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High temperature melts or use of organic solvents are not practicable approaches for encapsulating protein based or thermally labile drugs into degradable polymers. Here, we demonstrate that poly(ethylene glycol) (PEG) in combination with supercritical carbon dioxide (scCO2) can dramatically reduce the viscosity of polymer melts allowing enhanced uptake of CO2 into poly(D,L-lactide) (PLA). Both PEG and CO2 are approved excipients in drug delivery and it is well documented that individually both are effective plasticisers. Using high pressure rheology techniques (scCO₂ at 14 MPa) we demonstrate a synergistic impact leading to significantly lower processing temperatures with PEG employed as both a blended additive and as a component of a block copolymer.

A new method is presented for the extraction of single chain form factors and inter-chain 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 MA ≈ ½ MB By fitting Debye functions to the structure factors it was shown that there is good agreement between the molar mass of components obtained from SANS and from chromatography. The extraction method also enables, for the first time, to produce inter-chain scattering functions for scattering between chains of different lengths.

This work investigates the effects of primary compounding temperature and secondary melt processes on the mechanical response and electrical resistivity of polycarbonate filled with 3 wt % multiwalled carbon nanotubes (CNT). Nanocomposites were melt compounded in an industrial setting at a range of temperatures, and subsequently either injection molded or compression molded to produce specimens for the measurement of electrical resistivity, surface hardness, and uniaxial tensile properties. Secondary melt processing was found to be the dominant process in determining the final properties. The effects observed have been attributed to structural arrangements of the CNT network as suggested by morphological evidence of optical microscopy and resistivity measurements. Properties were found to be relatively insensitive to compounding temperature. The measured elastic moduli were consistent with existing micromechanical models.

Characterizing the mechanical response of the human amnion is essential to understand and to eventually prevent premature rupture of fetal membranes. In this study, a large set of macroscopic and microscopic mechanical tests have been carried out on fresh unfixed amnion to gain insight into the time-dependent material response and the underlying mechanisms. Creep and relaxation responses of amnion were characterized in macroscopic uniaxial tension, biaxial tension and inflation configurations. For the first time, these experiments were complemented by microstructural information from nonlinear laser scanning microscopy performed during in situ uniaxial relaxation tests. The amnion showed large tension reduction during relaxation and small inelastic strain accumulation in creep. The short-term relaxation response was related to a concomitant in-plane and out-of-plane contraction, and was dependent on the testing configuration. The microscopic investigation revealed a large volume reduction at the beginning, but no change of volume was measured long-term during relaxation. Tension–strain curves normalized with respect to the maximum strain were highly repeatable in all configurations and allowed the quantification of corresponding characteristic parameters. The present data indicate that dissipative behavior of human amnion is related to two mechanisms: (i) volume reduction due to water outflow (up to ∼20 s) and (ii) long-term dissipative behavior without macroscopic deformation and no systematic global reorientation of collagen fibers.

A viscoelastic, compressible model is proposed to rationalize the recently reported response of human amnion in multiaxial relaxation and creep experiments. The theory includes two viscoelastic contributions responsible for the short- and long-term time- dependent response of the material. These two contributions can be related to physical processes: water flow through the tissue and dissipative characteristics of the collagen fibers, respectively. An accurate agreement of the model with the mean tension and kinematic response of amnion in uniaxial relaxation tests was achieved. By variation of a single linear factor that accounts for the variability among tissue samples, the model provides very sound predictions not only of the uniaxial relaxation but also of the uniaxial creep and strip-biaxial relaxation behavior of individual samples. This suggests that a wide range of viscoelastic behaviors due to patient-specific variations in tissue composition.

Although the magnitudes of inelastic and viscoelastic effects in filled rubbers are small relative to that of the elastic response, these effects are nevertheless critical in applications such as gaskets, seals and dampers. This study investigates the role of deformation history on relaxation of rubber through time-dependent experiments following a range of deformation histories. Two grades of carbon-black filled EPDM were subjected to uniaxial tensile deformation followed by stress-relaxation or stress memory at fixed deformation. Stress relaxation was found to be highly dependent on strain levels following a single loading. When an additional load-unload cycle was added to the history, the rubbers relaxed an approximately constant fraction of stress after a given time, provided that the strain at stress relaxation was smaller than the historical maximum. This fraction was independent of both the applied strain and of the maximum strain, and suggests that the relaxation process is independent of scragging procedures used to control the modulus. Stress memory observed following load-unload cycles was also approximately independent of strain history.

