Composition dependency of the glass forming ability (GFA) in Mg—Ni—Si system by mechanical alloying

The pure elemental powder mixtures with the compositions of Mg₆₅Ni_xSi₃₅−_x (x = 10, 20, 25, 33 at.%) were subject to high-energy ball mill, and the structures of the mixtures at different intervals of milling were characterised by X-ray diffraction (XRD). The compositional dependency of the glass forming ability (GFA) in Mg–Ni–Si system was evaluated based on the experimental results and the theoretical calculation. The compositional dependency of GFA in Mg–Ni–Si system can be understood well by comparing the enthalpies of the crystalline and amorphous phases based on the Miedema's theory for the formation enthalpy of alloys. Increasing the Ni/Mg ratio and/or decreasing Si content can improve the amorphous formability. The calculation results might be of great help in optimising the composition with high GFA in Mg–Ni–Si system.

Investigation of nonisothermal crystallization behaviors of poly and silica nanocomposites using differential scanning calorimetry

Nonisothermal crystallization behaviors of PVA and poly (vinyl alcohol) and Silica (PVA/SiO2) nanocomposites prepared via a self-assembly monolayer (SAM) technique are investigated in this study. Differential scanning calorimetry (DSC) is used to measure the crystallization temperature and enthalpy of PVA and nanocomposites in nitrogen at various cooling rate. The results show that the degree of crystallinity of PVA and nanocomposites decreases when the SiO₂ content increases but increases with an increasing cooling rate. The peak crystallization temperature decreases with an increasing cooling rate.

Development of hybrid composites for automotive applications: effect of addition of SEBS on the morphology, mechanical, viscoelastic, crystallization and thermal degradation properties of PP/PS-xGnP composites

In this article, we report on a simple and cost effective approach for the development of light-weight, super-tough and stiff material for automotive applications. Nanocomposites based on PP/PS blend and exfoliated graphene nanoplatelets (xGnP) were prepared with and without SEBS. Mechanical, crystallization and thermal degradation properties were determined and correlated with phase morphology. The addition of xGnP to PP/PS blend increased the tensile modulus at the expense of toughness. The presence of xGnP increased the enthalpy of crystallization and enthalpy of fusion of PP in the blends, without affecting segmental mobility and thermal stability. Addition of polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS) improved the toughness of PP/PS blends, but decreased the stiffness. The incorporation of xGnP into this ternary blend generated a super-tough material with improved stiffness and tensile elongation, suitable for automotive applications. It is observed that the presence of SEBS diminished the tendency of agglomeration of xGnP and their unfavorable interactions with thermoplastics, which in turn reduced the internal friction in the matrix.

Effect of storage on the biochemical and processing quality of Adzuki Bean (Vigna angularis)

Storage of adzuki beans and other pulse grains causes biochemical and physical changes that affect the hydration properties of the beans. This affects the quality of products made from the beans such as the Japanese bean paste “ann.” Storage, particularly under unfavourable conditions, leads to the “hard shell” phenomenon, where beans fail to imbibe water when soaked and remain hard, and the “hard-to-cook” phenomenon where the seeds hydrate normally, but the cotyledon fails to hydrate and soften during cooking. The hard shell phenomenon is attributable to impermeability of the seed coat to water, which is due to biochemical changes in the seed coat, such as the formation of protein-tannin complexes, and biophysical changes such as reduction in size or closure of the straphiole aperture in the hilum area—the main area for water entry into the adzuki bean. The hard-to-cook phenomenon is due to changes in the cotyledon tissue, which include formation of insoluble pectinates, lignification of the cell wall and middle lamella, interaction of condensed tannins with proteins and starch, and changes to the structure and functionality of the cellular proteins and starch.

Effect of relaxation on pressure sensitivity index in a Zr-based metallic glass

Shear-banding features of as-cast and annealed Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 bulk metallic glass were investigated through Rockwell indentation tests. Isothermal annealing of the as-cast samples was conducted at temperatures below its glass transition temperature, Tg. The exothermal enthalpy during continuous heating below Tg decreases with increasing annealing temperature, indicating the gradual reduction of free-volume upon annealing. The observation on the morphology of shear-banding pattern around the indents implies a reduced shear bands activity in the annealed samples. The included angles (2θ) between two families of shear bands emanating from the edge of Rockwell indent decrease from 88° for the as-cast sample to 79° for the sample annealed at 633 K for 1 h, indicating a pressure sensitive plasticity. By Mohr–Coulomb criterion, the pressure sensitive index can be obtained on the basis of the measured 2θ, which increases with increasing annealing temperature, indicating an increase of “atomistic friction” due to the reduction of the free volume upon annealing.

