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Conventionally, specialty natural rubber (SpNR) latex, namely, deproteinized natural rubber (DPNR) latex and epoxidized natural rubber (ENR) latex, are prepared from low ammonia latex (LATZ) causing high material cost. To address this issue, the objective of this study is to prepare SpNR latex directly from freshly tapped NR latex. In this work, DPNR latex is prepared via a heat enzymatic hydrolysis process, while ENR latex is prepared via in situ epoxidation chemical modification process. In addition, both DPNR and ENR latex were concentrated to 60% total solid content via ultrafiltration process using membrane separation technology. Physiochemical properties of DPNR, ENR, and LATZ latex were compared. Results show that the total solid content, dry rubber content, and alkalinity level of the latexes achieved the targeted value. This study also found that nitrogen content of DPNR latex, LATZ latex, and ENR latex were at 0.11%, 0.29%, and 0.25%, respectively, indicating successful deproteinization of the DPNR latex. On the other hand, the epoxidation level of ENR latex produced in this study was at 46.3%, which is slightly lower than the targeted level of 50%. Rheological studies found that ENR latex exhibits the highest viscosity, followed by DPNR and LATZ, but all show characteristic shear-thinning behavior. This study also found that LATZ and DPNR latex are more liquid-like in nature, while ENR latex behaves more like an elastic solid. Non-ionic surfactants play a major role in influencing flow and deformation behavior of the ENR and DPNR latex.

Currently, there is significant demand for pillows with improved pressure-relief features made from natural materials, alternatives to petrochemical-based foams. To meet the requirements, this study’s approach is to develop latex foam pillows from deproteinized natural rubber (DPNR) latex with a unique dual-density cervical-shaped structure. In this work, DPNR latex foam pillows were produced at three different density levels which are high-density, medium-density and low-density. Extractable protein content of latex foam made from DPNR was confirmed lower than latex foam made from low ammonia NR latex (LATZ) and of commercial NR latex foams, making DPNR pillows more hypoallergenic than others. The physical properties of the produced DPNR latex foams were examined in accordance with Malaysian Standard MS679, and were found to comply with all requirements stipulated in standard specifications. A novel dual-density cervical-shaped DPNR latex foam pillow prototype was produced, where the pillow has lower density at the upper part and higher density at the lower part. Pressure-mapping was used to visualize the pressure distribution patterns and to measure the average peak pressure when a mannequin head was placed on top of the pillow. The study observed that decreasing the density increases the softness of the DPNR latex foam. Softer latex foams led to larger surface contact area, and hence a reduced average peak pressure value. This cervical-shaped structure further increased the surface contact area between the pillow and mannequin head, and thus reduced further the average peak pressure value.

Small specimen mechanical testing is an exciting and rapidly developing field in which fundamental deformation behaviours can be observed from experiments performed on comparatively small amounts of material. These methods are particularly useful when there is limited source material to facilitate a sufficient number of standard specimen tests, if any at all. Such situations include the development of new materials or when performing routine maintenance/inspection studies of in-service components, requiring that material conditions are updated with service exposure. The potentially more challenging loading conditions and complex stress states experienced by small specimens, in comparison with standard specimen geometries, has led to a tendency for these methods to be used in ranking studies rather than for fundamental material parameter determination. Classifying a specimen as ‘small’ can be subjective, and in the present work the focus is to review testing methods that utilise specimens with characteristic dimensions of less than 50 mm. By doing this, observations made here will be relevant to industrial service monitoring problems, wherein small samples of material are extracted and tested from operational components in such a way that structural integrity is not compromised. Whilst recently the majority of small specimen test techniques development have focused on the determination of creep behaviour/properties as well as sub-size tensile testing, attention is given here to small specimen testing methods for determining specific tensile, fatigue, fracture and crack growth properties. These areas are currently underrepresented in published reviews. The suitability of specimens and methods is discussed here, along with associated advantages and disadvantages.

