On visco-elastic modelling of polyethylene terephthalate behaviour during multiaxial elongations slightly over the glass transition temperature

The mechanical response of Polyethylene Terephthalate (PET) in elongation is strongly dependent on temperature, strain and strain rate. Near the glass transition temperature Tg, the stress-strain curve presents a strain softening effect vs strain rate but a strain hardening effect vs strain under conditions of large deformations. The main goal of this work is to propose a viscoelastic model to predict the PET behaviour when subjected to large deformations and to determine the material properties from the experimental data. To represent the non–linear effects, an elastic part depending on the elastic equivalent strain and a non-Newtonian viscous part depending on both viscous equivalent strain rate and cumulated viscous strain are tested. The model parameters can then be accurately obtained trough a comparison with the experimental uniaxial and biaxial tests. The in?uence of the temperature on the viscous part is also modelled and an evaluation of the adiabatic self heating of the specimen is compared to experimental results.

Coupled Temperature-Displacement Modelling of Injection Stretch Blow Moulding of PET bottles using Buckley Model

This study presents a fully coupled temperature–displacement finite element modelling of the injection stretch-blow moulding (ISBM) process of polyethylene terephthalate (PET) bottles using ABAQUS with a view to optimising the process conditions. A physically-based material model (Buckley model) was used to predict the mechanical behaviour of PET at temperatures slightly above its glass transition temperature. A model incorporating heat transfer between the stretch rod, the preform and the mould was built using axisymmetric solid elements. Extensive finite element analyses were carried out to predict the deformation, the distribution and history of strain and temperature during ISBM of a 20 g–330 ml bottle, which was made in an in situ test on a Sidel SB06 machine. Comparisons of numerical results with the measurements demonstrate that the model can satisfactorily model the sidewall thickness and material distributions. It is also shown that significant non-linear differentials exist in temperature and strain in both bottle thickness and length directions during the process. This justifies the employment of a volume approach to accurately predict the final mechanical properties of the bottles governed by the orientation and crystallinity which are highly temperature and strain dependent.

Degradation of poly-L-lactide. Part2 : increased temperature accelerated degradation

Poly-L-lactide (PLLA) is one of the most significant members of a group of polymers regarded as bioresorbable. The degradation of PLLA proceeds through hydrolysis of the ester linkages in the polymer's backbone; however, the time for the complete resorption of orthopaedic devices manufactured from PLLA is known to be in excess of five years in a normal physiological environment. To evaluate the degradation of PLLA in an accelerated time period, PLLA pellets were processed by compression moulding into tensile test specimens, prior to being sterilized by ethylene oxide gas (EtO) and degraded in a phosphate-buffered solution (PBS) at both 50°C and 70°C. On retrieval, at predetermined time intervals, procedures were used to evaluate the material's molecular weight, crystallinity, mechanical strength, and thermal properties. The results from this study suggest that at both 50°C and 70°C, degradation proceeds by a very similar mechanism to that observed at 37°C in vitro and in vivo. The degradation models developed also confirmed the dependence of mass loss, melting temperature, and glass transition temperature (Tg) on the polymer's molecular weight throughout degradation. Although increased temperature appears to be a suitable method for accelerating the degradation of PLLA, relative to its physiological degradation rate, concerns still remain over the validity of testing above the polymer's Tg and the significance of autocatalysis at increased temperatures.

Path-integral study of a two-dimensional Lennard-Jones glass

The glass transition in a quantum Lennard-Jones mixture is investigated by constant-volume path-integral simulations. Particles are assumed to be distinguishable, and the strength of quantum effects is varied by changing h from zero (the classical case) to one (corresponding to a highly quantum-mechanical regime). Quantum delocalization and zero point energy drastically reduce the sensitivity of structural and thermodynamic properties to the glass transition. Nevertheless, the glass transition temperature T-g can be determined by analyzing the phase space mobility of path-integral centroids. At constant volume, the T-g of the simulated model increases monotonically with increasing h. Low temperature tunneling centers are identified, and the quantum versus thermal character of each center is analyzed. The relation between these centers and soft quasilocalized harmonic vibrations is investigated. Periodic minimizations of the potential energy with respect to the positions of the particles are performed to determine the inherent structure of classical and quantum glassy samples. The geometries corresponding to these energy minima are found to be qualitatively similar in all cases. Systematic comparisons for ordered and disordered structures, harmonic and anharmonic dynamics, classical and quantum systems show that disorder, anharmonicity, and quantum effects are closely interlinked.

