Novolac-type bisphenol-F based molybdenum-phenolic resins/silane-modified aluminum nitride (Mo-BPF/m-AlN) composites were successfully prepared. In the preparation process, molybdate reacted with bisphenol-F based phenolic resins (BPF) to form a low cross-linked Mo-BPF with new Mo-O bonds which were confirmed by the FTIR and XPS spectra. Simultaneously, a special silane-modified aluminum nitride (m-AlN) was prepared with 3-aminopropyltriethoxysilane (APTES) modifier. Then, this m-AlN was fully mixed with Mo-BPF to form Mo-BPF/m-AlN which can be further cured with hexamethylenetetramine at 200 degrees C. The structure and characterization of BPF, Mo-BPF and Mo-BPF/m-AlN were determined by using FTIR, DSC, DMA, TGA, SEM, mechanical properties and contact angle measurements. SEM photographs show that m-AlN particles are uniformly distributed in the Mo-BPF/m-AlN composites. Also there are no gaps or void between m-AlN and Mo-BPF phases, which implies a strong physical bonding between the two phases. The glass transition temperature, thermal resistance, flexural strength, and hardness of Mo-BPF are respectively higher than those of BPF. This is due to the presence of Mo-O cross-linking bonds in Mo-BPF. When the m-AlN was additionally incorporated into Mo-BPF, the well-dispersed and well-adhered m-AlN can further promote all the above-mentioned properties of the composites. Typically, the glass transition temperature, decomposition temperature at 5% weight loss and flexural strength of Mo-BPF/m-AlN are 245 degrees C, 428 degrees C and 82.7 MPa respectively, which are much higher than the corresponding values of 184 degrees C, 358 degrees C and 58.2 MPa for BPF. In addition, the hygroscopic nature of BPF can be inhibited by treating with molybdate or incorporating with m-AlN. This is due to that the m-AlN is hydrophobic and Mo-O groups in Mo-BPF are more hydrophobic than OH groups in BPF. Furthermore, Mo-BPF/m-AlN was compared with BPF in the performance as a binder for diamond cutting wheels. Mo-BPF/m-AlN is a better binding resin than BPF so the cutting wheel made from the former resin has better cutting quality than that made from the latter resin. (C) 2013 Elsevier B. V. All rights reserved.