Advanced Sheet Moulding Compounds (ASMC) and unidirectional (UD) prepregs have been co-compression moulded to form a hybrid composite material. In-mould flow influences the UD fibre architecture in two ways. When UD fibres are aligned transversely to the ASMC flow direction, shearing occurs which causes local changes in fibre volume fraction and fibre waviness. When the UD fibres are aligned with the ASMC flow direction, ply migration takes place. In general, the composite stiffness follows a rule of mixtures relationship, with the stiffness proportional to the UD fibre content. A grid analysis method has been developed to quantify distortion in the UD plies. Staging the resin to 50% cure was shown to reduce ply distortion during moulding, whilst maintaining suitable inter-laminar shear strength. Adding an interfacial prepreg ply between the reinforcing UD fibres and the ASMC charge successfully prevented distortion in the UD fibres, avoiding shear thinning and fibre migration.

Polylactic acid and novel nanoplatelets of hydroxyapatite (HANP) were compounded in a laboratory scale twin-screw extruder and injection moulded to shape. The effect of HANP loading content, between 1 wt% and 10 wt%, and of HANP surface coating with tailored molecular dispersants, on the processability and rheological behaviour were investigated. Dispersion of HANP within the matrix system was determined qualitatively using transmission electron micrographs. Surface coating of HANP with dispersants was observed to change the state of HANP dispersion in the nanocomposites. This was also reflected in the changes of the nanocomposites’ rheological response with the moduli of coated HANP systems increasing at lower frequencies.

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.

A viscoelastic, compressible model is proposed to rationalize the recently reported response of human amnion in multiaxial relaxation and creep experiments. The theory includes two viscoelastic contributions responsible for the short- and long-term time- dependent response of the material. These two contributions can be related to physical processes: water flow through the tissue and dissipative characteristics of the collagen fibers, respectively. An accurate agreement of the model with the mean tension and kinematic response of amnion in uniaxial relaxation tests was achieved. By variation of a single linear factor that accounts for the variability among tissue samples, the model provides very sound predictions not only of the uniaxial relaxation but also of the uniaxial creep and strip-biaxial relaxation behavior of individual samples. This suggests that a wide range of viscoelastic behaviors due to patient-specific variations in tissue composition.

A recently developed peel test designed to simulate the automated tape lay-up (ATL) process was used to measure tack and dynamic stiffness of newly developed ATL prepregs. Resin was extracted from the prepreg process before impregnation of the fibres. Isothermal small amplitude frequency sweeps were carried out in shear rheology to determine time–temperature superposition parameters in the form of Williams–Landel–Ferry equation. Gel permeation chromatography and differential scanning calorimetry demonstrated that the resin was not significantly changed during the prepregging process. The WLF parameters were used to transpose isothermal tack and dynamic stiffness results with excellent agreement found. This relationship offers manufacturers using composite prepreg a method to maximise and maintain tack levels at different feed rates by appropriate changes in temperature. This is of significant importance in improving the reliability of automated composite lay-up processes such as AFP and ATL, whose feed rate must vary to accommodate lay-up operations.

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 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.

This work investigates the linear and non-linear viscoelastic melt rheology of four grades of polycarbonate melt-compounded with 3 wt% Nanocyl NC7000 multi-walled carbon nanotubes and of the matching matrix polymers. Amplitude sweeps reveal an earlier onset of non-linearity and a strain overshoot in the nanocomposites. Mastercurves are constructed from isothermal frequency sweeps using vertical and horizontal shifting. Although all nanocomposites exhibit a second plateau at ~105 Pa, the relaxation times estimated from the peak in loss tangent are not statistically different from those of pure melts estimated from cross-over frequencies: all relaxation times scale with molar mass in the same way, evidence that relaxation of the polymer network is the dominant mechanism in both filled and unfilled materials. Non-linear rheology is also measured in large amplitude oscillatory shear. A comparison of the responses from frequency and amplitude sweep experiments reveals the importance of strain and temperature history on the response of such nanocomposites.

