Ammonia effects on proton conductivity properties of coordination polymers

Crystalline metal phosphonates are referred to as a type of structurally versatile coordination polymers [1]. Many of them contain guest molecules (H2O, heterocyclics, etc.), acidic sites and, furthermore, their structure can be also amenable for post‐synthesis modifications in order to enhance desired properties [2]. In the present work, we examine the relationships between crystal structure and proton conductivity for several metal phosphonates derive from multifunctional ligands, such as 5-(dihydroxyphosphoryl)isophthalic acid (PiPhtA) [3] and 2-hydroxyphosphonoacetic acid (H3HPAA). Crystalline divalent metal derivatives show a great structural diversity, from 1D to 3D open-frameworks, possessing hydrogen-bonded water molecules and acid groups. These solids present a proton conductivity range between 7.2·10-6 and 1.3·10−3 S·cm-1. Upon exposure to ammonia vapor, from an aqueous solution, solid state transformations are observed accompanied of enhance proton conductivities. The stability of these solids under different environment conditions (temperature and relative humidities) as well as the influence of the ammonia adsorption on the proton conduction properties of the resulting solids will be discussed.

MULTISCALE MODELING OF LIQUID CRYSTALLINE/NANOTUBE COMPOSITES

The objective of this research is to synthesize structural composites designed with particular areas defined with custom modulus, strength and toughness values in order to improve the overall mechanical behavior of the composite. Such composites are defined and referred to as 3D-designer composites. These composites will be formed from liquid crystalline polymers and carbon nanotubes. The fabrication process is a variation of rapid prototyping process, which is a layered, additive-manufacturing approach. Composites formed using this process can be custom designed by apt modeling methods for superior performance in advanced applications. The focus of this research is on enhancement of Young's modulus in order to make the final composite stiffer. Strength and toughness of the final composite with respect to various applications is also discussed. We have taken into consideration the mechanical properties of final composite at different fiber volume content as well as at different orientations and lengths of the fibers. The orientation of the LC monomers is supposed to be carried out using electric or magnetic fields. A computer program is modeled incorporating the Mori-Tanaka modeling scheme to generate the stiffness matrix of the final composite. The final properties are then deduced from the stiffness matrix using composite micromechanics. Eshelby's tensor, required to calculate the stiffness tensor using Mori-Tanaka method, is calculated using a numerical scheme that determines the components of the Eshelby's tensor (Gavazzi and Lagoudas 1990). The numerical integration is solved using Gaussian Quadrature scheme and is worked out using MATLAB as well. . MATLAB provides a good deal of commands and algorithms that can be used efficiently to elaborate the continuum of the formula to its extents. Graphs are plotted using different combinations of results and parameters involved in finding these results

Investigating the mesh dependency and upscaling of 3D grain-based models for the simulation of brittle fracture processes in low-porosity crystalline rock

The application of 3D grain-based modelling techniques is investigated in both small and large scale 3DEC models, in order to simulate brittle fracture processes in low-porosity crystalline rock. Mesh dependency in 3D grain-based models (GBMs) is examined through a number of cases to compare Voronoi and tetrahedral grain assemblages. Various methods are used in the generation of tessellations, each with a number of issues and advantages. A number of comparative UCS test simulations capture the distinct failure mechanisms, strength profiles, and progressive damage development using various Voronoi and tetrahedral GBMs. Relative calibration requirements are outlined to generate similar macro-strength and damage profiles for all the models. The results confirmed a number of inherent model behaviors that arise due to mesh dependency. In Voronoi models, inherent tensile failure mechanisms are produced by internal wedging and rotation of Voronoi grains. This results in a combined dependence on frictional and cohesive strength. In tetrahedral models, increased kinematic freedom of grains and an abundance of straight, connected failure pathways causes a preference for shear failure. This results in an inability to develop significant normal stresses causing cohesional strength dependence. In general, Voronoi models require high relative contact tensile strength values, with lower contact stiffness and contact cohesional strength compared to tetrahedral tessellations. Upscaling of 3D GBMs is investigated for both Voronoi and tetrahedral tessellations using a case study from the AECL’s Mine-by-Experiment at the Underground Research Laboratory. An upscaled tetrahedral model was able to reasonably simulate damage development in the roof forming a notch geometry by adjusting the cohesive strength. An upscaled Voronoi model underestimated the damage development in the roof and floor, and overestimated the damage in the side-walls. This was attributed to the discretization resolution limitations.

