Two-phase synthesis of shape-controlled colloidal zirconia nanocrystals and their characterization

We have developed a two-phase approach for the synthesis of shape-controlled colloidal zirconia nanocrystals, including spherical-, teardrop-, rod-, and rice grain-shaped particles. We found that the key factors for controlling the shape were the reaction time, the nature of the capping agent, and the monomer concentration. We have analyzed the morphologies, crystallinity, optical properties, and structural features of the as-prepared ZrO2 nanoparticles by using transmission electron microscopy (TEM), high-resolution TEM, X-ray powder diffraction, and UV-vis absorption and fluorescence spectroscopy. The possible nucleation and growth process is also discussed.

Enhanced crystallization and phase transformation of amorphous silicon nitride under high pressure

The crystallization and phase transformation of amorphous Si3N4 ceramics under high pressure (1.0-5.0 GPa) between 800 and 1700 degreesC were investigated. A greatly enhanced crystallization and alpha-beta transformation of the amorphous Si3N4 ceramics were evident under the high pressure, as characterized by that, at 5.0 GPa, the amorphous Si3N4, began to crystallize at a temperature as low as 1000 degreesC (to transform to alpha modification). The subsequent alpha-beta transformation occurred completed between 1350 and 1420 degreesC after only 20 min of pressing at 5.0 GPa. In contrast, under 0.1 MPa N-2, the identical amorphous materials were stable up to 1400 degreesC without detectable crystallization, and only a small amount of a phase was detected at 1500 degreesC. The crystallization temperature and the alpha-beta transformation temperatures are reduced by 200-350 degreesC compared to that at normal pressure. The enhanced phase transformations of the amorphous Si3N4, were discussed on the basis of thermodynamic and kinetic consideration of the effects of pressure on nucleation and growth.

Differential Scanning Calorimetry Study and Computer Modeling of b a Phase Transformation in Ti-6Al-4V Alloy

The relationship between heat-treatment parameters and microstructure in titanium alloys has so far been mainly studied empirically, using characterization techniques such as microscopy. Calculation and modeling of the kinetics of phase transformation have not yet been widely used for these alloys. Differential scanning calorimetry (DSC) has been widely used for the study of a variety of phase transformations. There has been much work done on the calculation and modeling of the kinetics of phase transformations for different systems based on the results from DSC study. In the present work, the kinetics of the transformation in a Ti-6Al-4V titanium alloy were studied using DSC, at continuous cooling conditions with constant cooling rates of 5 °C, 10 °C, 20 °C, 30 °C, 40 °C, and 50 °C/min. The results from calorimetry were then used to trace and model the transformation kinetics in continuous cooling conditions. Based on suitably interpreted DSC results, continuous cooling–transformation (CCT) diagrams were calculated with lines of isotransformed fraction. The kinetics of transformation were modeled using the Johnson–Mehl–Avrami (JMA) theory and by applying the "concept of additivity." The JMA kinetic parameters were derived. Good agreement between the calculated and experimental transformed fractions is demonstrated. Using the derived kinetic parameters, the transformation in a Ti-6Al-4V alloy can be described for any cooling path and condition. An interpretation of the results from the point of view of activation energy for nucleation is also presented.

Free energy and molecular dynamics calculations for the cubic-tetragonal phase transition in zirconia

The high-temperature cubic-tetragonal phase transition of pure stoichiometric zirconia is studied by molecular dynamics (MD) simulations and within the framework of the Landau theory of phase transformations. The interatomic forces are calculated using an empirical, self-consistent, orthogonal tight-binding model, which includes atomic polarizabilities up to the quadrupolar level. A first set of standard MD calculations shows that, on increasing temperature, one particular vibrational frequency softens. The temperature evolution of the free-energy surfaces around the phase transition is then studied with a second set of calculations. These combine the thermodynamic integration technique with constrained MD simulations. The results seem to support the thesis of a second-order phase transition but with unusual, very anharmonic behavior above the transition temperature.

High‐temperature phase transitions in pure and deuterated ammonium dihydrogen phosphate: Conductivity and dielectric measurements

Results of axiswise measurements of the electrical conductivity (dc and ac) and dielectric constant of NH4H2PO4 confirm the occurrence of the recently suggested high‐temperature phase transition in this crystal (at 133 °C). The corresponding transition in ND4D2PO4 observed here for the first time takes place at 141.5 °C. The mechanism involved in these transitions and those associated with the electrical conduction and dielectric anomalies are explained on the basis of the motional effects of the ammonium ions in these crystals. Conductivity values for deuterated crystals give direct evidence for the predominance of protonic conduction throughout the entire range of temperatures studied (30–260 °C).

Magnetic phase separation in ordered alloys

We present a lattice model to study the equilibrium phase diagram of ordered alloys with one magnetic component that exhibits a low temperature phase separation between paramagnetic and ferromagnetic phases. The model is constructed from the experimental facts observed in Cu3-xAlMnx and it includes coupling between configurational and magnetic degrees of freedom that are appropriate for reproducing the low temperature miscibility gap. The essential ingredient for the occurrence of such a coexistence region is the development of ferromagnetic order induced by the long-range atomic order of the magnetic component. A comparative study of both mean-field and Monte Carlo solutions is presented. Moreover, the model may enable the study of the structure of ferromagnetic domains embedded in the nonmagnetic matrix. This is relevant in relation to phenomena such as magnetoresistance and paramagnetism

Critical behavior in nonequilibrium phase transitions

The nonequilibrium phase transitions occurring in a fast-ionic-conductor model and in a reaction-diffusion Ising model are studied by Monte Carlo finite-size scaling to reveal nonclassical critical behavior; our results are compared with those in related models.