This work investigates the linear and non-linear viscoelastic melt rheology of four grades of polycarbonate melt-compounded with 3 wt% Nanocyl NC7000 multi-walled carbon nanotubes and of the matching matrix polymers. Amplitude sweeps reveal an earlier onset of non-linearity and a strain overshoot in the nanocomposites. Mastercurves are constructed from isothermal frequency sweeps using vertical and horizontal shifting. Although all nanocomposites exhibit a second plateau at ~105 Pa, the relaxation times estimated from the peak in loss tangent are not statistically different from those of pure melts estimated from cross-over frequencies: all relaxation times scale with molar mass in the same way, evidence that relaxation of the polymer network is the dominant mechanism in both filled and unfilled materials. Non-linear rheology is also measured in large amplitude oscillatory shear. A comparison of the responses from frequency and amplitude sweep experiments reveals the importance of strain and temperature history on the response of such nanocomposites.

This work investigates the linear and non-linear viscoelastic melt rheology of four grades of polycarbonate melt-compounded with 3 wt% Nanocyl NC7000 multi-walled carbon nanotubes and of the matching matrix polymers. Amplitude sweeps reveal an earlier onset of non-linearity and a strain overshoot in the nanocomposites. Mastercurves are constructed from isothermal frequency sweeps using vertical and horizontal shifting. Although all nanocomposites exhibit a second plateau at ~105 Pa, the relaxation times estimated from the peak in loss tangent are not statistically different from those of pure melts estimated from cross-over frequencies: all relaxation times scale with molar mass in the same way, evidence that relaxation of the polymer network is the dominant mechanism in both filled and unfilled materials. Non-linear rheology is also measured in large amplitude oscillatory shear. A comparison of the responses from frequency and amplitude sweep experiments reveals the importance of strain and temperature history on the response of such nanocomposites.

Hydroxyapatite (HA) nanoparticles, similar to those seen in the structure of human bone, have been produced via hydrothermal synthesisand used to produce nanocomposite materials via melt blending with poly(lactic acid)(PLA). Both of these processes are scalable and commercially relevant. Tailored dispersants were developed and used to improve the dispersion of the HA. Modest improvements in flexural properties were observed (max increases 30% of dry modulus, 13% of wet strength). Rheometry is not suggestive of achieving percolation,so there is potential to improve mechanical properties further. It was established that very dry processing conditions are essential to maintaining the molecular weight of the PLA during processing and that the use of the tailored dispersants can also help to mitigateprocess-induced degradation.MicroCT has proved to be a useful quality control tool to support TEM analysis.

A viscoelastic, compressible model is proposed to rationalize the recently reported response of human amnion in multiaxial relaxation and creep experiments. The theory includes two viscoelastic contributions responsible for the short- and long-term time- dependent response of the material. These two contributions can be related to physical processes: water flow through the tissue and dissipative characteristics of the collagen fibers, respectively. An accurate agreement of the model with the mean tension and kinematic response of amnion in uniaxial relaxation tests was achieved. By variation of a single linear factor that accounts for the variability among tissue samples, the model provides very sound predictions not only of the uniaxial relaxation but also of the uniaxial creep and strip-biaxial relaxation behavior of individual samples. This suggests that a wide range of viscoelastic behaviors due to patient-specific variations in tissue composition.

Hydroxyapatite (HA) nanoparticles, similar to those seen in the structure of human bone, have been produced via hydrothermal synthesisand used to produce nanocomposite materials via melt blending with poly(lactic acid)(PLA). Both of these processes are scalable and commercially relevant. Tailored dispersants were developed and used to improve the dispersion of the HA. Modest improvements in flexural properties were observed (max increases 30% of dry modulus, 13% of wet strength). Rheometry is not suggestive of achieving percolation,so there is potential to improve mechanical properties further. It was established that very dry processing conditions are essential to maintaining the molecular weight of the PLA during processing and that the use of the tailored dispersants can also help to mitigateprocess-induced degradation.MicroCT has proved to be a useful quality control tool to support TEM analysis.

