聚合物、有机－无机复合纳米微粒的制备、表征及摩擦学行为研究
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摘要
本论文研究内容包括以下几个方面的工作：
（1）聚合物纳米微粒的制备、结构表征及摩擦学性能研究
本课题选择2，5-二巯基-1，3，4-噻二唑单体通过溶液聚合的方法制备了两种聚合物纳米微粒。然后采用多种现代分析仪器对所制备的产物进行结构表征。如采用透射电子显微镜（TEM）来表征纳米微粒的形貌；傅立叶红外光谱仪（FTIR）表征聚合物纳米微粒分子结构；差热分析（DTA）、微分热失重（DTG）和热重分析（TG）表征聚合物纳米微粒的热性能等。结果表明：所制备的纳米微粒粒径大小均匀，约为100nm以下，基本无团聚现象。
将聚合物纳米微粒用作水基添加剂在四球试验机上考察其宏观摩擦学性能。用扫描电子显微镜（SEM）对磨损表面进行了形貌研究。结果表明：聚合物纳米微粒用作水基添加剂与纯水相比，具有优良的减摩和抗磨作用。并提出如下润滑机理：在低负荷下，聚合物纳米微粒与摩擦表面金属发生物理吸附作用，形成一层起减摩作用的物理吸附膜，从而减小摩擦；随着负荷增加，物理吸附膜不能承受较高压力而部分破坏，吸附在摩擦表面的纳米粒子中的N、S等活性元素在摩擦热的作用下，直接与摩擦表面金属发生化学反应，生成强度较高的化学反应膜,使其具有良好的抗磨和减摩性能。
（2）四氟苯甲酸修饰SiO2纳米微粒的制备、结构表征及其摩擦学性能研究
在溶剂中采用表面修饰法合成了四氟苯甲酸修饰SiO2纳米微粒。 在石油醚、无水乙醇和液体石蜡等溶剂中检验了微粒的分散性，采用透射电子显微镜（TEM）、电子衍射（ED）、傅立叶红外光谱仪（FTIR）和热分析系统（DTA&DTG）等多种现代分析手段对微粒的形貌、结构及热性能进行了表征。结果表明：纳米微粒表
面存在有机修饰层，使得其在有机溶剂和润滑基础油中有良好的分散性。所得微粒粒径细小，平均粒径约30 nm，颗粒大小分布均匀。在四球试验机上考察了它们的摩擦学性能，发现修饰SiO2纳米微粒在中低负荷下具有良好的抗磨性能和一定的减摩作用，可明显提高液体石蜡的承载力。以扫描电子显微镜（SEM）对摩擦表面进行了分析，推测纳米微粒的润滑作用机理可能是在摩擦过程中生成了化学反应膜。
（3）含氟羧酸修饰TiO2纳米微粒的制备、结构表征及其摩擦学性能研究
在溶剂中采用表面修饰法，合成了两种含氟羧酸修饰的TiO2纳米微粒。采用透射电子显微镜（TEM）、傅立叶红外光谱仪（FTIR）和热分析系统（DTA&TG）X-射线粉末衍射（XRD）等多种现代分析手段对微粒的形貌、结构及热性能进行了表征。结果表明：纳米微粒平均粒径分别约为40 nm和100nm，粒度分布均匀。表面修饰层的存在改善了纳米微粒与有机介质的相容性。摩擦学性能测试表明，在中低负荷下，纳米微粒具有优良的减摩抗磨性能，这是因为纳米微粒与摩擦表面金属发生物理吸附作用，形成一层起减摩作用的物理吸附膜，从而减小摩擦。 随着负荷增加，在摩擦过程中纳米微粒分解并发生摩擦化学作用，生成了含有活性物质的化学反应膜，从而起到了良好的润滑效果。
In this thesis, the polymer and organics/inorganics complex nanoparticles were prepared and their structures and properties were studied. The tribological properties of these nanoparticles as additives were investigated.
The main research works are as follows:
(1) Preparation, Structure Characterization and Tribological Behavior of Polymer Nanoparticles
Polymer nanoparticles were synthesized using an solution polymeration method. The nanoparticles were characterized by Fourier transformation infrared ray (FTIR) spectroscopy and transmission electron microscope (TEM). Their thermal stability was investigated by means of differential thermal analysis (DTA)，differential thermogravimetry (DTG) and thermogravimetry (TG). TEM micrograph shows that the samples are under 100 nm and dimensionaluniformity. After added polymer nanoparticles into water, its tribological properties were tested with four ball testing machine. The morphologies on the worn surfaces of the lubricated GCr15 steel were investigated by means of scanning electron microscopy (SEM). The results show that those polymer nanoparticles have good reduce-friction and anti-wear properties, compared to water. The proposed mechanism is as follows: under low load, deposition films consisted of these nanoparticles on the surface of steel sphere, which make those nanoparticles have good reduce-friction and anti-wear properties. Under high load, films of 'tribochemical reaction' of those nanoparticles, which make those nanoparticles have a good reduce-friction and anti-wear.
