目的 探究空心玻璃微球（HGM）表面接枝不同长度聚氨酯预聚体链对聚氨酯（PU）复合材料力学及阻尼性能的影响规律。方法 采用不同分子量聚丙二醇（PPG1000、PPG2000、PPG3000、PPG4000）合成聚氨酯预聚体,通过硅烷偶联剂KH550将其接枝到HGM表面,制备不同接枝链长度的HGM填料。最后制成HGM/PU复合材料,通过傅里叶变换红外光谱（FTIR）、热重分析（TGA）和扫描电子显微镜（SEM）表征接枝效果与表面形貌;利用差示扫描量热法（DSC）分析玻璃化转变行为;通过万能试验机与动态热机械分析仪（DMA）分别测试材料的静态力学性能与动态力学性能。结果 接枝改性后,复合材料的拉伸强度显著提升,HGM-1000/PU的拉伸强度达10.06 MPa,较未改性样品（5.78 MPa）提高74%;但随着接枝链进一步增长,拉伸强度逐渐降低,断裂伸长率升高。动态力学分析表明,接枝链长度对阻尼性能的影响显著,在剪切模式下,HGM-3000/PU的损耗因子峰值最高,达到0.81,比未改性样品提升7%。结论 接枝改性有效改善了HGM与PU基体的界面相容性。较短的接枝链（如PPG1000）更有利于提升复合材料的静态力学强度,而中等长度的接枝链（如PPG3000）则能最有效地增强界面能量耗散能力,获得最优阻尼性能。该研究为通过精准调控界面结构设计高性能轻质阻尼材料提供了关键依据。
Abstract
The work aims to systematically investigate the effects of the grafted polyurethane prepolymer chain length on the mechanical and damping properties of hollow glass microsphere (HGM)/polyurethane composites.
A series of polyurethane (PU) prepolymers were synthesized from polypropylene glycol (PPG) with different molecular weights (PPG1000, PPG2000, PPG3000, PPG4000) and MDI-50 at a fixed NCO:OH ratio. The hydroxylated hollow glass microspheres (HGMs) were firstly functionalized with amino groups via the KH550 coupling agent. The synthesized prepolymers were then covalently grafted onto the functionalized HGM surfaces. Composites were prepared by incorporating 10wt.% of the resulting materials into a PU matrix. The samples were characterized through Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) to confirm chemical composition and grafting efficiency. Scanning electron microscopy (SEM) was employed for morphological examination, and differential scanning calorimetry (DSC) was used to analyze thermal behaviors. The mechanical properties were comprehensively evaluated through static mechanical tests and dynamic mechanical analysis (DMA).
The experimental results confirmed the successful grafting of PU prepolymers onto the HGM surfaces. The glass transition temperature of the modified HGM/PU composites increased compared to that of the unmodified material, showing a trend toward higher temperatures with the increasing grafted chain length. This shift resulted from enhanced molecular chain entanglement and intermolecular interactions. Thermogravimetric analysis (TGA) quantified the grafted organic content, revealing a substantial increase in weight loss for the modified HGMs (6.24%-7.94%) compared to the pristine material (1.62%). The TGA curves stabilized beyond 650 ℃, indicating complete decomposition of the PU prepolymer grafted onto the HGM surfaces, which conclusively confirmed successful surface grafting. Scanning electron microscopy (SEM) images showed that longer molecular chains entangled and aggregated on the HGM surface, forming increased granular and flocculent structures that enhanced surface roughness and structural complexity. Mechanically, the HGM-1000/PU composite demonstrated an optimal tensile strength of 10.06 MPa, representing a 74% improvement over the unmodified composite. However, this strengthening effect gradually diminished with longer grafted chains, while the elongation at break correspondingly increased. This behavior was attributed to increased chain slippage under tensile loads with longer grafts, leading to non-uniform stress distribution within the material. In compression, materials with shorter grafting lengths exhibited superior resistance. Dynamic mechanical analysis (DMA) results indicated that in tensile mode, the modified composites showed relatively higher storage modulus and increased loss modulus peaks. Under compression, longer grafted chains resulted in reduced storage modulus, while in shear mode, shorter grafting lengths produced higher loss modulus peaks. The HGM-3000/PU composite achieved the maximum loss factor peak of 0.81.
These results establish the grafted chain length as a critical parameter for tailoring the composite properties. Shorter chains facilitate efficient stress transfer and yield superior static mechanical strength through enhanced interfacial adhesion. In contrast, medium-length chains induce an optimal viscoelastic response at the interface, which maximizes energy dissipation under dynamic loading conditions. In shear mode, the modified HGM/PU material exhibits the most outstanding dynamic mechanical properties, indicating that interfacial shear slip is the primary mechanism for energy dissipation. This work provides a key basis for the design of high performance lightweight damping materials by precise regulation of interface structure.
关键词
空心玻璃微球 /
聚氨酯 /
化学接枝 /
界面改性 /
动态力学性能 /
阻尼性能
Key words
hollow glass microspheres /
polyurethane /
chemical grafting /
interface modification /
dynamic mechanical properties /
damping properties
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