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.

Formation ranges of icosahedral, amorphous and crystalline phases in rapidly solidified Ti-Zr-Hf-Ni alloys

From the quaternary Ti-Zr-Hf-Ni phase diagram. the cross-section at 20 at % Ni was selected for investigation. The icosahedral quasicrystalline, crystalline and amorphous phases were observed to form in nine kinds of rapidly solidified (TixZryHfz)(80)Ni-20 (x + y + z = 1) alloys at different compositions. The quasilattice constants of 0.519 and 0.531 nm were obtained for the icosahedral phase formed in the melt-spun Ti40Zr20Hf20Ni20 and Ti20Zr40Hf20Ni20 alloys. respectively. The icosahedral phase formed in the melt-spun Ti40Zr20Hf20Ni20 alloy especially is thermodynamically stable. The supercooled liquid region of the Ti20Zr20Hf40Ni20 glassy alloy reached 64 K. From these results a comparison of quasicrystal-forming and glass-forming abilities, was carried out. The quasicrystal-forming ability was reduced and glass-forming ability was improved with an increase in Hf and Zr contents in the (TixZryHfz)(80)Ni-20 alloys. On the other hand. an increase in Ti content caused an improvement in quasicrystal-forming ability.

Resolution of conflicting views on thermodynamics of glass transition: A unified model

Classical description of thermodynamic properties during glass transition has been questioned by the entropy-loss model. The uncompensated loss of entropy at the glass transition temperature and zero residual entropy is at the heart of the controversy. Both the models are critically reviewed. A unified model is presented which incorporates features of both entropy loss and residual entropy. It implies two different types of contributions to the entropy of the supercooled liquid, one of which vanishes at the transition and the other which contributes to residual entropy. Entropy gain during spontaneous relaxation of glass, and the nature of heat capacity `hysteresis' during cooling and heating through the glass transition range support the proposed model. Experiments are outlined for differentiating between the models.

Brownian dynamics simulation of dense binary colloidal mixtures. I. Structural evolution and dynamics

We have carried out Brownian dynamics simulations of binary mixtures of charged colloidal suspensions of two different diameter particles with varying volume fractions phi and charged impurity concentrations n(i). For a given phi, the effective temperature is lowered in many steps by reducing n(i) to see how structure and dynamics evolve. The structural quantities studied are the partial and total pair distribution functions g(tau), the static structure factors, the time average g(<(tau)over bar>), and the Wendt-Abraham parameter. The dynamic quantity is the temporal evolution of the total meansquared displacement (MSD). All these parameters show that by lowering the effective temperature at phi = 0.2, liquid freezes into a body-centered-cubic crystal whereas at phi = 0.3, a glassy state is formed. The MSD at intermediate times shows significant subdiffusive behavior whose time span increases with a reduction in the effective temperature. The mean-squared displacements for the supercooled liquid with phi = 0.3 show staircase behavior indicating a strongly cooperative jump motion of the particles.

Brownian dynamics simulation of dense binary colloidal mixtures. II. Translational and bond-orientational order

We report the Brownian dynamics simulation results on the translational and bond-angle-orientational correlations for charged colloidal binary suspensions as the interparticle interactions are increased to form a crystalline (for a volume fraction phi = 0.2) or a glassy (phi = 0.3) state. The translational order is quantified in terms of the two- and four-point density autocorrelation functions whose comparisons show that there is no growing correlation length near the glass transition. The nearest-neighbor orientational order is determined in terms of the quadratic rotational invariant Q(l) and the bond-orientational correlation functions g(l)(t). The l dependence of Q(l) indicates that icosahedral (l = 6) order predominates at the cost of the cubic order (l = 4) near the glass as well as the crystal transition. The density and orientational correlation functions for a supercooled liquid freezing towards a glass fit well to the streched-exponential form exp[-(t/tau)(beta)]. The average relaxation times extracted from the fitted stretched-exponential functions as a function of effective temperatures T* obey the Arrhenius law for liquids freezing to a crystal whereas these obey the Vogel-Tamman-Fulcher law exp[AT(0)*/(T* - T-0*)] for supercooled Liquids tending towards a glassy state. The value of the parameter A suggests that the colloidal suspensions are ''fragile'' glass formers like the organic and molecular liquids.

