Micropillar compression studies on a bulk metallic glass in different structural states

Uniaxial compression experiments on 0.3, 1 and 3 mu m diameter micropillars of a Zr-based bulk metallic glass in as-cast, shot-peened and structurally relaxed conditions were conducted. Shear band formation and stable propagation is observed to be the plastic deformation mode in all cases, with no detectable difference in yield strength according to either size or condition. The limitations of uniaxial compression tests in assessing the influence of various material conditions on plasticity, when it is inhomogeneous in nature, are illustrated.

Glass forming ability and stability: Ternary Cu bearing Ti, Zr, Hf alloys

Four Cu bearing alloys of nominal composition Zr25Ti25Cu50, Zr34Ti16Cu50, Zr25Hf25Cu50 and Ti25Hf25Cu50 have been rapidly solidified in order to produce ribbons. All the alloys become amorphous after meltspinning. In the Zr34Ti16Cu50 alloy localized precipitation of cF24 Cu5Zr phase can be observed in the amorphous matrix. The alloys show a tendency of phase separation at the initial stages of crystallization. The difference in crystallization behavior of these alloys with Ni bearing ternary alloys can be explained by atomic size, binary heat of mixing and Mendeleev number. It has been observed that both Laves and Anti-Laves phase forming compositions are suitable for glass formation. The structures of the phases, precipitated during rapid solidification and crystallization can be viewed in terms of Bernal deltahedra and Frank-Kasper polyhedra.

Genome sequencing of cells that live inside glass cages reveals their past history

One-quarter of the total primary production on earth is contributed by diatoms1. These are photosynthetic, unicellular algae with ornamented silica shells found in all aquatic and moist environments. They form the base of energy-efficient food webs that support all aquatic life forms. More than 250 genera of living diatoms, with as many as 100,000 species are known2. Fossil diatoms are known as early as the Cretaceous, 144–65 m.y. ago3. In India, deposits of diatoms occur in Rajasthan and are known as ‘multani mitti’. Multani mitti or Indian Fuller’s earth or diatomaceous earth as it is called in the West, is applied as a paste on the surface of the skin for 15–20 min and then washed-off. This leaves the skin feeling smooth, soft, moist and rejuvenated. Diatomaceous earth is now being used in the formulation of soaps, cleansing products, face powders and skincare preparations. Diatomaceous earth is a mineral material consisting mainly of siliceous fragments of various species of fossilized remains of diatoms.

Growing length and time scales in glass-forming liquids

The glass transition, whereby liquids transform into amorphous solids at low temperatures, is a subject of intense research despite decades of investigation. Explaining the enormous increase in relaxation times of a liquid upon supercooling is essential for understanding the glass transition. Although many theories, such as the Adam-Gibbs theory, have sought to relate growing relaxation times to length scales associated with spatial correlations in liquid structure or motion of molecules, the role of length scales in glassy dynamics is not well established. Recent studies of spatially correlated rearrangements of molecules leading to structural relaxation, termed ``spatially heterogeneous dynamics,'' provide fresh impetus in this direction. A powerful approach to extract length scales in critical phenomena is finite-size scaling, wherein a system is studied for sizes traversing the length scales of interest. We perform finite-size scaling for a realistic glass-former, using computer simulations, to evaluate the length scale associated with spatially heterogeneous dynamics, which grows as temperature decreases. However, relaxation times that also grow with decreasing temperature do not exhibit standard finite-size scaling with this length. We show that relaxation times are instead determined, for all studied system sizes and temperatures, by configurational entropy, in accordance with the Adam-Gibbs relation, but in disagreement with theoretical expectations based on spin-glass models that configurational entropy is not relevant at temperatures substantially above the critical temperature of mode-coupling theory. Our results provide new insights into the dynamics of glass-forming liquids and pose serious challenges to existing theoretical descriptions.

Influence of lanthanum doping on the dielectric, ferroelectric and relaxor behaviour of barium bismuth titanate ceramics

Barium lanthanum bismuth titanate (Ba1−(3/2)xLaxBi4Ti4O15, x = 0–0.4) ceramics were fabricated using the powders synthesized via the solid-state reaction route. X-ray powder diffraction analysis confirmed the above compositions to be monophasic and belonged to the m = 4 member of the Aurivillius family of oxides. The effect of the partial presence of La3+ on Ba2+ sites on the microstructure, dielectric and relaxor behaviour of BaBi4Ti4O15 (BBT) ceramics was investigated. For the compositions pertaining to x ≤ 0.1, the dielectric constant at both room temperature and in the vicinity of the temperature of the dielectric maximum (Tm) of the parent phase (BBT) increased significantly with an increase in x while Tm remained almost constant. Tm shifted towards lower temperatures accompanied by a decrease in the magnitude of the dielectric maximum (εm) with an increase in the lanthanum content (0.1 < x ≤ 0.4). The dielectric relaxation was modelled using the Vogel–Fulcher relation and a decrease in the activation energy for frequency dispersion with increasing x was observed. The frequency dispersion of Tm was found to decrease with an increase in lanthanum doping, and for compositions corresponding to x ≥ 0.3, Tm was frequency independent. Well-developed P(polarization)–E(electric field) hysteresis loops were observed at 150 °C for all the samples and the remanent polarization (2Pr) was improved from 6.3 µC cm−2 for pure BBT to 13.4 µC cm−2 for Ba0.7La0.2Bi4Ti4O15 ceramics. Dc conductivities and associated activation energies were evaluated using impedance spectroscopy.

