石墨烯量子点基复合湿敏膜的制备与特性研究
发布时间：2018-11-02 09:11
【摘要】：湿度作为环境监测中的重要物理参数,其实时监测在气象勘探、工业制造、农业种植、智能家居等方面都有着重要的意义。开发并制备高性能湿敏薄膜与湿度传感器是实现高精度、实时湿度监测重要前提。随着材料科学的发展,许多新型材料受到了科研人员的广泛关注。其中,石墨烯量子点作为新型零维材料,在保持了石墨烯众多优良特性的同时,具有量子限域效应和边界效应,其重要衍生物氧化石墨烯量子点通过在表面修饰大量的亲水含氧官能团使其成为一种高性能的湿敏材料。本文以石英晶体微天平(QCM)为传感器件,制备了聚合物/氧化石墨烯量子点和金属氧化物/氧化石墨烯量子点复合膜QCM湿度传感器,并对复合敏感薄膜进行了分析表征及湿敏性能测试,对并对其湿敏机理进行分析与模型建立。论文主要内容如下:1、采用气喷工艺QCM器件电极表面制备了聚乙烯亚胺/氧化石墨烯量子点(PEI/GOQDs)和聚乙烯醇/氧化石墨烯量子点(PVA/GOQDs)复合湿敏薄膜。测试表征并对比分析了PEI与GOQD混合复合、分层复合膜相较单一材料薄膜相比的湿敏特性。测试结果表明,PEI/GOQDs分层湿敏膜的灵敏度为16.59Hz/%RH,湿滞为2.88%RH,最小响应时间2s,最小恢复时间2s,具有良好的湿敏特性。通过透射电镜、傅立叶变换红外光谱等表征方法对复合薄膜进行表征,结果表明PEI与GOQDs间存在酰胺反应键合作用。结合湿敏测试与表征结果。提出了在低湿、中湿、高湿环境下的PEI/GOQDs分层薄膜QCM湿度传感器的湿敏机理,分析了湿滞产生原因。此外,本论文初步探讨了不同体积配比PVA/GOQDs复合薄膜QCM湿度传感器的湿敏特性,结果表明当PVA与GOQDs体积比为1:1时在97.3%相对湿度下具有最优响应1683Hz,其灵敏度为17.92 Hz/%RH,湿滞为2.416667%RH。由红外光谱证明了PVA与GOQDs存在酯化反应,并提出湿敏机理、分析湿滞产生原因。2、采用气喷工艺在QCM器件电极表面沉积氧化锌(ZnO)种子层,采用水热法制备ZnO纳米棒阵列、ZnO/PEI纳米棒阵列、ZnO/PEI/GOQDs纳米棒阵列QCM湿度传感器,对不同结构湿敏薄膜进行表征及湿敏测试,以研究比较其特性。湿敏测试表明,ZnO/PEI/GOQDs纳米棒QCM传感器在97.3%相对湿度下具有最优的响应值1354Hz,灵敏度为14.89 Hz/%RH。薄膜形貌表征表明,ZnO/PEI/GOQDs三元复合的纳米棒结构更致密,直径分布均匀,且纳米棒上覆盖有PEI薄膜。通过红外光谱可以推测PEI与GOQDs附生长在ZnO纳米棒上。通过分析湿敏表征与测试结果,复合薄膜的湿敏性能增益可归因于附生长在ZnO纳米棒上的PEI与GOQDs提供了更多的水分子吸附点位,同时提出了低湿、中湿、高湿环境下的ZnO/PEI/GOQDs纳米棒阵列薄膜QCM湿度传感器的湿敏机理,分析了湿滞产生的原因。
[Abstract]:Humidity as an important physical parameter in environmental monitoring, its real-time monitoring is of great significance in meteorological exploration, industrial manufacturing, agricultural planting, intelligent home and so on. Developing and fabricating high performance humidity sensitive film and humidity sensor is an important prerequisite to realize high precision and real time humidity monitoring. With the development of material science, many new materials are paid more and more attention by researchers. As a new zero-dimensional material, graphene quantum dots (QDs) have quantum limiting and boundary effects while maintaining many excellent properties of graphene. Its important derivative graphene oxide quantum dots (QDs) become a high performance humidity sensitive material by modifying a large number of hydrophilic oxygen-containing functional groups on the surface. In this paper, QCM humidity sensors with polymer / graphene oxide quantum dots and metal oxide / graphene oxide quantum dots composite films were fabricated using quartz crystal microbalance (QCM) as sensing device. The composite sensitive film was characterized and its humidity sensitivity was tested. The mechanism of humidity sensitivity was analyzed and the model was established. The main contents of this thesis are as follows: 1. Poly (ethylene imide / graphene oxide) quantum dots (PEI/GOQDs) and polyvinyl alcohol / graphene