(2) Preparation, Structure Characterization and Tribological Behavior of Tetrafluorobenzoic Acid-modified SiO2 Nanoparticles
Tetrafluorobenzoic acid-modified SiO2 nanoparticles were prepared using method
of surface-modified. The nanoparticles were characterized by means of electron diffraction (ED), TEM, FTIR, DTA and differential thermogravimetry (DTG). The surface modified sample disperses in organic solvents such as petroleum ether, liquid paraffin at room temperature. TEM micrograph shows that the mean graininess of the modified sample is about 30 nm, and the ED micrograph indicates that the structure of tetrafluorobenzoic acid-modified SiO2 nanoparticles is amorphous. After added nanometer SiO2 into liquid paraffin, its tribological properties were tested with four ball testing machine. The morphologies on the worn surfaces of the lubricated GCr15 steel were investigated by means of SEM. The results showed: the antiwear and load capability of liquid paraffin increased after adding nanometer SiO2. We inferred that is attributed to the generation of a surface film by way of tribochemical reaction.
(3) Preparation, Structure Characterization and Tribological Behavior of Surface-modified TiO2 Nanoparticles
Surface-modified TiO2 nanoparticles were synthesized in the ethanol with the surface modification agent of tetrafluorobenzoic acid and trifluoroacetic acid. Some analytical tools such as X-Ray Diffraction (XRD), TEM, TG and DTA were used to characterize the structure of surface modified nanoparticles. The nanoparticles exhibit good dispersity in the organic solvent and base oil. The results show that the mean sizes of the modified samples are about 40 nm and 100nm, and the XRD micrograph indicates that the structure of nanoparticles is amorphous. The tribological properties of nanoparticles as oil additive were investigated with a four-ball tribometer. The morphologies on the worn surfaces of the lubricated GCr15 steel were investigated by means of SEM. The result show that they are of good anti-wear and reduce-friction properties at mid-low applied load. We inferred that is was attributed to the generation of a surface protective film by way of tribochemical reaction.
（1）聚合物纳米微粒的制备、结构表征及摩擦学性能研究
本课题选择2，5-二巯基-1，3，4-噻二唑单体通过溶液聚合的方法制备了两种聚合物纳米微粒。然后采用多种现代分析仪器对所制备的产物进行结构表征。如采用透射电子显微镜（TEM）来表征纳米微粒的形貌；傅立叶红外光谱仪（FTIR）表征聚合物纳米微粒分子结构；差热分析（DTA）、微分热失重（DTG）和热重分析（TG）表征聚合物纳米微粒的热性能等。结果表明：所制备的纳米微粒粒径大小均匀，约为100nm以下，基本无团聚现象。
将聚合物纳米微粒用作水基添加剂在四球试验机上考察其宏观摩擦学性能。用扫描电子显微镜（SEM）对磨损表面进行了形貌研究。结果表明：聚合物纳米微粒用作水基添加剂与纯水相比，具有优良的减摩和抗磨作用。并提出如下润滑机理：在低负荷下，聚合物纳米微粒与摩擦表面金属发生物理吸附作用，形成一层起减摩作用的物理吸附膜，从而减小摩擦；随着负荷增加，物理吸附膜不能承受较高压力而部分破坏，吸附在摩擦表面的纳米粒子中的N、S等活性元素在摩擦热的作用下，直接与摩擦表面金属发生化学反应，生成强度较高的化学反应膜,使其具有良好的抗磨和减摩性能。
（2）四氟苯甲酸修饰SiO2纳米微粒的制备、结构表征及其摩擦学性能研究
在溶剂中采用表面修饰法合成了四氟苯甲酸修饰SiO2纳米微粒。 在石油醚、无水乙醇和液体石蜡等溶剂中检验了微粒的分散性，采用透射电子显微镜（TEM）、电子衍射（ED）、傅立叶红外光谱仪（FTIR）和热分析系统（DTA&DTG）等多种现代分析手段对微粒的形貌、结构及热性能进行了表征。结果表明：纳米微粒表
面存在有机修饰层，使得其在有机溶剂和润滑基础油中有良好的分散性。所得微粒粒径细小，平均粒径约30 nm，颗粒大小分布均匀。在四球试验机上考察了它们的摩擦学性能，发现修饰SiO2纳米微粒在中低负荷下具有良好的抗磨性能和一定的减摩作用，可明显提高液体石蜡的承载力。以扫描电子显微镜（SEM）对摩擦表面进行了分析，推测纳米微粒的润滑作用机理可能是在摩擦过程中生成了化学反应膜。
（3）含氟羧酸修饰TiO2纳米微粒的制备、结构表征及其摩擦学性能研究
在溶剂中采用表面修饰法，合成了两种含氟羧酸修饰的TiO2纳米微粒。采用透射电子显微镜（TEM）、傅立叶红外光谱仪（FTIR）和热分析系统（DTA&TG）X-射线粉末衍射（XRD）等多种现代分析手段对微粒的形貌、结构及热性能进行了表征。结果表明：纳米微粒平均粒径分别约为40 nm和100nm，粒度分布均匀。表面修饰层的存在改善了纳米微粒与有机介质的相容性。摩擦学性能测试表明，在中低负荷下，纳米微粒具有优良的减摩抗磨性能，这是因为纳米微粒与摩擦表面金属发生物理吸附作用，形成一层起减摩作用的物理吸附膜，从而减小摩擦。 随着负荷增加，在摩擦过程中纳米微粒分解并发生摩擦化学作用，生成了含有活性物质的化学反应膜，从而起到了良好的润滑效果。
In this thesis, the polymer and organics/inorganics complex nanoparticles were prepared and their structures and properties were studied. The tribological properties of these nanoparticles as additives were investigated.
