Synthesis and properties of peroxy derivatives of epoxy resins based on Bisphenol A: Effects of the presence of boron trifluoride ethereate

Oligomers containing peroxy groups have been synthesized on the basis of epoxides reacting with tert–butylhydroperoxide in the presence of boron trifluoride etherate. Dependence of reaction rates upon the quantity of catalyst, temperature and also nature of hydroperoxide has been investigated: A kinetic equation for the process has been formulated and also a kinetic scheme for the reaction taking into account the presence of boron trifluoride etherate is proposed. Structures of the synthesized peroxy oligomers have been confirmed by IR- and NMR-spectroscopy. The reaction initiating properties of the oligomers so synthesized were studied using as the example the styrene polymerization reaction. Electronic Publication     

Mechanical improvement of concrete by irradiated polypropylene fibers

Fiber reinforced concrete (FRC) contains fibers physically mixed with gravel, sand, cement, and water. So far, adequate mechanical performance of FRC has been obtained at high cost and using complex technologies; important here is the geometry and surface characteristics of the polymers. We have modified polymeric‐fiber surfaces by using gamma radiation. Irradiated polypropylene (PP) fibers were submitted to 0, 5, 10, 50, and 100 kGy of gamma irradiation dosages. First, tensile strength of PP fibers was evaluated, and then fibers blended at 0, 1.0, 1.5, and 2.0% in volume with Portland cement, gravel, sand, and water. The highest values of compressive strength were obtained with irradiated‐fibers at 10 kGy and 1.5% in volume of fiber. The result is 101 MPa, as compared to 35 MPa for simple concrete without fibers. POLYM. ENG. SCI., 45:1426–1431, 2005. © 2005 Society of Plastics Engineers     

An optimization of allocation of information granularity in the interpretation of data structures: toward granular fuzzy clustering

Clustering forms one of the most visible conceptual and algorithmic framework of developing information granules. In spite of the algorithm being used, the representation of information granules-clusters is predominantly numeric (coming in the form of prototypes, partition matrices, dendrograms, etc.). In this paper, we consider a concept of granular prototypes that generalizes the numeric representation of the clusters and, in this way, helps capture more details about the data structure. By invoking the granulation-degranulation scheme, we design granular prototypes being reflective of the structure of data to a higher extent than the representation that is provided by their numeric counterparts (prototypes). The design is formulated as an optimization problem, which is guided by the coverage criterion, meaning that we maximize the number of data for which their granular realization includes the original data. The granularity of the prototypes themselves is treated as an important design asset; hence, its allocation to the individual prototypes is optimized so that the coverage criterion becomes maximized. With this regard, several schemes of optimal allocation of information granularity are investigated, where interval-valued prototypes are formed around the already produced numeric representatives. Experimental studies are provided in which the design of granular prototypes of interval format is discussed and characterized.     

Effects of carbon black on tribology of blends of poly(vinylidene fluoride) with irradiated and non-irradiated ultrahigh molecular weight polyethylene

Friction and wear resistance are two vital tribological properties of polymer-based materials but optimization of both is rarely attempted. We have investigated blends of 70 wt% poly(vinylidene fluoride) (PVDF)+30% ultra high molecular weight polyethylene, the latter either un-irradiated or else γ-irradiated. Each sample contained varying amounts of carbon black (CB) and also had a varied degree of crosslinking and irradiation dose. We have determined static and dynamic friction, scratch resistance, and sliding wear in multiple scratching tests. Effects of the irradiation dose and CB concentration have been quantified. The electric conductivity threshold is reflected in a drop of static friction; formation of a continuous phase of the lubricant affects tribology as well as electrical properties—both for irradiated and for un-irradiated samples. The scratch resistance as represented by the residual (healing) depth is affected by crosslinking, by the stage at which irradiation is applied (before or after blending) and by CB addition. Crosslinking by moderate amounts of irradiation provides shallower residual depths while higher doses cause adverse results. Similarly, the CB lubricant can either improve or worsen the scratch resistance. A combination of both approaches produces either better or else worse results than crosslinking alone. Lower friction seems accompanied by higher scratch resistance. A combination of a specific irradiation dose and an optimized CB concentration lowers the sliding wear significantly. Strain hardening in sliding wear determination takes place for all materials studied, irrespective of the extent or radiation-induced crosslinking and of the presence and concentration of carbon black.     