Non-ambient solid-state characterization of crystalline molecular organic semiconductors

The research project is focused on the investigation of the polymorphism of crystalline molecular material for organic semiconductor applications under non-ambient conditions, and the solid-state characterization and crystal structure determination of the different polymorphic forms. In particular, this research project has tackled the investigation and characterization of the polymorphism of perylene diimides (PDIs) derivatives at high temperatures and pressures, in particular N,N’-dialkyl-3,4,9,10-perylendiimide (PDI-Cn, with n = 5, 6, 7, 8). These molecules are characterized by excellent chemical, thermal, and photostability, high electron affinity, strong absorption in the visible region, low LUMO energies, good air stability, and good charge transport properties, which can be tuned via functionalization; these features make them promising n-type organic semiconductor materials for several applications such as OFETs, OPV cells, laser dye, sensors, bioimaging, etc. The thermal characterization of PDI-Cn was carried out by a combination of differential scanning calorimetry, variable temperature X-ray diffraction, hot-stage microscopy, and in the case of PDI-C5 also variable temperature Raman spectroscopy. Whereas crystal structure determination was carried out by both Single Crystal and Powder X-ray diffraction. Moreover, high-pressure polymorphism via pressure-dependent UV-Vis absorption spectroscopy and high-pressure Single Crystal X-ray diffraction was carried out in this project. A data-driven approach based on a combination of self-organizing maps (SOM) and principal component analysis (PCA) is also reported was used to classify different π-stacking arrangements of PDI derivatives into families of similar crystal packing. Besides the main project, in the framework of structure-property analysis under non-ambient conditions, the structural investigation of the water loss in Pt- and Pd- based vapochromic potassium/lithium salts upon temperature, and the investigation of structure-mechanical property relationships in polymorphs of a thienopyrrolyldione endcapped oligothiophene (C4-NT3N) are reported.

Electronic And Structural Study Of Pt-modified Au Vicinal Surfaces: A Model System For Pt-au Catalysts.

Two single crystalline surfaces of Au vicinal to the (111) plane were modified with Pt and studied using scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS) in ultra-high vacuum environment. The vicinal surfaces studied are Au(332) and Au(887) and different Pt coverage (θPt) were deposited on each surface. From STM images we determine that Pt deposits on both surfaces as nanoislands with heights ranging from 1 ML to 3 ML depending on θPt. On both surfaces the early growth of Pt ad-islands occurs at the lower part of the step edge, with Pt ad-atoms being incorporated into the steps in some cases. XPS results indicate that partial alloying of Pt occurs at the interface at room temperature and at all coverage, as suggested by the negative chemical shift of Pt 4f core line, indicating an upward shift of the d-band center of the alloyed Pt. Also, the existence of a segregated Pt phase especially at higher coverage is detected by XPS. Sample annealing indicates that the temperature rise promotes a further incorporation of Pt atoms into the Au substrate as supported by STM and XPS results. Additionally, the catalytic activity of different PtAu systems reported in the literature for some electrochemical reactions is discussed considering our findings.

The Crystal-t Algorithm: A New Approach To Calculate The Sle Of Lipidic Mixtures Presenting Solid Solutions.

Lipidic mixtures present a particular phase change profile highly affected by their unique crystalline structure. However, classical solid-liquid equilibrium (SLE) thermodynamic modeling approaches, which assume the solid phase to be a pure component, sometimes fail in the correct description of the phase behavior. In addition, their inability increases with the complexity of the system. To overcome some of these problems, this study describes a new procedure to depict the SLE of fatty binary mixtures presenting solid solutions, namely the Crystal-T algorithm. Considering the non-ideality of both liquid and solid phases, this algorithm is aimed at the determination of the temperature in which the first and last crystal of the mixture melts. The evaluation is focused on experimental data measured and reported in this work for systems composed of triacylglycerols and fatty alcohols. The liquidus and solidus lines of the SLE phase diagrams were described by using excess Gibbs energy based equations, and the group contribution UNIFAC model for the calculation of the activity coefficients of both liquid and solid phases. Very low deviations of theoretical and experimental data evidenced the strength of the algorithm, contributing to the enlargement of the scope of the SLE modeling.

Triboelectricity In Insulating Polymers: Evidence For A Mechanochemical Mechanism.

Transfer of reaction products formed on the surfaces of two mutually rubbed dielectric solids makes an important if not dominating contribution to triboelectricity. New evidence in support of this statement is presented in this report, based on analytical electron microscopy coupled to electrostatic potential mapping techniques. Mechanical action on contacting surface asperities transforms them into hot-spots for free-radical formation, followed by electron transfer producing cationic and anionic polymer fragments, according to their electronegativity. Polymer ions accumulate creating domains with excess charge because they are formed at fracture surfaces of pulled-out asperities. Another factor for charge segregation is the low polymer mixing entropy, following Flory and Huggins. The formation of fractal charge patterns that was previously described is thus the result of polymer fragment fractal scatter on both contacting surfaces. The present results contribute to the explanation of the centuries-old difficulties for understanding the triboelectric series and triboelectricity in general, as well as the dissipative nature of friction, and they may lead to better control of friction and its consequences.