Nutritional aspects of food extrusion: a review

Extrusion cooking, as a multi-step, multi-functional and thermal/mechanical process, has permitted a large number of food applications. Effects of extrusion cooking on nutritional quality are ambiguous. Beneficial effects include destruction of antinutritional factors, gelatinisation of starch, increased soluble dietary fibre and reduction of lipid oxidation. On the other hand, Maillard reactions between protein and sugars reduce the nutritional value of the protein, depending on the raw material types, their composition and process conditions. Heat-labile vitamins may be lost to varying extents. Changes in proteins and amino acid profile, carbohydrates, dietary fibre, vitamins, mineral content and some non-nutrient healthful components of food may be either beneficial or deleterious. The present paper reviews the mechanisms underlying these changes, as well as the influence of process variables and feed characteristics. Mild extrusion conditions (high moisture content, low residence time, low temperature) improve the nutritional quality, while high extrusion temperatures (200 °C), low moisture contents (<15%) and/or improper formulation (e.g. presence of high-reactive sugars) can impair nutritional quality adversely. To obtain a nutritionally balanced extruded product, careful control of process parameters is essential.

Indentation study on the pressure sensitivity of a ZR-based bulk metallic glass

Spherical indentation test was conducted on as-cast and annealed Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 bulk metallic glass, and the evolution of the morphology of the deformation zone of indents upon annealing was investigated. The DSC traces of the as-cast and annealed samples show that the enthalpy change at the glass transition, ΔH, decreases with the increasing of annealing temperature, indicating the reduction of the free volume upon annealing. The morphology of the indents implies a reduced shear band activity in the annealed samples. The included angles (2θ) between two families of shear bands emanating from the edge of spherical indent in the as-cast and the annealed samples were measured to be in the range of 88-79°, which decrease with the increasing of annealing temperature, indicating pressure sensitive plasticity in the as-cast and annealed samples. By Mohr–Coulomb criterion, the pressure sensitive index, α, can be obtained on the basis of the measured 2θ. The sensitivity index increases with increasing temperature, implying an increase of 'atomistic friction' due to the reduction of the free volume upon annealing.

Thermodynamics of lipophilic drug binding to intestinal fatty acid binding protein and permeation across membranes

Intestinal fatty acid binding protein (I-FABP) is present at high levels in the absorptive cells of the intestine (enterocytes), where it plays a role in the intracellular solubilization of fatty acids (FA). However, I-FABP has also been shown to bind to a range of non-FA ligands, including some lipophilic drug molecules. Thus, in addition to its central role in FA trafficking, I-FABP potentially serves as an important intracellular carrier of lipophilic drugs. In this study we provide a detailed thermodynamic analysis of the binding and stability properties of I-FABP in complex with a series of fibrate and fenamate drugs to provide an insight into the forces driving drug binding to I-FABP. Drug binding and selectivity for I-FABP are driven by the interplay of protein−ligand interactions and solvent processes. The Gibbs free energies (ΔG°) determined from dissociation constants at 25 °C ranged from −6.2 to −10 kcal/mol. The reaction energetics indicate that drug binding to I-FABP is an enthalpy−entropy driven process. The relationship between I-FABP stability and drug binding affinity was examined by pulse proteolysis. There is a strong coupling between drug binding and I-FABP stability. The effect of an I-FABP protein sink on the kinetics and thermodynamics of tolfenamic acid permeation across an artificial phospholipid membrane were investigated. I-FABP significantly decreased the energy barrier for desorption of tolfenamic acid from the membrane into the acceptor compartment. Taken together, these data suggest that the formation of stable drug−I-FABP complexes is thermodynamically viable under conditions simulating the reactant concentrations likely observed in vivo and maybe a significant biochemical process that serves as a driving force for passive intestinal absorption of lipophilic drugs.