Characterizing the mechanical response of the human amnion is essential to understand and to eventually prevent premature rupture of fetal membranes. In this study, a large set of macroscopic and microscopic mechanical tests have been carried out on fresh unfixed amnion to gain insight into the time-dependent material response and the underlying mechanisms. Creep and relaxation responses of amnion were characterized in macroscopic uniaxial tension, biaxial tension and inflation configurations. For the first time, these experiments were complemented by microstructural information from nonlinear laser scanning microscopy performed during in situ uniaxial relaxation tests. The amnion showed large tension reduction during relaxation and small inelastic strain accumulation in creep. The short-term relaxation response was related to a concomitant in-plane and out-of-plane contraction, and was dependent on the testing configuration. The microscopic investigation revealed a large volume reduction at the beginning, but no change of volume was measured long-term during relaxation. Tension–strain curves normalized with respect to the maximum strain were highly repeatable in all configurations and allowed the quantification of corresponding characteristic parameters. The present data indicate that dissipative behavior of human amnion is related to two mechanisms: (i) volume reduction due to water outflow (up to ∼20 s) and (ii) long-term dissipative behavior without macroscopic deformation and no systematic global reorientation of collagen fibers.

High temperature melts or use of organic solvents are not practicable approaches for encapsulating protein based or thermally labile drugs into degradable polymers. Here, we demonstrate that poly(ethylene glycol) (PEG) in combination with supercritical carbon dioxide (scCO2) can dramatically reduce the viscosity of polymer melts allowing enhanced uptake of CO2 into poly(D,L-lactide) (PLA). Both PEG and CO2 are approved excipients in drug delivery and it is well documented that individually both are effective plasticisers. Using high pressure rheology techniques (scCO₂ at 14 MPa) we demonstrate a synergistic impact leading to significantly lower processing temperatures with PEG employed as both a blended additive and as a component of a block copolymer.

A viscoelastic, compressible model is proposed to rationalize the recently reported response of human amnion in multiaxial relaxation and creep experiments. The theory includes two viscoelastic contributions responsible for the short- and long-term time- dependent response of the material. These two contributions can be related to physical processes: water flow through the tissue and dissipative characteristics of the collagen fibers, respectively. An accurate agreement of the model with the mean tension and kinematic response of amnion in uniaxial relaxation tests was achieved. By variation of a single linear factor that accounts for the variability among tissue samples, the model provides very sound predictions not only of the uniaxial relaxation but also of the uniaxial creep and strip-biaxial relaxation behavior of individual samples. This suggests that a wide range of viscoelastic behaviors due to patient-specific variations in tissue composition.

This work investigates the effects of primary compounding temperature and secondary melt processes on the mechanical response and electrical resistivity of polycarbonate filled with 3 wt % multiwalled carbon nanotubes (CNT). Nanocomposites were melt compounded in an industrial setting at a range of temperatures, and subsequently either injection molded or compression molded to produce specimens for the measurement of electrical resistivity, surface hardness, and uniaxial tensile properties. Secondary melt processing was found to be the dominant process in determining the final properties. The effects observed have been attributed to structural arrangements of the CNT network as suggested by morphological evidence of optical microscopy and resistivity measurements. Properties were found to be relatively insensitive to compounding temperature. The measured elastic moduli were consistent with existing micromechanical models.

Craze initiation stress was measured in three-point bending isochronal creep tests on a series of entangled bimodal blends of polystyrenes of narrow dispersity, on three polystyrenes of broad dispersity, and on four blends of polystyrenes of broad dispersity. Crazing stress was found to increase rapidly with small additions of the higher molar mass component, quickly reaching a plateau. A simple model based on the weighted addition of the crazing stress contributions of the individual weight fractions obtained from an established piecewise linear crazing law was able to predict the crazing stress accurately in the bimodal blends using a power law exponent of 2.59 (90% CI [1.75–17.34]). In broad dispersity systems, in particular where short unentangled chains dilute the polymer, it was found necessary to modify the model using dynamic tube dilution theory. Dilution leads to a change in the entanglement length and hence in the molar mass at which transitions to disentanglement and chain scission crazing occur. With the improved model, crazing stress could be predicted even for the broad dispersity polymers with wide and bimodal distributions. This represents an opportunity for the molecular design of polymers by blending to achieve improved resistance to craze initiation.