oxide (PVA/GOQDs) composite humidity sensitive films were prepared on the electrode surface of QCM devices by gas jet technology. The humidity sensitivity of PEI / GOQD composite film was compared with that of single material film. The results show that the sensitivity of the PEI/GOQDs layered humidity sensitive film is 16.59 Hz / r, the humidity lag is 2.88 RH, the minimum response time is 2 s and the minimum recovery time is 2 s. The composite films were characterized by transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR). The results showed that there was amide-bond cooperation between PEI and GOQDs. Combined with the results of humidity sensitivity test and characterization. The humidity sensing mechanism of PEI/GOQDs layered film QCM humidity sensor under low, medium and high humidity conditions is proposed, and the causes of moisture lag are analyzed. In addition, the humidity sensitivity of PVA/GOQDs composite film QCM humidity sensor with different volume ratio is discussed. The results show that when the volume ratio of PVA to GOQDs is 1:1, the optimal response is 1683 Hz at 97.3% relative humidity. The sensitivity is 17.92 Hz/%RH, and the humidity lag is 2.416667RH. The esterification reaction between PVA and GOQDs was proved by infrared spectroscopy, and the mechanism of humidity sensitivity was put forward, and the reason of wet hysteresis was analyzed. 2. QCM nanorods array was prepared by hydrothermal method by gas jet deposition of ZnO (ZnO) seed layer on the surface of QCM device electrode. ZnO/PEI nanorod array and ZnO/PEI/GOQDs nanorod array QCM humidity sensor were used to characterize the humidity sensitive films with different structures and to study and compare their characteristics. The humidity sensitivity test shows that the ZnO/PEI/GOQDs nanorod QCM sensor has the best response value of 1354 Hz at 97.3% relative humidity, and the sensitivity is 14.89 Hz/%RH.. The morphology of the films shows that the nanorods with ZnO/PEI/GOQDs ternary composites have more compact structure and uniform diameter distribution, and the nanorods are covered with PEI thin films. It is inferred by IR spectra that PEI and GOQDs are attached to ZnO nanorods. Through the analysis of the results of hygroscopic characterization and measurement, the gain of the humidity sensitivity of the composite film can be attributed to the fact that the PEI and GOQDs attached to the ZnO nanorods provide more adsorption sites for water molecules. At the same time, the low humidity and moderate humidity are proposed. The humidity sensing mechanism of ZnO/PEI/GOQDs nanorod array thin film QCM humidity sensor in high humidity environment was analyzed.
