CN110511569A - 一种基于带刺空心碳微球超灵敏度压力传感薄膜及其制备方法 - Google Patents

一种基于带刺空心碳微球超灵敏度压力传感薄膜及其制备方法 Download PDF

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CN110511569A
CN110511569A CN201910674945.4A CN201910674945A CN110511569A CN 110511569 A CN110511569 A CN 110511569A CN 201910674945 A CN201910674945 A CN 201910674945A CN 110511569 A CN110511569 A CN 110511569A
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武利民
石澜
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Fudan University
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Abstract

本发明涉及一种基于带刺空心碳微球超灵敏度压力传感薄膜及其制备方法。本发明方法制备的带刺碳空心微球复合聚二甲基硅氧烷传感薄膜中，带刺碳空心微球均匀分散于基体中。带刺结构有助于微球间发生F‑N隧穿效应，提升材料灵敏度；通过前驱体转化法制备的碳材料，含有适量氮元素掺杂，有效的提高了微球的电子传输能力，空心结构既可以调控填料的密度，又有助于提高该材料的温度稳定性。将带刺空心有机纳米微球的制备；通过惰性气体保护下的煅烧工艺将带刺空心有机纳米微球转化为带刺空心碳微球，并调控其含氮量与石墨化程度；制备带刺空心碳纳米微球与聚二甲基硅氧烷的复合薄膜。本发明所得材料具备超高灵敏度、高阵列密度、透明、低延迟、无温度干扰，本发明方法制备简单、工艺成熟、对环境无污染。

