Thermal, mechanical and rheological behaviors of nanocomposites based on UHMWPE/paraffin oil/carbon nanofiller obtained by using different dispersion techniques.

Ultra-high molecular weight polyethylene (UHMWPE) is a very attractive polymer employed as a high performance material. For its high viscosity, dispersion of fillers is considered a critical point in UHMWPE nanocomposites preparation process. Currently, paraffin oil (PO) is used extensively to overcome this issue in an assisted melt-mixing process. In this work, we have prepared nanocomposites based on UHMWPE, carbon nanofiller (CNF) and PO mixed by different mixing methods: magnetic stirring, ball milling (BM), ultrasonic and Mini-Lab extruder (EX). The aim of this work was to check the effect of the dispersion method on the mechanical and thermal features of UHMWPE/CNF nano composites in order to obtain a material with improved mechanical and physical properties. The samples were characterized by calorimetric, density, mechanical tensile and rheological analyses. Experimental results highlighted that the nanocomposites produced by EX and BM exhibits the best dispersion, good filler matrix interaction and had significantly improved mechanical properties compared to pure UHMWPE. For instance, for the BM method, the yield strength improved to 18.6 MPa (+96%), the yield strain improved by 60%, while stress at break improved by 13%. In summary, the EX improved the stiffness while the BM produced better ductility, melting temperature and the crystalline degree of the nanocomposites

Processing and characterization of bio-polyester reactive blends: From thermoplastic blends to cross-linked networks

The addition of ethyl ester L-lysine tri-isocyanate (LTI) to mixtures of poly(lactide)/poly(ε-caprolactone) has been reported to improve the compatibility of the resulting blends. In the present work, we have investigated the influence of adding increasing amounts of LTI to the mechanical and thermal properties of the blends. Torque trends, plate-plate rheology, differential scanning calorimetry, scanning electron microscopy, and uniaxial tensile characterization were conducted on samples with amounts of LTI comprised between 0.5 and 5 phr. Results suggests that by increasing the content of LTI over 0.5 phr the mechanical and thermal behaviour of the blends tend to change from that of a thermoplastic to that of a cross-linked, rubber-like material with outstanding mechanical properties. Morphological investigations show a very fine, well-dispersed morphology in all cases. Numerical models have been applied to rheological experiments to identify processes and phases in the studied blends, further supporting the hypothesis of a cross-linked phase formed for blends containing more than 0.5 phr of LTI

Effect of Ethyl Ester L-Lysine Triisocyanate addition to produce reactive PLA/PCL bio-polyester blends for biomedical applications

We report in this paper the effects of Ethyl Ester L-Lysine Triisocyanate (LTI) on the physical-mechanical properties of Poly(lactide)/Poly(ε-caprolactone) (PLA/PCL) polyesters blends. The PLA/PCL ratios considered were 20/80, 50/50 and 80/20 (wt/wt %) and LTI was added in amounts of 0.0-0.5-1.0 phr. PLA and PCL reacted with LTI during processing in a Brabender twin screw internal mixer to produce block copolymers in-situ. The resulting blends have been characterized by torque measurements, uniaxial tensile tests, Differential Scanning Calorimeter, contact angle measurements with a Phosphate Buffered Saline (PBS) solution, ATR analysis and morphological SEM observations. Experimental results highlighted how LTI enhanced interaction and dispersion of the two components, resulting into a synergic effect in mechanical properties. Mechanical and physical properties can be tailored by changing the blend composition. The most noticeable trend was an increase in ductility of the mixed polymers. Besides, LTI decreased blend’s wet ability in PBS and lowered the starting of crystalline phase formation for both polymers, confirming an interaction among them. These reactive blends could find use as biomedical materials, e.g. absorbable suture threads or scaffolds for cellular growth

Evaluating the irritant factors of silicone and hydrocolloid skin contact adhesives using trans-epidermal water loss, protein stripping, erythema, and ease of removal

YesA composite silicone skin adhesive material was designed to improve its water vapor permeability to offer advantages to wearer comfort compared to existing skin adhesive dressings available (including perforated silicone and hydrocolloid products). The chemical and mechanical properties of this novel dressing were analyzed to show that it has a high creep compliance, offering anisotropic elasticity that is likely to place less stress on the skin. A participant study was carried out in which 31 participants wore a novel silicone skin adhesive (Sil2) and a hydrocolloid competitor and were monitored for physiological response to the dressings. Trans-epidermal water loss (TEWL) was measured pre- and postwear to determine impairment of skin barrier function. Sil2 exhibited a higher vapor permeability than the hydrocolloid dressings during wear. Peel strength measurements and dye counter staining of the removed dressings showed that the hydrocolloid had a higher adhesion to the participants’ skin, resulting in a greater removal of proteins from the stratum corneum and a higher pain rating from participants on removal. Once the dressings were removed, TEWL of the participants skin beneath the Sil2 was close to normal in comparison to the hydrocolloid dressings that showed an increase in skin TEWL, indicating that the skin had been highly occluded. Analysis of the skin immediately after removal showed a higher incidence of erythema following application of hydrocolloid dressings (>60%) compared to Sil2, (T.S. received partial funding to study skin adhesive materials from a Medical Research Council Confidence in Concept grant obtained by John Bridgeman at the University of Bradford (MC_PC_19030). Initial formulation and characterization work benchmarking the Sil2 material was funded in part by Trio Healthcare Ltd., who have had no role in the analysis or interpretation of the data presented. All data was obtained independently by staff at the University of Bradford. We also wish to thank the Royal Society of Chemistry for funding Edward Dyson’s position as a research technician via a Research Enablement Grant (E21-8346952505)