Morphology and thermal properties of two polymethacrylates modified by a polymer liquid crystal

We have studied blends of a polymer liquid crystal (PLC) with poly(cyclohexylethyl methacrylate) (PCHEMA) or poly(cyclohexylpropyl methacrylate) (PCHPMA). The PLC is PET/0.6PHB where PET = poly(ethylene terephthalate), PHB = p-hydroxybenzoic acid and 0.6 is the mole fraction of the latter in the copolymer. The microstructure was studied by scanning electron microscopy (SEM). PCHEMA + PLC (20 wt% of the latter, blend E) has a fine texture with LC islands evenly distributed in the matrix and good adhesion between the phases resulting from their partial miscibility. The PCHPMA + PLC (20 wt% of the latter, blend P) shows only limited compatibility. The SEM results are confirmed by values of the glass transition temperatures T_g determined via thermal mechanical analysis. The T_g value of the blend E is shifted towards the T_g of PLC; T_g of blend P is practically equal to that of PCHPMA. The linear isobaric expansivity α_L values for both blends are lower than the respective values for pure PCHPMA and PCHEMA. Thermal stabilities of the blends determined by thermogravimetry are also better than those of pure polymethacrylates. The temperature of 50% weight degradation for blend E is higher than that for pure PCHEMA by more than 60 K Copyright © 2004 Society of Chemical Industry     

Structural Abnormalities of the Optic Nerve and Retina in Huntington’s Disease Pre-Clinical and Clinical Settings

Huntington’s disease (HD) is a fatal neurodegenerative disorder caused by a polyglutamine expansion in the huntingtin protein. HD-related pathological remodelling has been reported in HD mouse models and HD carriers. In this study, we studied structural abnormalities in the optic nerve by employing Spectral Domain Optical Coherence Tomography (SD-OCT) in pre-symptomatic HD carriers of Caucasian origin. Transmission Electron Microscopy (TEM) was used to investigate ultrastructural changes in the optic nerve of the well-established R6/2 mouse model at the symptomatic stage of the disease. We found that pre-symptomatic HD carriers displayed a significant reduction in the retinal nerve fibre layer (RNFL) thickness, including specific quadrants: superior, inferior and temporal, but not nasal. There were no other significant irregularities in the GCC layer, at the macula level and in the optic disc morphology. The ultrastructural analysis of the optic nerve in R6/2 mice revealed a significant thinning of the myelin sheaths, with a lamellar separation of the myelin, and a presence of myelonoid bodies. We also found a significant reduction in the thickness of myelin sheaths in peripheral nerves within the choroids area. Those ultrastructural abnormalities were also observed in HD photoreceptor cells that contained severely damaged membrane disks, with evident vacuolisation and swelling. Moreover, the outer segment of retinal layers showed a progressive disintegration. Our study explored structural changes of the optic nerve in pre- and clinical settings and opens new avenues for the potential development of biomarkers that would be of great interest in HD gene therapies.     

Assessment of the Influence of the Selected Range of Visible Light Radiation on the Durability of the Gel with Ascorbic Acid and Its Derivative

(1) Background: Depending on the type of hydrophilic polymer used, different types of hydrogels may be chemically stable or may degrade and eventually disintegrate, or dissolve upon exposure to sunlight. Many over-the-counter medications are now stored with a limited control of temperature, humidity and lighting. Therefore, in this study, the photostability of a gel made of cross-linked polyacrylic acid (PA), methylcellulose (MC) and aristoflex (AV) was assessed, and the interaction between the polymers used and ascorbic acid and its ethylated derivative was investigated. (2) Methods: The samples were continuously irradiated at constant temperature for six hours. The stability of the substance incorporated into the gels was assessed using a UV-Vis spectrophotometer. FTIR-ATR infrared spectroscopy was used to measure changes during the exposure. (3) Results: Ascorbic acid completely decomposed between the first and second hours of illumination in all samples. The exception is the preparation based on polyacrylic acid with glycerol, in which the decomposition of ascorbic acid slowed down significantly. After six hours of irradiation, the ethylated ascorbic acid derivative decomposed in about 5% for the polyacrylic acid-based gels and aristoflex, and in the methylcellulose gel it decomposed to about 2%. In the case of ascorbic acid, the most stable formulation was a gel based on polyacrylic acid and polyacrylic acid with glycerol, and in the case of the ethyl derivative, a gel based on methylcellulose. (4) Conclusions: The experiment showed significant differences in the decomposition rate of both compounds, resulting from their photostability and the polymer used in the hydrogel.