New insight into non-isothermal crystallization of PVA-graphene composites

The melt crystallization of poly(vinyl alcohol) (PVA) and PVA composites has been a controversial subject due to inconclusive evidence and different opinions for its decomposition during crystallization. Using graphene as a model, the melt crystallization of PVA and PVA-graphene composites occurring during single-cycle and multiple-cycle non-isothermal annealing processes was systematically analyzed using different characterization techniques. The results obtained using single-cycle non-isothermal annealing indicated that the entire crystallization process took place through two main stages. The graphene in the PVA matrix regulates the nucleation and crystal growth manner of the PVA, yet resulting in retardation of the entire crystallization. The FTIR and Raman spectroscopic results particularly demonstrated that the annealing process not only improved the crystallinity but also led to clear decomposition in PVA and PVA-graphene composites, such as the elimination of hydroxyl groups and the production of C=C double bonds. The newly produced C=C double bonds were found to be responsible for the retardation of PVA macromolecule crystallization and the breaking of hydrogen bonds among the hydroxyl groups in the PVA chains. In addition, the morphological observation and multi-cycle non-isothermal crystallization further confirmed the existence of decomposition based on the surface damage as well as decreased crystallization enthalpy and crystallization peak temperature. Therefore, the non-isothermal crystallizations of the pure PVA and the PVA-graphene composites were in fact the combination of non-isothermal crystallization and non-isothermal degradation processes.

Simultaneous crystallization and decomposition of PVA/MMT composites during non-isothermal process

Decomposition of poly(vinyl alcohol)/montmorillonite clay (PVA/MMT) composites during melting-crystallization was experimentally confirmed by morphology and molecular structure changes. In particular, FTIR spectra show the shift of O-H stretching band as well as enhanced intensities of C-O stretching and CH2 rocking vibrational modes. Furthermore, Raman deconvolution indicates that C-H wagging, CH2-CH wagging, CH-CO bending and CH2 wagging modes in amorphous domains were all decreased greatly. Moreover, this decomposition leads to decreased melting enthalpy, melting point, crystallization enthalpy and crystallization temperature. Crystallization analysis shows that the MMT incorporated slows down the crystallization process in the PVA matrix regardless of the nucleation capability of MMT. Despite the severe decomposition, the crystallization kinetics still corroborated well with common classical models. As a result, molecular structure changes and crystallization retardation observed in this study clearly indicate the strong effects of the thermal degradation on the non-isothermal crystallization of PVA/MMT composites.

Simulation of oleuropein structural conformation in vacuum, water and triolein-water systems using molecular dynamics

Oleuropein, the main phenolic compound of olive leaves, exhibits a unique blend of biological activities and has been shown to locate itself at the oil-water (O/W) interface. This behavior could influence the physico-chemical properties of dispersed systems such as emulsions. In this work, we study the effect of the microenvironment (vacuum, water, and triolein-water) on the conformational preferences of oleuropein using molecular dynamics (MD) simulations at 300K for at least 30ns. The seven torsions that describe the flexible skeleton of oleuropein were monitored together with the distance between the glucose (Glu) and hydroxytyrosol (Hyd) moieties (dglu-hyd) of the molecule. The obtained trajectories demonstrated that oleuropein adopts different conformations that depend on the environment. The preferential conformers in each system were analyzed for their molecular geometry and internal energy. In vacuum, the oleuropein preferential conformation is tight with the glucose moiety in close proximity with the hydroxytyrosol moiety. In water, oleuropein preferential conformers presented large differences in their structural properties, varying from a close like U form, and a semi-opened form, to an opened form characterized by high fluctuations in dglu-hyd values. In a triolein-water system, oleuropein tends to adopt a more open form where the glucose moiety could be approximately aligned with the hydroxytyrosol and elenolic acid moieties. Based on a calculation at the HF/6-31G* level, these flexibilities of oleuropein required energy of 19.14kcal/mol in order to adopt the conformation between water and triolein-water system. A radial distribution function (RDF) analysis showed that specific hydroxyl groups of Hyd and Glu interact with water molecules, enabling us to understand the amphiphilic character of oleuropein at the triolein-water interface. MD calculations together with interfacial tension measurements revealed that the oleuropein binding at O/W interface is an enthalpy driven mechanism.