Hydroxyl‐functional polyurethanes and polyesters: synthesis,properties and potential biomedical application

This mini review gives an overview of the synthesis of polyurethanes and polyesters with pendant hydroxyl groups performed mainly in our group. Significant for the synthesis of most of these polymers with hydroxyl‐functional side groups is that no protection groups are needed. This is realised either by generating the OH group during polymer synthesis—demonstrated by the preparation of hydroxyl‐functional polyurethanes from dicarbonate monomers and diamines—or by using catalysts which discriminate between primary and secondary OH groups—demonstrated by the synthesis of hydroxyl‐functional polyesters based on malic acid using scandium triflate as catalyst. In addition, the potential of carbonate couplers for the synthesis of multifunctional polyurethane is presented. The application of such multifunctional polyurethanes as antimicrobial polymers and coatings is briefly discussed. Copyright © 2012 Society of Chemical Industry     

Effect of biogas technology on nutrient flows for small- and medium-scale pig farms in Vietnam

Increased demand for meat products has led to increased livestock production in Vietnam, which now risks environmental pollution from inappropriate animal manure management on livestock farms. Biogas technology is generally considered an efficient solution for such farms to produce renewable biofuel for use in the household and to reduce the pollution impact from animal waste. However, with biogas technology, farmers may reduce their use of manure for fertilising crops. This field survey investigated nutrient flows on small- and medium-scale livestock farms with and without biogas in Northern Vietnam, in order to identify existing problems and possibilities for sustainable livestock production. A field survey was conducted on 12 pig farms with biogas and 12 pig farms without biogas in Quoc Oai district, Hanoi city. In general, the non-biogas pig farms used on average 3.8 ton compost and 3.1 ton fresh solid manure ha^?1?crop^?1 for each of three crops typically grown per year on their arable land. They discharged on average 16?% of the total manure produced into the environment in liquid form through the public sewage system. On biogas pig farms, the use of fresh solid manure for crops and discharge of liquid manure was lower, as manure was used to produce biogas. However, excessive use of washing water on several of these farms resulted in very dilute slurry (solid manure:water ratio 1:11) entering the biogas digester. This lowered the retention time in the digester (below the optimum range of 35?C55?days), leading to low biogas production rates and possible accumulation of sediment. The digestate was also highly diluted and hence difficult and costly to transport and apply to crops, so it was largely (60?%) discharged to the environment. The input volume of washing water should therefore be reduced to a ratio of 1:5. For better sustainability, appropriate technologies are needed to absorb nutrients from the digestate before discharge and to recycle these nutrients to crops.     

Recycling soil nutrients by using channel deposits as fertilizers?

Topsoil constituents are eroded from agricultural sites and leached towards drainage channels. This transfer can affect aquatic ecosystems and deteriorate the efficiency of drainage systems and fertilisers. As long as erosion cannot be completely avoided, the recycling of sediments and associated nutrients may offer a sustainable solution to these problems. The aim of our case study at the island Sant Erasmo, lagoon of Venice (Italy) was to assess the ecological problems and potentials of sediment recycling. With our assessment we concentrated on (1) the origin of channel sediments, (2) the benefit of sediment application for increasing the nutrient stocks of the soils, and (3) the risk of heavy metal (HM) contamination of arable soils by sediment application. Samples from soils of horticultural sites, sediments, and waters from adjacent drainage channels and lagoon sediments were analyzed for the concentrations of nutrients (P and K) and HM (Cu, Pb, and Zn). Potentially available channel sediment masses and element stocks were calculated for the soil fertility classes of Sant Erasmo based on local measurements of sediment depths and analyses of aerial photographs by a geographic information system. In a column experiment, leaching of both nutrients and Cu from recently dredged sediments was analyzed. Heavy metal concentrations of soils and channel sediments were much higher than of lagoon sediments. The similarity of the chemical properties of the channel sediments and of top soil samples implies that topsoil material is eroded into the channels. The amount of sediments accumulated in the channels corresponded to soil erosion rates between 2 and 23?t?ha^?1?a^?1. Channel sediments contained higher concentrations of nutrients and organic carbon but slightly lower concentrations of HM than the soils of adjacent horticultural sites. Sediment P and K yields would be sufficient to replace fertiliser application at the horticultural sites for up to 51 and 35?years, respectively. The column experiment indicated that Cu mobilization induced by oxidation processes is restricted to the first years after sediments are applied to the soils. Our study emphasizes that for a comprehensive assessment of sediment recycling in agricultural systems the available sediment stocks as well as the contents of nutrients and pollutants of the sediment in relation to soils have to be considered.     

Fluidization of micronic particles in a conical fluidized bed: Experimental and numerical study of static bed height effect

The numerical simulations and experimental data of bed hydrodynamics in a conical fluidized bed unit are compared. Experimental studies have been carried out in a bed containing TiO₂ particles belonging to A/C boundary of Geldart's classification with a wide particle‐size distribution. Thus, pressure measurements and an optical fiber technique allowed determining the effect of static bed height on the fluidization characteristics of micronic particles. Numerical simulations have then been performed to evaluate the sensitivity of gas‐solids drag models. The Eulerian multiphase model has been used with different drag models and three boundary conditions (BC) consisting of no‐slip, partial‐slip, and free‐slip. The numerical predictions using the Gidaspow drag model and partial‐slip BC agreed reasonably well with the experimental bed pressure drop measurements. The simulation results obtained for bed expansion ratio show that the Gidaspow model with the free‐slip BC best fit with the experimental data. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Formation of a Ti-siliceous trimodal material with macroholes, mesopores and zeolitic features via a one-pot templating synthesis

Based on a facile one-pot templating synthesis, using a TS-1 zeolite recipe whereby part of the zeolite structure directing agent is replaced by a mesopore templating agent, a trimodal material is formed. The resulting meso-TSM material combines mesoporosity (Ti-MCM-41) with zeolitic features (TS-1) and a unique sheet-like morphology with uniform macroporous voids (macroholes). Moreover, the macrohole formation, mesoporosity and zeolitic properties of the meso-TSM material can be controlled in a straightforward way by adjusting the length of the hydrothermal treatment. This newly developed material may imply great potential for catalytic redox applications and diffusion limitated processes because of its highly tunable character in all three dimensions (micro-, meso- and macroporous scale).     