Although the magnitudes of inelastic and viscoelastic effects in filled rubbers are small relative to that of the elastic response, these effects are nevertheless critical in applications such as gaskets, seals and dampers. This study investigates the role of deformation history on relaxation of rubber through time-dependent experiments following a range of deformation histories. Two grades of carbon-black filled EPDM were subjected to uniaxial tensile deformation followed by stress-relaxation or stress memory at fixed deformation. Stress relaxation was found to be highly dependent on strain levels following a single loading. When an additional load-unload cycle was added to the history, the rubbers relaxed an approximately constant fraction of stress after a given time, provided that the strain at stress relaxation was smaller than the historical maximum. This fraction was independent of both the applied strain and of the maximum strain, and suggests that the relaxation process is independent of scragging procedures used to control the modulus. Stress memory observed following load-unload cycles was also approximately independent of strain history.

A new method is presented for the extraction of single chain form factors and inter-chain 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 MA ≈ ½ MB By fitting Debye functions to the structure factors it was shown that there is good agreement between the molar mass of components obtained from SANS and from chromatography. The extraction method also enables, for the first time, to produce inter-chain scattering functions for scattering between chains of different lengths.

Advanced Sheet Moulding Compounds (ASMC) and unidirectional (UD) prepregs have been co-compression moulded to form a hybrid composite material. In-mould flow influences the UD fibre architecture in two ways. When UD fibres are aligned transversely to the ASMC flow direction, shearing occurs which causes local changes in fibre volume fraction and fibre waviness. When the UD fibres are aligned with the ASMC flow direction, ply migration takes place. In general, the composite stiffness follows a rule of mixtures relationship, with the stiffness proportional to the UD fibre content. A grid analysis method has been developed to quantify distortion in the UD plies. Staging the resin to 50% cure was shown to reduce ply distortion during moulding, whilst maintaining suitable inter-laminar shear strength. Adding an interfacial prepreg ply between the reinforcing UD fibres and the ASMC charge successfully prevented distortion in the UD fibres, avoiding shear thinning and fibre migration.

Polylactic acid and novel nanoplatelets of hydroxyapatite (HANP) were compounded in a laboratory scale twin-screw extruder and injection moulded to shape. The effect of HANP loading content, between 1 wt% and 10 wt%, and of HANP surface coating with tailored molecular dispersants, on the processability and rheological behaviour were investigated. Dispersion of HANP within the matrix system was determined qualitatively using transmission electron micrographs. Surface coating of HANP with dispersants was observed to change the state of HANP dispersion in the nanocomposites. This was also reflected in the changes of the nanocomposites’ rheological response with the moduli of coated HANP systems increasing at lower frequencies.

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.

A recently developed peel test designed to simulate the automated tape lay-up (ATL) process was used to measure tack and dynamic stiffness of newly developed ATL prepregs. Resin was extracted from the prepreg process before impregnation of the fibres. Isothermal small amplitude frequency sweeps were carried out in shear rheology to determine time–temperature superposition parameters in the form of Williams–Landel–Ferry equation. Gel permeation chromatography and differential scanning calorimetry demonstrated that the resin was not significantly changed during the prepregging process. The WLF parameters were used to transpose isothermal tack and dynamic stiffness results with excellent agreement found. This relationship offers manufacturers using composite prepreg a method to maximise and maintain tack levels at different feed rates by appropriate changes in temperature. This is of significant importance in improving the reliability of automated composite lay-up processes such as AFP and ATL, whose feed rate must vary to accommodate lay-up operations.

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.

This work investigates the linear and non-linear viscoelastic melt rheology of four grades of polycarbonate melt-compounded with 3 wt% Nanocyl NC7000 multi-walled carbon nanotubes and of the matching matrix polymers. Amplitude sweeps reveal an earlier onset of non-linearity and a strain overshoot in the nanocomposites. Mastercurves are constructed from isothermal frequency sweeps using vertical and horizontal shifting. Although all nanocomposites exhibit a second plateau at ~105 Pa, the relaxation times estimated from the peak in loss tangent are not statistically different from those of pure melts estimated from cross-over frequencies: all relaxation times scale with molar mass in the same way, evidence that relaxation of the polymer network is the dominant mechanism in both filled and unfilled materials. Non-linear rheology is also measured in large amplitude oscillatory shear. A comparison of the responses from frequency and amplitude sweep experiments reveals the importance of strain and temperature history on the response of such nanocomposites.

