High Reactivity of Metal-Organic Frameworks under Grinding Conditions: Parallels with Organic Molecular Materials

Interconversion made easy: Metal–organic frameworks (MOFs) are surprisingly reactive under grinding conditions and can perform various rearrangements (see picture). In this respect, the results reveal clear parallels between MOFs and organic molecular materials.

Mechanochemical interconversion between discrete complexes and coordination networks - formal hydration/dehydration by LAG

Using a small planetary ball mill, liquid-assisted grinding (LAG) of metal salts or oxides (ZnO, CdO, CdCO3, Cu(OAc)(2)center dot H2O, Co(OAc)(2)center dot 4H(2)O, Mn(OAc)(2)center dot 4H(2)O, Ni(OAc)(2)center dot 4H(2)O, FeSO4 center dot 7H(2)O) with two equivalents of isonicotinic acid (HINA) and small amounts of water ( up to 5.6 molar equivalents) gave discrete aquo complexes trans-[M(INA)(2)(OH2)(4)] (M = Zn, Cd, Cu, Fe, Co, Ni, Mn) efficiently within 30 min. For M = Zn, Cd and Cu these complexes readily undergo reversible formal dehydration to the extended network structures [M(INA)(2)] (M = Zn, Cu) or [Cd(INA)(2)(OH2)]center dot DMF by further LAG with non-aqueous liquids such as methanol or DMF. Overall, the mechanochemical dehydrations are more effective than heating or immersion in bulk solvents. The work demonstrates a two-step mechanochemical synthesis of coordination networks via discrete aquo complexes which may be preferable to single step reactions or grinding-annealing procedures in some cases. For example, the two step method was the only way to prepare [Cd(INA)(2)(OH2)]center dot DMF mechanochemically and the porous network Cu(INA)(2) could not be obtained from the aquo complex by heating.

Mechanochemical preparation of Ag catalysts for the n-octane-SCR de-NOx reaction: Structural and reactivity effects

Mechanochemical preparation of Ag/Al2O3 catalysts used for the selective catalytic reduction of NOx using hydrocarbons has been shown to substantially increase the activity of the catalyst in comparison with Ag/Al2O3 prepared by wet impregnation. The effect of using different ball-milling experimental parameters on both the structure of the material as well as the catalyst activity has been investigated and the optimum conditions established. A phase transition from γ- to α-alumina was observed milling at high speeds which was found to result in lower catalyst activities. At lower milling speeds both fracturing and agglomeration of the alumina support can be observed depending on the grinding time. However, due to ball-milling, a general enhancement in the NOx reduction activity was observed for all catalysts compared with the conventionally prepared catalysts irrespective of the reductant used. Transient DRIFTS-MS experiments were performed to investigate the effect of H2 in the absence and presence of water on the SCR reaction over catalysts prepared by both ball milling and wet impregnation. In-situ DRIFTS-MS analysis revealed significant differences in both gas phase and surface species. Most notably, isocyanate species were formed significantly more quickly and at higher surface concentration in the case of the mechanochemically prepared catalyst.

Milling plant and soil material in plastic tubes over-estimates carbon and under-estimates nitrogen concentrations

Milling of plant and soil material in plastic tubes, such as microcentrifuge tubes, over-estimates carbon (C) and under-estimates nitrogen (N) concentrations due to the introduction of polypropylene into milled samples, as identified using Fourier-transform infra-red spectroscopy.

This study compares C and N concentrations of roots and soil milled in microcentrifuge tubes versus stainless steel containers, demonstrating that a longer milling time, greater milling intensity, smaller sample size and inclusion of abrasive sample material all increase polypropylene contamination from plastic tubes leading to overestimation of C concentrations by up to 8 % (0.08 g g(-1)).

Erroneous estimations of C and N, and other analytes, must be assumed after milling in plastic tubes and milling methods should be adapted to minimise such error.