Description

一种基于带刺空心碳微球超灵敏度压力传感薄膜及其制备 方法
技术领域
本发明属于涉及一种基于带刺空心碳微球超灵敏压力传感薄膜及其制备方法，属于柔性电子材料的制备技术领域。
背景技术
压力传感材料是指在材料表面受到一定的压力之后，因其材料内部微结构的改变，导致了材料整体电学性质的变化，通过检测材料的电学信号变化即可实现压力传感的功能，压力传感材料是实现这一过程的核心。压力传感器广泛应用于航天、航空、航海、石油化工、动力机械、医疗、气象、地质等各个行业和领域。在工业领域，压力传感器可用于检测各类仪器设备的实时应力状况。例如，用于测试患者呼吸、油气输运管道的承压，铁轨使用中的变形，设备运行中是否碰到异物，发动机进气口的动态畸变等等。
传统的压力传感器通常使用微机电系统传感器，其稳定性好，测试精度也相对较高，但在大面积应用与非平面应用上有较大限制。基于有机无机复合的柔性压力传感材料可以很好的应用于这两个领域。
柔性压力传感器有多种实现途径，包括电阻式，电容式，压电式，摩擦发电式，磁性传感，光纤传感等。其中对于静态力的作用最常用的是电阻式和电容式的柔性压力传感器。
发明内容
本发明的目的在于提供了一种基于带刺空心碳微球超灵敏压力传感薄膜及其制备方法。在具备超高灵敏度的同时，还具备平行于受压方向有信号响应，垂直于受压方向不反馈信号的能力，为其在超高密度阵列传感的应用奠定了基础，其理论检测密度点每平方厘米可达320万个以上。并且该体系传感材料具备很好的环境稳定性，它可以在水下正常工作，同时应力检测能力不受温度变化的影响，也兼顾优异的抗疲劳性能，在大规模生产方面也具备一定优势，兼容目前已经成熟的旋涂等薄膜制备工艺，从而具有很好的理论研究和实际应用价值。
本发明提出的一种基于带刺空心碳微球超灵敏度压力传感薄膜，所述压力传感薄膜包括可导电的带刺空心碳微球与具有介电性能的硅氧烷类材料，所述带刺空心碳微球与硅氧烷类材料的质量百分比为0.5%~20%。
本发明中，所述压力传感薄膜的膜厚为0.1μm~200μm。
本发明中，带刺空心碳微球中，氮元素与碳元素的质量百分比为0.2%~15%；氧元素与碳元素的质量百分比为2%~35%。
本发明提出的一种基于带刺空心碳微球超灵敏度压力传感薄膜的制备方法，具体步骤如下：
（1）、10~30℃下，量取10 mL 去离子水，加入空心模板纳米微球0.1~1g，和前驱体0.1~0.5g，超声分散８-12分钟后，密封搅拌溶胀1-8 小时，然后加入与前驱体对应聚合引发剂，搅拌18-28小时后，离心，冷冻干燥，得到带刺空心有机纳米微球；
（2）、将步骤（1）得到的带刺空心有机纳米微球置于惰性气体（Ar或N2）中，加热至330-360℃，保温50-70分钟，再升温至600~950℃，保温1~2小时后随炉冷却，即可获得带刺空心碳微球；
（3）、取制备薄膜的载体基板，在其上涂布一层牺牲层，得到基材，备用；
（4）、取步骤（2）所得带刺空心碳微球与硅氧烷类材料，带刺空心碳微球与硅氧烷类材料的质量百分比为0.5%~20%，在冰浴条件下，高速搅拌4.5-5.5小时，即可获得用于制备压力传感薄膜的浆料；
（5）、将步骤（4）所得压力传感薄膜的浆料通过成膜工艺成型于步骤（3）所得基材上，于60-120℃烘箱中，固化15~180分钟；取出后置于可溶解牺牲层的溶剂中浸泡2小时，即可获得一种具备超高灵敏度的压力传感薄膜。
本发明中，步骤（１）所述前驱体包含苯胺、吡咯、多巴胺、三聚氰胺或氨基酸中的至少一种。
本发明中，步骤（１）中空心模板纳米微球包含纳米聚苯乙烯微球、纳米二氧化硅微球或纳米聚甲基丙烯酸甲酯微球中的至少一种。
本发明中，步骤（２）所得带刺空心碳微球的粒径为100 nm~1000 nm。
本发明中，步骤（５）所述的成膜工艺包含旋涂法、流延法、喷涂法、刮涂法、滴涂法或倒模法中的任一种。
本发明中，步骤（３）中所述牺牲层材料包含聚乙烯醇、聚甲基丙烯酸甲酯或葡聚糖中的至少一种。
本发明中，步骤（４）中硅氧烷类材料为聚二甲基硅氧烷。
本发明中制备的压力传感材料的有益效果在于：
（1）由于碳微球成分的合理调控，其载流子输运能力十分优良，作为应力传感体系中的固定位点，能够有效的提高传感的可靠性。
（2）该传感材料经过合理的优化设计，其特定的质量浓度使其工作在以F-N隧穿效应为主的条件下，材料收到极其微小的应力即可呈超指数的将应力变形反应为信号变化，实现了超高的灵敏度传感。
（3）由于其填充单元为薄壁空心碳球，在与聚二甲基硅氧烷基体复合后，空心结构可以有效吸收因外界温度变化带来的内部结构分布变化，从而使其表现为对温度无响应的一种压力传感材料。
（4）由于其超薄的薄膜设计结构，大大缩减了其受压回弹的行程，从而提高了其信号响应速率，并增加了透明性。