Terpenes are ideal candidates for sustainable polymer feedstocks, due to their natural abundance and availability from existing waste streams. Previously, we have shown that a range of terpene(meth)acrylate monomers can be synthesised from the most commonly available terpenes (α-pinene, β-pinenene and limonene) and that these readily undergo radical polymerisation. We now report the synthesis of well-defined polymers and precise di- and multiblock copolymer architectures by use of RAFT control. A very wide range of Tg values are observed for the terpene (meth)acrylate homopolymers, from −3 °C for poly(limonene acrylate), up to +168 °C for poly(α-pinene methacrylate), and we exploit these to create renewably-sourced hard–soft block copolymers. We also report the synthesis of difunctional poly(α- and β-pinene methacrylate) macro-RAFT agents and the preparation of ABA triblock copolymers. Promising adhesive properties are observed for a triblock copolymer comprised of poly(α-pinene methacrylate) and poly(butyl acrylate) blocks. A range of fully terpene-based triblock copolymers containing poly(limonene acrylate) soft blocks are also reported.

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 behavior 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.

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 study of the cure kinetics of a one-part water-scavenging silicone elastomer was carried out under conditions of controlled humidity and temperature using rectangular bars subjected to oscillatory torsional shear. Characteristic cure times were obtained from Hsich model fits to the storage modulus evolution. A modified Arrhenius-style cure model is proposed that accounts for both the temperature dependence and for the proportionality between rate of cure and concentration of atmospheric water. The 2-parameter model is fitted to a broad dataset and allows accurate predictions of cure times.

Liquid-infused polymeric surfaces have demonstrated promising icephobicity. However, the capability to maintain the icephobic performance after material damage has been a challenge, both in terms of conserving a smoother surface and the replenishment of infused liquid. Cetacean skin possesses a microscopically smooth texture in the form of cells lubricated with lipid proteins and consists of structural fibres that ensure durability. Concerning the structure of cetacean skin, glycerol infused fibre-reinforced polyurethane coatings (GIFRP) were proposed. Instead of hosting the lipid proteins, the coatings were infused with glycerol, a known cryoprotectant to induce the supercooling of water, a strategy inspired by wood frogs and red flat dark beetles to prevent freezing. The inclusion of glycerol delayed water droplet freezing duration by 659%, while negligible frost accumulated on the fabricated coatings during anti-icing tests. The reinforcement of fibres was effective and the surface damage was reduced by a factor of 4, compared to the pure polyurethane coatings under erosion impact. The incorporation of fibres has proven to be beneficial for infused-liquid replenishment and the slow-releasing capabilities of GIFRP coatings. Minimised surface deterioration and the continued presence of glycerol on GIFRP coatings demonstrated a small increase in ice adhesion from 0.22 kPa to 0.77 kPa after the erosion tests, one of the lowest values reported in the literature after substantial surface damage. The concept inspired by cetacean skin and the cryoprotective features of chionophiles was instrumental in keeping the ice adhesion under 1 kPa after erosion impact.

A comparative study of de-icing evaluation methods was conducted in this work, and their variations in response to surface characteristics were investigated. The mechanical de-icing measurements include centrifugal, push, and tensile methods. The centrifugal and the horizontal push (shear) methods suggested a linear relationship of ice adhesion strength with surface roughness, whereas the tensile (normal) method indicated an inverse curvilinear relationship with contact angle hysteresis. A partial correlation of contact angle hysteresis on the shear-based methods was also indicated over a specified range of surface roughness. Further attempts were also made on 1H,1H,2H,2H-perfluorooctyltriethoxysilane-coated surfaces, and the ice adhesion indicated a clear reduction in the normal de-icing method, whereas the shear-based methods did not show a considerable change in ice adhesion, highlighting their mechanical forces-centric response. Lastly, a further evaluation using a hybrid de-icing method was conducted, to verify the influence of surface characteristics on ice removal involving heating, which demonstrated a partial correlation of energy consumption with the ice adhesion strength over a specified range of surface roughness. The results obtained in this study provide crucial information on the influence of surface characteristics on ice adhesion and offer material-dependent correlations of the popular de-icing evaluation methods. The conclusions could be applied to define an appropriate testing method for the evaluation of icephobic surfaces and coatings. Graphical abstract