Energy efficiency improvement of dimethyl ether purification process by utilizing dividing wall columns

The alternative fuel, dimethyl ether (DME), which can be synthesized from natural gas, coal or biomass syngas, has been traditionally used as a diesel substitute or additive. DME purification processes with a conventional distillation sequence consume a large amount of energy. We used dividing wall columns (DWCs) to improve the energy efficiency and reduce the capital cost of the DME purification process. Various possible DWC arrangements were explored to find the potential benefits derived from thermally coupled distillations. The results show that utilizing DWCs can significantly reduce both the energy consumption and investment cost of the DME purification process. The lower energy consumption also results in the reduction of the CO₂ emission.     

Synthesis of pure aragonite by sonochemical mineral carbonation

The objective of this work was to promote the formation of the aragonite polymorph of calcium carbonate, which has some valuable applications in industry, via the mineral carbonation route. The combination of ultrasound with magnesium ions promoted the formation of pure aragonite crystals at optimum conditions. It was possible to synthesize high purity aragonite precipitates at temperatures ranging from 24 °C to 70 °C, with the resulting powders possessing varying particle size distributions (from sub-micron up to 20 μm) and crystal morphologies (from acicular needles to novel hubbard squash-like particles). Several process parameters were found to influence the produced calcium carbonate polymorph ratios (aragonite over calcite). Higher values of magnesium-to-calcium ratio, intermediate ultrasound amplitude (60%), continuous ultrasound application (100% cycle), introduction of ultrasound pre-breakage, lowering of the CO₂ flow rate, and increase in the relative concentration (g/L Ca(OH)₂), all promoted aragonite formation. A potential route for industrial production of this material has been identified via a fed-batch process, which effectively reutilizes magnesium chloride while maintaining high aragonite yield. The results presented herein are significantly superior to aragonite formation using only single promoting techniques, typically found in literature, and go beyond by focusing on pure (>99%) aragonite formation.     

Synthesis of single-crystal SnO2 nanowires for NOx gas sensors application

Single-crystal SnO₂ nanowires (NWs) were successfully synthesized and characterized as sensing materials for long-term NO_x stability detection in environmental monitoring. Reproducible and selective growths of the SnO₂ NWs on a patterned, 5 nm-thick gold catalyst coated on a SiO₂/Si wafer as substrate were conducted by evaporating SnO powder source at 960 °C in a mixture of argon/oxygen ambient gas (Ar: 50 sccm/O₂: 0.5 sccm). The as-obtained products were characterized by field-emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Raman scattering, and photoluminescence (PL). The SEM and HRTEM images revealed that the products are single-crystal SnO₂ NWs with diameter and length ranges of 70 nm–150 nm and 10 μm–100 μm, respectively. The three observed Raman peaks at 476, 633, and 774 cm⁻¹ indicated the typical rutile phase, which is in agreement with the XRD results. The NWs showed stable PL with an emission peak centered at around 620 nm at room-temperature, indicating the existence of oxygen vacancies in the NW samples. The electrical properties of synthesized SnO₂ NWs sensor were also investigated and it exhibited a negative temperature coefficient of resistance in the measured range (300–525 K). The calculated activation energy E_c of SnO₂ NWs was 0.186 eV. Moreover, the SnO₂ NW sensors exhibited good response to NO_x gas. The response of the sensors to 5 ppm NO_x reached 105% at an operating temperature of 200 °C.     

Nanostructured supported palladium catalysts—Non-oxidative methane coupling

The Pd on α-Al₂O₃ catalysts with Pd particles in the low nanometer range have been prepared by a sonochemical reduction and a colloidal method, respectively. The two catalysts differ in their particle size, the widths of their particle size distributions and the amount of carbon incorporation in the Pd lattice.The adsorptive properties of the Pd/Al₂O₃ samples are different as a result of the different preparation methods. The methane adsorption capacity of that sample with smaller particles is lower than that of the catalyst with larger particles and the energy of activation is nearly doubled. DRIFTS and TPD results of CO adsorption supported by transmission electron microscopy data indicate that the PdSON catalyst with smaller and more homogeneous particles than PdCOL is highly dispersed which influences the coupling-hydrogenolysis process.The catalytic activity evidenced the formation of different adspecies during methane coupling and chemisorption on both catalysts. During the hydrogenation the carbon adspecies formed mainly methane at low adsorption temperatures. The significant amount of adsorbed methane at 773 K is governed by the highly active coordination unsaturated sites at the surface.     

Densification of alumina by SPS and HP: A comparative study

In this study, the densification of alumina by spark plasma sintering (SPS) was investigated and compared to conventional hot pressing. It was shown that SPS is very effective in the sintering of alumina leading to higher densities and allows to work at lower temperatures and with shorter sintering cycles. The effect of the heating rate is dependent on the heating mode (SPS or HP). The identification of active sintering mechanisms was attempted by an isothermal and an anisothermal methods, showing that other mechanisms probably related to electrical effects enhance the densification. We suggest the higher contribution of surface diffusion mainly during the initial stage of sintering and an influence of the presence of impurities segregated at the grain boundaries. They could create conductive layers and also introduce ions with a lower valence than Al³⁺; defects are created in the surface layers and the diffusion of the species is increased.