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.

Morphological structure of bismuth-doped n-type amorphous germanium sulphide semiconductors

Recent observation of n-type conduction in amorphous Ge20Ss_xBix at large bismuth concentrations (x = 11), which otherwise shows p-type conduction, has aroused considerable interest in the international scientific community [1]. The mechanism of such impurity incorporation in a germanium chalcogenide glass is not understood and is a topic of current interest. In our recent publications [2-10] we have brought to light some hitherto unknown and interesting features of bismuth dopants in chalcogen-rich Ge-X (X -- S, Se) glassy compositions. In this communication we present our new results of investigations on vitreous semiconductors Ge20S80 Bi using electron microscopy, electron diffraction of as-prepared and annealed/pressure quenched compositions. Our results provide conclusive support to the formation of composite clusters containing all the three elements, germanium, sulphur and bismuth, which crystallize in simpler stoichiometric compounds Bi2S3 and GeS2.

Pressure-Induced transitions in amorphous TlxSe100-x alloys

The electrical resistivity of bulk semiconducting amorphous TlxSe100-x alloys with 0 ≤ x ≤ 25 has been investigated up to a pressure of 14 GPa and down to liquidnitrogen temperature by use of a Bridgman anvil device. All the glasses undergo a discontinuous pressure-induced semiconducting-to-metal transition. X-ray diffraction studies on the pressure-recovered samples show that the high-pressure phase is the crystalline phase. The pressure-induced crystalline products are identified to be a mixture of Se having a hexagonal structure with a = 4·37 Aring and c = 4·95 Aring and TlSe having a tetragonal structure with a = 8·0 Aring and c = 7·0 Aring

Impurity states in Sb-doped amorphous semiconductors

A systematic investigation of the effects of antimony dopant on the electronic transport properties of amorphous (GeSe3.5)100−xSbx under high pressure (up to 120 kbar) has been carried out down to liquid-nitrogen temperature for the first time. Differential thermal analysis and x-ray diffraction methods were used for the characterization of freshly prepared and pressure-quenched materials which indicated the presence of structural phase transition in both GeSe3.5 and (GeSe3.5)100−xSbx around 105 kbar pressure. Electrical transport data revealed the strong compositional dependence of the electronic conduction process. A distinct kink in the conductivity temperature plot at pressures>15 kbar was observed in the Sb-doped compositions indicating the presence of different conduction processes. An attempt has been made to interpret the pressure-induced effect in the transport properties of these glasses considering the possible presence of both thermally activated conduction in the extended states and hopping process in the localized tail states. However, the interpretation of the transport data is not straightforward and the pressure dependence of the thermoelectric power will be needed to complete the picture. Journal of Applied Physics is copyrighted by The American Institute of Physics.

Chemical bond approach to determining conductivity band gaps in amorphous chalcogenides and pnictides

The minimum energy required for the formation of conjugate pair of charged defects is found to be approximately equal to the experimental activation energy for d.c. conductivity in a number of amorphous chalcoganides and pnictides. This observation implies that the defect pair formation energy represents an intrinsic gap for transport in amorphous chalcogenides.

On the structural features of doped amorphous chalcogenide semiconductors

A study of Bi-doped amorphous (Ge42S58)100−xBix and Ge20S80−xBix has been carried out by differential thermal analysis (DTA) and X-ray diffraction methods so as to elucidate the impurity-induced modifications in the semiconductors. Thermal analysis reveals the presence of complex structural units in the modified material. An interesting feature of this study is the existence of a double glass transition in Ge20S80−xBix, which is reported for the first time in this system.

Site-Specific Functionalization of Hyperbranched Polymers Using ``Click'' Chemistry

Different strategies for functionalization of the core region and periphery of core-shell type hyperbranched polymers (HBP) using the ``click'' reaction have been explored. For achieving periphera functionalization, an AB(2) + A-R-1 + A-R-2 type copolymerization approach was used, where A-R-1 is heptaethylene glycol monomethyl ether (HPEG-M) and A-R-2 is tetraethylene glycol monopropargyl ether (TEG-P). A very small mole fraction of the propargyl containing monomer, TEG-P, was used to ensure that the water-solubility of the hyperbranched polymer is minimally affected. Similarly, to incorporate propargyl groups in the core region, a new propargyl group bearing B-2-typ monomer was designed and utilized in an AB(2) + A(2) + B-2 + A-R-1 type copolymerization, such that the total mole fraction of B-2 + A(2) is small and their mole-ratio is 1: 1. Further, using a combination of both the above approaches, namely AB(2) + A(2) + B-2 + A-R-1 + A-R-2, hyperbranched structures that incorporate propargyl groups both at theperiphery and within the core were synthesized. Since the AB(2) monomer carries a hexamethylene spacer (C-6) and the periphery is PEGylated all the derivatized polymers form core-shell type structures in aqueous solutions. Attempts were made to ascertain and probe the location of the propargyl groups in these HBP's, by ``clicking'' azidomethylpyrene, onto them. However, the fluorescence spectra of aqueous solutions of the pyrene derivatized polymers were unable to discriminate between the various locations, possibly because the relatively hydrophobic pyrene units insert themselves into the core region to minimize exposure to water.

