Co-doping effects of (Al,Ti, Mg) on the microstructure and electrical behavior of ZnO-based ceramics

Co-doped ZnO-based ceramics using Al, Ti, and Mg ions in different ratios were synthesized with the objective to investigate the doping effects on the crystalline features, microstructure and the electrical behavior. For Al and Ti doping, a coexistence of crystalline phases was shown with a major wurtzite ZnO structure and secondary spinel phases (ZnAl₂O₄, Zn₂TiO₄, or Zn_aTi_bAl_cO_d), while Mg doping did not alter significantly the structural features of the wurtzite ZnO phase. The electrical behavior induced by Al, Ti, and Mg co-doping in different ratios was investigated using Raman, electron paramagnetic resonance (EPR) and ²⁷Al and ⁶⁷Zn solid-state nuclear magnetic resonance (NMR). Al doping induces a high electrical conductivity compared to other doping elements. In particular, shallow donors from Zn_i-Al_Zn defect structures are inferred from the characteristic NMR signal at about 185 ppm; that is, quite far from the usual oxygen coordinated Al. The Knight shift effect emanating from a highly conducting Al-doped ZnO ceramics was considered as the origin of this observation. Oppositely, as Ti doping leads to the formation of secondary spinel phases, EPR analysis shows a high concentration of Ti³⁺ ions which limit the electrical conductivity. The correlation between the structural features at the local order, the involved defects and the electrical behavior as function of the doping process are discussed.     

Bioraffinerien auf Basis schwach verholzter Biomasse

Weakly lignified biomass, like brewers' spent grain and grass silage, is good feedstock for biorefineries. The biomass can be separated and converted into valuable products in different ways. In this study, brewers' spent grain is used to investigate solid state fermentations with Cellulomonas uda. Additionally, hydrothermal pretreatment and subsequent enzymatic saccharification, as well as formation of inhibitory compounds, is demonstrated. Hydrothermal pretreatment combined with simultaneous saccharification and fermentation is shown as an example for the utilization of grass silage.     

Local analysis of Marangoni effects during and after droplet formation

The influence on the mass transfer in liquid-liquid extraction was investigated during droplet formation in a quiescent aqueous continuous phase for the two transition components, acetone and acetonitrile, in toluene. Both transition components have similar characteristics. However, an approximately eight times slower mass transfer of a droplet hanging on a capillary in relation to a rising droplet could be observed. The droplet formation time and the initial solute concentration are decisive for the mass transfer behaviour. A lower volumetric flow leads to slower droplet formation and a higher specific mass transfer area enhancing mass transfer, which is visualized via laser induced fluorescence (LIF). Additionally, as expected, higher initial solute concentrations promote Marangoni turbulences and thus mass transfer, which is measured via confocal Raman spectroscopy inside a fixed hanging droplet.     

Synthesis of end-branched poly(ethylene glycol)s by aqueous atom transfer radical polymerization

Summary This article reports the synthesis of novel hydrophilic end-branched poly(ethylene glycol)s, in aqueous media by atom transfer radical polymerization (ATRP). Poly(ethylene glycol)s with molecular weights 10,000 and 16,000 were end-functionalized and used as bifunctional initiators for the polymerization of a poly(ethylene glycol) macromonomer with a molecular weight of 2,000 (PEGMA), either by aqueous ATRP or in a watedmethanol (l/l V/V) mixture. For both macroinitiators a DP of 10 was the target, giving an average of 5 branches in each end. The rates of polymerization were of the same order of magnitude when the polymerizations were initiated by either of the two macroinitiators in watedmethanol (l/l V/V). When a bifunctional oligo(ethy1ene glycol) initiator (M_n = 600) was used to study the polymerization of PEGMA in water/methanol a reduction in the rate of polymerization was observed indicating an influence of the molecular weight of the initiator on the rate of polymerization. Received 25 Maich 2002/Revised 8 November 2002/Accepted 8 November 2002 Correspondence to Jorgen Kops     

Large-Scale Hydrogen Production

There is a growing need for hydrogen in processing heavier and dirtier fossil fuels and a future hydrogen economy is widely suggested as the next generation fuel/energy source once fossil fuels diminish in availability. Sustainable fuels are still regarded as too expensive given the large amounts of natural gas and a projected, ample supply of fossil fuels beyond the next twenty-plus years. Today, the steam reforming of hydrocarbons is the most favorable route to H₂. If CO₂ sequestration were ever to become widely practiced, fossil fuels would continue to play an important role in the future hydrogen economy.     

Modification of margarine fats by enzymatic interesterification: Evaluation of a solid-fat-content-based exponential model with two groups of oil blends

Lipozyme TL IM-catalyzed interesterification for the modification of margarine fats was carried out in a batch reactor at 70°C with a lipase dosage of 4%. Solid fat content (SFC) was used to monitor the reaction progress. Lipase-catalyzed interesterification, which led to changes in the SFC, was assumed to be a first-order reversible reaction. Accordingly, the change in SFC vs. reaction time was described by an exponential model. The model contained three parameters, each with a particular physical or chemical meaning: (i) the initial SFC (SFC₀), (ii) the change in SFC (ΔSFC) from the initial to the equilibrium state, and (iii) the reaction rate constant value (k). SFC_o and ΔSFC were related to only the types of blends and the blend ratios. The rate constant k was related to lipase activity on a given oil blend. Evaluation of the model was carried out with two groups of oil blends, i.e., palm stearin/coconut oil in weight ratios of 90∶10, 80∶20, and 70∶30, and soybean oil/fully hydrogenated soybean oil in weight ratios of 80∶20, 65∶35, and 50∶50. Correlation coefficients higher than 0.99 between the experimental and predicted values were observed for SFC at temperatures above 30°C. The model is useful for predicting changes in the SFC during lipase-catalyzed interesterification with a selected group of oil blends. It also can be used to control the process when particular SFC values are targeted.