Effect of reinforcement and heat treatment on elevated temperature sliding of electroless Ni–P/SiC composite coatings

The investigation is focused on the wear behaviour at elevated test temperature of composite Ni–P/SiC deposit, with varying concentration of the reinforcing SiC particles. The phase evolution measured by X-ray diffraction suggests slight crystallisation during wear testing at 200 °C. In coating without reinforcing particles, adhesive wear is accompanied by microcracks. The thermal heat generated and the cyclic loading could have induced sub-surface microcracks. Owing to the effective matrix-ceramics system in composite coatings, fine grooves, abrasive polishing and uniform wearing are observed. Reinforcing particles in the matrix hinder microcrack formation and significantly reduce the wear rate. Triboxidation is confirmed from energy dispersive X-ray spectrometry.

Persistent luminescence of SrAl2O4:Ce(III), Dy, Eu nanotubes, nanowires and core-shells for people with disabilities: nano-emergency

Este estudo transversal está focado na propriedade de luminescência persistente do aluminato de estrôncio co-dopado com cério (III), disprósio (III) e európio (II), SrAl2O4:Ce3+, Dy3+, Eu2+, em sistemas de sinalização de áreas de risco e emergências para pessoas com deficiências. Na área da ciência e engenharia dos materiais, foram desenvolvidos novos materiais com características nanométricas, nanotubos, nanoarames e nanobastões luminescentes de SrAl2O4:Ce3+, Dy3+, Eu2+ para aplicações na área da reabilitação e acessibilidade de pessoas com deficiências. Os nanotubos foram obtidos a partir de micro- e nano-partículas precursoras sintetizadas por reacção do estado-sólido e tratamento térmico de recozedura (1273-1473 K). Os nanoarames e nanobastões foram preparados por moagem, sonificação e recozedura (373 K). Novas nanocápsulas de aluminatos luminescentes dopados com cério (III) e encapsulados com TiO2 foram criadas de modo a obter-se materiais multifuncionais, designadamente com acção fotocatalítica antimicrobiana, antibacteriana e resistência à água. Tais aluminatos podem ser amplamente aplicados como superfícies higiénicas, auto-limpantes, em biomateriais, no domínio de medicamentos antibióticos, na formulação de vacinas, e com ênfase à aplicação em cerâmicas fotoluminescentes. As metodologias de obtenção de tais nanoestruturas de aluminato de estrôncio dopado com cério (III) e do seu encapsulamento, desenvolvidas no âmbito desta tese, são aplicáveis a diversos aluminatos dopados com outros iões lantanídeos (Ln consiste em La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Tm ou Lu) com a fórmula M(1-x-y)N2O4:Cex, Lny, onde M é Be, Mg, Ca, Sr ou Ba. Na área da oftalmologia, foi desenvolvido um equipamento médico para o diagnóstico de biofuncionalidade das células retinais fotoreceptoras, e como suporte à telemedicina oftalmológica. Este equipamento foi utilizado para realizar testes de visão cromática FM100HUE em fundo branco/preto para a personalização de materiais luminescentes. Os resultados demonstraram uma biofuncionalidade celular à visibilidade fotópica das cores em fundo preto superior no grupo de tratamento, composto por pessoas com retinopatia diabética (n=38), em comparação ao grupo de referência (n=38). Estes resultados sugerem a recomendação de materiais com fotoluminescência persistente (λem=485-555 nm), incluindo SrAl2O4:Ce3+, Dy3+, Eu2+, para o referido grupo de tratamento, em sinalização de emergência e em ambientes de baixa iluminação. Na área da arquitectura, foi proposta uma nova aplicação dos referidos nanomateriais luminescentes à base de SrAl2O4:Ce3+, Dy3+, Eu2+ em cerâmica de revestimento, tendo em vista a sua boa visibilidade e uso por pessoas com deficiências. Novos pavimentos, cerâmicos, fotoluminescentes, foram desenhados com propriedades multisensoriais (contraste táctil, sonoro e visual) e antimicrobianas, para pessoas portadoras de deficiências utilizarem, no escuro, com a prioridade de salvar vidas em emergências. Tais pisos, com relevos, podem ser combinados de modo a compor um sistema exclusivo de sinalização fotoluminescente multisensorial que possibilita a rápida evacuação mediante o uso de auxílios de mobilidade (e.g. bengala, cadeira de rodas, andadores, muletas). A solução integrada de tais inovações que potencializa a propriedade de luminescência persistente de SrAl2O4:Ce3+, Dy3+, Eu2+ de modo acessível para as pessoas com deficiências, pode contribuir para salvar vidas, no escuro, em emergências.

