A kinetic model is presented to explain the metal organic vapor phase epitaxy (MOVPE) growth of GaN. The model is based upon measured desorption rates and assumptions on the precursor dissociation and sticking probabilities. The model shows how the growth temperature and V/III ratio are linked for the growth of high quality GaN films. From a comparison of growth conditions cited in the literature to the quality of GaN produced, optimal film growth appears to occur when the V/III ratio is chosen to be slightly larger than the N to Ga desorption ratio. The relationship between the growth temperature, V/III ratio, and GaN quality are explained in terms of how the growth parameters influence the incorporation of Ga and N atoms into the growing film. The Ga and N diffusion lengths are estimated to be 2–20 nm and <1 nm at 1050 °C, respectively, for practical MOVPE growth rates. Growth conditions for smooth (0001) surface morphology are described in terms of the growth model, as well as possible origins for defect incorporation in GaN. As a result of the large N desorption rate, it is suggested that during growth N is incorporated into the GaN lattice via an adsorption/desorption cycle. Application of the growth model to establishing the growth process conditions and run-to-run reproducibility are also discussed.

Pine (Pinus strobus) sawdust was pyrolyzed in a fluidized-bed reactor between the temperatures of 400 and 600 °C. The fixed-bed volume and residence time were optimized to maximize the liquid yield. We report the detailed physical and chemical properties of the bio-oil fraction collected during fast pyrolysis. The liquid yield was maximized at 500 °C, whereas increased gas formation occurred at 600 °C. 13C NMR of the bio-oil fractions indicated a decrease in the carbohydrate fraction and an increase in the aromatic fraction when pyrolysis temperatures were increased from 500 to 600 °C. Over the ranges of our investigation, the effects of the fixed-bed volume and residence time were negligible on the chemical composition of the bio-oil. Toluene and ethyl acetate bio-oil extracts were analyzed by gas chromatography/mass spectrometry following chemical derivatization. At increased reaction temperatures, the process favored conversion of guaiacols to catechols.

Determination of the molecular composition of biofuels is critical to process development. Because biofuels, such as pyrolysis oil, contain hundreds of compounds, quantitative determination of the mixtures is a formidable task and is often not necessary for routine development work. 13 C and 1 H nuclear magnetic resonance (NMR) offer a reasonable trade-off between functional group identification and analytical measurement effort. However, accuracy depends upon selection of chemical-shift regions, baseline compensation, and correction for incomplete longitudinal relaxation effects. We propose chemical-shift assignments and T 1 correction factors based on 13 C and 1 H NMR measurements of over 50 compounds that have been previously identified in pyrolysis oils and several plant natural products, especially terpenes. The results are intended to allow for a semiquantitative assessment of molecular composition of bio-oils on a time scale of 1-8 h to provide feedback for process development.

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