Effect of Ethyl Ester L-Lysine Triisocyanate addition to produce reactive PLA/PCL bio-polyester blends for biomedical applications

This paper was accepted for publication in the journal Journal of the Mechanical Behavior of Biomedical Materials and the definitive published version is available at http://dx.doi.org/10.1016/j.jmbbm.2017.02.018We report in this paper the effects of Ethyl Ester L-Lysine Triisocyanate (LTI) on the physical-mechanical properties of Poly(lactide)/Poly(ε-caprolactone) (PLA/PCL) polyesters blends. The PLA/PCL ratios considered were 20/80, 50/50 and 80/20 (wt/wt %) and LTI was added in amounts of 0.0-0.5-1.0 phr. PLA and PCL reacted with LTI during processing in a Brabender twin screw internal mixer to produce block copolymers in-situ. The resulting blends have been characterized by torque measurements, uniaxial tensile tests, Differential Scanning Calorimeter, contact angle measurements with a Phosphate Buffered Saline (PBS) solution, ATR analysis and morphological SEM observations. Experimental results highlighted how LTI enhanced interaction and dispersion of the two components, resulting into a synergic effect in mechanical properties. Mechanical and physical properties can be tailored by changing the blend composition. The most noticeable trend was an increase in ductility of the mixed polymers. Besides, LTI decreased blend’s wet ability in PBS and lowered the starting of crystalline phase formation for both polymers, confirming an interaction among them. These reactive blends could find use as biomedical materials, e.g. absorbable suture threads or scaffolds for cellular growth

Antiplasticization of Polymer Materials: Structural Aspects and Effects on Mechanical and Diffusion-Controlled Properties

Antiplasticization of glassy polymers, arising from the addition of small amounts of plasticizer, was examined to highlight the developments that have taken place over the last few decades, aiming to fill gaps of knowledge in the large number of disjointed publications. The analysis includes the role of polymer/plasticizer molecular interactions and the conditions leading to the cross-over from antiplasticization to plasticization. This was based on molecular dynamics considerations of thermal transitions and related relaxation spectra, alongside the deviation of free volumes from the additivity rule. Useful insights were gained from an analysis of data on molecular glasses, including the implications of the glass fragility concept. The effects of molecular packing resulting from antiplasticization are also discussed in the context of physical ageing. These include considerations on the effects on mechanical properties and diffusion-controlled behaviour. Some peculiar features of antiplasticization regarding changes in Tg were probed and the effects of water were examined, both as a single component and in combination with other plasticizers to illustrate the role of intermolecular forces. The analysis has also brought to light the shortcomings of existing theories for disregarding the dual cross-over from antiplasticization to plasticization with respect to modulus variation with temperature and for not addressing failure related properties, such as yielding, crazing and fracture toughness

Polyurethane Foams Loaded with Carbon Nanofibers for Oil Spill Recovery: Mechanical Properties under Fatigue Conditions and Selective Absorption in Oil/Water Mixtures

Marine pollution due to spillage of hydrocarbons represents a well-known current environmental problem. In order to recover the otherwise wasted oils and to prevent pollution damage, polyurethane foams are considered suitable materials for their ability to separate oils from sea-water and for their reusability. In this work we studied polyurethane foams filled with carbon nanofibers, in varying amounts, aimed at enhancing the selectivity of the material towards the oils and at improving the mechanical durability of the foam. Polyurethane-based foams were experimentally characterized by morphological, surface, and mechanical analyses (optical microscopy observation, contact angle measurement, absorption test according to ASTM F726-99 standard and compression fatigue tests according to ISO 24999 standard). Results indicated an increase in hydrophobic behavior and a good oleophilic character of the composite sponges besides an improved selective absorption of the foam toward oils in mixed water/oil media. The optimal filler amount was found to be around 1 wt% for the homogeneous distribution inside the polymeric foam. Finally, the fatigue test results showed an improvement of the mechanical properties of the foam with the growing carbon filler amount

Antiplasticization of polymer materials: Structural aspects and effects on mechanical and diffusion-controlled properties

Antiplasticization of glassy polymers, arising from the addition of small amounts of plasticizer, was examined to highlight the developments that have taken place over the last few decades, aiming to fill gaps of knowledge in the large number of disjointed publications. The analysis includes the role of polymer/plasticizer molecular interactions and the conditions leading to the cross-over from antiplasticization to plasticization. This was based on molecular dynamics considerations of thermal transitions and related relaxation spectra, alongside the deviation of free volumes from the additivity rule. Useful insights were gained from an analysis of data on molecular glasses, including the implications of the glass fragility concept. The effects of molecular packing resulting from antiplasticization are also discussed in the context of physical ageing. These include considerations on the effects on mechanical properties and diffusion-controlled behaviour. Some peculiar features of antiplasticization regarding changes in Tg were probed and the effects of water were examined, both as a single component and in combination with other plasticizers to illustrate the role of intermolecular forces. The analysis has also brought to light the shortcomings of existing theories for disregarding the dual cross-over from antiplasticization to plasticization with respect to modulus variation with temperature and for not addressing failure related properties, such as yielding, crazing and fracture toughness