In automated layup manufacturing processes of fiber-reinforced polymer composites, the quality of the manufactured part is strongly dependent on frictional behavior. Improper control of frictional forces can lead to defect formation. Frictional sliding rheometry tests provide an innovative methodology to accurately characterize the tool-ply friction of unidirectional (UD) prepreg employing unique annular plate geometries. The effect of processing parameters (temperature, velocity, and normal force) on the frictional response of a carbon fiber prepreg was studied. Moreover, utilizing custom designed plate geometries coupled with optically transparent fixtures allowed for in-situ quantification of the prepreg-rigid surface contact area along with simultaneous characterization of the process parameter-dependent frictional mechanisms. Our findings highlight the reduction in frictional forces with increasing temperature, attributed to the increased resin flowability, while increases in sliding rates resulted in a pronounced increase in the frictional forces. The effect of applied load on the frictional characteristics was more complicated due to contributions from both the adhesive and normal forces. Finally, the results were interpreted in light of the contact area measurements performed at different temperatures, normal force, and sliding rate.

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.

As our understanding of disease grows, it is becoming established that treatment needs to be personalized and targeted to the needs of the individual. In this paper we show that multi-material inkjet-based 3D printing, when backed with generative design algorithms, can bring a step change in the personalization of medical devices. We take cell-instructive materials known for their resistance to bacterial biofilm formation and reformulate for multi-material inkjet-based 3D printing. Specimens with customizable mechanical moduli are obtained without loss of their cell-instructive properties. The manufacturing is coupled to a design algorithm that takes a user-specified deformation and computes the distribution of the materials needed to meet the target under given load constraints. Optimisation led to a voxel map file defining where different materials should be placed. Manufactured products were assessed against the mechanical and cell-instructive specifications and ultimately showed how multifunctional personalization emerges from generative design driven 3D printing.

A single-stage peel method was employed to determine the relationship between key processing parameters and tack for a standard aerospace carbon/epoxy prepreg subjected to various levels of room-temperature out-time. The temperature-dependent viscoelasticity of the resin was studied using parallel plate rheometry and modelled using a simple Arrhenius equation. Differential scanning calorimetry and gel permeation chromatography results showed that, over a period of 35 days under ambient conditions, resin Tg increased, while no significant change in polymer chain length was observed. Time-temperature superposition was applied to construct tack master curves for each out-time interval, which were shown to approximately coincide when considering shift factors attributed to changes in Tg. Process maps considering prepreg out-time were generated using tack master curves to inform process parameters and achieve desirable tack levels. This type of tailored process control is anticipated to improve resource utilization when manufacturing large preforms which take several days to complete.

The roles of surface roughness on icephobicity including ice adhesion strength have been long debated in icephobicity studies. However, the direct/systematic influence of surface roughness on ice adhesion strength while keeping other surface characteristics such as surface wettability and interfacial cavitation unchanged are seldom reported. In this paper, systematic reduction of ice adhesion strength with the decrease in surface roughness regardless of the surface wettability was demonstrated across all the studied material types, i.e. metallic surfaces and polymeric coatings with different surface wettability. In-situ icing observation studies indicated that the ice did not anchor on smooth metallic surfaces and polymeric coatings but anchored on rough surfaces including superhydrophobic coatings. Effect of surface wettability was argued against the ice adhesion strength based on our results and similar ice adhesion strength was found on materials having different wettability (i.e. hydrophilic and hydrophobic coatings, and surfaces having different contact angle hysteresis). On the contrary, the introduction of low surface energy chemicals (via deposition and/or functionalization) on the surface having similar surface roughness showed a direct reduction of ice adhesion strength. These results indicated the surface roughness is vital in achieving icephobic performance, however, the ultra-low ice adhesion strength could be achieved by the synergetic effect of low surface roughness and low interfacial cavitation (in line with the interfacial correlation factor).

