Pore anisotropy and microporosity in nanostructured mesoporous solids

In this study, we carried out an investigation related to the determination of the anisotropy (b) of pores as well as the extent of microporosity (mic%) in various groups of nanostructured mesoporous materials. The mesoporous materials examined were fifteen samples belonging to the following groups of solids: MCM-48s, SBA-15s, SBA-16s, and mesoporous TiO2 anatases. The porosities of those materials were modified either during preparation or afterward by the addition of Cu(II) species and/or 3(5)-(2-pyridinyl) pyrazole (PyPzH) into the pores. The modification of porosity in each group took place to make possible the internal comparison of the b and mic% values within each group. The estimation of both the b and mic% parameters took place from the corresponding nitrogen adsorption-desorption isotherms. The new proposed method is able to detect a percentage of microporosity as low as a few percent, which is impossible by any of the methods used currently, without the use of any reference sample or standard isotherms. A meaningful inverse relationship is apparent between the b and mic% values, indicating that large values of b correspond to small values of mic%.

Slicing of soft, flexible solids with industrial applications

Thin slices of soft flexible solids have negligible bending resistance and hence store negligible elastic strain energy; furthermore such offcuts are rarely permanently deformed after slicing. Cutting forces thus depend only on work of separation (toughness work) and friction. These simplifying assumptions are not as restrictive as it might seem, and the mechanics are found to apply to a wide variety of foodstuffs and biological materials. The fracture toughness of such materials may be determined from cutting experiments: the use of scissors instrumented for load and displacement is a popular method where toughness is obtained from the work areas beneath load–displacement plots. Surprisingly, there is no analysis for the variation of forces with scissor blade opening and this paper provides the theory. Comparison is made with experimental results in cutting with scissors. The analysis is generalised to cutting with blades of variable curvature and applied to a commercial food cutting device having a rotating spiral plan form blade. The strong influence of the ‘slice/push ratio’ (blade tangential speed to blade edge normal speed) on the cutting forces is revealed. Small cutting forces are important in food cutting machinery as damage to slices is minimised. How high slice/push ratios may be achieved by choice of blade profile is discussed.

Texture development in ice cream - effects of adding cocoa solids

Dynamic rheological techniques can aid the understanding of the factors contributing to ice cream structure, though the data obtained differs from that deduced from destructive techniques. Studies have shown that ice cream systems are both strain- and frequency-dependent. Chocolate ice cream is normally more viscous than the equivalent vanilla ice cream during mix preparation and has more body on freezing. Ice creams were prepared with and without cocoa solids and frequency sweeps were made from 0.1 to 100 Hz at 0.1% strain. With rapidly frozen ice creams, both G' and G" increased in the presence of cocoa solids. Comparison of mixes made with and without low-fat cocoa powder or non-gelatinizing starch demonstrated a similar relationship, with higher apparent viscosities in those mixes containing either cocoa powder or the starch. The results were consistent with the cocoa particles adding to the effect of the fat globules in increasing viscosity.

Building integration photovoltaic module with reference to Ghana: using triple junction amorphous silicon

This paper assesses the potential for using building integrated photovoltaic (BIPV) roof shingles made from triple-junction amorphous silicon (3a-Si) for electrification and as a roofing material in tropical countries, such as Accra, Ghana. A model roof was constructed using triple-junction amorphous (3a-Si) PV on one section and conventional roofing tiles on the other. The performance of the PV module and tiles were measured, over a range of ambient temperatures and solar irradiance. PVSyst (a computer design software) was used to determine the most appropriate angle of tilt. It was observed that 3a-Si performs well in conditions such as Accra, because it is insensitive to high temperatures. Building integration gives security benefits, and reduces construction costs and embodied energy, compared to freestanding PV systems. Again, it serves as a means of protection from salt spray from the oceans and works well even when shaded. However, compared to conventional roofing materials, 3a-Si would increase the indoor temperature by 1-2 °C depending on the surface area of the roof covered with the PV modules. The results presented in this research enhance the understanding of varying factors involved in the selection of an appropriate method of PV installation to offset the short falls of the conventional roofing material in Ghana.