Collective Effects on Single Particle Orientational Relaxation in Slow Dipolar Liquids

Theoretical and computer simulation studies of orientational relaxation in dense molecular liquids are presented. The emphasis of the study is to understand the effects of collective orientational relaxation on the single-particle orientational dynamics. The theoretical analysis is based on a recently developed molecular hydrodynamic theory which allows a self-consistent description of both the collective and the single-particle orientational relaxation. The molecular hydrodynamic theory can be used to derive a relation between the memory function for the collective orientational correlation function and the frequency-dependent dielectric function. A novel feature of the present work is the demonstration that this collective memory function is significantly different from the single-particle rotational friction. However, a microscopic expression for the single-particle rotational friction can be derived from the molecular hydrodynamic theory where the collective memory function can be used to obtain the single-particle orientational friction. This procedure allows, us to calculate the single-particle orientational correlation function near the alpha-beta transition in the supercooled liquid. The calculated correlation function shows an interesting bimodal decay below the bifurcation temperature as the glass transition is approached from above. Brownian dynamics simulations have been carried out to check the validity of the above procedure of translating the memory function from the dielectric relaxation data. We have also investigated the following two issues important in understanding the orientational relaxation in slow liquids. First, we present an analysis of the ''orientational caging'' of translational motion. The value of the translational friction is found to be altered significantly by the orientational caging. Second, we address the question of the rank dependence of the dielectric friction using both simulation and the molecular hydrodynamic theory.

Characterization of the dynamics of glass-forming liquids from the properties of the potential energy landscape

We develop a framework for understanding the difference between strong and fragile behavior in the dynamics of glass-forming liquids from the properties of the potential energy landscape. Our approach is based on a master equation description of the activated jump dynamics among the local minima of the potential energy (the so-called inherent structures) that characterize the potential energy landscape of the system. We study the dynamics of a small atomic cluster using this description as well as molecular dynamics simulations and demonstrate the usefulness of our approach for this system. Many of the remarkable features of the complex dynamics of glassy systems emerge from the activated dynamics in the potential energy landscape of the atomic cluster. The dynamics of the system exhibits typical characteristics of a strong supercooled liquid when the system is allowed to explore the full configuration space. This behavior arises because the dynamics is dominated by a few lowest-lying minima of the potential energy and the potential energy barriers between these minima. When the system is constrained to explore only a limited region of the potential energy landscape that excludes the basins of attraction of a few lowest-lying minima, the dynamics is found to exhibit the characteristics of a fragile liquid.

Decoupling of diffusion from viscosity: Difference scenario for translational and rotational motions

Recent experiments have indicated a dramatically different viscosity dependence of the translational and the rotational diffusion coefficients in a supercooled liquid as the glass transition temperature is approached from above. While the translational motion seems to be decoupled from the rising viscosity (eta), the rotational motion seems to remain firmly coupled to eta. In order to understand the microscopic origin of this behavior, we have carried nut detailed theoretical calculations of both the quantities by using a self-consistent mode-coupling theory (MCT). it is found that when the size of the solute is same as that of the solvent molecules, the conventional MCT fails to predict the observed decoupling. The solvent inhomogeneity is found to play a decisive role in determining the decoupling. The difference in the viscosity dependence between rotation and translational diffusion coefficient is discussed.

Novel Fe70Zr10Ni6Al4Si6B4 thick metallic glass coating produced by laser cladding

A novel multicomponent thick metallic glass coating has been synthesised by laser cladding. The maximum coating thickness was I mm. The clad cooling rate restrained the epitaxial growth of dendrites in the metallic glass coating. The metallic glass had high glass forming ability with a wide supercooled liquid region ranging from 59 to 70 K. The metallic glass coating also revealed high hardness and good corrosion resistance.