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.

Bacterial Biofilm Resistant Composite Devices Medical implants would benefit from bespoke 3D printing, however microbial infection remains a challenge. By combining functional materials, voxelated manufacturing and algorithmic design, Morgan R. Alexander, Ricky D. Wildman, and co‐workers demonstrate in article number 2100249 a multi‐material inkjet 3D printed device that inhibits the development of bacterial biofilm, while achieving highly customizable geometry and local stiffness, opening further opportunities for biomedical 3D printing. [Image: see text]

The relationship between prepreg tack and the degree of intimate contact (DoIC) between prepreg and a rigid substrate was explored in the context of a continuous application-and-peel test method. Tack for a unidirectional prepreg tape was characterised for different surface combinations and varying test parameters (material feed rate, temperature) at a constant compaction pressure. Application of the prepreg to a transparent rigid substrate (glass), was carried out at matching test conditions to the prepreg tack measurements. Optical microscopy was utilised to acquire images of the contact area at the prepreg-glass interface. Image analysis of the micrographs enabled quantification of the contact area. The time- and temperature-dependent viscoelastic behaviour of the resin was explored directly on the prepreg using oscillatory parallel plate rheometry, and time-temperature superposition was applied to construct both tack and DoIC master curves. The shifted DoIC data showed that true contact area increases with decreasing shifted feed rates, until maximum contact area is achieved. Similarly, tack increases with decreasing shifted feed rates. However, at a critical feed rate, the bond failure mechanism switches from adhesive to cohesive failure. In cohesive failure, tack decreases with decreasing feed rate despite the high levels of DoIC.

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.

A finite element (FE) model has been developed to simulate the double diaphragm forming (DDF) process, to identify potential defects when forming complex 3D preforms from 2D biaxial non-crimp fabric plies. Three different metrics have been introduced to predict and characterise defects, which include local shear angles to determine ply wrinkling induced by over-shear, compressive strains in the primary fibre directions to determine bundle wrinkling, and tensile stresses in the primary fibre directions to determine fabric bridging. The FE simulation is in good agreement with experiments performed on a demonstrator component. Results indicate that fabric bridging occurs in large-curvature regions, which is the dominant defect in DDF, as wrinkling is generally lower than in matched-tool forming due to relatively low forming pressures (up to 1 bar). The axial tensile stress in fibres has been used as a measure to identify suitable positions and orientations for darts, to alleviate fabric bridging and improve surface conformity, whilst minimising the effect on the mechanical performance of the component.

As the understanding of disease grows, so does the opportunity for personalization of therapies targeted to the needs of the individual. To bring about a step change in the personalization of medical devices it is shown that multi‐material inkjet‐based 3D printing can meet this demand by combining functional materials, voxelated manufacturing, and algorithmic design. In this paper composite structures designed with both controlled deformation and reduced biofilm formation are manufactured using two formulations that are deposited selectively and separately. The bacterial biofilm coverage of the resulting composites is reduced by up to 75% compared to commonly used silicone rubbers, without the need for incorporating bioactives. Meanwhile, the composites can be tuned to meet user defined mechanical performance with ±10% deviation. Device manufacture is coupled to finite element modelling and a genetic algorithm that takes the user‐specified mechanical deformation and computes the distribution of materials needed to meet this under given load constraints through a generative design process. Manufactured products are assessed against the mechanical and bacterial cell‐instructive specifications and illustrate how multifunctional personalization can be achieved using generative design driven multi‐material inkjet based 3D printing., Multi‐material inkjet‐based 3D printing is used for the design and manufacture of personalized medical devices. A design optimization approach is used to specify the location of two different materials, each with a different moduli, but both with the ability to resist bacterial colonization (up to 75% better than medical silicones), such that they meet user‐defined, complex design constraints.

