Dairy Ingredients for Chocolate and Confectionery Products.

End of Project ReportHigh free-fat, spray-dried powders were successfully produced at a lower fat content (40% rather than 56%) using ultrafiltration. Chocolates made from these powders had improved flow properties and superior quality. The stability, viscosity and firmness of toffees were improved by optimising the casein, whey protein and lactose levels of skim milk powders used in their manufacture.Department of Agriculture, Food and the Marin

Tetrahedral displacive disorder in the scheelite-type oxide RbReO4

Oxides exhibiting the scheelite-type structure are an important class of functional materials with notable applications in photocatalysis, luminescence and ionic conductivity. Like all materials, understanding their atomic structure is fundamental to engineering their physical properties. This study outlines a detailed structural investigation of scheelite-type oxide RbReO4, which exhibits a rare long-range phase transition from I41/a to I41/amd upon heating. Additionally, in the long-range I41/a model, the Re-O tetrahedral distance undergoes significant contraction upon warming. Recent studies of other scheelite oxides have attributed this apparent contraction to incoherent local scale tetrahedral rotations. In this study we use X-ray pair distribution function analysis to show that RbReO4 undergoes a unique symmetry lowering process on the local scale, which involves incoherent tetrahedral displacements. The rare I41/a to I41/amd long-range phase transition was found to occur via a change from static to dynamic disorder on the local scale, which is due to the combination of the size of the A-site cation and lattice expansion. This demonstrates how careful manipulation of the ionic radius of the A-site in the scheelite structure can be used to induce local scale disorder, which has valuable implications for tailoring the physical properties of related materials

Neutron diffraction study of the tetragonal – monoclinic phase transition in NdNbO4 and NdTaO4

Phase transition and high-temperature properties of NdNbO4 and NdTaO4 were studied in situ using powder neutron diffraction methods. Both oxides undergo a reversible phase transition from a monoclinic I2/a phase at low temperatures to a tetragonal I41/a phase at high temperatures. The phase transition has been investigated through analysis of the spontaneous strains and symmetry distortion modes. Well below the transition temperature, Tc, the thermal evolution of the lattice parameters and symmetry modes suggest the transition is continuous, although a small discontinuity in both the spontaneous strains and symmetry distortion modes shows the transition is strictly first order. Analysis of the refined structures reveals that the Nb and Ta cations are best described as having a distorted 6-coordinate arrangement in the monoclinic structure, with four short and two long bonds. Breaking of the two long bonds at high temperatures, resulting in a transformation of the Nb(Ta) coordination to a regular tetrahedron, is believed to be responsible for the first order nature of the transition

Structure and electronic properties of a mu-oxo ruthenium bromide

The crystal structure of potassium μ-oxo-bis[pentabromoruthenate] K4Ru2OBr10, determined from synchrotron X-ray powder diffraction, is described. Each Ru atom is surrounded by five Br atoms and one O atom. Magnetic measurements show the complex to be diamagnetic as a result of strong Ru–Ru interactions facilitated by the linear Ru–O–Ru linkage

Structural And Magnetic Properties Of Some Vacancy Ordered Osmium Halide Perovskites

The structures and magnetic properties of the Os4+ (5d4) halides K2OsCl6, K2OsBr6, Na2OsBr6 and Na2OsBr6.6H2O are described. K2OsCl6 and K2OsBr6 have a cubic vacancy-ordered double perovskites structure but undergo different symmetry lowering structural phase transitions upon cooling associated with a combination of the relative size of the ions and differences in their chemical bonding. The structure of Na2OsBr6.6H2O has been determined for the first time and the thermal stability of this established using a combination of in-situ diffraction and TGA. Na2OsBr6.6H2O and Na2OsBr6 are isostructural with the analogous iridium chlorides, Na2IrCl6.6H2O and Na2IrCl6, dehydration proceeds via different intermediate phases. The magnetic moments of four compounds display Kotani-like behaviour consistent with a Jeff = 0 ground state, however the magnetic susceptibility measurements reveal unusual low temperature properties indicative of a weakly magnetic ground state

Experimental and Computational Insights into the Anomalous Thermal Expansion of NH¬4ReO4

The temperature dependence of the structure and the ground state properties of scheelite type NH4ReO4 have been studied using neutron powder diffraction (NPD) and Density Functional Theory (DFT), respectively. Despite the large incoherent background in the experimental NPD, associated with the presence of hydrogen, accurate and precise structural parameters were obtained. Comparison of the results of the NPD and DFT studies shows that the observed anomalous thermal contraction in NH4ReO4 is a consequence of thermally induced rotational disorder of the NH4 groups. Comparing the experimentally determined and optimized structures reveals deformation of the NH4 tetrahedra that is responsible for the unusual tetragonal distortion of this material. The Raman Spectra of NH4ReO4 is presented and the modes are assigned based on the DFT calculations

Long-Range A-Site Cation Disorder in NaA(MO4)2 (M = Mo, W) Double Scheelite Oxides

Synchrotron X-ray and neutron powder diffraction methods have been used to obtain accurate long-range average structures of some double scheelite compounds of the type NaA(BO4)2 (A = La, Pr, Nd, Sm, Lu, and Bi; B = Mo, W) at room temperature. Phase pure samples were synthesized using standard solid-state methods. Rietveld refinements using combined synchrotron X-ray diffraction (SXRD) and neutron diffraction (NPD) revealed a random distribution of the Na and A-type cations regardless of the presence of 6s2 lone pairs (such as Bi3+) and the difference in oxidation states and ionic radii between the cations. The NaA(BO4)2 (A = La, Pr, Nd, Sm, Lu, and Bi) series displayed linear trends in lattice parameters and AO8 polyhedra volume with the ionic radius of the A-type cation for the lanthanoids, but a deviation from the trend was observed for A = Bi3+. The NaBi(BO4)2 structure has a smaller than expected unit cell volume than based on extrapolation from the corresponding NaLn(BO4)2 series, possibly due to short-range ordering of the 6s2 lone pair electrons