Studies on glass transition and starch re-crystallization in wheat bread during staling using electrical impedance spectroscopy

Bread staling is a very complex phenomenon that is not yet completely understood. The present work explains how the electrical impedance spectroscopy technique can be utilized to investigate the effect of staling on the physicochemical properties of wheat bread during storage. An instrument based on electrical impedance spectroscopy technique is developed to study the electrical properties of wheat bread both at its crumb and crust with the help of designed multi-channel ring electrodes. Electrical impedance behavior, mainly capacitance and resistance, of wheat bread at crust and crumb during storage (up to 120 h) is investigated. The variation in capacitance showed the glass transition phenomenon at room temperature in bread crust after 96 h of storage with 18% of moisture in it. The resistance changes at bread crumb showed the starch recrystallization during staling.

Direct precipitation of lead zirconate titanate by the hydrothermal method

Direct precipitation of fine powders of lead zirconate titanate (PZT) in the complete range of solid solution, is investigated under hydrothermal conditions, starting from lead oxide and titania/zirconia mixed gels. The perovskite phase is formed in the temperature range of 165 – 340°C. Sequence of the hydrothermal reactions is studied by identifying the intermediate phases. The initial formation of PbO: TiO2 solid solution is followed by the reaction of the same with the remaining mixed gels giving rise to X-ray amorphous PZT phase. Further, through crystallite growth, the X-ray crystalline PZT is formed. This method can be extended for the preparation of PLZT powder as well. The resulting powders are sinterable to high density ceramics.

Analysis of Raman bandwidths and bandshapes of glasses through their glass-transition temperatures

Raman bandwidths and bandshapes of some molecular and ionic glasses have been investigated through the glass-transition region. Widths of both polarised and depolarised bands exhibit step-like changes during the glass transition. Molecular and ionic glasses differ with respect to the magnitude and the nature of variations in bandwidths and reorientational times. An attempt has been made to understand the changes in bandwidths around the glass-transition temperature.

Cluster model of the glass transition

A cluster model of the glass transition has been developed, treating the relative size of the cluster as an order parameter. The model accounts for some of the features of the glass transition.

Characterisation and processing of amorphous binary mixtures with low glass transition temperature

The number of drug substances in formulation development in the pharmaceutical industry is increasing. Some of these are amorphous drugs and have glass transition below ambient temperature, and thus they are usually difficult to formulate and handle. One reason for this is the reduced viscosity, related to the stickiness of the drug, that makes them complicated to handle in unit operations. Thus, the aim in this thesis was to develop a new processing method for a sticky amorphous model material. Furthermore, model materials were characterised before and after formulation, using several characterisation methods, to understand more precisely the prerequisites for physical stability of amorphous state against crystallisation. The model materials used were monoclinic paracetamol and citric acid anhydrate. Amorphous materials were prepared by melt quenching or by ethanol evaporation methods. The melt blends were found to have slightly higher viscosity than the ethanol evaporated materials. However, melt produced materials crystallised more easily upon consecutive shearing than ethanol evaporated materials. The only material that did not crystallise during shearing was a 50/50 (w/w, %) blend regardless of the preparation method and it was physically stable at least two years in dry conditions. Shearing at varying temperatures was established to measure the physical stability of amorphous materials in processing and storage conditions. The actual physical stability of the blends was better than the pure amorphous materials at ambient temperature. Molecular mobility was not related to the physical stability of the amorphous blends, observed as crystallisation. Molecular mobility of the 50/50 blend derived from a spectral linewidth as a function of temperature using solid state NMR correlated better with the molecular mobility derived from a rheometer than that of differential scanning calorimetry data. Based on the results obtained, the effect of molecular interactions, thermodynamic driving force and miscibility of the blends are discussed as the key factors to stabilise the blends. The stickiness was found to be affected glass transition and viscosity. Ultrasound extrusion and cutting were successfully tested to increase the processability of sticky material. Furthermore, it was found to be possible to process the physically stable 50/50 blend in a supercooled liquid state instead of a glassy state. The method was not found to accelerate the crystallisation. This may open up new possibilities to process amorphous materials that are otherwise impossible to manufacture into solid dosage forms.

Pressure and temperature dependence of the electrical resistivity of bulk Al23 Te77 glass

Electrical resistivity of bulk amorphous Al23T77 samples has been studied as a function of pressure (up to 80 kbar) and temperature (down to 77 K). At atmospheric pressure the temperature dependence of resistivity obeys the relation = π0 exp(δE/RT) with two activation energies. In the temperature range 300 K T > 234 K the activation energy is 0.58 eV and for 234 >T 185 K the value is δE = 0.30 ev. The activation energy has been measured as a function of pressure. The electrical resistivity decreases exponentially with the increase of pressure and at 70 kbar pressure the electrical behaviour of the sample shows a metallic nature with a positive temperature coefficient. The high pressure phase of the sample is found to be a crystalline hexagonal phase.

Pressure induced polymorphous crystallization in bulk Ge20Te80 glass

The pressure and temperature dependence of the electrical resistivity of bulk glassy Ge20Te80 is reported. The effect of annealing is also studied. The glass undergoes a polymorphous or congruent crystallization under high pressures. The high pressure phase is found to have fcc structure with Image . Under thermal treatment the glass undergoes the double stage crystallization. The sample annealed at the first crystallization temperature shows a pressure induced semiconductor-to-metal transition at 4.0 GPa pressure and the crystalline Ge20Te80 samples show the transition at 7 GPa pressure.