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.

This work investigates the linear and non-linear viscoelastic melt rheology of four grades of polycarbonate melt-compounded with 3 wt% Nanocyl NC7000 multi-walled carbon nanotubes and of the matching matrix polymers. Amplitude sweeps reveal an earlier onset of non-linearity and a strain overshoot in the nanocomposites. Mastercurves are constructed from isothermal frequency sweeps using vertical and horizontal shifting. Although all nanocomposites exhibit a second plateau at ~105 Pa, the relaxation times estimated from the peak in loss tangent are not statistically different from those of pure melts estimated from cross-over frequencies: all relaxation times scale with molar mass in the same way, evidence that relaxation of the polymer network is the dominant mechanism in both filled and unfilled materials. Non-linear rheology is also measured in large amplitude oscillatory shear. A comparison of the responses from frequency and amplitude sweep experiments reveals the importance of strain and temperature history on the response of such nanocomposites.

A viscoelastic, compressible model is proposed to rationalize the recently reported response of human amnion in multiaxial relaxation and creep experiments. The theory includes two viscoelastic contributions responsible for the short- and long-term time- dependent response of the material. These two contributions can be related to physical processes: water flow through the tissue and dissipative characteristics of the collagen fibers, respectively. An accurate agreement of the model with the mean tension and kinematic response of amnion in uniaxial relaxation tests was achieved. By variation of a single linear factor that accounts for the variability among tissue samples, the model provides very sound predictions not only of the uniaxial relaxation but also of the uniaxial creep and strip-biaxial relaxation behavior of individual samples. This suggests that a wide range of viscoelastic behaviors due to patient-specific variations in tissue composition.

This work investigates the linear and non-linear viscoelastic melt rheology of four grades of polycarbonate melt-compounded with 3 wt% Nanocyl NC7000 multi-walled carbon nanotubes and of the matching matrix polymers. Amplitude sweeps reveal an earlier onset of non-linearity and a strain overshoot in the nanocomposites. Mastercurves are constructed from isothermal frequency sweeps using vertical and horizontal shifting. Although all nanocomposites exhibit a second plateau at ~105 Pa, the relaxation times estimated from the peak in loss tangent are not statistically different from those of pure melts estimated from cross-over frequencies: all relaxation times scale with molar mass in the same way, evidence that relaxation of the polymer network is the dominant mechanism in both filled and unfilled materials. Non-linear rheology is also measured in large amplitude oscillatory shear. A comparison of the responses from frequency and amplitude sweep experiments reveals the importance of strain and temperature history on the response of such nanocomposites.

Craze initiation stress was measured in three-point bending isochronal creep tests on a series of entangled bimodal blends of polystyrenes of narrow dispersity, on three polystyrenes of broad dispersity, and on four blends of polystyrenes of broad dispersity. Crazing stress was found to increase rapidly with small additions of the higher molar mass component, quickly reaching a plateau. A simple model based on the weighted addition of the crazing stress contributions of the individual weight fractions obtained from an established piecewise linear crazing law was able to predict the crazing stress accurately in the bimodal blends using a power law exponent of 2.59 (90% CI [1.75–17.34]). In broad dispersity systems, in particular where short unentangled chains dilute the polymer, it was found necessary to modify the model using dynamic tube dilution theory. Dilution leads to a change in the entanglement length and hence in the molar mass at which transitions to disentanglement and chain scission crazing occur. With the improved model, crazing stress could be predicted even for the broad dispersity polymers with wide and bimodal distributions. This represents an opportunity for the molecular design of polymers by blending to achieve improved resistance to craze initiation.

