即为具有极大长径比的特殊水热反应釜,在上述条件下,石墨烯分散液即可生成水凝胶并负载至纤维表面。石墨烯水凝胶负载纤维缓慢通过水洗涤,以去除水热反应后残留的还原剂及其他杂质。
本具体实施方式步骤三中干燥生成不同孔隙结构及孔径大小的石墨烯气凝胶负载纤维
具体实施方式二:本实施方式与具体实施方式一不同的是:步骤二中所述的预处理后的纤维为引入羧基、羟基和氨基的纤维。其它与具体实施方式一相同。
具体实施方式三:本实施方式与具体实施方式一或二之一不同的是:所述的引入羧基、羟基和氨基的纤维为利用聚多巴胺处理、等离子体处理或酸化处理抽提过的纤维得到的。其它与具体实施方式一或二相同。
具体实施方式四:本实施方式与具体实施方式一至三之一不同的是:所述的抽提过的纤维为对PBO纤维、碳纤维、芳纶纤维、聚酯纤维、聚酰胺纤维、聚乙烯醇纤维、聚丙烯腈纤维、聚丙烯纤维、聚氯乙烯纤维或玻璃纤维进行抽提。其它与具体实施方式一至三相同。
具体实施方式五:本实施方式与具体实施方式一至四之一不同的是:步骤三中所述的干燥为室温干燥、超临界干燥、真空干燥或冷冻干燥。其它与具体实施方式一至四相同。
具体实施方式六:本实施方式与具体实施方式一至五之一不同的是:步骤一中将氧化石墨烯加入水中,得到氧化石墨烯分散液,然后向20mL氧化石墨烯分散液中加入100mg还原剂,超声处理2h,得到石墨烯分散液。其它与具体实施方式一至五相同。
具体实施方式七:本实施方式与具体实施方式一至六之一不同的是:步骤一中所述的氧化石墨烯分散液的浓度为5mg/mL。其它与具体实施方式一至六相同。
具体实施方式八:本实施方式与具体实施方式一至七之一不同的是:步骤二中在温度为90℃的条件下,水热还原5h。其它与具体实施方式一至七相同。
具体实施方式九:本实施方式与具体实施方式一至八之一不同的是:步骤四中所述的小分子染料为吲哚菁绿、亚甲基蓝、甲基橙或柠檬黄。其它与具体实施方式一至八相同。
具体实施方式十:本实施方式与具体实施方式一至九之一不同的是:步骤三中将石墨烯水凝胶负载的纤维绕卷,然后在温度为-56℃的条件下冷冻2天,得到石墨烯气凝胶负载纤维。其它与具体实施方式一至九相同。
采用以下实施例验证本发明的有益效果:
实施例一:
一种在纤维表面生长复合石墨烯气凝胶的方法是按以下步骤进行:
一、石墨烯分散液的制备:
将氧化石墨烯加入水中,得到氧化石墨烯分散液,然后向20mL氧化石墨烯分散液中加入100mg还原剂,超声处理2h,得到石墨烯分散液;
所述的氧化石墨烯分散液的浓度为5mg/mL;所述的还原剂为抗坏血酸;
二、石墨烯水凝胶在纤维表面的生长:
配制浓度为2mg/mL的多巴胺缓冲液,然后向浓度为2mg/mL的多巴胺缓冲液中加入HCl及TRIS直至pH为8.5,得到处理液,将抽提过的PBO纤维加入到处理液中,浸泡24h,取出后多次用水清洗,室温干燥10h,得到预处理后的纤维,将预处理后的纤维置于超细管状模具中并固定纤维两端,然后将石墨烯分散液注入超细管状模具中,用酒精灯烧毛细管的两端封口,然后在温度为90℃的条件下,水热还原5h,将水热还原后的纤维水洗涤,得到石墨烯水凝胶负载的纤维;
所述的超细管状模具内径为0.9mm;
三、石墨烯气凝胶负载纤维的制备:
将石墨烯水凝胶负载的纤维绕卷,然后在温度为-56℃的条件下冷冻2天,得到石墨烯气凝胶负载纤维;
四、复合石墨烯气凝胶负载纤维的制备:
向10mL甲醇中加入0.2g六水合硝酸锌,得到六水合硝酸锌溶液,将石墨烯气凝胶负载纤维加入到六水合硝酸锌溶液中浸泡12h,然后加入浓度为0.04g/mL的二甲基咪唑的甲醇溶液10mL,浸泡12h,取出后洗涤,得到石墨烯气凝胶复合纤维。
步骤一采用现有公开的方法制备氧化石墨烯,即申请号为201010561022.7的《石墨烯/TiO2基抗近红外/紫外辐射高分子复合薄膜及其制备方法》中记载的制备方法。