Influence of the anion on the electrical conductivity and glass formation of 1-butyl-3-methylimidazolium ionic liquids

Six ionic liquids based on the 1-butyl-3-methylimidazolium cation have been studied. As anions Cl-, Br-, I-, [NCS](-), [N(CN)(2)](-), and [BF4](-) were selected. The electrical conductivities were determined between 173 and 393 K based on impedance measurements in the frequency range from 0.1 to 10(7) Hz. The electrical conductivity increases, whereas the glass transition temperature, the fragility, and the low temperature activation energy decrease with increasing anion size. The results can be understood from the changing anion-cation interaction strength with changing anion size and from the energy landscape interpretation of the glass transition dynamics. (C) 2010 American Institute of Physics. [doi:10.1063/1.3455892]

Poly(epsilon-caprolactone) and poly(epsilon-caprolactone)-polyvinylpyrrolidone-iodine blends as ureteral biomaterials: characterisation of mechanical and surface properties, degradation and resistance to encrustation in vitro.

This study describes the physicochemical properties and in vitro resistance to encrustation of solvent cast films composed of either poly(epsilon-caprolactone) (PCL), prepared using different ratios of high (50,000) to low (4000) (molecular weight) m.wt., or blends of PCL and the polymeric antimicrobial complex, poly(vinylpyrrolidone)-iodine (PVP-I). The incorporation of PVP-I offered antimicrobial activity to the biomaterials. Films were characterised in terms of mechanical (tensile analysis, dynamic mechanical thermal analysis) and surface properties (dynamic contact angle analysis, scanning electron microscopy), whereas degradation (at 37degreesC in PBS at pH 7.4) was determined gravimetrically. The resistance of the films to encrustation was evaluated using an in vitro encrustation model. Reductions in the ratio of high:low-m.wt. PCL significantly reduced the ultimate tensile strength, % elongation at break and the advancing contact angle of the films. These effects were attributed to alterations in the amorphous content and the more hydrophilic nature of the films. Conversely, there were no alterations in Young's modulus, the viscoelastic properties and glass-transition temperature. Incorporation of PVP-I did not affect the mechanical or rheological properties of the films, indicative of a limited interaction between the two polymers in the solid state. Manipulation of the high:low m.wt. ratio of PCL significantly altered the degradation of the films, most notably following longer immersion periods, and resistance to encrustation. Accordingly, maximum degradation and resistance to encrustation was observed with the biomaterial composed of 40:60 high:low m.wt. ratios of PCL; however, the mechanical properties of this system were considered inappropriate for clinical application. Films composed of either 50:50 or 60:40 ratio of high:low m.wt. PCL offered an appropriate compromise between physicochemical properties and resistance to encrustation. This study has highlighted the important usefulness of degradable polymer systems as ureteral biomaterials

The manufacture and characterisation of hot-melt extruded enteric tablets

The aim of this highly novel study was to use hot-melt extrusion technology as an alternative process to enteric coating. In so doing, oral dosage forms displaying enteric properties may be produced in a continuous, rapid process, providing significant advantages over traditional pharmaceutical coating technology. Eudragit (R) L100-55, an enteric polymer, was pre-plasticized with triethyl citrate (TEC) and citric acid and subsequently dry-mixed with 5-aminosalicylic acid, a model active pharmaceutical ingredient (API), and an optional gelling agent (PVP (R) K30 or Carbopol (R) 971P). Powder blends were hot-melt extruded as cylinders, cut into tablets and characterised using powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC) and dissolution testing conducted in both pH 1.2 and pH 6.8 buffers. Increasing the concentration of TEC significantly lowered the glass transition temperature (T,) of Eudragit (R) L100-55 and reduced temperatures necessary for extrusion as well as the die pressure. Moreover, citric acid (17% w/w) was shown to act as a solid-state plasticizer. HME tablets showed excellent gastro-resistance, whereas milled extrudates compressed into tablets released more than 10% w/w of the API in acidic media. Drug release from HME tablets was dependent upon the concentration of TEC, the presence of citric acid, PVP K30, and Carbopol (R) 971P in the matrix, and pH of the dissolution media. The inclusion of an optional gelling agent significantly reduced the erosion of the matrix and drug release rate at pH 6.8; however, the enteric properties of the matrix were lost due to the formation of channels within the tablet. Consequently this work is both timely and highly innovative and identifies for the first time a method of producing an enteric matrix tablet using a continuous hot-melt extrusion process.

