Additive Manufacturing of Polyolefins.

Polyolefins are semi-crystalline thermoplastic polymers known for their good mechanical properties, low production cost, and chemical resistance. They are amongst the most commonly used plastics, and many polyolefin grades are regarded as engineering polymers. The two main additive manufacturing techniques that can be used to fabricate 3D-printed parts are fused filament fabrication and selective laser sintering. Polyolefins, like polypropylene and polyethylene, can, in principle, be processed with both these techniques. However, the semi-crystalline nature of polyolefins adds complexity to the use of additive manufacturing methods compared to amorphous polymers. First, the crystallization process results in severe shrinkage upon cooling, while the processing temperature and cooling rate affect the mechanical properties and mesoscopic structure of the fabricated parts. In addition, for ultra-high-molecular weight polyolefins, limited chain diffusion is a major obstacle to achieving proper adhesion between adjunct layers. Finally, polyolefins are typically apolar polymers, which reduces the adhesion of the 3D-printed part to the substrate. Notwithstanding these difficulties, it is clear that the successful processing of polyolefins via additive manufacturing techniques would enable the fabrication of high-end engineering products with enormous design flexibility. In addition, additive manufacturing could be utilized for the increased recycling of plastics. This manuscript reviews the work that has been conducted in developing experimental protocols for the additive manufacturing of polyolefins, presenting a comparison between the different approaches with a focus on the use of polyethylene and polypropylene grades. This review is concluded with an outlook for future research to overcome the current challenges that impede the addition of polyolefins to the standard palette of materials processed through additive manufacturing.

Melting Kinetics of Nascent Poly(tetrafluoroethylene) Powder.

The melting behavior of nascent poly(tetrafluoroethylene) (PTFE) was investigated by way of differential scanning calorimetry (DSC). It is well known that the melting temperature of nascent PTFE is about 344 ∘ C, but reduces to 327 ∘ C for once molten material. In this study, the melting temperature of nascent PTFE crystals was found to strongly depend on heating rate, decreasing considerably for slow heating rates. In addition, during isothermal experiments in the temperature range of 327 ∘ C < T < 344 ∘ C, delayed melting of PTFE was observed, with complete melting only occurring after up to several hours. The melting kinetics of nascent PTFE were analyzed by means of the isoconversional methodology, and an apparent activation energy of melting, dependent on the conversion, was determined. The compensation effect was utilized in order to derive the pre-exponential factor of the kinetic model. The numerical reconstruction of the kinetic model was compared with literature models and an Avrami-Erofeev model was identified as best fit of the experimental data. The predictions of the kinetic model were in good agreement with the observed time-dependent melting of nascent PTFE during isothermal and constant heating-rate experiments.

Three-dimensional printing of hierarchical liquid-crystal-polymer structures.

Fibre-reinforced polymer structures are often used when stiff lightweight materials are required, such as in aircraft, vehicles and biomedical implants. Despite their very high stiffness and strength1, such lightweight materials require energy- and labour-intensive fabrication processes2, exhibit typically brittle fracture and are difficult to shape and recycle3,4. This is in stark contrast to lightweight biological materials such as bone, silk and wood, which form by directed self-assembly into complex, hierarchically structured shapes with outstanding mechanical properties5-11, and are circularly integrated into the environment. Here we demonstrate a three-dimensional (3D) printing approach to generate recyclable lightweight structures with hierarchical architectures, complex geometries and unprecedented stiffness and toughness. Their features arise from the self-assembly of liquid-crystal polymer molecules into highly oriented domains during extrusion of the molten feedstock material. By orienting the molecular domains with the print path, we are able to reinforce the polymer structure according to the expected mechanical stresses, leading to stiffness, strength and toughness that outperform state-of-the-art 3D-printed polymers by an order of magnitude and are comparable with the highest-performance lightweight composites1,12. The ability to combine the top-down shaping freedom of 3D printing with bottom-up molecular control over polymer orientation opens up the possibility to freely design and realize structures without the typical restrictions of current manufacturing processes.

Characterization and modelling of Langmuir interfaces with finite elasticity.

Interfaces differ from bulk materials in many ways, one particular aspect is that they are compressible. Changing the area per molecule or per particle changes the thermodynamic state variables such as surface pressure. Yet, when compressing to high surface pressures, dense packing of the interfacial species induces phase transitions, with highly structured phases, which can display elastic or strongly viscoelastic behaviour. When these are deformed, in addition to the changes in the surface pressure, extra and deviatoric stresses can be induced. The traditional tool to study the phase behaviour of monolayers is a rectangular Langmuir-Pockels trough, but as both the area and shape of the interface are changed upon compression, the interfacial-strain field in this instrument is mixed with a priori unknown amounts of dilatational and shear deformations, making it difficult to separate the rheological and equilibrium thermodynamic effects. In the present work, the design of a radial trough is described, in which the deformation field is simple, purely dilation or compression. The possibility to now independently measure the compressional properties of different strains and the development of an appropriate finite strain constitutive model for elastic interfaces make it possible to interrogate the underlying constitutive behaviour. This is shown here for a strongly elastic, soft glassy polymer monolayer during its initial compression but is easily generalised to many viscoelastic soft matter interfaces.

From drop-shape analysis to stress-fitting elastometry.