High temperature melts or use of organic solvents are not practicable approaches for encapsulating protein based or thermally labile drugs into degradable polymers. Here, we demonstrate that poly(ethylene glycol) (PEG) in combination with supercritical carbon dioxide (scCO2) can dramatically reduce the viscosity of polymer melts allowing enhanced uptake of CO2 into poly(D,L-lactide) (PLA). Both PEG and CO2 are approved excipients in drug delivery and it is well documented that individually both are effective plasticisers. Using high pressure rheology techniques (scCO₂ at 14 MPa) we demonstrate a synergistic impact leading to significantly lower processing temperatures with PEG employed as both a blended additive and as a component of a block copolymer.

Characterizing the mechanical response of the human amnion is essential to understand and to eventually prevent premature rupture of fetal membranes. In this study, a large set of macroscopic and microscopic mechanical tests have been carried out on fresh unfixed amnion to gain insight into the time-dependent material response and the underlying mechanisms. Creep and relaxation responses of amnion were characterized in macroscopic uniaxial tension, biaxial tension and inflation configurations. For the first time, these experiments were complemented by microstructural information from nonlinear laser scanning microscopy performed during in situ uniaxial relaxation tests. The amnion showed large tension reduction during relaxation and small inelastic strain accumulation in creep. The short-term relaxation response was related to a concomitant in-plane and out-of-plane contraction, and was dependent on the testing configuration. The microscopic investigation revealed a large volume reduction at the beginning, but no change of volume was measured long-term during relaxation. Tension–strain curves normalized with respect to the maximum strain were highly repeatable in all configurations and allowed the quantification of corresponding characteristic parameters. The present data indicate that dissipative behavior of human amnion is related to two mechanisms: (i) volume reduction due to water outflow (up to ∼20 s) and (ii) long-term dissipative behavior without macroscopic deformation and no systematic global reorientation of collagen fibers.

A new method is presented for the extraction of single chain form factors and inter-chain 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 MA ≈ ½ MB By fitting Debye functions to the structure factors it was shown that there is good agreement between the molar mass of components obtained from SANS and from chromatography. The extraction method also enables, for the first time, to produce inter-chain scattering functions for scattering between chains of different lengths.

Although the magnitudes of inelastic and viscoelastic effects in filled rubbers are small relative to that of the elastic response, these effects are nevertheless critical in applications such as gaskets, seals and dampers. This study investigates the role of deformation history on relaxation of rubber through time-dependent experiments following a range of deformation histories. Two grades of carbon-black filled EPDM were subjected to uniaxial tensile deformation followed by stress-relaxation or stress memory at fixed deformation. Stress relaxation was found to be highly dependent on strain levels following a single loading. When an additional load-unload cycle was added to the history, the rubbers relaxed an approximately constant fraction of stress after a given time, provided that the strain at stress relaxation was smaller than the historical maximum. This fraction was independent of both the applied strain and of the maximum strain, and suggests that the relaxation process is independent of scragging procedures used to control the modulus. Stress memory observed following load-unload cycles was also approximately independent of strain history.

This work investigates the effects of primary compounding temperature and secondary melt processes on the mechanical response and electrical resistivity of polycarbonate filled with 3 wt % multiwalled carbon nanotubes (CNT). Nanocomposites were melt compounded in an industrial setting at a range of temperatures, and subsequently either injection molded or compression molded to produce specimens for the measurement of electrical resistivity, surface hardness, and uniaxial tensile properties. Secondary melt processing was found to be the dominant process in determining the final properties. The effects observed have been attributed to structural arrangements of the CNT network as suggested by morphological evidence of optical microscopy and resistivity measurements. Properties were found to be relatively insensitive to compounding temperature. The measured elastic moduli were consistent with existing micromechanical models.

Advanced Sheet Moulding Compounds (ASMC) and unidirectional (UD) prepregs have been co-compression moulded to form a hybrid composite material. In-mould flow influences the UD fibre architecture in two ways. When UD fibres are aligned transversely to the ASMC flow direction, shearing occurs which causes local changes in fibre volume fraction and fibre waviness. When the UD fibres are aligned with the ASMC flow direction, ply migration takes place. In general, the composite stiffness follows a rule of mixtures relationship, with the stiffness proportional to the UD fibre content. A grid analysis method has been developed to quantify distortion in the UD plies. Staging the resin to 50% cure was shown to reduce ply distortion during moulding, whilst maintaining suitable inter-laminar shear strength. Adding an interfacial prepreg ply between the reinforcing UD fibres and the ASMC charge successfully prevented distortion in the UD fibres, avoiding shear thinning and fibre migration.