Multi-phase microstructure design of a novel high strength TRIP steel through experimental methodology

The multi-phase structure of a novel low-alloy transformation induced plasticity (TRIP) steel was designed through experimental analysis. The evolutions of both microstructure and mechanical properties during the two-stage heat treatment were analyzed. The phase transformations during the intercritical annealing and the isothermal bainitic transformation were investigated by means of dilatometry. It was shown that two types of C diffusion were detected during intercritical annealing and a complex microstructure was formed after heat treatment. The processing parameters were selected in such a way to obtain microstructures with systematically different volume fractions of ferrite, bainite and retained austenite. The volume fractions of ferrite and retained austenite were found to be two main factors controlling the ductility. Furthermore, a high volume fraction of C-rich retained austenite, which was stabilized at room temperature, was the origin of a TRIP effect. The resulting material demonstrates a significant improvement in the ultimate tensile strength (1077. MPa) with good uniform elongation (22.5%), as compared to conventional TRIP steels. © 2014 Elsevier B.V.

Recent advances in machining of Austempered Ductile Iron to avoid machining induced microstructural phase transformation reaction

Austempered Ductile Iron (ADI) is a type of nodular, ductile cast iron subjected to heat treatments-austenitising and austempering. Whilst machining is conducted prior to heat treatment and offers no significant difficulty, machining post heat treatment is demanding and often avoided. Phase transformation of retained austenite to martensite leading to poor machinability characteristics is a common problem experienced during machining. Study of phase transformations is an investigative study on the factors-plastic strain (εp) and thermal energy (Q) which effect phase transformations during machining. The experimental design consists of face milling grade 1200 at variable Depth of Cut (DoC) range from 1 to 4 mm, coolant on/off, at constant speed, 1992 rpm and feed rate, 0.1 mm/tooth. Plastic strain (εp) and martensite content (M) at fracture point for each grade was evaluated by tensile testing. The effect of thermal energy (Q) on phase transformations was also verified through temperature measurements at DoC 3 and 1 mm using thermocouples embedded into the workpiece. Finally, the amount of plastic strain (εp) and thermal energy (Q) responsible for a given martensite increase (M) during milling was related and calculated using a mathematical function, M=f (εp, Q). The future work of the thesis involves an in-depth study on the new link discovered through this research: mathematical model relating the role of plastic strain and thermal energy in martensite formation.

Completeness of beta-phase decomposition reaction in Cu-Al-Ag alloys

The completeness of beta-phase decomposition reaction in the Cu-11wt%Al-xwt%Ag alloys (x = 0, 1, 2, and 3) was studied using differential scanning calorimetry (DSC), X-ray diffractometry (XRD), and optical microscopy (OM). The results indicated that beta-phase transformations are highly dependent on cooling rate and on the presence of Ag. on slow cooling, the silver presence prevents the beta- and beta(1)-phase decomposition; thus, inducing the martensitic phase formation. After rapid cooling, a new thermal event is observed and the reverse martensitic transformation is shifted to lower temperatures.

A Simple Visual Demonstration of Phase Diagram Concepts for an Introductory Materials Science Course Using Colored Solvents

A simple and effective demonstration to help students comprehend phase diagrams and understand phase equilibria and transformations is created using common chemical solvents available in the laboratory. Common misconceptions surrounding phase diagram operations, such as components versus phases, reversibility of phase transformations, and the lever rule are addressed. Three different binary liquid mixtures of varying compatibility create contrastive phase equilibrium cases, where colorful dyes selectively dissolved in each of corresponding phases allow for quick and unambiguous perceptions of solubility limit and phase transformations. Direct feedback and test scores from a group of students show evidence of the effectiveness of the visual and active teaching tool.

The constitution of delta-phase alloys of the system uranium-zirconium-titanium /

"March 22, 1955."

Crystallization as a Tool for Controlling and Designing Properties of Pharmaceutical Solids

The ability to deliver the drug to the patient in a safe, efficacious and cost-effective manner depends largely on the physicochemical properties of the active pharmaceutical ingredient (API) in the solid state. In this context, crystallization is of critical importance in pharmaceutical industry, as it defines physical and powder properties of crystalline APIs. An improved knowledge of the various aspects of crystallization process is therefore needed. The overall goal of this thesis was to gain better understanding of the relationships between crystallization, solid-state form and properties of pharmaceutical solids with a focus on a crystal engineering approach to design technological properties of APIs. Specifically, solid-state properties of the crystalline forms of the model APIs, erythromycin A and baclofen, and the influence of solvent on their crystallization behavior were investigated. In addition, the physical phenomena associated with wet granulation and hot-melting processing of the model APIs were examined at the molecular level. Finally, the effect of crystal habit modification of a model API on its tabletting properties was evaluated. The thesis enabled the understanding of the relationship between the crystalline forms of the model APIs, which is of practical importance for solid-state control during processing and storage. Moreover, a new crystalline form, baclofen monohydrate, was discovered and characterized. Upon polymorph screening, erythromycin A demonstrated high solvate-forming propensity thus emphasizing the need for careful control of the solvent effects during formulation. The solvent compositions that yield the desirable crystalline form of erythromycin A were defined. Furthermore, new examples on solvent-mediated phase transformations taking place during wet granulation of baclofen and hot-melt processing of erythromycin A dihydrate with PEG 6000 are reported. Since solvent-mediated phase transformations involve the crystallization of a stable phase and hence affect the dissolution kinetics and possibly absorption of the API these transformations must be well documented. Finally, a controlled-crystallization method utilizing HPMC as a crystal habit modifier was developed for erythromycin A dihydrate. The crystals with modified habit were shown to posses improved compaction properties as compared with those of unmodified crystals. This result supports the idea of morphological crystal engineering as a tool for designing technological properties of APIs and is of utmost practical interest.