We studied the concentration dependence of nu(C-H)'s in IR and (1)J(C,H) in NMR for binary water-tetrahydrofuran (THF) mixtures and found different trends for the two types of CH(2) groups in the five-membered ring. The changes of the nu(C-O) spectra showed that complexes of THF associated with water are formed, in which the number of water molecules increases with the water concentration. We suggested that hydration proceeds through the formation of 1:1, and 1:2 complexes of [THF:water] up to X(H(2)O) approximately 0.9, where X(H)((2))(O) is the mole fraction of the water in the mixtures. We carried out ab initio MO and DFT calculations to optimize the geometries of a THF dimer as a model of THF molecules in pure liquid, and 1:1 and 1:2 complexes of [THF:water] to simulate observed concentration dependence of nu(C-H)'s in IR and (1)J(C,H) in NMR. The changes of the calculated nu(C-H) spectra and (1)J(C,H) values for the optimized complexes are in agreement with those observed with varying X(H)((2))(O), supporting our proposal. From the vibrational and NBO analyses of the optimized complexes, the observed blue shift of nu(C-H)'s and the increase of (1)J(C,H) for the CH(2) groups neighboring to the ether oxygen were explained in terms of the changes in the stereoelectronic effect, resulting from HO-H...O< hydrogen bonding. The optimized 1:2-complex contains two weak C-H...OH(2) hydrogen bonds, and blue shift of nu(C-H)'s and increase of (1)J(C,H) were demonstrated from the same analyses of the complexes. This result of simulation also supports that the blue shift of nu(C-H)'s and increase of (1)J(C,H) observed for both the type of CH(2) groups at 0.6 X(H)((2))(O) < 0.9 are attributed to these interactions. On the basis of all these results, we propose that the formation of the 1:2-complex involving weak C-H...OH(2) hydrogen bonds is responsible dominantly for the hydrophobic hydration of THF.

In high-velocity oxy-fuel (HVOF) spraying of WC-Co coatings, the decomposition and decarburization of WC during deposition are responsible for their much lower toughness compared with a sintered bulk WC-Co. In a previous study, Warm Spray (WS) process, which is capable to control the flame temperature used to propel powder particles, was successfully applied in an attempt to suppress such detrimental reactions by keeping particlesÕ temperature lower than their melting point. The coatings deposited by WS process showed no or little formation of W 2 C and g phases and demonstrated moderately improved fracture properties. However, there is still a gap in fracture toughness between WS coatings and the corresponding sintered bulk. In order to optimize the properties of the WS coatings, the effect of original powder sizes were investigated. Microstructural characterization and phase analysis were carried out on deposited coatings by SEM and XRD. The results show that the feedstock powder size has substantial effects on the properties of the coatings, i.e., the smaller powder showed improved properties.

The high-velocity oxy-fuel (HVOF) process is commonly used to deposit WC-Co coatings. There are some problems with this process; especially the decomposition and decarburization of WC during spraying make a coating brittle. To suppress such degradation, the warm spray (WS) process was applied to deposit WC-Co coatings, which is capable of controlling the flame temperature in the range of 500-2000°C. The microstructure and phases of the deposited coatings were characterized by using SEM and XRD, and the mechanical properties such as hardness, fracture toughness, and wear properties were also investigated. WS process successfully suppressed the formation of the detrimental phases such as W 2 C and W, which are usually observed in HVOF coatings. The WS coatings showed the similar trend of the hardness variation for Co content with a sintered bulk material. Improvement of toughness and wear behavior was also observed in WS coatings.