Eucalyptus fibers were modified with N-β(aminoethyl)-γ-aminopropyl trimethoxy silane to research the fiber surface’s changes and the influence of the treatment on the mechanical properties, flame resistance, thermal conductivity and microstructure of eucalyptus fiber composite phenolic foams (EFCPFs). The results showed that the partial of hemicelluloses, waxes, lignin and impurities from the fiber surface were dissolved and removed. Compared with untreated EFCPFs, the mechanical properties of treated EFCPFs were increased dramatically; The size of cells was smaller and the distribution was more uniform; The thermal conductivities were basically reduced; Especially the ratio of mass loss decreased obviously. However limited oxygen indexs (LOIs) reduced. And the mechanical properties and LOIs of EFCPFs were basically decreased with the increase of eucalyptus fibers. By comprehensive analysis, the results showed that the interfacial compatibility has been significantly improved between eucalyptus fibers and phenolic resin. And the suitable dosage of eucalyptus fibers was about 5%.
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