（5）由于F-N隧穿效应与纳米粒子统计行为的统一机制，实现了其平行于受压方向有信号响应，垂直于受压方向不反馈信号的能力，为其在超高密度阵列传感的应用奠定了基础。
（6）由于其合成工艺简单，原材料成本较低，复合薄膜成型工艺成熟，为其在大面积应用方面提供了便利。
（7）本发明制得的带刺空心碳纳米微球/聚二甲基硅氧烷复合薄膜压力传感材料具备超高灵敏度、高阵列密度、透明、低延迟、无温度干扰，可用于复杂的环境中（如液下检测、高低温变换环境、复杂的表面等），且制备方法简单、工艺成熟、对环境无污染。
附图说明
图1为600nm可导电带刺微球的扫描透射电镜和透射电镜照片。
图2为该压力传感薄膜的实物图。
图3为该薄膜的光线透过率谱图。
图4为该传感薄膜的电阻-压力曲线和灵敏度-压力曲线。
图5为该传感薄膜弛豫响应曲线。
图6为该传感薄膜疲劳响应测试曲线。
图7为该传感薄膜在25℃到160℃下不同压力对应的电阻值。
图8为该传感薄膜用于PBS液下测试的实施图。
图9为该传感薄膜在PBS中测试的电阻-压力曲线和灵敏度-压力曲线。
图10为该传感薄膜应用于64×64阵列电极上的传感测试演示。其中：（ａ）为阵列电极测试图，（ｂ）为实时结果显示图。
图11展示了实施例1的X射线光电能谱分析结果。
图12展示了实施例2传感薄膜在不同压力条件下的电阻强弱，并计算了其具体的灵敏度指标。
图13展示了实施例2的X射线光电能谱分析结果。
具体实施方式
下面结合具体实施例与附图对本发明做进一步阐述，但本发明并不限于以下实施例。所述方法如无特别说明均为常规方法。所述原材料如无特别说明均能从公开商业途径获得。
实施例１：首先将粒径为600 nm的聚苯乙烯微球0.5g于10mL去离子水中，在室温下超声分散10min，然后加入0.5g苯胺前驱体，磁力搅拌3小时，转速100rpm。再向该溶液中加入100mL 0.5M Fe(NO3)3水溶液，室温下磁力搅拌24小时，转速300rpm。将获得的溶液用去离子水和乙醇溶液在5000rpm的离心机中分别洗涤三次，置于冷冻干燥机，干燥48小时。
其次将干燥获得的粉末放入氮气气氛保护的管式炉中，升温至350℃保温１小时，再升温至900℃保温１小时，然后随炉冷却，即可获得可导电的带刺空心微球，图1是其扫描透射电镜和透射电镜的微观照片。
将获得的可导电带刺空心微球取0.4g 分散于A:B组分10：1的10mL聚二甲基硅氧烷（道康宁184）中，在冰浴条件下磁力搅拌5小时，转速500rpm。通过旋涂方法将搅拌后的浆料旋涂在表面涂有PVA牺牲层的培养皿上，旋涂程序为：600rpm，9s，5000rpm，35s。给旋涂好的培养皿中倒入30mL去离子水，室温下静置浸泡12小时，即可得到具有超高灵敏度的透明传感薄膜。如图2所示。
图3展示了该薄膜对不同波段光线的透过能力，其透明性接近盖玻片。
图4展示了该传感薄膜在不同压力条件下的电阻强弱，并计算了其具体的灵敏度指标。
图5展示了该传感薄膜对于压力的响应速度，其受压响应时间为60ms，释放压力响应时间为30ms。
图6展示了该传感薄膜在5000次加载-释放过程中的压力响应信号。
图7展示了该传感薄膜在25℃到160℃时，在不同压力状态下所传出的电阻信号。
图8展示了该传感薄膜在深入模拟人体体液环境PBS溶液中20cm后，对压力的响应测试。
图9展示了上述PBS溶液中该传感薄膜对压力信号的检测能力。
图10展示了该传感薄膜在具有64×64个的3.2×3.2cm大小检测电极阵列上对于两个轻微物体的质量分辨能力
图11展示了实施例1的X射线光电能谱分析结果。
实施例2：首先将粒径为800 nm的聚苯乙烯微球0.8g于10mL PH=8.5的Trish缓冲液中，在室温下超声分散10min，然后加入0.3g多巴胺前驱体，后加入0.1g过硫酸铵，磁力搅拌12小时，转速200rpm。将获得的溶液用去离子水和乙醇溶液在12000rpm的离心机中分别洗涤三次，置于冷冻干燥机，干燥48小时。
其次将干燥获得的粉末放入氮气气氛保护的管式炉中，升温至350℃保温１小时，再升温至800℃保温１小时，然后随炉冷却，即可获得可导电的空心微球，
将获得的可导电带刺空心微球取0.35g 分散于A:B组分10：1的10mL聚二甲基硅氧烷（道康宁184）中，在冰浴条件下磁力搅拌5小时，转速500rpm。通过旋涂方法将搅拌后的浆料旋涂在表面涂有PVA牺牲层的培养皿上，旋涂程序为：600rpm，9s，5000rpm，35s。给旋涂好的培养皿中倒入30mL去离子水，室温下静置浸泡12小时，即可得到具有高灵敏度的透明传感薄膜。
图12展示了实施例2传感薄膜在不同压力条件下的电阻强弱，并计算了其具体的灵敏度指标。
图13展示了实施例2的X射线光电能谱分析结果。