Measurement of Polymer-to-Polymer Contact Friction in Thermoforming

Contact friction plays a critical role in all the major thermoforming processes for polymers. However, these effects are very difficult to measure in practice and, as a result, have received little scientific investigation. In this work, two independently developed test methods for the measurement of elevated temperature polymer-to-polymer contact friction are presented, and their results are compared in detail for the first time. One is based on a modified moving sled friction test, whereas the other uses a rotational rheometer. In each case, friction tests were conducted between two plug and two sheet materials. The results show that broadly similar coefficients of friction were obtained from the two test methods. The measured values were quite low (<0.3) at lower temperatures and typically were higher for polypropylene (PP) sheet than for polystyrene (PS). On approaching the glass transition temperature for PS (95°C) and the crystalline melting point for PP (165°C), the friction coefficients rose very sharply, and both test techniques became increasingly unreliable. It was concluded that despite their physical differences, both test techniques were able to capture the highly temperature sensitive nature of friction between polymer materials used in thermoforming.

Morphology, barrier, and mechanical properties of biaxially deformed poly(ethylene terephthalate)-mica nanocomposites

Nanocomposites of poly(ethylene terephthalate) PET with a partially synthetic fluoromica were prepared by melt mixing and extruded into sheet and subjected to large-scale biaxial stretching. Transmission electron microscopy (TEM) analysis of the mica tactoids showed that biaxial stretching had caused the tactoids to be more orientated and with improved exfoliation. The moduli of the nanocomposites were enhanced with increasing mica loading and the reinforcement effect was higher when the stretch ratio was 2 or 2.5, accommodated by having more aligned tactoids and reduced agglomeration. Enhancement in modulus was less pronounced for a stretch ratio of 3. Storage modulus was enhanced more significantly above the glass transition temperature. The barrier properties were enhanced by addition of mica before and after stretching. The Halpin-Tsai theory underpredicted the relative modulus of the PET nanocomposites, whereas the Nielsen model over-predicted the relative permeability. POLYM. ENG. SCI., 2012. (c) 2011 Society of Plastics Engineers

Thermodynamical studies of irreversible sorption of CO2 by Wyodak coal

Differential scanning calorimetry (DSC), temperature programmed desorption mass spectrometry (TPD-MS) and small angle neutron scattering (SANS) were used to investigate CO2 uptake by the Wyodak coal. The adsorption of carbon dioxide on Wyodak coal was studied by DSC. The exotherms evident at low temperatures are associated with the uptake of CO2 suggesting that carbon dioxide interacts strongly with the coal surface. The reduction in the value of the exotherms between the first and second runs for the Wyodak coal suggests that some CO2 is irreversibly bound to the structure even after heating to 200 °C DSC results also showed that adsorption of CO2 on the coal surface is an activated process and presumably at the temperature of the exotherms there is enough thermal energy to overcome the activation energy for adsorption. The adsorption process is instantly pursued by much slower diffusion of the gas molecules into the coal matrix (absorption). Structural rearrangement in coal by CO2 is examined by change in the glass transition temperature of coal after CO2 uptake at different pressures. The amount of gas dissolved in the coal increases with increasing CO2 pressure. TPD-MS showed that CO2 desorption from the Wyodak coal follows a first order kinetic model. Increase in the activation energy for desorption with pre-adsorbed CO2 pressure suggests that higher pressures facilitate the transport of CO2 molecules through the barriers therefore the amount of CO2 uptake by the coal is greater at higher pressures and more attempts are required to desorb CO2 molecules sorbed at elevated pressures. These conclusions were further confirmed by examining the Wyodak coal structure in high pressure CO 2 by SANS.

Study of structural change in Wyodak coal in high pressure CO2 by small-angle neutron scattering

Small angle neutron scattering (SANS) has been applied to examine the effect of high pressure CO2 on the structure of Wyodak coal. Significant decrease in the scattering intensities upon exposure of the coal to high pressure CO2 showed that high pressure CO2 rapidly adsorbs on the coal and reaches to all pores in the structure. This is confirmed by strong and steep exothermic peaks observed on DSC scans during coal/ CO2 interactions. In situ small angle neutron scattering on coal at high pressure CO2 atmosphere showed an increase in scattering intensities with time suggesting that after adsorption, high pressure CO2 immediately begins to diffuse into the coal matrix, changes the macromolecular structure of the coal, swells the matrix and probably creates microporosity in coal structure by extraction of volatile components from coal. Significant decrease in the glass transition temperature of coal caused by high pressure CO2 also confirms that CO2 at elevated pressures dissolve in the coal matrix, results in significant plasticization and physical rearrangement of the coal’s macromolecular structure.