图1为实施例一制备的石墨烯气凝胶复合纤维的SEM图;采用XPS,SEM等分析测试手段对制备得到的石墨烯气凝胶复合纤维进行分析。以SEM为例简要说明,如附图1所示,在毛细管内负载了石墨烯气凝胶的纤维表面粗糙度明显增加,且疏松多孔,复合纤维的直径明显增加,其直径大小随毛细管的直径的变化而变化,可根据需要选择合适直径的毛细管,较大的孔隙率及比表面积赋予了纤维较强的吸附能力,为后续功能材料的引入提供了足够的空间。测试结果显示,通过毛细管的形状固定作用,本实施例可以很好的在纤维表面生长孔隙率高,比表面积大的石墨烯气凝胶,使两者较好的复合,进而实现纤维表面的功能化。
通过BET测试本实施例制备的石墨烯气凝胶复合纤维比表面积为180平方米每克,大大提高了纤维的吸附性能。
本实施例制备的石墨烯气凝胶复合纤维单丝拉伸强度为5.1Gpa。
Claims (6)
1.一种在纤维表面生长复合石墨烯气凝胶的方法,其特征在于一种在纤维表面生长复合石墨烯气凝胶的方法是按以下步骤进行:
一、石墨烯分散液的制备:
将氧化石墨烯加入水中,得到氧化石墨烯分散液,然后向氧化石墨烯分散液中加入还原剂,超声处理1h~2h,得到石墨烯分散液;
所述的氧化石墨烯与还原剂的质量比为1:(0.3~1);所述的氧化石墨烯分散液的浓度为1mg/mL~10mg/mL;
所述的还原剂为抗坏血酸、亚硫酸氢钠、乙二胺、水合肼或碘化氢;
二、石墨烯水凝胶在纤维表面的生长:
配制浓度为2mg/mL的多巴胺缓冲液,然后向浓度为2mg/mL的多巴胺缓冲液中加入HCl及TRIS直至pH为8.5,得到处理液,将抽提过的纤维加入到处理液中,浸泡24h,取出后多次用水清洗,室温干燥10h,得到预处理后的纤维,将预处理后的纤维置于超细管状模具中并固定纤维两端,然后将石墨烯分散液注入超细管状模具中,密封,然后在温度为90℃~180℃的条件下,水热还原5h~18h,将水热还原后的纤维水洗涤,得到石墨烯水凝胶负载的纤维;
所述的超细管状模具内径为0.05mm~5mm;
三、石墨烯气凝胶负载纤维的制备:
将石墨烯水凝胶负载的纤维绕卷,干燥生成孔隙结构,得到石墨烯气凝胶负载纤维;
四、复合石墨烯气凝胶负载纤维的制备:
向10mL甲醇中加入0.2g六水合硝酸锌,得到六水合硝酸锌溶液,将石墨烯气凝胶负载纤维加入到六水合硝酸锌溶液中浸泡12h,然后加入浓度为0.04g/mL的二甲基咪唑的甲醇溶液10mL,浸泡12h,取出后洗涤,得到石墨烯气凝胶复合纤维。
2.根据权利要求1所述的一种在纤维表面生长复合石墨烯气凝胶的方法,其特征在于步骤二中所述的抽提过的纤维为对PBO纤维、碳纤维、芳纶纤维、聚酯纤维、聚酰胺纤维、聚乙烯醇纤维、聚丙烯腈纤维、聚丙烯纤维、聚氯乙烯纤维或玻璃纤维进行抽提。
3.根据权利要求1所述的一种在纤维表面生长复合石墨烯气凝胶的方法,其特征在于步骤三中所述的干燥为室温干燥、超临界干燥、真空干燥或冷冻干燥。
4.根据权利要求1所述的一种在纤维表面生长复合石墨烯气凝胶的方法,其特征在于步骤一中将氧化石墨烯加入水中,得到氧化石墨烯分散液,然后向20mL氧化石墨烯分散液中加入100mg还原剂,超声处理2h,得到石墨烯分散液。
5.根据权利要求1所述的一种在纤维表面生长复合石墨烯气凝胶的方法,其特征在于步骤一中所述的氧化石墨烯分散液的浓度为5mg/mL。
6.根据权利要求1所述的一种在纤维表面生长复合石墨烯气凝胶的方法,其特征在于步骤三中将石墨烯水凝胶负载的纤维绕卷,然后在温度为-56℃的条件下冷冻2天,得到石墨烯气凝胶负载纤维。
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