Abrasion, transport and distribution of sediment in selected streams of Southern Ontario and Western New York /

The rate of decrease in mean sediment size and weight per square metre along a 54 km reach of the Credit River was found to depend on variations in the channel geometry. The distribution of a specific sediment size consist of: (1) a transport zone; (2) an accumulation zone; and (3) a depletion zone. These zones shift downstream in response to downcurrent decreases in stream competence. Along a .285 km man-made pond, within the Credit River study area, the sediment is also characterized by downstream shifting accumulation zones for each finer clast size. The discharge required to initiate movement of 8 cm and 6 cm blocks in Cazenovia Creek is closely approximated by Baker and Ritter's equation. Incipient motion of blocks in Twenty Mile Creek is best predicted by Yalin's relation which is more efficient in deeper flows. The transport distance of blocks in both streams depends on channel roughness and geometry. Natural abrasion and distribution of clasts may depend on the size of the surrounding sediment and variations in flow competence. The cumulative percent weight loss with distance of laboratory abraded dolostone is defined by a power function. The decrease in weight of dolostone follows a negative exponential. In the abrasion mill, chipping causes the high initial weight loss of dolostone; crushing and grinding produce most of the subsequent weight loss. Clast size was found to have little effect on the abrasion of dolostone within the diameter range considered. Increasing the speed of the mill increased the initial amount of weight loss but decreased the rate of abrasion. The abrasion mill was found to produce more weight loss than stream action. The maximum percent weight loss determined from laboratory and field abrasion data is approximately 40 percent of the weight loss observed along the Credit River. Selective sorting of sediment explains the remaining percentage, not accounted for by abrasion.

Surface effect ferromagnetism in pure and reduced strontium titanate

A room temperature ferromagnetic hysteresis is observed in single crystal strontium titanate substrates as purchased from several manufacturers. It was found that polishing all sides of the substrates removed this observed hysteresis, suggesting that the origin of the ferromagnetic behavior resides on the surface of the substrates. X-ray diffraction and energy dispersive x-ray spectra were measured however they were unable to detect any impurity phases. In similar semiconducting oxides it was previously suggested that ferromagnetism could originate in oxygen vacancies or from disorder within the single crystal. To this end substrates were annealed in both air and vacuum in a range of temperatures (600°C to 1100°G) to both create bulk oxygen vacancies and to heal surface damage. Annealing in vacuum was found to create a measureable number of oxygen vacancies however their creation could not be correlated to the ferromagnetic signal of the substrate. Annealing in air was found to effect the remnant moment of the substrate as well as the width of the x-ray diffraction peaks on the unpolished face, weakly suggesting a relation between surface based disorder and ferromagnetism. Argon ion bombardment was employed to create a layer of surface disorder in the polished crystal, however it was not found to induce ferromagnetism. It was found that acid etching was sufficient to remove the ferromagnetism from as purchased samples and similarly simulated handling with stainless steel tweezers was sufficient to re-create the ferromagnetism. It is suggested that the origin of this ferromagnetism in SrTi03 is surface contaminants (mainly iron).