Numerical Study Of Pile-Up In Bulk Metallic Glass During Spherical Indentation

Pile-up around indenter is usually observed during instrumented indentation tests on bulk metallic glass. Neglecting the pile-up effect may lead to errors in evaluating hardness, Young's modulus, stress-strain response, etc. Finite element analysis was employed to implement numerical simulation of spherical indentation tests on bulk metallic glass. A new model was proposed to describe the pile-up effect. By using this new model, the contact radius and hardness of Zr41.2Ti13.8Cu12.5Ni10Be22.5 bulk metallic glass were obtained under several different indenter loads with pile-up, and the results agree well with the data generated by numerical simulation.

Synthesis of thick Ni66Cr5Mo4Zr6P15B4 amorphous alloy coating and large glass-forming ability by laser cladding

A thick amorphous alloy (a-alloy) coating was synthesized by laser cladding. The a-alloy had a multicomponent chemistry, i.e., Ni66Cr5MO4Zr6P15B4 (in atom%). The maximum thickness of the coating is 0.8 mm. The a-alloy coating had large glass-forming ability (GFA) with wide supercooled liquid region (SLR) ranging from 52 to 61 K through the coating. The reason for high GFA in the a-alloy coating was discussed. (C) 2002 Published by Elsevier Science B.V.

CHARACTERIZATION OF SHEAR BANDS IN TWO BULK METALLIC GLASSES WITH DIFFERENT INHERENT PLASTICITY

Shear banding characterization of Zr64.13Cu15.75Ni10.12Al10 and Zr65Cu15Ni10Al10 bulk metallic glasses (BMGs) with significant difference in inherent plasticity and quite similar chemical composition was studied by depth sensitive macroindentaion tests with conical indenter. Well-developed shear band pattern can be found for both BMGs after indentation. Distinct difference in the shear band spacing, scale of plastic deformation region and the shear band branching in the two BMGs account for the different plasticity.

Characterization Of Shear Bands In Two Bulk Metallic Glasses With Different Inherent Plasticity

Shear banding characterization of Zr64.13Cu15.75Ni10.12Al10 and Zr65Cu15Ni10Al10 bulk metallic glasses (BMGs) with significant difference in inherent plasticity and quite similar chemical composition was studied by depth sensitive macroindentaion tests with conical indenter. Well-developed shear band pattern can be found for both BMGs after indentation. Distinct difference in the shear band spacing, scale of plastic deformation region and the shear band branching in the two BMGs account for the different plasticity.

Glass formation ability and mechanical properties of Ti40Cu40Zr10Ni10 alloy

Melt-spun ribbon and bulk samples in cylindrical rod form with diameter ranging from 2 mm to 4 mm of Ti40Cu40Zr10Ni10 alloy were prepared by melt-spinning technique and copper mould casting method, respectively. The microstructure, thermal stability and mechanical properties of the bulk samples were investigated. A completely glassy single phase is formed in the 2 mm rod sample. Increasing the diameter of the rod samples resulted in the formation of CuTi crystalline phase in the 3 mm and 4 mm rod samples.

MICROSTRUCTURE AND MECHANICAL PROPERTIES OF TI-BASED METALLIC GLASS MATRIX COMPOSITES

Ti40Cu40Ni10Zr10-xScx (x = 0.5 and 1, at%) alloys were prepared by copper mould casting method. Microstructures of the phi 3 mm rod alloys were investigated by XRD and SEM. The results showed that the phi 3 mm rods were glassy matrix with TiCu crystalline phase. Mechanical properties were studied by compressive test. Ti40Cu40Ni10Zr9Sc1 alloy exhibited good compressive strength over 2200 MPa and superior compressive deformation is about 7.9%.