A toolbox for parameter-free predictions of solid-state properties of monodisperse glassy polymers with frozen-in molecular orientation

A toolbox that allows designers to predict the properties of oriented glassy polymers using only existing material constants is constructed from a constitutive model applicable to both polymer solids and polymer melts. Two solid-state properties of practical engineering interest are considered: optical birefringence, and craze initiation stress. Predictions from the toolbox are compared to new experimental measurements on well characterized grades of monodisperse polystyrene, and confirm that the toolbox can account for the effect of polymer molecular weight

Modeling non-linear rheology of PLLA : comparison of Giesekus and Rolie-Poly constitutive models

Rheological models for biobased plastics can assist in predicting optimum processing parameters in industrial forming processes for biobased plastics and their composites such as film blowing, or injection stretch-blow molding in the packaging industry. Mathematical descriptions of polymer behavior during these forming processes are challenging, as they involve highly nonlinear, time-, temperature-, and strain-dependent physical deformation processes in the material, and have not been sufficiently tested against experimental data in those regimes. Therefore, the predictive capability of two polymer models, a classical Giesekus and a physically-based Rolie-Poly, is compared here for extensional and shear rheology data obtained on a poly(L-lactide) (PLLA) across a wide range of strain rates of relevance to those forming processes. Generally, elongational and shear melt flow behavior of PLLA was predicted to a satisfactory degree by both models across a wide range of strain rates (for strain rates 0.05–10.0 s−1), within the strain window up to 1.0. Both models show a better predictive capability for smaller strain rates, and no significant differences between their predictions were found. Hence, as the Giesekus model generally needs a smaller number of parameters, this class of models is more attractive when considering their use in computationally demanding forming simulations of biobased thermoplastics

Large deformations in oriented polymer glasses: experimental study and a new glass-melt constitutive model

An experimental study was made of the effects of prior molecular orientation on large tensile deformations of polystyrene in the glassy state. A new hybrid glass-melt constitutive model is proposed for describing and understanding the results, achieved by parallel coupling of the ROLIEPOLY molecularly-based melt model with a model previously proposed for polymer glasses. Monodisperse and polydisperse grades of polystyrene are considered. Comparisons between experimental results and simulations illustrate that the model captures characteristic features of both the melt and glassy states. Polystyrene was stretched in the melt state and quenched to below Tg, and then tensile tested parallel to the orientation direction near the glass transition. The degree of strain-hardening was observed to increase with increasing prior stretch of molecules within their entanglement tubes, as predicted by the constitutive model. This was explored for varying temperature of stretching, degree of stretching, and dwell time before quenching. The model in its current form, however, lacks awareness of processes of subentanglement chain orientation. Therefore, it under-predicts the orientation-direction strain hardening and yield stress increase, when stretching occurs at the lowest temperatures and shortest times, where it is dominated by subentanglement orientation

A method for the determination and correction of the effect of thermal degradation on the viscoelastic properties of degradable polymers

Small amplitude oscillatory shear is carried out during isothermal degradation of poly(lactic acid) (PLA) in order to determine the evolution of the characteristic relaxation time with degradation time and temperature. After reducing the relaxation time data to a single mastercurve, a 4-parameter function is fitted to the data to allow prediction of the change in relaxation time following an arbitrary thermal history. The method enables separation of the effects of temperature and of degradation on the relaxation time, both of which lead to a horizontal shift of dynamic data along the frequency axis, and hence enable a correction for thermal degradation during rheometry to be carried out. To validate the method, two isothermal frequency sweeps were measured with different temperature histories, producing different mastercurves due to dissimilar in-test thermal degradation. After correcting for thermal degradation using the function and the thermal histories, the two frequency sweeps reduce to the same viscoelastic mastercurve in the undegraded pre-test state

An adaptable flexural test fixture for miniaturised polymer specimens

An adaptable flexural test fixture is proposed to characterise the mechanical properties of miniature beam specimens (≤10 mg) at ambient conditions or in the presence of fluids at elevated temperatures. The fixture is validated using representative amorphous and semi-crystalline polymers. The response of miniature specimens is compared against that of medium-sized specimens (≤1 g) on the same fixture and on conventional test equipment. Good agreement is found between the specimen sizes for all materials, but the comparisons highlight small differences attributed to factors such as specimen dimensional accuracy, crystallinity and span-to-thickness ratios. Flexural tests in water at 37 o C using both specimen sizes were performed to investigate the evolution of mechanical behaviour of hydrolytically degraded polylactides. Here, specimen size influences the diffusion timescale of acidic by-products which can reduce or enhance autocatalysis