Meat yield and quality of Tanzania Shorthorn Zebu cattle finished on molasses/maize grain with agro-processing by-products in 90 days feedlot period

This study was conducted to evaluate the effects of feeding molasses or maize grain with agro-processing by-products on yield and quality of meat from Tanzania shorthorn zebu (TSZ) cattle. Forty five steers aged 2.5 to 3.0 years with 200 +/- 5.4 kg body weight were allocated into five dietary treatments namely hominy feed with molasses (HFMO), rice polishing with molasses (RPMO), hominy feed with maize meal (HFMM), rice polishing with maize meal (RPMM) and maize meal with molasses (MMMO). Ad libitum amount of each dietary treatment and hay were offered to nine steers for 90 days. Cooking loss (CL) and Warner Bratzler shear force (WBSF) values were determined on M. longissimus thoracis et lumborum aged for 3, 6, 9 and 12 days. Steers fed on HFMO diet had higher (P < 0.05) nutrient intake (86.39 MJ/d energy; 867 g/d CP), weight gain (919 g/d) and half carcass weight (75.8 kg) than those fed other diets. Meat of steers from all diets was tender with average WBSF values of 47.9 N cm^(−2). The CL (22.0 +/- 0.61%) and WBSF (53.4 +/- 0.70 N cm^(−2)) were highest in meat aged for 3 days followed by 6, 9 and 12 days. WBSF values for meat aged for 9 and 12 days from steers fed HFMO and RPMM diets were similar and lower than those on other dietary treatments x aging periods. Overall, molasses and hominy feed can be used to replace maize meal in feedlot finishing diets to spare its use in animal feeds.

A Multi-scale Model for Copper Dishing in Chemical-Mechanical Polishing

The present success in the manufacture of multi-layer interconnects in ultra-large-scale integration is largely due to the acceptable planarization capabilities of the chemical-mechanical polishing (CMP) process. In the past decade, copper has emerged as the preferred interconnect material. The greatest challenge in Cu CMP at present is the control of wafer surface non-uniformity at various scales. As the size of a wafer has increased to 300 mm, the wafer-level non-uniformity has assumed critical importance. Moreover, the pattern geometry in each die has become quite complex due to a wide range of feature sizes and multi-level structures. Therefore, it is important to develop a non-uniformity model that integrates wafer-, die- and feature-level variations into a unified, multi-scale dielectric erosion and Cu dishing model. In this paper, a systematic way of characterizing and modeling dishing in the single-step Cu CMP process is presented. The possible causes of dishing at each scale are identified in terms of several geometric and process parameters. The feature-scale pressure calculation based on the step-height at each polishing stage is introduced. The dishing model is based on pad elastic deformation and the evolving pattern geometry, and is integrated with the wafer- and die-level variations. Experimental and analytical means of determining the model parameters are outlined and the model is validated by polishing experiments on patterned wafers. Finally, practical approaches for minimizing Cu dishing are suggested.

A Multi-scale Model for Copper Dishing in Chemical-Mechanical Polishing

The present success in the manufacture of multi-layer interconnects in ultra-large-scale integration is largely due to the acceptable planarization capabilities of the chemical-mechanical polishing (CMP) process. In the past decade, copper has emerged as the preferred interconnect material. The greatest challenge in Cu CMP at present is the control of wafer surface non-uniformity at various scales. As the size of a wafer has increased to 300 mm, the wafer-level non-uniformity has assumed critical importance. Moreover, the pattern geometry in each die has become quite complex due to a wide range of feature sizes and multi-level structures. Therefore, it is important to develop a non-uniformity model that integrates wafer-, die- and feature-level variations into a unified, multi-scale dielectric erosion and Cu dishing model. In this paper, a systematic way of characterizing and modeling dishing in the single-step Cu CMP process is presented. The possible causes of dishing at each scale are identified in terms of several geometric and process parameters. The feature-scale pressure calculation based on the step-height at each polishing stage is introduced. The dishing model is based on pad elastic deformation and the evolving pattern geometry, and is integrated with the wafer- and die-level variations. Experimental and analytical means of determining the model parameters are outlined and the model is validated by polishing experiments on patterned wafers. Finally, practical approaches for minimizing Cu dishing are suggested.