The Role Of Edaphic Environment And Climate In Structuring Phylogenetic Pattern In Seasonally Dry Tropical Plant Communities.

Seasonally dry tropical plant formations (SDTF) are likely to exhibit phylogenetic clustering owing to niche conservatism driven by a strong environmental filter (water stress), but heterogeneous edaphic environments and life histories may result in heterogeneity in degree of phylogenetic clustering. We investigated phylogenetic patterns across ecological gradients related to water availability (edaphic environment and climate) in the Caatinga, a SDTF in Brazil. Caatinga is characterized by semiarid climate and three distinct edaphic environments - sedimentary, crystalline, and inselberg -representing a decreasing gradient in soil water availability. We used two measures of phylogenetic diversity: Net Relatedness Index based on the entire phylogeny among species present in a site, reflecting long-term diversification; and Nearest Taxon Index based on the tips of the phylogeny, reflecting more recent diversification. We also evaluated woody species in contrast to herbaceous species. The main climatic variable influencing phylogenetic pattern was precipitation in the driest quarter, particularly for herbaceous species, suggesting that environmental filtering related to minimal periods of precipitation is an important driver of Caatinga biodiversity, as one might expect for a SDTF. Woody species tended to show phylogenetic clustering whereas herbaceous species tended towards phylogenetic overdispersion. We also found phylogenetic clustering in two edaphic environments (sedimentary and crystalline) in contrast to phylogenetic overdispersion in the third (inselberg). We conclude that while niche conservatism is evident in phylogenetic clustering in the Caatinga, this is not a universal pattern likely due to heterogeneity in the degree of realized environmental filtering across edaphic environments. Thus, SDTF, in spite of a strong shared environmental filter, are potentially heterogeneous in phylogenetic structuring. Our results support the need for scientifically informed conservation strategies in the Caatinga and other SDTF regions that have not previously been prioritized for conservation in order to take into account this heterogeneity.

Descrições estruturais cristalinas de zeólitos

Crystalline structures of zeolites can be studied using different representations: the internal symmetry obtained by X-Ray or neutron diffraction crystallography techniques or a systematic analysis of the basic structural units which can be arranged to build the geometries of each kind of zeolite. In this work the basic concepts of three building units, SBU (Secondary Building Units), SSU (Structural SubUnits) and PBU (Periodic Building Units) are presented. The properties of the resulting crystalline structures are discussed (pores, cavities, channels), describing the influence of each one of these properties in processes of physical-chemical interest. Representative case studies of known zeolite crystalline structures are also discussed in terms of their space group classification.

Influência da embalagem de polietileno de baixa densidade e da temperatura na conservação do repolho minimamente processado

This research studied the effect of low density polyethylene packaging and storage temperature on the preservation of fresh-cut (minimally processed) cabbage. The cabbages, previously cooled to a temperature of 10 ºC, were selected, washed, cut in four parts (with the central stalk removed), sanitized, cut in strips, rinsed, put in the centrifuge, weighed and stored in plastic packaging of low density polyethylene (70 µm), and then stored in cold chambers at temperatures of 1 and 10 ºC for 20 days. The following aspects were evaluated: carbon dioxide, oxygen and ethylene in the internal atmosphere of the package as well as, pH, titratable acidity, total soluble solids, vitamin C, loss of fresh mass and the total soluble solids/acidity in the fresh-cut cabbage ratio. The experimental design was entirely casual, with three repetitions. The analysis parameters, except for the vitamin C, loss of fresh mass and ethylene, presented significant variation between the temperatures and days of storage. The cabbage stored at a temperature of 1 ºC presented a shelf life of around 15 days, significantly higher than that stored at 10 ºC. At this temperature, on the 8th day of storage, the product was completely decayed, unfit for commercialization or consumption.

Modelos de transferência de metal pesado na cana-de-açúcar adubada com composto de lixo urbano

The research approaches recycling of urban waste compost (UWC) as an alternative fertilizer for sugarcane crop and as a social and environmental solution to the solids residuals growth in urban centers. A mathematical model was used in order to know the metal dynamics as decision support tool, aiming to establish of criteria and procedures for UWC's safe use, limited by the amount of heavy metal. A compartmental model was developed from experimental data in controlled conditions and partially checked with field data. This model described the heavy metal transference in the system soil-root-aerial portion of sugarcane plants and concluded that nickel was metal to be concern, since it takes approximately three years to be attenuated in the soil, reaching the aerial portions of the plant at high concentrations. Regarding factors such as clay content, oxide level and soil pH, it was observed that for soil with higher buffering capacity, the transfer of the majority of the metals was slower. This model may become an important tool for the attainment of laws regarding the UWC use, aiming to reduce environment contamination the waste accumulation and production costs.