Absence of reptation in highly confined polymers

We present results of mechanical stress relaxation measurements on polymers confined at the air-water interface in the form of a monolayer. Systematic measurements allow, to our knowledge, for the first time, observation of the scaling of the stress relaxation time of the highly confined polymers as a function of both surface concentration and molecular weight. The observed scaling is found to be very close to that expected for motion of unentangled polymer solutions with hydrodynamic interactions. Our experimental observations thus clearly rule out the possibility of entanglement and hence reptation as a mode of relaxation in such highly confined polymeric systems.

Nonlinear transport in semiconducting polymers at high carrier densities

Conducting and semiconducting polymers are important materials in the development of printed, flexible, large-area electronics such as flat-panel displays and photovoltaic cells. There has been rapid progress in developing conjugated polymers with high transport mobility required for high-performance field-effect transistors (FETs), beginning(1) with mobilities around 10(-4) cm(2) V-1 s(-1) to a recent report(2) of 1 cm(2) V-1 s(-1) for poly(2,5-bis(3-tetradecylthiophen-2-yl) thieno[3,2-b] thiophene) (PBTTT). Here, the electrical properties of PBTTT are studied at high charge densities both as the semiconductor layer in FETs and in electrochemically doped films to determine the transport mechanism. We show that data obtained using a wide range of parameters (temperature, gate-induced carrier density, source-drain voltage and doping level) scale onto the universal curve predicted for transport in the Luttinger liquid description of the one-dimensional `metal'.

Direct electrochemical formation of nanostructured amorphous Co(OH)2 on gold electrodes with enhanced activity for the oxygen evolution reaction.

The oxides of cobalt have recently been shown to be highly effective electrocatalysts for the oxygen evolution reaction (OER) under alkaline conditions. In general species such as Co3O4 and CoOOH have been investigated that often require an elevated temperature step during their synthesis to create crystalline materials. In this work we investigate the rapid and direct electrochemical formation of amorphous nanostructured Co(OH)2 on gold electrodes under room temperture conditions which is a highly active precursor for the OER. During the OER some conversion to crystalline Co3O4 occurs at the surface, but the bulk of the material remains amorphous. It is found that the underlying gold electrode is crucial to the materials enhanced performance and provides higher current density than can be achieved using carbon, palladium or copper support electrodes. This catalyst exhibits excellent activity with a current density of 10 mA cm-2 at an overpotential of 360 mV with a high turnover frequency of 2.1 s-1 in 1 M NaOH. A Tafel slope of 56 mV dec-1 at low overpotentials and a slope of 122 mV dec-1 at high overpotentials is consistent with the dual barrier model for the electrocatalytic evolution of oxygen. Significantly, the catalyst maintains excellent activity for up to 24 hr of continuous operation and this approach offers a facile way to create a highly effective and stable material.

Origin of anomalous photoinduced transformations in amorphous Ge-based chalcogenide thin films

Anomalous photoinduced transformations in amorphous Ge-based chalcogenide thin films are established as being due to photochemical modification of the surfaces, by photoemission studies. Mass measurements indicate that the giant thickness reduction on irradiation is predominantly due to the loss of material as a result of photogenerated volatile high vapor pressure oxide fractions on the surface. This extrinsic contribution contradicts the models of the phenomenon proposed so far, which are based purely on intrinsic structural transformations.

Metallization and crystallization of semiconducting amorphous Ga20Te80 alloy under high pressure

Pressure and temperature dependence of the electrical resistivity of amorphous Ga20Te80 alloy is reported for the first time. The alloy undergoes a pressure induced amorphous semiconductor-to-crystalline metal phase transition at 6.5 ± 0.5 GPa. The high pressure crystalline phase is a mixture of Te and GaTe3 phases.