Drop-shape analysis using pendant or sessile drops is a well-established experimental technique for measuring the interfacial or surface tension, and changes thereof. The method relies on deforming a drop by either gravity or buoyancy and fitting the Young-Laplace equation to the drop shape. Alternatively one can prescribe the shape and measure the pressure inside the drop or bubble using pressure tensiometry. However, when an interface with a complex microstructure is present, extra and anisotropic interfacial stresses may develop due to lateral interactions between the surface-active moieties, leading to deviations of the drop shape or even a wrinkling of the interface. To extract surface-material properties of these complex interfaces using drop-shape analysis or pressure tensiometry, the Young-Laplace law needs to be generalized in order to account for the extra and anisotropic stresses at the interface. In the present work, we review the different approaches that have been proposed to date to extract the surface tension as the thermodynamic state variable, as well as other rheological material properties such as the compression and the shear modulus. To evaluate the intrinsic performance of the methods, computer generated drops are subjected to step-area changes and then subjected to analysis using the different methods. Shape-fitting methods, now combined with an adequate constitutive method, do however perform rather poorly in determining the elastic stresses, especially at small area strains. An additional measurement o f the pressure or capillary-pressure tensiometry is required to improve the sensitivity. However, pressure-based methods still require the knowledge of the undeformed reference state, which may be difficult to achieve in practice. Moreover, it is not straightforward to judge from what point onwards one needs to go beyond the Young-Laplace equation. To overcome these limitations, a method based on stress fitting, which uses a local force balance method, is introduced here. One aspect of this new method is the use of the Chebyshev transform to numerically describe the contour shape of the drop interface. For all methods we present a detailed error analysis to evaluate if, and with what precision, surface material parameters can be extracted. Depending on the desired information, different ideal experimental conditions and most suitable methods are discussed, in addition to having a criterion to investigate if extra and anisotropic stresses matter.

Modeling energy storage and structural evolution during finite viscoplastic deformation of glassy polymers.

The enthalpic response of amorphous polymers depends strongly on their thermal and deformation history. Annealing just below the glass transition temperature (T_{g}) causes a large endothermic overshoot of the isobaric heat capacity at T_{g} as measured by differential scanning calorimetry, while plastic deformation (cold work) can erase this overshoot and create an exothermic undershoot. This indicates that a strong coupling exists between the polymer structure, thermal response, and mechanical deformation. In this work, we apply a recently developed thermomechanical model for glassy polymers that couples structural evolution and viscoplastic deformation to investigate the effect of annealing and plastic deformation on the accumulation of stored energy during cold work and calorimetry measurements of heat flow. The thermomechanical model introduces the effective temperature as an additional state variable in a nonequilibrium thermodynamics setting to describe the structural evolution of the material. The results show that the model accurately describes the stress and enthalpy response of quenched and annealed polymers with different plastic predeformations. The model also shows that at 30% strain in uniaxial compression, 45% of the applied work is converted into stored energy, which is consistent with experimental data from literature.

Small hook thread (Quill) and soft felt internal splint to increase the primary repair strength of lacerated rabbit Achilles tendons: biomechanical analysis and considerations for hand surgery.

BACKGROUND: For the prevention of re-rupture during early healing phase, the primary repair strength of repaired lacerated tendons in hand surgery should be maximal and the reconstructed diameter minimal. Two new repair methods (small hook thread and internal splint) were assessed for strength and reconstructed diameter characteristics. METHODS: Achilles tendons of 43 female New Zealand White rabbits were sectioned 2 cm above the calcaneus. Specimens were divided into 7 groups and repaired as follows: Kirchmayr method 2-strand with 4.0 polypropylene thread; Becker method 4-strand; 6-strand; internal splint; Kirchmayr method small hook 2-strand; Becker method small hook 4-strand, non-modified tendon. Load until failure, load until gap formation, gap length, cross-sectional area and failure stress were determined. FINDINGS: The small hook 2-strand suture had 1.3 fold higher loads until failure compared to a conventional 2-strand suture, P<0.05. The internal splint had a similar load until failure (22 N (SD 6)) as the conventional 2-strand suture (23 N (SD 4)); around half the load until failure of the conventional 4-strand suture (38 N (SD 9)). Load until gap formation correlated positively with load until failure (y=0.65+3.6; r(2)=0.72). The running suture increased the cross-sectional area at the repair site by a factor of 1.3. INTERPRETATION: Using a small hook thread instead of a 4.0 polypropylene thread significantly increases the primary repair strength with the same number of strands. Internal splints may be an alternative to conventional 2-strand sutures for bridging large gaps.

The effect of size and density on the mean retention time of particles in the reticulorumen of cattle ( Bos primigenius f. taurus), muskoxen ( Ovibos moschatus) and moose ( Alces alces).

Particle passage from the reticulorumen (RR) depends on particle density and size. Forage particle density and size are related and change over time in the RR. Particle density mainly influences sorting in the reticulum, whereas particle size influences particle retention in the fibre mat of stratified rumen contents ('filter-bed' effect). We investigated these effects independently, by inserting plastic particles of different sizes (1, 10 and 20 mm) and densities (1·03, 1·20 and 1·44 mg/ml) in the RR of cattle (Bos primigenius f. taurus) as a pilot study, and of muskoxen (Ovibos moschatus; n 4) and moose (Alces alces; n 2) both fed two diets (browse and grass). Faeces were analysed for plastic residues for 13 d after dosing to calculate mean retention times (MRT). The results confirmed previous findings of differences in absolute MRT between species. Comparing muskoxen with moose, there was no difference in the effect of particle density on the MRT between species but particle size had a more pronounced effect on the MRT in muskoxen than in moose. This indicated a stronger 'filter-bed effect' in muskoxen, in accord with the reports of stratified RR contents in this species v. the absence of RR content stratification in moose. Low-density particles were retained longer in both species fed on grass diets, indicating a contribution of forage type to the 'filter-bed effect'. The results indicate that retention based on particle size may differ between ruminant species, depending on the presence of a fibre mat in the RR, whereas the density-dependent mechanism of sedimentation in the RR is rather constant across species.