王梅桂,王湘玲,叶相元.氨基化氟化石墨烯增强热塑性聚氨酯的制备与性能研究[J].表面技术,2022,51(9):141-150.
WANG Mei-gui,WANG Xiang-ling,YE Xiang-yuan.Preparation and Properties of the Amino-modified Fluorinated Graphene Enhanced Thermoplastic Polyurethane[J].Surface Technology,2022,51(9):141-150 |
| 氨基化氟化石墨烯增强热塑性聚氨酯的制备与性能研究 |
| Preparation and Properties of the Amino-modified Fluorinated Graphene Enhanced Thermoplastic Polyurethane |
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| DOI：10.16490/j.cnki.issn.1001-3660.2022.09.014 |
| 中文关键词: 热塑性聚氨酯 氨基化氟化石墨烯 力学性能 摩擦系数 磨损体积 |
| 英文关键词:thermoplastic polyurethane amino-modified fluorinated graphene mechanical properties friction coefficient wear volume |
| 基金项目:国家自然科学基金(51805007);陕西省青年创新团队建设科研计划项目(21JP004) |
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| 中文摘要: |
| 目的 制备氨基化氟化石墨烯/热塑性聚氨酯复合材料，进一步提升热塑性聚氨酯(TPU)的综合性能。方法 通过亲核取代反应将尿素分子修饰在氟化石墨烯(FG)表面，得到氨基化氟化石墨烯(AFG)。将AFG作为填料与TPU复合，得到不同质量浓度的氨基化氟化石墨烯/热塑性聚氨酯(AFG/TPU)复合薄膜。通过SEM、TEM、AFM、XPS、XRD、Raman对FG、AFG粉末和AFG/TPU复合薄膜进行表征，使用万能材料试验机、多功能摩擦磨损试验机对AFG/TPU复合薄膜进行力学、摩擦学性能测试。结果 经过尿素分子与FG表面的C—F亲核取代反应，得到表面氨基化的AFG，使AFG片层表面不仅有大量的氟元素，而且有能与TPU分子链形成氢键作用力的氨基官能团，从而保证了AFG可均匀分散于TPU基体中。3.25-AFG/TPU复合材料的拉伸强度为5.97 MPa，较3.25-FG/TPU复合薄膜的拉伸强度(4.37 MPa)增加了36.6%，较纯TPU的拉伸强度(2.51 MPa)增加了137.8%。纯TPU磨损体积为0.56 mm3，3.25-FG/TPU复合材料的磨损体积为0.42 mm3，较纯TPU减小了25%;3.25-AFG/TPU复合材料的磨损体积为0.18 mm3，较纯TPU减小了67.8%。3.25-AFG/TPU复合薄膜的磨损率为1.67×10–2 mm3/(N.m)，较TPU的磨损率(5.18×10–2 mm3.N–1.m–1)降低了67.8%。结论 当FG和AFG分别作为纳米填料时，发现3.25-AFG/TPU力学性能和摩擦学性能均优于3.25-FG/TPU，这是因为AFG不仅保持了FG良好的分散性，使得其可以均匀分散在TPU基体中，而且表面氨基更赋予了AFG与TPU分子链形成氢键作用力的能力，使得拉伸应力和摩擦剪切力可以通过TPU分子链传递到AFG纳米材料表面，最终有效增强了TPU的抗拉伸强度和耐磨损性能。复合材料拉伸断面的微观形貌分析表明，应力可以从TPU分子链传递到AFG表面，AFG起到了分散应力的作用。磨损表面分析表明，TPU和AFG/TPU复合薄膜的磨损机制主要为疲劳磨损。因此，AFG增强AFG与TPU界面的相互作用，最终增强了TPU的力学性能和摩擦学性能。 |
| 英文摘要: |
| The paper aims to prepare the amino-modified fluorinated graphene/thermoplastic polyurethane composites to further improve the comprehensive properties of thermoplastic polyurethane (TPU). In this paper, amino-modified fluorinated graphene (AFG) is obtained by modifying urea molecules on the surface of fluorinated graphene (FG) by nucleophilic substitution reaction. Using AFG as filler, a series of amino-modified fluorinated graphene/thermoplastic polyurethane (AFG/TPU) composite films with different mass concentration are acquired. The surface morphology and lamellar thickness of FG and AFG nanosheets are analyzed by Scanning Electron Microscope (SEM), Transmission Electron Microscopy (TEM) and Atomic Force Microscopy (AFM). X-ray Photoelectron Spectroscopy (XPS), X-ray Diffractometer (XRD) and Raman Spectrometer (Raman) are used to identify the distribution of elemental changes, crystal type structure and substance composition of FG and AFG nanosheets. The mechanical and tribological properties of AFG/TPU composite films are tested by universal material testing machine and multifunctional friction and wear testing machine. AFG is obtained after the nucleophilic substitution reaction between urea molecules and the C-F bond on FG surface, which makes AFG lamellar surface not only have a large number of fluorine elements, but also have amino functional groups that can form hydrogen bond force with TPU molecular chain, thus, ensuring that AFG can be evenly dispersed in TPU matrix. The tensile strength of 3.25-AFG/TPU composite film is 5.97 MPa, which is 36.6% higher than that of 3.25-FG/TPU composite film (4.37 MPa). Compared with pure TPU, which tensile strength is 2.51 MPa, the tensile strength of 3.25-AFG/TPU composite film is increased by 137.8%. The wear volume of pure TPU is 0.56 mm3, and that of 3.25-FG/TPU composite is 0.42 mm3, the wear volume is decrease by 25% than pure TPU. The wear volume of 3.25-AFG/TPU composite is 0.18 mm3, compared with pure TPU, the wear volume of 3.25-AFG/TPU is reduce by 67.8%. The wear rates of 3.25-AFG/TPU composite films is 1.67×10-2 mm3/(N.m), compared with the wear rate of TPU (5.18×10-2 mm3.N-1.m-1), it decreased by 67.8%. When AFG is used as nano filler, AFG with mass fraction of 3.25% is the best addition, which can effectively enhance the mechanical and tribological properties of TPU. FG and AFG are used as nano fillers respectively, it is found that the mechanical and tribological properties of 3.25-AFG/TPU are better than 3.25-FG/TPU, on account of AFG maintains good dispersion of FG, which makes it uniformly dispersed in the TPU matrix, and the surface amino group gives the AFG and the TPU molecular chain to form hydrogen bonding force, so that the tensile stress and friction shear force can be transmitted to the AFG nanomaterial surface through the TPU molecular chain, and ultimately effectively enhance the TPU of tensile strength and wear resistance. The micro-morphological analysis of the composite tensile section shows that the stress can be transmitted from the TPU molecular chain to the AFG surface, and the AFG plays a role in a dispersion stress. Wear surface analysis indicates that the wear mechanism of TPU and AFG/TPU composite film is mainly fatigue wear. Therefore, the AFG nanosheets enhance the interaction between AFG and TPU matrix, which ultimately not only improves the TPU of mechanical property, but also the TPU of tribological property can be enhanced. |
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