Effect of Surface Grafting Modification of Hollow Glass Microspheres on Dynamic Mechanical Properties of Polyurethane Composites

CHEN Ziang; WANG Jianlong; WANG Wenqun; WANG Yanbin; ZHANG Songsong; MA Teng; WANG Guojun

doi:10.16490/j.cnki.issn.1001-3660.2026.09.016

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Surface Technology ›› 2026, Vol. 55 ›› Issue (9) : 202-212. DOI: 10.16490/j.cnki.issn.1001-3660.2026.09.016

Surface and Interface Strengthening Technology

Effect of Surface Grafting Modification of Hollow Glass Microspheres on Dynamic Mechanical Properties of Polyurethane Composites

CHEN Ziang¹, WANG Jianlong¹, WANG Wenqun², WANG Yanbin¹, ZHANG Songsong^1,*, MA Teng¹, WANG Guojun¹

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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.

Key words

hollow glass microspheres / polyurethane / chemical grafting / interface modification / dynamic mechanical properties / damping properties

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CHEN Ziang, WANG Jianlong, WANG Wenqun, WANG Yanbin, ZHANG Songsong, MA Teng, WANG Guojun. Effect of Surface Grafting Modification of Hollow Glass Microspheres on Dynamic Mechanical Properties of Polyurethane Composites[J]. Surface Technology. 2026, 55(9): 202-212

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