Utilização de 1-metilciclopropeno e resfriamento rápido na conservação de pêssegos

Postharvest losses vary among the different vegetable products. However, among fruits and vegetables the losses generally range from 30% to 50%. Thus, this paper aimed the application of 1-methylcycloprene (1-MCP) and fast cooling with forced air (PC) on peaches, in order to estimate their effects in the ripening process of this fruit. Physiological analyses were performed, such as loss of fresh mass, firmness, pH, titratable acidity, soluble solids, ratio and CO2 production, as well as sensorial analyses such as color, texture and flavor. The experiment was divided in two phases. In the first one, concentrations of 30, 60, and 90 nL/L 1-MCP, applied at 0 ºC and 20 ºC, were tested. The fruits treated without 1-MCP were denominated control for both temperatures studied. The second phase was composed by the following treatments: cold storage (CS) or control, cooling with forced air (CFA), cooling with forced air followed by 1-MCP application (CFA + 1-MCP) and 1-MCP application (1-MCP). Among these, the CFA + 1-MCP treatment provided more firmness of the fruits in comparison to the control fruits. The respiratory rate of peaches under CFA and CFA + 1-MCP treatments decreased in comparison to the control fruit respiratory rates.

Avaliação de índices de firmeza para abacaxi minimamente processado em fatias tratadas com soluções de sais de cálcio

Fresh-cut sliced fruits and vegetables are ready to eat immediately and their sensorial characteristics should be similar to fresh product. Although most of the studies in this area are focused on vegetables, there is a great market potential for fresh-cut sliced fruits, mainly for those which exhibit some commercialization or preparation difficulties such as pineapple. The objective of this work was to evaluate the effect of 1% and 3% concentrations of calcium salts (chloride, sulphate and lactate) on pH, total soluble solids and firmness values of minimally processed pineapple slices. Two types of indenters and three firmness indexes were investigated aiming to identify the best index. Results showed that calcium sulphate 3% kept average firmness index up to 44.45% higher than the index value of the control. Even though both indenters exhibited similar variability the cylindrical one was able to point out more differences between control and treatments than the cylindrical borer indenter.

Determinação em tempo real da magnitude de danos físicos por impacto em linhas de beneficiamento e em condições de laboratório e seus efeitos na qualidade de tomate

Tomatoes are one of the most important vegetable crops grown in Brazil and are among the crops that have one of the highest post-harvest losses indexes in the country. The present work aimed at evaluating impact damage observed in packing lines of fresh tomatoes as well as to determine, under laboratory conditions, quality alterations of tomato fruits submitted to impact damage in different surface types. Critical points evaluation was accomplished using an instrumented sphere. Critical transference points found showed variations in acceleration levels from 30 to 129 G (m s-2). Tests carried out under laboratory conditions showed that padded surfaces reduced up to 31% impact damage. Incidence of severe internal physical damage was evaluated by a subjective scale and increased by 79% on hard surfaces for the highest fall drop. On the other hand, it was observed an effective reduction in physical damage on fruits when padded surfaces were used. When a 10-cm drop was performed, the maximum reduction measured was 10% for hard surfaces and 5% for previously padded surfaces. For quality parameters, it was observed for high drops on hard surfaces, highest values for weight loss, total acidity, lower values for vitamin C and Soluble Solids.

Qualidade pós-colheita de caqui 'fuyu' com utilização de diferentes concentrações de cobertura comestível

One of the main objectives of applying edible coatings on fruits surface is to create a protective film to reduce weight loss due to evaporation and transpiration and also to decrease the risk of fruit rot caused by environmental contamination, in order to improve the visual aspect. Therefore, it is possible to increase shelf life, and decrease post harvest losses. Persimmon is a much appreciated fruit, with high potential for export, but sensitive to handling and storage. This study aimed to evaluate the effect of applying the edible coating Megh Wax ECF-124 (18% of active composts, consisting of emulsion of carnauba wax, anionic surfactant, preservative and water) produced by Megh Industry and Commerce Ltda in three different concentrations (25, 50 and 100%) on post harvest quality of 'Fuyu' persimmon stored for 14 days. The attributes evaluated for quality were: firmness, pH, acidity, soluble solids, weight loss and color. The results showed that application of carnauba wax in different concentrations was effective on decreasing weight loss of persimmon cv. Fuyu and maintenance of color aspects. Treatment at lower concentration, 25%, showed lower rate of discharge, but high concentrations showed lower values of mass loss. Carnauba wax application showed a high potential for use on postharvest conservation, and can be applied together with other technologies, helping to maintain quality for export.