The development of a novel technique for small ring specimen tensile testing

The wide scale use of small specimens in routine testing programs could significantly reduce material resource requirements (factors of 10 are easily achievable). This is a major benefit to situations where there is not enough material to manufacture conventional, full-size specimens, such as first-stage gas turbine blade roots. However, limitations exist due to concerns over size effects, manufacturing difficulties, uncertainties related to the application of representative loading conditions and complex interpretation procedures of non-standard data. Due to these limitations, small specimen testing techniques have been mostly applied in ranking exercises and to determine approximate or simple material parameters such as Young’s modulus, minimum creep strain rate and fracture toughness. The small ring method is a novel, high sensitivity small specimen technique for creep testing that has been extended in the present work to the determination of tensile material properties. The main advantages of the small ring specimen are that it is self-aligning and has a large equivalent gauge length in comparison to other small specimens, resulting in much higher testing sensitivity. In the present work, this specimen type mimics conventional, full-size, monotonic testing, allowing for observations of elastic and plastic material response to be made. Wrought aluminium alloy 7175-T7153 small rings were tested at room temperature at 5 different loading (displacement) rates and the results compared to conventional, full-size, monotonic specimen equivalents. Finite element analysis was conducted in order to evaluate the equivalent gauge section and equivalent gauge length in the small ring specimen (which varied between circa 0.35–1.4 mm2 and 25–45 mm, respectively) to facilitate these comparisons. An analytical solution has also been derived in order to validate the finite element analysis

A phenomenological constitutive model for the viscoelastic deformation of elastomers

This study proposes a one-dimensional constitutive model for elastomeric materials based on recent observations regarding the separation of elastic and viscous contributions in uniaxial cyclic tensile experiments on EPDM rubber. The focus is on capturing the changes in constitutive behaviour and energy dissipation associated with the Mullins effect. In the model, this is achieved through the evolution of both permanent set and hyperelastic parameters of an Edwards-Vilgis function to account for the Mullins effect, and with a viscosity associated with the effective stretch rate of the network to describe the non-linear flow stress. The simulations are able to reproduce the observed constitutive response and its change with increasing levels of pre-deformation. The model is less able to accurately reproduce the virgin loading response, which is achieved via extrapolation to zero pre-strain. However, for practical purposes, where scragging of elastomeric products is the norm, the model is able to predict the cyclic response and the dissipated energy, and their change with different scragging levels in good agreement with experimental data

Modeling non-linear rheology of PLLA: comparison of Giesekus and Rolie-Poly constitutive models

Rheological models for biobased plastics can assist in predicting optimum processing parameters in industrial forming processes for biobased plastics and their composites such as film blowing, or injection stretch-blow molding in the packaging industry. Mathematical descriptions of polymer behavior during these forming processes are challenging, as they involve highly nonlinear, time-, temperature-, and strain-dependent physical deformation processes in the material, and have not been sufficiently tested against experimental data in those regimes. Therefore, the predictive capability of two polymer models, a classical Giesekus and a physically-based Rolie-Poly, is compared here for extensional and shear rheology data obtained on a poly(L-lactide) (PLLA) across a wide range of strain rates of relevance to those forming processes. Generally, elongational and shear melt flow behavior of PLLA was predicted to a satisfactory degree by both models across a wide range of strain rates (for strain rates 0.05–10.0 s−1), within the strain window up to 1.0. Both models show a better predictive capability for smaller strain rates, and no significant differences between their predictions were found. Hence, as the Giesekus model generally needs a smaller number of parameters, this class of models is more attractive when considering their use in computationally demanding forming simulations of biobased thermoplastics

A Novel Method of Extraction of Blend Component Structure from SANS Measurements of Homopolymer Bimodal Blends

A new method is presented for the extraction of single-chain form factors and interchain interference functions from a range of small-angle neutron scattering (SANS) experiments on bimodal homopolymer blends. The method requires a minimum of three blends, made up of hydrogenated and deuterated components with matched degree of polymerization at two different chain lengths, but with carefully varying deuteration levels. The method is validated through an experimental study on polystyrene homopolymer bimodal blends with inline image. By fitting Debye functions to the structure factors, it is shown that there is good agreement between the molar mass of the components obtained from SANS and from chromatography. The extraction method also enables, for the first time, interchain scattering functions to be produced for scattering between chains of different lengths

Rheological techniques for determining degradation of polylactic acid in bioresorbable medical polymer systems

© 2015 AIP Publishing LLC. A method developed in the 1980s for the conversion of linear rheological data to molar mab distribution is revisited in the context of degradable polymers. The method is first applied using linear rheology for a linear polystyrene, for which all conversion parameters are known. A proof of principle is then carried out on four polycarbonate grades. Finally, preliminary results are shown on degradable polylactides. The application of this method to degrading polymer systems, and to systems containing nanofillers, is also discubed. This work forms part of a wider study of bioresorbable nanocomposites using polylactides, novel hydroxyapatite nanoparticles and tailored dispersants for medical applications