The main research works are as follows:
(1) Preparation, Structure Characterization and Tribological Behavior of Polymer Nanoparticles
Polymer nanoparticles were synthesized using an solution polymeration method. The nanoparticles were characterized by Fourier transformation infrared ray (FTIR) spectroscopy and transmission electron microscope (TEM). Their thermal stability was investigated by means of differential thermal analysis (DTA)，differential thermogravimetry (DTG) and thermogravimetry (TG). TEM micrograph shows that the samples are under 100 nm and dimensionaluniformity. After added polymer nanoparticles into water, its tribological properties were tested with four ball testing machine. The morphologies on the worn surfaces of the lubricated GCr15 steel were investigated by means of scanning electron microscopy (SEM). The results show that those polymer nanoparticles have good reduce-friction and anti-wear properties, compared to water. The proposed mechanism is as follows: under low load, deposition films consisted of these nanoparticles on the surface of steel sphere, which make those nanoparticles have good reduce-friction and anti-wear properties. Under high load, films of 'tribochemical reaction' of those nanoparticles, which make those nanoparticles have a good reduce-friction and anti-wear.
(2) Preparation, Structure Characterization and Tribological Behavior of Tetrafluorobenzoic Acid-modified SiO2 Nanoparticles
Tetrafluorobenzoic acid-modified SiO2 nanoparticles were prepared using method
of surface-modified. The nanoparticles were characterized by means of electron diffraction (ED), TEM, FTIR, DTA and differential thermogravimetry (DTG). The surface modified sample disperses in organic solvents such as petroleum ether, liquid paraffin at room temperature. TEM micrograph shows that the mean graininess of the modified sample is about 30 nm, and the ED micrograph indicates that the structure of tetrafluorobenzoic acid-modified SiO2 nanoparticles is amorphous. After added nanometer SiO2 into liquid paraffin, its tribological properties were tested with four ball testing machine. The morphologies on the worn surfaces of the lubricated GCr15 steel were investigated by means of SEM. The results showed: the antiwear and load capability of liquid paraffin increased after adding nanometer SiO2. We inferred that is attributed to the generation of a surface film by way of tribochemical reaction.
(3) Preparation, Structure Characterization and Tribological Behavior of Surface-modified TiO2 Nanoparticles
Surface-modified TiO2 nanoparticles were synthesized in the ethanol with the surface modification agent of tetrafluorobenzoic acid and trifluoroacetic acid. Some analytical tools such as X-Ray Diffraction (XRD), TEM, TG and DTA were used to characterize the structure of surface modified nanoparticles. The nanoparticles exhibit good dispersity in the organic solvent and base oil. The results show that the mean sizes of the modified samples are about 40 nm and 100nm, and the XRD micrograph indicates that the structure of nanoparticles is amorphous. The tribological properties of nanoparticles as oil additive were investigated with a four-ball tribometer. The morphologies on the worn surfaces of the lubricated GCr15 steel were investigated by means of SEM. The result show that they are of good anti-wear and reduce-friction properties at mid-low applied load. We inferred that is was attributed to the generation of a surface protective film by way of tribochemical reaction.
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