Properties of poly(ethylene terephthalate) containing epoxy‐functionalized polyhedral oligomeric silsesquioxane

Poly(ethylene terephthalate) (PET) containing epoxy‐functionalized polyhedral oligomeric silsesquioxane (POSS) was prepared by melt‐mixing and in situ polymerization methods. The melt‐mixed composite showed phase separation while the in situ polymerized composite did not, based on SEM characterization. During melt mixing, the reaction between the epoxy groups of POSS and hydroxyl groups of PET occurred, based on DSC results. DSC results on the in situ polymerization product showed formation of a lower‐melting component compared with PET. The tensile strength and modulus of the melt‐mixed composite fiber decreased compared with those properties of PET, whereas those of the in situ polymerized composite showed slightly higher values than PET despite the relatively small amounts (1 wt%) of POSS used. Dynamic mechanical analysis results showed an increase in storage modulus for the in situ polymerized composite of POSS and PET compared with PET over the temperature range of 40 °C to 140 °C. Copyright © 2004 Society of Chemical Industry     

Thermal conductivity of a clay-based aerogel

Aerogel materials exhibit superior thermal insulation characteristics due largely to their highly porous internal structure. A recently developed class of montmorillonite clay-based aerogels provides the attractive thermal properties of traditional aerogel materials using constituents that are chemically benign and abundantly available. Results are compared for aerogels made from clay alone and those with polyvinyl alcohol introduced during processing. Results demonstrate that as well as strength advantages, the addition of the polymer also leads to a reduction in thermal conductivity. Experimental thermal conductivity data as well as a model to describe the mechanisms involved in impeding thermal transport are presented.     

Influence of carbon support microstructure on the polarization behavior of a polymer electrolyte membrane fuel cell membrane electrode assemblies

The influence of carbon support morphology on the polarization behavior of a PEM fuel cell membrane electrode assembly has been investigated in this communication. Nanometer sized platinum electrocatalyst particles were deposited on lower surface area fibrous (carbon nanofibers) and particulate carbon supports (carbon blacks) by the well-documented ethylene glycol route for supported electrocatalyst synthesis. These supported catalyst systems were subsequently utilized to prepare catalyst inks and membrane electrode assemblies (MEA) in conjunction with a perflurosulfonated ionomeric membrane-Nafion^®. Level of liquid Nafion binder in the supported catalyst inks was varied and the ramifications of such a variation on polarization behavior of the MEA determined. The trend in polarization performance was found to be independent of the carbon support morphology in the various ink compositions. The two varieties of carbon supports were also mixed together in various weight ratios and platinum was deposited by the glycol method. Key parameters such as the platinum content on carbon and platinum particle size were determined to be independent of the nature of the supports on which the particles had been deposited. The results indicate that lower surface area carbon supports of vastly contrasting morphologies can be interchangeably employed as catalyst support materials in a PEM fuel cell MEA.     

Complex admittance of AgI—Ag oxysalt high conducting solids

Complex admittance determination allowed it to be established that the high ionic conductivity of the 4 AgIAg₂XO₄ (X  W, Mo, Cr) solids does not depend on the granular arrangement of the investigated salt powders: it was indeed found that the overall conductance of the cells increased with decreasing grain-size probably because both intergranular contacts and grain-boundary conduction play some role in the ionic migration; however this dependence, though evident, was not so large as expected for a dominant intergranular or grain boundary migration process.     

Surface of poly(ethylene terephthalate/isophthalate) copolyesters studied by atomic force microscopy

An atomic force microscope (AFM) operating in Tapping™ and contact modes has been used to study the surface topography and the molecular organization of poly(ethylene terephthalate) (PET) films containing 2% (PET‐2I) and 10% (PET‐10I) isophthalate, and of injection/blow molded bottles containing 2.6% (PET‐2.6I) and 10% isophthalate. Large‐scale (15‐μm × 15‐μm) AFM images have shown that both surfaces are fairly flat and heterogeneous in nature, often containing inclusions. Whereas the PET surface appears to be formed mainly by microfibrils, isophthalic acid (IPA) incorporation at the 2–10 mol % level gives the surface a granular appearance. The IPA‐containing PET surfaces are frequently coated by a lacelike film consisting of submicron “beads” joined together by filaments. These “strings of beads” form bundles and can also connect bundles. AFM images of PET‐2I closely resemble those generated for PET films. By contrast, the lacelike structure becomes a dominant feature of the PET‐10I surface. The level of inclusions observed on film surfaces appears to correlate with the levels of extractable oligomers present in the polymers. Nanometer‐scale AFM images of PET‐10I exhibit surfaces composed of short stacks of plates or rods, with 30–50‐nm voids or pores between these stacks. Whereas surface deposits of what we suggest is most likely an oligomer correlates with isophthalate concentration, we see no gross structural features in PET‐2I and PET‐10I that explain the observed improvement in gas diffusion barrier in these polymers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 750–762, 2001     

Potential of Biofermentative Unsulfated Chondroitin and Hyaluronic Acid in Dermal Repair

