Influence of curing thermal history on cross-linking degree of a polydimethylsiloxane: Swelling and mechanical analyses

In this work, the change of the elastic properties induced by a change in cross-linking conditions of polydimethylsiloxane is investigated by measuring its shear modulus by dynamic mechanical analysis and correlating it to that predicted from swelling measurements. Polymer cross-linking is performed at different curing temperatures reached with ramps at different heating rates. From both mechanical and swelling measurements, the molecular weight between cross-links, MC, is determined, and its dependency on the applied thermal history is analyzed. The main results are: (i) the elastic modulus of the cured material is not significantly affected by the heating rate adopted, while (ii) the curing temperature has a significant influence on the polydimethylsiloxane mechanical properties. In addition, (iii) MC evaluation from swelling measurements is in good agreement with that estimated from mechanical measurements when appropriate theories are considered. This last result suggests that swelling experiments can be considered as a reliable tool to predict the elastic modulus of the polydimethylsiloxane studied. The quantitative information reported in this paper, also obtainable by the suggested method if other thermal curing histories are applied, is extremely useful for the proper design of devices based on polydimethylsiloxane

Capillary breakup and electrospinning of PA6 solutions containing FeCl3: experimental findings and correlations

In several applications, ranging from electronic to chemical sensing, great interest has grown for the exploitation of conducting polymer nanofibers, whose processing is, however, not straightforward, due to polymer low solubility and presence of rigid backbones. An interesting method to overcome this issue consists in the electrospinning of a spinnable polymer to obtain a template for the successive in situ polymerization of the conducting polymer monomers. Considering PANI nanofibers, a suitable template can be electrospun from PA6 solutions in formic acid containing FeCl3. In this system, the ionic salt may perturb or prevent H-bonds formation between amide groups of PA6 backbones: this could modify solution viscoelasticity, and thus affect fibres morphology. The aim of the present work is to identify the effect of FeCl3 on the solution rheological behaviour and to correlate it to electrospun fibres morphology. To this aim, solutions at several salt content underwent electrospinning and were characterized both in shear, by rotational rheometry, and extension, by capillary breakup rheometry, while fibres morphology and crystallinity were evaluated through SEM and DSC. The rheological analysis enlightens that a critical FeCl3 content exists above which the viscous component of the viscoelastic response becomes predominant. At the same concentration, the SEM observations of the electrospun fibres show the formation of severely inhomogeneous structures. A correlation between these results is proposed through the adimensional analysis of competing viscoelastic stabilization and surface tension-driven instability phenomena. Besides the aforementioned effects, the FeCl3 content affects also fibre crystallinity, as above a critical concentration fibres turn out to be completely amorphous. Interestingly, this concentration coincides with the one at which a transition is observed in the rheological behaviour

A 3D Numerical Model for the Optimization of Running Tracks Performance

In previous works, a finite element model of the shock absorbing characteristics of athletics tracks was developed, able to give sufficiently reliable predictions from laboratory tests performed on suitable material samples. The model proved to be effective in discriminating the effects of geometry (i.e. thickness) and material properties (essentially the elastic characteristics) on force reduction, thus allowing a first optimization of the tracks in view of their approval by the International Association of Athletics Federations (IAAF). This simplified 2D model neglected the real track structure, considering it as a single layer of material having homogenized properties. In the present study, a new 3D model was developed to accurately describe the structure of multi-layered tracks, with properties and geometrical construction (e.g. solid or honeycomb) differing from one layer to another. Several tracks having different combinations of top/bottom layers varying in both material formulation (i.e. chemical composition) and geometry were thus considered. Mechanical properties of the individual elements constituting the track were measured with small-scale laboratory tests, taking into account their strain-rate dependence. The 3D model allowed a complete representation of the loads acting on the track and it gave results which are in very good agreement with the experiments. This proves it to be a valuable tool for the purpose of optimizing the track in terms of material formulation as well as layer geometrical construction and arrangement: as an example, the effect of changing the cell size of the honeycomb pattern was investigated

Modeling of shock absorption in athletics track surfaces

In this work, the possibility of predicting the force reduction (FR) characterizing the shock absorption capability of track surfaces by finite element modeling was investigated. The mechanical responses of a typical sport surface and of a reference material were characterized by quasi-static uniaxial compression experiments and fitted by Neo-Hookean and Mooney–Rivlin’s hyperelastic models to select the more appropriate one. Furthermore, in order to examine the materials behavior at strain rates typical of athletics applications, the rate dependence of the constitutive parameters was investigated. A finite element model, taking into consideration the post-impact nonlinear dynamics of the track surface and of the system (track surface + artificial athlete), was developed and validated through comparison with the results of FR tests. The simulations showed a very good agreement with the experiments and allowed to interpret the experimentally observed combined effect of track thickness and material intrinsic properties on the overall surface behavior

