Three series of potassium carbonate and thiocarbonate salts were synthesized, and the corresponding (13)C isotropic solid-state NMR and the aqueous solution (13)C and (1)H NMR data were collected. The series of compounds that were studied consists of (1) the parent compounds, i.e., potassium carbonate, K(2)CO(3), potassium hydrogen carbonate, KHCO(3), potassium monothiocarbonate, K(2)CO(2)S, potassium dithiocarbonate, K(2)COS(2), and potassium trithiocarbonate, K(2)CS(3), (2) the oxygen monoalkyl substituted derivatives of the parent compounds (OR series), i.e., three potassium O-alkylcarbonates, KO(2)COR, three potassium O-alkylmonothiocarbonates, KOSCOR, and three potassium O-alkyldithiocarbonates, KS(2)COR, all with R = CH(3), CH(2)CH(3), CH(CH(3))(2), and (3) the sulfur monoalkyl substituted derivatives of the parent compounds (SR series), i.e., two potassium S-alkylmonothiocarbonates, KO(2)CSR; two potassium S-alkyldithiocarbonates, KOSCSR, and two potassium S-alkyltrithiocarbonates, KS(2)CSR, all with R = CH(3) or CH(2)CH(3). The preparation and proper characterization of KO(2)CSR and KOSCSR with R = CH(3) and CH(2)CH(3) along with new IR and X-ray powder diffraction data for several other compounds in the series are reported for the first time in this study. Solution NMR data for KO(2)CSR (R = CH(3), CH(2)CH(3)) and KOSCSR (R = CH(3)) and solid-state NMR data for K(2)CO(2)S and K(2)COS(2) could not be obtained because they are unstable under the corresponding measurement conditions. The isotropic chemical shift values of the central carbon atoms obtained from solid-state MAS (magic angle spinning) NMR experiments deviate at most by 3 ppm from the corresponding solution values. Two major trends in the (13)C chemical shift values of the central carbon atoms were found. First, if an oxygen atom in a parent compound or in an alkyl-substituted derivative is replaced by a sulfur atom, a significantly higher chemical shift value is observed. This trend is discussed in terms of the paramagnetic contribution to the chemical shielding constant. Second, the size of the alkyl group in the monoalkyl derivatives has a very small effect on the chemical shift values of the central carbon atoms. This observation is explained using the concept of varying inductive effects produced by alkyl groups. The trends observed for the (13)C and (1)H chemical shift values of the alkyl groups follow common concepts on the structure dependency of chemical shifts.
In Australia, plantation forests have increased in area by around 50% in the last 10 years. While this expansion has seen a modest 8% increase for softwoods, hardwood plantations have dramatically increased by over 150%. Hardwood plantations grown for high quality sawn timber are slow to mature, with a crop rotation time potentially reaching 35 years. With this long lead-time, each year the risk from fire, pests and adverse weather events dramatically increases, while not translating into substantially higher financial returns to the grower. To justify continued expansion of Australia's current hardwood plantation estate, it is becoming necessary to develop higher value end-uses for both pulpwood and smaller 'sawlog' resources. The use of the low commercial value stems currently culled during thinning appears to be a necessary option to improve the industry profitability and win new markets. This paper provides background information on Australian forests and plantations and gives an overview of potential uses of Australian hardwood plantation thinning logs, as their mechanical properties. More specifically, this paper reports on the development of structural Veneer Based Composite (VBC) products from hardwood plantation thinning logs, taking advantage of a recent technology developed to optimise the processing of this resource. The process used to manufacture a range of hollow-form veneer laminated structural products is presented and the mechanical characteristics of these products are investigated in the companion paper. The market applications and future opportunities for the proposed products are also discussed, as potential benefits to the timber industry.
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