Chondroitin obtained through biotechnological processes (BC) shares similarities with both chondroitin sulfate (CS), due to the dimeric repetitive unit, and hyaluronic acid (HA), as it is unsulfated. In the framework of this experimental research, formulations containing BC with an average molecular size of about 35 KDa and high molecular weight HA (HHA) were characterized with respect to their rheological behavior, stability to enzymatic hydrolysis and they were evaluated in different skin damage models. The rheological characterization of the HHA/BC formulation revealed a G’ of 92 ± 3 Pa and a G″ of 116 ± 5 Pa and supported an easy injectability even at a concentration of 40 mg/mL. HA/BC preserved the HHA fraction better than HHA alone. BTH was active on BC alone only at high concentration. Assays on scratched keratinocytes (HaCaT) monolayers showed that all the glycosaminoglycan formulations accelerated cell migration, with HA/BC fastening healing 2-fold compared to the control. In addition, in 2D HaCaT cultures, as well as in a 3D skin tissue model HHA/BC efficiently modulated mRNA and protein levels of different types of collagens and elastin remarking a functional tissue physiology. Finally, immortalized human fibroblasts were challenged with TNF-α to obtain an in vitro model of inflammation. Upon HHA/BC addition, secreted IL-6 level was lower and efficient ECM biosynthesis was re-established. Finally, co-cultures of HaCaT and melanocytes were established, showing the ability of HHA/BC to modulate melanin release, suggesting a possible effect of this specific formulation on the reduction of stretch marks. Overall, besides demonstrating the safety of BC, the present study highlights the potential beneficial effect of HHA/BC formulation in different damage dermal models.     

Evaluation of electrochemical performance for surface-modified carbons as catalyst support in polymer electrolyte membrane (PEM) fuel cells

The electrochemical performance of platinum (Pt) catalyst deposited on various functionalized carbon supports was investigated and compared with that of a commercial catalyst, Pt on Vulcan XC-72 carbon. The supports employed were graphitic or amorphous with a wide range of surface areas. Cyclic voltammetry (CV) and rotating disk electrode (RDE) studies on the supported catalysts indicated equivalent platinum catalyst activities. Fuel cell performance was determined for membrane electrode assemblies (MEA) fabricated from the supported catalysts. The use of high surface area supports did not necessarily translate into a higher electrochemical utilization of platinum. Electrochemical impedance spectroscopy (EIS) measurements indicated lower ohmic losses for low surface area carbon MEAs. This is explained by the supported catalyst electrode microstructures and their intrinsic resistivities. Correlation of all data indicates that for low surface carbons, nature of the support does not significantly affect the Pt catalytic activity. The influence of the support is more critical when high surface area carbons are used because of the vastly different electrode morphology and resistivity.     

Novel Absorbent Materials Created via Ice Templating

Ice‐templated aerogels made from water soluble/dispersible raw materials are formed through an environmentally friendly freeze‐drying process. The structures that result from ice templating are capable of absorbing liquids into their large void volume. The effects of polymer chemistry and material loading on the absorption into the dried materials are studied. Low‐density samples were able to absorb liquids rapidly but the liquid‐saturated structures lacked mechanical integrity. The higher‐density samples absorbed liquids more slowly and again retained little structural integrity. The addition of fibers and firing of low‐density clay aerogels into ceramics provide multiple routes to creating structures exhibiting rapid absorption and a rigid, stable structure when saturated.

     

Molecular Fingerprint of Human Pathological Synoviocytes in Response to Extractive Sulfated and Biofermentative Unsulfated Chondroitins

Pharma-grade extractive chondroitin sulfate (CS) is widely used for osteoarthritis (OA) treatment. Recently, unsulfated biofermentative chondroitin (BC) proved positive effects in OA in vitro model. This study, based on primary pathological human synoviocytes, aimed to analyze, by a multiplex assay, a panel of OA-related biomarkers in response to short-term treatments with bovine (CS_b), pig (CS_p) and fish (CS_f) chondroitins, in comparison to BC. As expected, all samples had anti-inflammatory properties, however CS_b, CS_f and especially BC affected more cytokines and chemokines. Based on these results and molecular weight similarity, CS_f and BC were selected to further explore the synoviocytes’ response. In fact, Western blot analyses showed CS_f and BC were comparable, downregulating OA-related biomarkers such as the proteins mTOR, NF-kB, PTX-3 and COMP-2. Proteomic analyses, performed by applying a nano-LC-MS/MS TMT isobaric labelling-based approach, displayed the modulation of both common and distinct molecules to chondroitin treatments. Thus, CS_f and BC modulated the biological mediators involved in the inflammation cascade, matrix degradation/remodeling, glycosaminoglycans’ synthesis and cellular homeostasis. This study helps in shedding light on different molecular mechanisms related to OA disease that may be potentially affected not only by animal-source chondroitin sulfate but also by unsulfated biofermentative chondroitin.     

Oil absorption performance of polymer/clay aerogel materials

Oil absorption performance of aerogels produced from poly(amide‐imides), epoxies, and acrylic polymers were dependent upon freezing conditions, which in turn dictated solid state structures of these materials. Denser aerogels have less void space, and are more efficient at filling that space with oil, supporting the hypothesis that capillary spacing plays a vital role in determining oil absorption. Lower molecular weight epoxy‐based polymers produced aerogels with small capillary radii, again allowing increasing amounts of the liquid to penetrate between the aerogel layers. Aerogels produced from acrylic emulsions outperformed the other two systems tested in terms of volume per volume absorption. The initial difficulty with these materials, the fact that they still retain some hydrophilicy and absorb water, was overcome by simple post curing treatment, which was able to reduce water absorption to near zero levels. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45844.