Sergei Nazarenko

Oxygen barrier properties of crystallized and talc-filled poly(ethylene terephthalate)

The improvement in oxygen barrier properties of poly(ethylene terephthalate) (PET) by incorporation of an impermeable phase such as crystallinity or talc platelets was examined. Crystallinity was induced by crystallization from the glassy state (cold crystallization). Microlayering was used to create talc-filled structures with controlled layer architecture. The reduction of permeability in crystallized and talc-filled PET was well described by Nielsens model. Changes in permeability of crystalline PET could not be ascribed to the filler effect of crystallites only. Our data on solubility, obtained on the basis of measurements of the oxygen transport coefficients, confirmed a previous finding that the amorphous phase density of PET decreases upon crystallization. The data were amenable to interpretation by free volume theory. Talc-filled materials processed by different methods showed the same permeability; however, much better mechanical properties were achieved by microlayering.

Spray-deposition and photopolymerization of organic-inorganic thiol-ene resins for fabrication of superamphiphobic surfaces.

Superamphiphobic surfaces, exhibiting high contact angles and low contact angle hysteresis to both water and low surface tension liquids, have attracted a great deal attention in recent years because of the potential of these materials in practical applications such as liquid-resistant textiles, self-cleaning surfaces, and antifouling/anticorrosion coatings. In this work, we present a simple strategy for fabricating of superamphiphobic coatings based on photopolymerization of hybrid thiol-ene resins. Spray-deposition and UV photopolymerization of thiol-ene resins containing hydrophobic silica nanoparticles and perfluorinated thiols provide a multiscale topography and low-energy surface that endows the surface with superamphiphobicity. The wettability and chemical composition of the surfaces were characterized by contact-angle goniometry and X-ray photoelectron spectroscopy, respectively. The hierarchical roughness features of the thiol-ene surfaces were investigated with field-emission scanning electron microscopy. Droplet impact and sandpaper abrasion tests indicate the coatings respectively possess a robust antiwetting behavior and good mechanical durability.

Characterization of mouthguard materials: Thermal properties of commercialized products

OBJECTIVES Several mechanisms have been purported to describe how mouthguards protect the orofacial complex against injury. As the properties needed for these mechanisms to be effective are temperature and frequency dependent, the specific aim of this study was to provide a comprehensive thermal characterization of commercial mouthguard materials. METHODS Five commercially representative thermoplastic mouthguard materials (Essix Resin, Erkoflex, Proform-regular, Proform-laminate, and Polyshok) were tested. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) techniques were implemented to measure thermal transitions and mechanical properties. Measurements were conducted three times per sample. One-way ANOVA and one-sample t-tests were used to test for differences between commercial products on selected mean thermal property values. RESULTS The DSC measurements indicated no differences between commercial materials for mean glass transition (p=0.053), onset melt (p=0.973), or peak melt (p=0.436) temperatures. Likewise, DMA measurements revealed no differences between commercial materials for the mean glass transition (p=0.093), storage modulus (p=0.257), or loss modulus (p=0.172) properties, respectively. The one-sample t-tests revealed that glass transition temperatures were different from intra-oral temperature (p<0.005) for all materials. SIGNIFICANCE Commercialized mouthguard materials are sensitive to repetitive heating and cooling cycles, prolonged thermal treatment, and have glass transitions well below their end-use intra-oral temperature. As such, these materials are functioning as elastomers and not optimal mechanical damping materials. Dental clinicians, healthcare practitioners, or end-users should be aware that these materials are at best problematic with respect to this protective mechanism.

Synthesis and Characterization of Styrene-Butadiene Rubber-Clay Nanocomposites With Enhanced Mechanical and Gas Barrier Properties

Abstract Five styrene-butadiene rubber (SBR)/clay nanocomposite or hybrid systems were synthesized via mechanical mixing of SBR using a Brabender mixer and a 2-roll mill in the presence of unmodified sodium montmorillonite (Na-MMT) clay, MMT modified with octadecylamine (C18amine), MMT modified with a zwitterionic surfactant, octadecyldimethyl betaine (C18DMB), and MMT modified with a polymerizable cationic surfactant, vinylbenzyl octadecyldimethyl ammonium chloride (VODAC) or vinylbenzyl dodecyldimethyl ammonium chloride (VDAC). The surfactant chain length and functional groups affected the dispersion of clay nanolayers in the matrix and the overall properties of the nanocomposites. X-ray diffraction (XRD) revealed peaks corresponding to intercalated structures; transmission electron microscopy (TEM) observations agreed well with XRD assessment of the composites. SBR/VODAC-MMT system exhibited the best dispersion among the nanocomposites studied. VODAC-MMT was partially exfoliated in SBR matrix and the a...