Beyond the Ionic Radii: A Multifaceted Approach to Understand Differences between the Structures of LnNbO4 and LnTaO4 Fergusonites

Synchrotron X-ray powder diffraction methods have been used to obtain accurate structures of the lanthanoid tantalates, LnTaO4, at room temperature. Three different structures are observed, depending on the size of the Ln cation: P21/c (Ln = La, Pr), I2/a (Ln = Nd-Ho), and P2/c (Ln = Tb-Lu). BVS analysis indicated that TaV is six-coordinate in these structures, with four short bonds and two longer bonds. Synchrotron X-ray powder diffraction methods were also used to observe the impact of Ta doping on the orthoniobates, Ln(Nb1-xTax)O4 (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Ho, Yb and Lu). Where both the niobate and tantalate oxide were isostructural (fergusonite structure, space group I2/a), complete solid solutions were prepared. In these solid solutions, the unit cell volume decreases as the Ta content increases. The subtle interaction evident between the LnO8 and BO6 sublattices in the fergusonite-type oxides was not observed in the related pyrochlore oxides. A combined synchrotron X-ray and neutron powder diffraction study of the series Ho(Nb1-xTax)O4 was used to determine accurate atomic positions of the anions, and hence, bond lengths. This revealed a change in the (Nb/Ta)-O bond lengths, reflective of the difference in the valence orbitals of Nb(4d) and Ta(5d). Examination of the partial density of states demonstrates differences in the electronics between Nb and Ta, leading to a difference in the bandgap. This study highlights the importance of the long B-O contacts in the fergusonite structures, and its potential impact on the I2/a to I41/a phase transition

Optical coherence tomography-based contact indentation for diaphragm mechanics in a mouse model of transforming growth factor alpha induced lung disease

Funding provided by the National Health and Medical Research Council (NHMRC) of Australia (1027218). P.N. and K.W. are supported by NHMRC Fellowships (1045824, 1090888). P.W. was supported by the William and Marlene Schrader Postgraduate Scholarship, The University of Western Australia, and C.A. by an NHMRC Preterm Infants CRE top-up scholarship.This study tested the utility of optical coherence tomography (OCT)-based indentation to assess mechanical properties of respiratory tissues in disease. Using OCT-based indentation, the elastic modulus of mouse diaphragm was measured from changes in diaphragm thickness in response to an applied force provided by an indenter. We used a transgenic mouse model of chronic lung disease induced by the overexpression of transforming growth factor-alpha (TGF-α), established by the presence of pleural and peribronchial fibrosis and impaired lung mechanics determined by the forced oscillation technique and plethysmography. Diaphragm elastic modulus assessed by OCT-based indentation was reduced by TGF-α at both left and right lateral locations (p < 0.05). Diaphragm elastic modulus at left and right lateral locations were correlated within mice (r = 0.67, p < 0.01) suggesting that measurements were representative of tissue beyond the indenter field. Co-localised images of diaphragm after TGF-α overexpression revealed a layered fibrotic appearance. Maximum diaphragm force in conventional organ bath studies was also reduced by TGF-α overexpression (p < 0.01). Results show that OCT-based indentation provided clear delineation of diseased diaphragm, and together with organ bath assessment, provides new evidence suggesting that TGF-α overexpression produces impairment in diaphragm function and, therefore, an increase in the work of breathing in chronic lung disease.Publisher PDFPeer reviewe

Cation and lone pair order-disorder in the polymorphic mixed metal bismuth scheelite Bi3FeMo2O12

The Bi3FeMo2O12 system is examined as a rare example of a transition metal oxide which, upon heating, undergoes a symmetry lowering and 2:1 ordering of the transition metal cations. The compound was synthesised in the tetragonal scheelite structure (S.G. #88: I41/a) by a sol-gel method and converted into the monoclinic polymorph (S.G. #15: C2/c) by calcination above 500 °C. The structure of both polymorphs was analysed using a combination of X-ray and neutron diffraction data, and the temperature-dependent phase transition between these was investigated in situ using variable temperature neutron powder diffraction and scanning transmission electron microscopy. The results show that the structural phase transition takes place at low temperature (~500 °C) and is 1st order in nature, as evident from the coexistence of both structures. The transition from tetragonal to monoclinic results in reduction of the equivalent unit cell volume. The role of the Bi3+ 6s lone pairs in the temperature-driven phase transition has been studied using neutron pair distribution function analysis. Local structure analysis via neutron total scattering revealed the Bi3+ 6s lone pairs to be stereochemically active in both structures, with short correlation lengths in the tetragonal structure and long correlation lengths in the monoclinic structure, leading to the facile phase conversion and to a more efficient packing density with highly correlated lone pairs in the monoclinic structure. Magnetization isotherms of the tetragonal structure collected at 1.8 K exhibit ferromagnetic behavior, suggesting that the interplay between the observed short-range monoclinic order, defects and surface-to-bulk effects alters the magnetic interaction, leading to short range ferromagnetic interactions, which is highly unexpected given the low temperature antiferromagnetic order observed in the monoclinic structure