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 °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.

Employing a test method with coupled application and peel phases, tack was characterised for a UD prepreg tape. Different aspects of tack were explored by varying test parameters and material condition. In addition, different surface combinations were studied. In general, the test parameters, feed rate and temperature, affect the balance between cohesion within the resin and adhesion between resin and substrate. Exploring a range of parameters is required to understand the effect of viscoelastic resin properties on tack. The application pressure determines the true contact area between prepreg and substrate and hence affects tack. Changes in molecular mobility in the resin related to specimen conditioning, i.e. ageing or moisture uptake, result in maximum tack to occur at lower or higher feed rates, respectively. Differences in tack for different material combinations can be attributed to different molecular interactions at the contact interfaces and different resin distributions on the prepreg surfaces.

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.

© 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved. 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.

Icephobicity is intrinsically affected by rough asperities and the surface voids provide anchoring points for the ice. The anchor of ice is likely to form on the surface under high humidity conditions. In-situ water condensation and icing observation were conducted to understand water condensation and ice retracting patterns in controlled humidity, pressure and temperature conditions. It was observed that water micro-condensation and icing occurred on rougher surfaces and the water droplets condensed along the surface cracks of the superhydrophobic polydimethylsiloxane (PDMS) based nanocomposite coatings. Further analysis revealed that ice anchoring was present on both aluminum and superhydrophobic coating surface, but it was more severe and intensified on the as-received aluminum substrates. No water condensation or subsequent icing was found on smooth PDMS hydrophobic surfaces due to the incapacity of the smooth surfaces to anchor water drops. It is the first time to validate ice anchoring over retracting ice on different wettability surfaces from in-situ icing observation. Ice adhesion strengths were also measured on the studied surfaces and the results indicated a strong linkage between centrifugal shearing of ice and anchoring mechanism due to surface rough voids, and there was no clear relevancy between ice adhesion strength and the surface wettability or hydrophobicity.

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.

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 can be represented by the model without the need of recalibration and parameter identification.

This study presents a toolbox for the prediction of birefringence and craze initiation stress in oriented monodis- perse linear amorphous polymers. The toolbox is assembled from a previously proposed melt-solid constitutive model that provides the necessary residual stress components required for predictions of birefringence and craze initiation stress. The Likhtman-McLeish theory for linear rheology of entangled polymers is used to generate the low reduced frequency part of the linear viscoelastic spectrum, the only molar mass- dependent input parameter. All other parameters are obtained by experiment or from literature and can be considered mate- rial constants. Toolbox predictions are compared to new exper- imental data on two grades of linear monodisperse polystyrene (PS) of known molar mass but unknown rheology and to literature data. The toolbox is able to account for the role of molar mass on birefringence and craze initiation stress of PS subjected to supraentanglement orientation processes. V C 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 50: 1748-1756, 2012

Simultaneous experimental measurements of stress, strain and electrical resistivity were carried out by exposing two carbon black filled cross-linked elastomers and two nanocomposites of thermoplastic polyurethane and multiwalled carbon nanotubes to a series of cyclic strain histories. It was found that the resistivity–strain relationships of the materials exhibited different hysteresis and dependence on prestrain. The resistivity of the nanotube filled elastomers changed dramatically with prestrain, making them suitable for memory sensor applications. During cyclic loading, the carbon black filled elastomers exhibit a lower resistivity during the loading part of the cycles than during the unloading part; the opposite effect was seen in the nanotube filled elastomers. The phenomena can be explained in terms of plastic flow processes in the thermoplastics, and of cohesive forces between carbon black particles in the cross-linked elastomers. Bending and buckling of the nanotubes give rise to a regio...

This study presents several designs for flash moulds intended to aid the damage-free production of polymeric specimens for mechanical and structural characterisation. The designs consist of interlocking metal parts that produce appropriately shaped cavities in which polymer specimens are moulded, and that are easily dismantled after moulding to allow removal of the specimens from the moulds. Very limited sample preparation is required after removal of the specimens. Several of the proposed designs have been manufactured and successfully employed in the production of rectangular specimens for characterisation of a range of polymers.