A stress relaxation model for the viscoelastic solids based on the steady-state creep equation

Creep and stress relaxation are inherent mechanical behaviors of viscoelastic materials. It is considered that both are different performances of one identical physical phenomenon. The relationship between the decay stress and time during stress relaxation has been derived from the power law equation of the steady-state creep. The model was used to analyse the stress relaxation curves of various different viscoelastic materials (such as pure polycrystalline ice, polymers, foods, bones, metal, animal tissues, etc.). The calculated results using the theoretical model agree with the experimental data very well. Here we show that the new mathematical formula is not only simple but its parameters have the clear physical meanings. It is suitable to materials with a very broad scope and has a strong predictive ability.

Biomineralisation by earthworms: an investigation into the stability and distribution of amorphous calcium carbonate

Background Many biominerals form from amorphous calcium carbonate (ACC), but this phase is highly unstable when synthesised in its pure form inorganically. Several species of earthworm secrete calcium carbonate granules which contain highly stable ACC. We analysed the milky fluid from which granules form and solid granules for amino acid (by liquid chromatography) and functional group (by Fourier transform infrared (FTIR) spectroscopy) compositions. Granule elemental composition was determined using inductively coupled plasma-optical emission spectroscopy (ICP-OES) and electron microprobe analysis (EMPA). Mass of ACC present in solid granules was quantified using FTIR and compared to granule elemental and amino acid compositions. Bulk analysis of granules was of powdered bulk material. Spatially resolved analysis was of thin sections of granules using synchrotron-based μ-FTIR and EMPA electron microprobe analysis. Results The milky fluid from which granules form is amino acid-rich (≤ 136 ± 3 nmol mg−1 (n = 3; ± std dev) per individual amino acid); the CaCO3 phase present is ACC. Even four years after production, granules contain ACC. No correlation exists between mass of ACC present and granule elemental composition. Granule amino acid concentrations correlate well with ACC content (r ≥ 0.7, p ≤ 0.05) consistent with a role for amino acids (or the proteins they make up) in ACC stabilisation. Intra-granule variation in ACC (RSD = 16%) and amino acid concentration (RSD = 22–35%) was high for granules produced by the same earthworm. Maps of ACC distribution produced using synchrotron-based μ-FTIR mapping of granule thin sections and the relative intensity of the ν2: ν4 peak ratio, cluster analysis and component regression using ACC and calcite standards showed similar spatial distributions of likely ACC-rich and calcite-rich areas. We could not identify organic peaks in the μ-FTIR spectra and thus could not determine whether ACC-rich domains also had relatively high amino acid concentrations. No correlation exists between ACC distribution and elemental concentrations determined by EMPA. Conclusions ACC present in earthworm CaCO3 granules is highly stable. Our results suggest a role for amino acids (or proteins) in this stability. We see no evidence for stabilisation of ACC by incorporation of inorganic components.

The role of copper in the thermal conductivity of thermoelectric oxychalcogenides: do lone pairs matter?

Understanding the underlying mechanisms that suppress thermal conduction in solids is of paramount importance for the targeted design of materials for thermal management and thermoelectric energy conversion applications. Bismuth copper oxychalcogenides, BiOCuQ (Q = Se, Te), are highly crystalline thermoelectric materials with an unusually low lattice thermal conductivity of approx. 0.5 Wm-1K-1, a value normally found in amorphous materials. Here we unveil the origin of the unusual thermal transport properties of these phases. First principles calculations of the vibrational properties combined with analysis of in-situ neutron diffraction data, demonstrate that weak bonding of copper atoms within the structure leads to an unexpected vibrational mode at low frequencies, which is likely to be a major contributor to the low thermal conductivity of these materials. In addition, we show that anharmonicity and the large Grüneisen parameter in these oxychalcogenides are mainly related to the low frequency copper vibrations, rather than to the Bi3+ lone pairs.