Polylactic acid and novel nanoplatelets of hydroxyapatite (HANP) were compounded in a laboratory scale twin-screw extruder and injection moulded to shape. The effect of HANP loading content, between 1 wt% and 10 wt%, and of HANP surface coating with tailored molecular dispersants, on the processability and rheological behaviour were investigated. Dispersion of HANP within the matrix system was determined qualitatively using transmission electron micrographs. Surface coating of HANP with dispersants was observed to change the state of HANP dispersion in the nanocomposites. This was also reflected in the changes of the nanocomposites’ rheological response with the moduli of coated HANP systems increasing at lower frequencies.

Hydroxyapatite (HA) nanoparticles, similar to those seen in the structure of human bone, have been produced via hydrothermal synthesisand used to produce nanocomposite materials via melt blending with poly(lactic acid)(PLA). Both of these processes are scalable and commercially relevant. Tailored dispersants were developed and used to improve the dispersion of the HA. Modest improvements in flexural properties were observed (max increases 30% of dry modulus, 13% of wet strength). Rheometry is not suggestive of achieving percolation,so there is potential to improve mechanical properties further. It was established that very dry processing conditions are essential to maintaining the molecular weight of the PLA during processing and that the use of the tailored dispersants can also help to mitigateprocess-induced degradation.MicroCT has proved to be a useful quality control tool to support TEM analysis.

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.

Craze initiation stress was measured in three-point bending isochronal creep tests on a series of entangled bimodal blends of polystyrenes of narrow dispersity, on three polystyrenes of broad dispersity, and on four blends of polystyrenes of broad dispersity. Crazing stress was found to increase rapidly with small additions of the higher molar mass component, quickly reaching a plateau. A simple model based on the weighted addition of the crazing stress contributions of the individual weight fractions obtained from an established piecewise linear crazing law was able to predict the crazing stress accurately in the bimodal blends using a power law exponent of 2.59 (90% CI [1.75–17.34]). In broad dispersity systems, in particular where short unentangled chains dilute the polymer, it was found necessary to modify the model using dynamic tube dilution theory. Dilution leads to a change in the entanglement length and hence in the molar mass at which transitions to disentanglement and chain scission crazing occur. With the improved model, crazing stress could be predicted even for the broad dispersity polymers with wide and bimodal distributions. This represents an opportunity for the molecular design of polymers by blending to achieve improved resistance to craze initiation.

High temperature melts or use of organic solvents are not practicable approaches for encapsulating protein based or thermally labile drugs into degradable polymers. Here, we demonstrate that poly(ethylene glycol) (PEG) in combination with supercritical carbon dioxide (scCO2) can dramatically reduce the viscosity of polymer melts allowing enhanced uptake of CO2 into poly(D,L-lactide) (PLA). Both PEG and CO2 are approved excipients in drug delivery and it is well documented that individually both are effective plasticisers. Using high pressure rheology techniques (scCO₂ at 14 MPa) we demonstrate a synergistic impact leading to significantly lower processing temperatures with PEG employed as both a blended additive and as a component of a block copolymer.

Although the magnitudes of inelastic and viscoelastic effects in filled rubbers are small relative to that of the elastic response, these effects are nevertheless critical in applications such as gaskets, seals and dampers. This study investigates the role of deformation history on relaxation of rubber through time-dependent experiments following a range of deformation histories. Two grades of carbon-black filled EPDM were subjected to uniaxial tensile deformation followed by stress-relaxation or stress memory at fixed deformation. Stress relaxation was found to be highly dependent on strain levels following a single loading. When an additional load-unload cycle was added to the history, the rubbers relaxed an approximately constant fraction of stress after a given time, provided that the strain at stress relaxation was smaller than the historical maximum. This fraction was independent of both the applied strain and of the maximum strain, and suggests that the relaxation process is independent of scragging procedures used to control the modulus. Stress memory observed following load-unload cycles was also approximately independent of strain history.