A study has been made of crazing stress in oriented glassy polystyrene. The aim was to develop a methodology for prediction of crazing stress in glassy polymers with frozen-in molecular orientation. Oriented specimens of two grades of monodisperse polystyrene (PS) and one grade of polydisperse PS were produced by uniaxial melt-drawing and subsequent quenching of compression-moulded bars. Birefringence and crazing stress parallel to the draw direction (in the presence of diethylene glycol) were measured on miniature beam specimens cut from them. The crazing stress increased substantially with orientation, and the magnitude of the increase relaxed approximately on a timescale associated with the longest Rouse time. Specifically, a linear correlation was found, to within experimental scatter, between the increase in crazing stress and the orientation expressed in terms of frozen-in conformational stress, as predicted by the theory of Maestrini and Kramer [13]. The inverse gradient (constant β in the theory) was found to be 0.059 ± 0.002, when inferring the conformational stress from the measured birefringence. Crazing was found to be suppressed in favour of yielding in the most highly oriented specimens, and this could be explained in terms of the differing sensitivities of crazing and yield to molecular orientation. © 2011 Elsevier Ltd. All rights reserved.

A miniature test method is presented for measuring craze initiation stress in tension on very small specimens of glassy polymers (less than 10 mg). The method consists of three-point bending creep experiments followed by low-power optical microscopy to determine the length of the crazed region, and hence the stress at which crazes initiate within a given time. The test method is especially suitable when extremely limited quantities of material are available. It is illustrated by application to two monodisperse and one polydisperse polystyrenes (PS). In polydisperse PS crazed in diethylene glycol, craze initiation stress and time dependence are close to those of the monodisperse PS with the same Mw, but in polydisperse PS crazed in air, crazes initiate at larger stresses, and the time-dependence is close to that of the monodisperse PS with the same Mn. The findings are discussed in terms of changes in craze initiation mechanisms from disentanglement crazing to chain scission crazing with increasing molecular weight and decreasing time. © 2007 Elsevier Ltd. All rights reserved.

High-pressure rheology has been used to assess the effects of supercritical carbon dioxide (scCO2) on the melting point (Tm) and viscosity of poly (e-caprolactone) (PCL) over a range of temperatures and pressures up to 300 bar over a wide range of shear rates. Plots of the storage and loss moduli against temperature show a significant shift of Tm to lower temperatures in the presence of CO2, indicating that the polymer crystals melt at temperatures much lower than the ambient pressure Tm. Furthermore, a significant decrease in the viscosity of two PCL grades with different molecular weight (Mn ~ 10 kDa and 80 kDa) was also detected upon increasing the CO2 pressure to 300 bar. Experimental viscosity data were fitted to the Carreau model to quantify the extent of the plasticising effects on the zero-shear viscosity and relaxation time under different conditions. Similar analyses were conducted under high-pressure nitrogen, to compare the effects obtained in the presence of a non-plasticising gas.

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.

A method developed in the 1980s for the conversion of linear rheological data to molar mass 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 discussed. This work forms part of a wider study of bioresorbable nanocomposites using polylactides, novel hydroxyapatite nanoparticles and tailored dispersants for medical applications.

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 simple model of deploying tree leaves is assembled in different arrangements to produce polygonal foldable membranes for use as deployable structures. One family of folding patterns exhibits a small strain mechanism, which is investigated. Variations on the basic arrangements can be used to fold membranes with a discretized curvature.

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 [Formula: see text]. 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. [Formula: see text].

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. © 2013 The Authors. Published by Elsevier Ltd. All rights reserved.