Claims (10)

1.一种基于带刺空心碳微球超灵敏度压力传感薄膜，其特征在于，所述压力传感薄膜包括可导电的带刺空心碳微球与具有介电性能的硅氧烷类材料，所述带刺空心碳微球与硅氧烷类材料的质量百分比为0.5%~20%。
2.根据权利要求1所述的压力传感薄膜，其特征在于，所述压力传感薄膜的膜厚为0.1μm~200μm。
3.根据权利要求1所述的压力传感薄膜，其特征在于，带刺空心碳微球中，氮元素与碳元素的质量百分比为0.2%~15%；氧元素与碳元素的质量百分比为2%~35%。
4.一种如权利要求1所述的基于带刺空心碳微球超灵敏度压力传感薄膜的制备方法，其特征在于，具体步骤如下：
（1）、10~30℃下，量取10 mL 去离子水，加入空心模板纳米微球0.1~1g，和前驱体0.1~0.5g，超声分散８-12分钟后，密封搅拌溶胀1-8 小时，然后加入与前驱体对应聚合引发剂，搅拌18-28小时后，离心，冷冻干燥，得到带刺空心有机纳米微球；
（2）、将步骤（1）得到的带刺空心有机纳米微球置于惰性气体（Ar或N2）中，加热至330-360℃，保温50-70分钟，再升温至600~950℃，保温1~2小时后随炉冷却，即可获得带刺空心碳微球；
（3）、取制备薄膜的载体基板，在其上涂布一层牺牲层，得到基材，备用；
（4）、取步骤（2）所得带刺空心碳微球与硅氧烷类材料，带刺空心碳微球与硅氧烷类材料的质量百分比为0.5%~20%，在冰浴条件下，高速搅拌4.5-5.5小时，即可获得用于制备压力传感薄膜的浆料；
（5）、将步骤（4）所得压力传感薄膜的浆料通过成膜工艺成型于步骤（3）所得基材上，于60-120℃烘箱中，固化15~180分钟；取出后置于可溶解牺牲层的溶剂中浸泡2小时，即可获得一种具备超高灵敏度的压力传感薄膜。
5.根据权利要求4所述的制备方法，其特征在于，步骤（1）所述前驱体包含苯胺、吡咯、多巴胺、三聚氰胺或氨基酸中的至少一种。
6.根据权利要求4所述的制备方法，其特征在于，步骤（1）中空心模板纳米微球包含纳米聚苯乙烯微球、纳米二氧化硅微球或纳米聚甲基丙烯酸甲酯微球中的至少一种。
7.根据权利要求4所述的制备方法，其特征在于，步骤（２）所得带刺空心碳微球的粒径为100 nm~1000 nm。
8.根据权利要求4所述的制备方法，其特征在于，步骤（５）所述的成膜工艺包含旋涂法、流延法、喷涂法、刮涂法、滴涂法或倒模法中的任一种。
9.根据权利要求4所述的制备方法，其特征在于，步骤（３）中所述牺牲层材料包含聚乙烯醇、聚甲基丙烯酸甲酯或葡聚糖中的至少一种。
10.根据权利要求4所述的制备方法，其特征在于，步骤（４）中硅氧烷类材料为聚二甲基硅氧烷。
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