Pressure-induced electrical and structural anomalies in Pb(1-x)Ca(x)TiO(3) thin films grown at various oxygen pressures by chemical solution route

Lead calcium titanate (Pb(1-x)Ca(x)TiO(3) or PCT) thin films have been thermally treated under different oxygen pressures, 10, 40 and 80 bar, by using the so-called chemical solution deposition method. The structural, morphological, dielectric and ferroelectric properties were characterized by x-ray diffraction, FT-infrared and Raman spectroscopy, atomic force microscopy and polarization-electric-field hysteresis loop measurements. By annealing at a controlled pressure of around 10 and 40 bar, well-crystallized PCT thin films were successfully prepared. For the sample submitted to 80 bar, the x-ray diffraction, Fourier transformed-infrared and Raman data indicated deviation from the tetragonal symmetry. The most interesting feature in the Raman spectra is the occurrence of intense vibrational modes at frequencies of around 747 and 820 cm(-1), whose presence depends strongly on the amount of the pyrochlore phase. In addition, the Raman spectrum indicates the presence of symmetry-breaking disorder, which would be expected for an amorphous (disorder) and mixed pyrochlore-perovskite phase. During the high-pressure annealing process, the crystallinity and the grain size of the annealed film decreased. This process effectively suppressed both the dielectric and ferroelectric behaviour. Ferroelectric hysteresis loop measurements performed on these PCT films exhibited a clear decrease in the remanent polarization with increasing oxygen pressure.

Synthesis and characterization of phosphate glass microspheres for radiotherapy applications

Class microspheres containing the radioisotope (32)P, a beta(-) particle emitter, and half-life of 14.3 days, can be easily introduced in specific human organs such as liver, pancreas. and uterus to kill cancer cells. In the present work phosphate glass microspheres were produced with different compositions and particle size distribution in the range of 20- 30 mu m. Two different thermal processes were used to spherodize glass particles originally with irregular shapes. Samples were characterized by X-rays diffraction to check the amorphous structure, energy dispersive X-rays fluorescence spectroscopy to determine the final glass composition, and Fourier transformed infrared spectroscopy to determine the structural groups in the glass structure. The dissolution rate of glass samples in water was determined at 90 degrees C, and in simulated body fluid (SBF) at 37 degrees C. Classes with dissolution rates close to 10(-5) g/(cm(2) day) were obtained, which make them suitable for the present application. Scanning electron microscopy was used to evaluate the shape of the microspheres before and after the dissolution tests. The cytotoxicity tests showed that these microspheres can be used for biological applications. (C) 2008 Elsevier B.V. All rights reserved.

CONTRA: Improving the performance of dynamic investigations in natural abundance organic solids by mirror-symmetric constant-time CODEX

We present a minor but essential modification to the CODEX 1D-MAS exchange experiment. The new CONTRA method, which requires minor changes of the original sequence only, has advantages over the previously introduced S-CODEX, since it is less sensitive to artefacts caused by finite pulse lengths. The performance of this variant, including the finite pulse effect, was confirmed by SIMPSON calculations and demonstrated on a number of dynamic systems. (C) 2007 Elsevier Inc. All rights reserved.

Kinetics of autocatalytic acid hydrolysis of cellulose with crystalline and amorphous fractions

The acid hydrolysis of cellulose with crystalline and amorphous fractions is analyzed on the basis of autocatalytic model with a positive feedback of acid production from the degraded biopolymer. In the condition of low acid rate production compared with hydrolysis rate, both fraction of cellulose decrease exponentially with linear and cubic time dependence, and the normalized number of scissions per cellulose chain follows a sigmoid behavior with reaction time. The model predicts that self generated acidic compounds from cellulose accelerate the degradation of the biopolymer. However, if the acidic compounds produced are volatile species, then their release under low pressure will reduce the global rate of degradation of cellulose toward its intrinsic rate value determined by the residual acid catalyst present in the starting material.