Effect of processing on the environmental stress cracking resistance of high-impact polystyrene

Processing conditions have a strong effect on the final mechanical properties of products made of polymeric materials. Relevant phenomena most commonly include thermal stresses, physical ageing, frozen-in strains and molecular orientation. In this work, two different high-impact polystyrenes, processed by thermoforming, were considered: a “standard” one and a grade specifically resistant to Environmental Stress Cracking (ESC). The main effect induced by thermoforming was molecular orientation. The local degree of orientation was measured on a thermoformed product and its effect on the material ESC behavior in sunflower oil was studied. A Fracture Mechanics approach was applied to evaluate the fracture resistance of the two materials. Results show that a higher degree of orientation increases the fracture resistance in air but has no effect on the (expectedly lower) resistance in the active oil environment

Retentive device for intravesical drug delivery based on water-induced shape memory response of poly(vinyl alcohol): design concept and 4D printing feasibility

The use of shape memory polymers exhibiting water-induced shape recovery at body temperature and water solubility was proposed for the development of indwelling devices for intravesical drug delivery. These could be administered via catheter in a suitable temporary shape, retained in the bladder for a programmed period of time by recovery of the original shape and eliminated with urine following dissolution/erosion. Hot melt extrusion and fused deposition modeling 3D printing were employed as the manufacturing techniques, the latter resulting in 4D printing because of the shape modifications undergone by the printed item over time. Pharmaceutical-grade poly(vinyl alcohol) was selected based on its hot-processability, availability in different molecular weights and on preliminary data showing water-induced shape memory behavior. Specimens having various original and temporary geometries as well as compositions, successfully obtained, were characterized by differential scanning calorimetry and dynamic-mechanical thermal analysis as well as for fluid uptake, mass loss, shape recovery and release behavior. The samples exhibited the desired ability to recover the original shape, consistent in kinetics with the relevant thermo-mechanical properties, and concomitant prolonged release of a tracer. Although preliminary in scope, this study indicated the viability of the proposed approach to the design of retentive intravesical delivery systems

Effect of Polyethylene Glycol Content and Molar Mass on Injection Molding of Hydroxypropyl Methylcellulose Acetate Succinate-Based Gastroresistant Capsular Devices for Oral Drug Delivery

Capsular devices for oral drug delivery were recently proposed and manufactured by injection molding (IM) as an evolution of traditional reservoir systems comprising a core and a functional coating. IM allowed the fabrication of capsule shells with release-controlling features based on the employed materials and the design characteristics. These features are independent of the drug, with significant savings in development time and costs. In previous work, IM was used to produce enteric-soluble capsules from blends of hydroxypropyl methylcellulose acetate succinate, with polyethylene glycol (PEG) as the plasticizer. In this work, the range of plasticizer concentrations and molar mass was broadened to evaluate in-depth how those parameters affect material processability and capsule performance over time. As expected, increasing the amount of the low molar mass plasticizer decreased the viscosity and modulus of the material. This simplified the molding process and enhanced the mechanical resistance of the shell, as observed during assembly. However, some samples turned out translucent, depending on several factors including storage conditions. This was attributed to plasticizer migration issues. Such results indicate that higher molar mass PEGs, while not significantly impacting on processability, lead to capsular devices with consistent performance in the investigated time lapse

Pectin-based bioinks for 3D models of neural tissue produced by a pH-controlled kinetics

Introduction: In the view of 3D-bioprinting with cell models representative of neural cells, we produced inks to mimic the basic viscoelastic properties of brain tissue. Moving from the concept that rheology provides useful information to predict ink printability, this study improves and expands the potential of the previously published 3D-reactive printing approach by introducing pH as a key parameter to be controlled, together with printing time. Methods: The viscoelastic properties, printability, and microstructure of pectin gels crosslinked with CaCO3 were investigated and their composition was optimized (i.e., by including cell culture medium, HEPES buffer, and collagen). Different cell models representative of the major brain cell populations (i.e., neurons, astrocytes, microglial cells, and oligodendrocytes) were considered. Results and Discussion: The outcomes of this study propose a highly controllable method to optimize the printability of internally crosslinked polysaccharides, without the need for additives or post-printing treatments. By introducing pH as a further parameter to be controlled, it is possible to have multiple (pH-dependent) crosslinking kinetics, without varying hydrogel composition. In addition, the results indicate that not only cells survive and proliferate following 3D-bioprinting, but they can also interact and reorganize hydrogel microstructure. Taken together, the results suggest that pectin-based hydrogels could be successfully applied for neural cell culture