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 timescales scale with molar mass in the same way, evidence that the 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 study has been made of birefringence in oriented glassy polystyrene. The aim was to develop a methodology for the prediction of birefringence in glassy polymers with frozen-in molecular orientation. The predictive approach employed was to use a recently proposed constitutive model, consisting of a coupling between the Likhtman-Graham Rolie-Poly model for polymer melt rheology and a previously established model for polymer glasses. The methodology was validated with an experimental study of oriented glassy polystyrenes with known melt-stretching histories. It was found that, for orientation processes sufficiently far above Tg (i.e., not including subentanglement stretch), birefringence could be predicted accurately in monodisperse materials. © 2011 American Chemical Society.

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 underpredicts 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. © 2010 Wiley Periodicals, Inc.

Visible craze initiation stress has been measured for a wide range of linear and branched monodisperse polystyrenes (PS) soaked in diethylene glycol. Results show that, for a given time under stress, craze initiation in linear PS is disentanglement-dominated below a critical molar mass and chain scission-dominated above it. Branched monodisperse PS behaves similarly, with the relevant molar mass in this case being the span molar mass. Disentanglement craze initiation stress is found to vary linearly with log molar mass and log time. These observations can be explained in terms of Eyring-type stress acceleration of the process of chain retraction, required to achieve me entanglement loss necessary for creation of craze fibril surfaces. A single effective activation volume of 1.8 nm3 accounts for the dependence of crazing stress on molar mass, time, and temperature under uniaxial tensile stress, both as observed in the present data and in a previous study of rate/temperature dependence. © 2008 American Chemical Society.

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.

This study concerns the thermal and mechanical response of several commercial grades of ethylene – tetrafluoroethylene copolymer films. Differential scanning calorimetry was used to show that, although films have similar degrees of crystallinity and melting temperature, the melting endotherms and crystallisation exotherms differ between materials, suggesting small changes in composition between manufacturers. Films were deformed in tension at a range of temperatures and rates. Selected films were unloaded immediately after stretching, and measurement of the elastic recovery highlighted further differences between materials. Batches of films were pre-drawn uniaxially above the glass transition and immediately quenched. When these materials were subsequently re-drawn below the glass transition temperature, most of them exhibited much improved yield stress, modulus and tensile strength (improving by factors of 5, 5 and 4, respectively at a draw ratio of 3), but a reduced strain to failure. In most of the films, the pre-drawing, as well as the initial orientation of the films, is accounted for by a simple shift in the true strain axis. This is indicative of a material response dominated by entropic network stretch. It also suggests that, in the cases where strain superposition does not work, a different arrangement of crystalline lamellae may be present, limiting the extent to which improved properties can be achieved in some materials.

Icephobic performance of low-ice adhesion polymeric coatings has been studied intensively for passive ice protection. However, limited efforts were conducted to identify strategies for enhancing the durability of the coatings to maintain low ice adhesion after erosion impact. In this work, we developed and investigated several polyurethane-based nanocomposite and fibre-reinforced coatings to understand the deteriorating behaviour of the coatings under rigorous impinging erosion tests and the subsequent impact on ice adhesion. The inclusion of fillers resulted in up to 38 points increase in Shore hardness relative to the pristine PU coatings. The ice adhesion strengths on 3 wt% nanoparticle-reinforced coatings after the erosion tests were nearly halved, whereas, a 5-fold reduction was observed on 3 wt% fibre-reinforced coatings compared to that of the pure PU coatings. Our results indicated that the incorporation of fillers was effective in reducing the ice anchoring points, and that, after the impingement, the icephobic performance was retained by either lowering surface roughness or by minimizing surface deterioration. Fibres took a more effective role in limiting crack initiation and resisting crack propagation. The ice adhesion strength of the coatings increased from 5.6 kPa to 8.4 kPa with 20 wt% carbon fibres incorporated PU coatings, essentially keeping the adhesion below 10 kPa even after rigorous impinging tests and a ∼10-fold reduction in ice adhesion strength as compared to the pure PU coatings. The incorporation of the fibres led to enhanced durability and retention of excellent icephobic performance via a mechanism that is adaptable to other polymeric coatings.