Fast Self-Healing of Polyelectrolyte Multilayer Nanocoating and Restoration of Super Oxygen Barrier

A self-healable gas barrier nanocoating, which is fabricated by alternate deposition of polyethyleneimine (PEI) and polyacrylic acid (PAA) polyelectrolytes, is demonstrated in this study. This multilayer film, with high elastic modulus, high glass transition temperature, and small free volume, has been shown to be a super oxygen gas barrier. An 8-bilayer PEI/PAA multilayer assembly (≈700 nm thick) exhibits an oxygen transmission rate (OTR) undetectable to commercial instrumentation (<0.005 cc (m-2 d-1 atm-1 )). The barrier property of PEI/PAA nanocoating is lost after a moderate amount of stretching due to its rigidity, which is then completely restored after high humidity exposure, therefore achieving a healing efficiency of 100%. The OTR of the multilayer nanocoating remains below the detection limit after ten stretching-healing cycles, which proves this healing process to be highly robust. The high oxygen barrier and self-healing behavior of this polymer multilayer nanocoating makes it ideal for packaging (food, electronics, and pharmaceutical) and gas separation applications.

Thermal Conductivity Performance of Polypropylene Composites Filled with Polydopamine-Functionalized Hexagonal Boron Nitride

Mussel-inspired approach was attempted to non-covalently functionalize the surfaces of boron nitride (BN) with self-polymerized dopamine coatings in order to reduce the interfacial thermal barrier and enhance the thermal conductivity of BN-containing composites. Compared to the polypropylene (PP) composites filled with pristine BN at the same filler content, thermal conductivity was much higher for those filled with both functionalized BN (f-BN) and maleic anhydride grafted PP (PP-g-ma) due to the improved filler dispersion and better interfacial filler-matrix compatibility, which facilitated the development of more thermal paths. Theoretical models were also applied to predict the composite thermal conductivity in which the Nielsen model was found to fit well with the experimental results, and the estimated effective aspect ratio of fillers well corresponded to the degree of filler aggregation as observed in the morphological study.

Influence of cyclobutane segments in cycloaliphatic decahydronaphthalene-containing copolyesters

Melt transesterification polycondensation enabled the incorporation of rigid, cycloaliphatic diols (2,2,4,4-tetramethylcyclobutane-1,3-diol) into decahydronaphthalene-containing copolyesters, which resulted in amorphous, optically clear materials. Glass transition temperatures approached 155°C and followed predictable trends using the Fox equation for randomly sequenced copolymers. Dynamic mechanical analysis identified several low-temperature relaxations attributed to the complex motions of the decahydronaphthalate and cyclohexyl rings within the polymer backbone. Furthermore, incorporating cyclobutane rings suppressed the low-temperature local mobility, revealing a strong structural dependence on these relaxations. The rheological simplicity of these nonassociating chains permitted analysis over a large frequency window using time–temperature superposition. As a result, the characteristic relaxation times provided insight into chain dynamics and the propensity for chain entanglements. Finally, positron annihilation lifetime spectroscopy probed hole-free volume and reinforced the trends observed with oxygen permeability measurements.

Unraveling substituent effects on the glass transition temperatures of biorenewable polyesters

Converting biomass-based feedstocks into polymers not only reduces our reliance on fossil fuels, but also furnishes multiple opportunities to design biorenewable polymers with targeted properties and functionalities. Here we report a series of high glass transition temperature (Tg up to 184 °C) polyesters derived from sugar-based furan derivatives as well as a joint experimental and theoretical study of substituent effects on their thermal properties. Surprisingly, we find that polymers with moderate steric hindrance exhibit the highest Tg values. Through a detailed Ramachandran-type analysis of the rotational flexibility of the polymer backbone, we find that additional steric hindrance does not necessarily increase chain stiffness in these polyesters. We attribute this interesting structure-property relationship to a complex interplay between methyl-induced steric strain and the concerted rotations along the polymer backbone. We believe that our findings provide key insight into the relationship between structure and thermal properties across a range of synthetic polymers.Biorenewable feedstocks allow the design of polymers with targeted properties and functionalities. Here the authors report a series of high glass transition temperature sugar-based polyesters and investigate how substituents affect their thermal properties.

Thermotropic, side-chain ordered polymeric coatings: gas permeability switching via a thermal stimulus

Rapid access to large areas of stimuli-responsive materials is attractive in the field of membrane science for purification systems and molecular valves. Thermotropic liquid crystalline (LC) systems show sharp property changes through the smectic–LC transition induced by temperature. Comparison of similar amorphous and liquid crystalline systems allows for the elucidation of the characteristics of the LC phase. Lightly crosslinked C6F13 and C8F17 perfluorinated side-chain acrylate networks were UV cured as thin films resulting in amorphous and thermotropic liquid crystalline thin films, respectively. Thermal and morphological characterization indicates a restructuring of the liquid crystalline phase through the isotropic transition giving rise to an increase in transport and free volume properties. The amorphous film showed no dramatic change in transport or free volume properties.