【学位授予单位】：电子科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.2;TH765.51
本文编号：2305591
[Abstract]:Humidity as an important physical parameter in environmental monitoring, its real-time monitoring is of great significance in meteorological exploration, industrial manufacturing, agricultural planting, intelligent home and so on. Developing and fabricating high performance humidity sensitive film and humidity sensor is an important prerequisite to realize high precision and real time humidity monitoring. With the development of material science, many new materials are paid more and more attention by researchers. As a new zero-dimensional material, graphene quantum dots (QDs) have quantum limiting and boundary effects while maintaining many excellent properties of graphene. Its important derivative graphene oxide quantum dots (QDs) become a high performance humidity sensitive material by modifying a large number of hydrophilic oxygen-containing functional groups on the surface. In this paper, QCM humidity sensors with polymer / graphene oxide quantum dots and metal oxide / graphene oxide quantum dots composite films were fabricated using quartz crystal microbalance (QCM) as sensing device. The composite sensitive film was characterized and its humidity sensitivity was tested. The mechanism of humidity sensitivity was analyzed and the model was established. The main contents of this thesis are as follows: 1. Poly (ethylene imide / graphene oxide) quantum dots (PEI/GOQDs) and polyvinyl alcohol / graphene oxide (PVA/GOQDs) composite humidity sensitive films were prepared on the electrode surface of QCM devices by gas jet technology. The humidity sensitivity of PEI / GOQD composite film was compared with that of single material film. The results show that the sensitivity of the PEI/GOQDs layered humidity sensitive film is 16.59 Hz / r, the humidity lag is 2.88 RH, the minimum response time is 2 s and the minimum recovery time is 2 s. The composite films were characterized by transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR). The results showed that there was amide-bond cooperation between PEI and GOQDs. Combined with the results of humidity sensitivity test and characterization. The humidity sensing mechanism of PEI/GOQDs layered film QCM humidity sensor under low, medium and high humidity conditions is proposed, and the causes of moisture lag are analyzed. In addition, the humidity sensitivity of PVA/GOQDs composite film QCM humidity sensor with different volume ratio is discussed. The results show that when the volume ratio of PVA to GOQDs is 1:1, the optimal response is 1683 Hz at 97.3% relative humidity. The sensitivity is 17.92 Hz/%RH, and the humidity lag is 2.416667RH. The esterification reaction between PVA and GOQDs was proved by infrared spectroscopy, and the mechanism of humidity sensitivity was put forward, and the reason of wet hysteresis was analyzed. 2. QCM nanorods array was prepared by hydrothermal method by gas jet deposition of ZnO (ZnO) seed layer on the surface of QCM device electrode. ZnO/PEI nanorod array and ZnO/PEI/GOQDs nanorod array QCM humidity sensor were used to characterize the humidity sensitive films with different structures and to study and compare their characteristics. The humidity sensitivity test shows that the ZnO/PEI/GOQDs nanorod QCM sensor has the best response value of 1354 Hz at 97.3% relative humidity, and the sensitivity is 14.89 Hz/%RH.. The morphology of the films shows that the nanorods with ZnO/PEI/GOQDs ternary composites have more compact structure and uniform diameter distribution, and the nanorods are covered with PEI thin films. It is inferred by IR spectra that PEI and GOQDs are attached to ZnO nanorods. Through the analysis of the results of hygroscopic characterization and measurement, the gain of the humidity sensitivity of the composite film can be attributed to the fact that the PEI and GOQDs attached to the ZnO nanorods provide more adsorption sites for water molecules. At the same time, the low humidity and moderate humidity are proposed. The humidity sensing mechanism of ZnO/PEI/GOQDs nanorod array thin film QCM humidity sensor in high humidity environment was analyzed.
【学位授予单位】：电子科技大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.2;TH765.51
【参考文献】
相关期刊论文 前3条
1 张超灿;刘丹;王涛;;新型支化聚乙烯亚胺螯合树脂的制备及吸附性能研究[J];离子交换与吸附;2006年01期
2 蔡智,陈春郁,李月英;湿度发生器及湿度测量[J];仪表技术与传感器;1997年04期
3 易惠中;;湿度传感器用湿敏材料[J];仪表材料;1990年02期
相关博士学位论文 前1条
1 王竹仪;电阻式纳米氧化物湿敏元件的特性研究[D];吉林大学;2009年
，本文编号：2305591
本文链接：https://www.wllwen.com/guanlilunwen/gongchengguanli/2305591.html
