Dynamic mechanical properties and morphology of poly(benzyl methacrylate)/epoxy thermoset blends

Poly(benzyl methacrylate) (PBzMA)/epoxy thermoset blends of composition 5 to 25 wt% of PBzMA were prepared curing with 4,4′diaminodiphenylmethane (DDM), to study the influence of composition on the morphology and dynamic‐mechanical properties of the blends. The cured blends are phase separated in PBzMA‐rich phase and epoxy rich‐phase. As the PBzMA content increases, the morphology evolves from nodular, to combined and to totally inverted. The analysis of the α‐mechanical relaxations indicates that the glass transition temperatures (T_g) of PBzMA and of epoxy in the blends are different from the neat polymers, this is related to a noncomplete phase separation on curing. The profiles of the loss modulus‐temperature curves are correlated with the change in morphology that appears increasing the PBzMA content. The storage modulus‐temperature curves are highly dependent on the morphology of the samples. The storage modulus‐composition dependence is predicted using several models for two phase composites. POLYM. ENG. SCI., 50:1820–1830, 2010. © 2010 Society of Plastics Engineers     

Vulcanization of EPDM rubber compounds with and without blowing agents: Identification of reaction events and TTT‐diagram using DSC data

Vulcanization of industrial‐like ethylene propylene diene termonomer rubber compound is studied using a differential scanning calorimetry (DSC). The analysis starts with DSC information to obtain the total transformation heat, followed by an isothermal‐dynamic temperature ramp that captures diffusion‐controlled reaction kinetics. The vulcanization is modeled by an auto‐catalytic Kamal–Sourour model, complemented with a Kissinger model for the prediction of one energy of activation, DiBenedetto's equation for the glass transition temperature, and adjusted reaction constants to include diffusion mechanisms. Two rubber formulations, with and without blowing agents, containing crosslinking agents, primary and secondary accelerators, activators, promoters, and processing aids are studied. The identification and separation of multiple reaction events, occurring during crosslinking of the compound without a blowing agent, is done through a 2^k design of experiments. Time–temperature–transformation (TTT) diagrams are calculated, integrating the kinetic model, thereby delineating processability windows, providing avenues for optimization, design, and online processing control. According to the kinetics and the TTT diagrams, the blowing agent induces several differences to the vulcanization reaction: decreases reaction temperatures while increasing reaction heats. It eliminates the exothermic peak before vulcanization and decreases the fully cured resin's glass transition temperature. Therefore, the presence of the blowing agent drives a shift in the vitrification line, resulting in a reduced operational window. POLYM. ENG. SCI., 55:2073–2088, 2015. © 2014 Society of Plastics Engineers     

COMPARING PRONOUN RESOLUTION ALGORITHMS

This paper discusses the comparative evaluation of five well-known pronoun resolution algorithms conducted with the help of a purpose-built tool for consistent evaluation in anaphora resolution, termed the evaluation workbench. The workbench enables the evaluation and comparison of pronoun resolution algorithms on the basis of the same preprocessing tools and test data. The tool is controlled by the user who can conduct the evaluation according to a variety of parameters, with regard to the types of anaphors and the samples used for evaluation. The extensive comparative evaluation of the pronoun resolution algorithms showed that their performance was significantly lower than the figures reported in the original papers describing the algorithms. The evaluation study concluded that the main reason for this drop in performance is the fact that all algorithms operate in a fully automatic mode.     

Photochemistry and photopolymerization activity of perester derivatives of benzophenone

The spectroscopic properties and photopolymerization activities of a mono- and tetraperester derivative of benzophenone are examined and compared with those of benzophenone. Their photopolymerization activity in methyl methacrylate (MMA) and an ethoxylated bis-phenol-A diacrylate have been studied using a combination of gel permeation chromatography (GPC), and real time Fourier transform infrared spectroscopy (RTFTIR) as well as the commercial pendulum hardness test. Using GPC analysis on the poly(methyl methacrylate) samples the tetra--t-butyl perester derivative of benzophenone is found to give a higher weight average (M_w) and number average (M_n) molecular weight polymer than that produced using the mono perester. For the two peresters of benzophenone photopolymerization efficiency using real time FTIR increases with increasing initiator concentration, and no self-termination is observed up to 0.75% w/w concentration with the mono perester derivative being the more efficient initiator. Similar results were obtained using the commercial pendulum hardness tester with a triacrylate/epoxyurethane acrylate resin with benzophenone exhibiting the lowest activity. Photopolymerization activities of the initiators correlate well with their spectroscopic properties. The phosphorescence quantum yield is higher for the monoperester than the tetraperester derivative and is consistent with a shorter lifetime and lower photolysis quantum yields in 2-propanol. Compared with benzophenone, phosphorescence analysis indicates that the perester groups impart a degree of charge-transfer content to the molecule which is consistent with the degree of substitution. Ketyl radical formation on microsecond flash photolysis follows the order benzophenone > mono- > tetraperester derivative and is consistent with the phosphorescence quantum yields. On nanosecond laser flash photolysis in nitrogen-saturated acetonitrile, triplettriplet absorption is extremely weak for both the perester derivatives, being stronger for the monoperester.     

Patent families: When do different definitions really matter?

Data on patent families is used in economic and statistical studies for many purposes, including the analysis of patenting strategies of applicants, the monitoring of the globalization of inventions and the comparison of the inventive performance and stock of technological knowledge of different countries. Most of these studies take family data as given, as a sort of black box, without going into the details of their underlying methodologies and patent linkages. However, different definitions of patent families may lead to different results. One of the purposes of this paper is to compare the most commonly used definitions of patent families and identify factors causing differences in family outcomes. Another objective is to shed light into the internal structure of patent families and see how it affects patent family outcomes based on different definitions. An automated characterization of the internal structures of all extended families with earliest priorities in the 1990s, as recorded in PATSTAT, found that family counts are not affected by the choice of patent family definitions in 75% of families. However, different definitions may really matter for the 25% of families with complex structures and lead to different family compositions, which might have an impact, for instance, on econometric studies using family size as a proxy of patent value.     

The multifinality constraints effect: How goal multiplicity narrows the means set to a focal end.

In the presence of several objectives, goal conflict may be avoided via multifinal means, which advance all of the active goals at once. Because such means observe multiple constraints, they are fewer in number than the unconstrained means to a single goal. Five experimental studies investigated the process of choosing or generating such means for multiple goals. We found that the simultaneous activation of multiple goals restricted the set of acceptable means to ones that benefitted (or at least, did not harm) the entire set of active goals. Two moderators of this phenomenon were identified: (a) the feasibility of identifying multifinal means, which was dependent on the relations between the different active goals, and (b) the enhanced importance of the focal goal, which resulted in the inhibition of its alternatives and the consequent relaxation of multifinality constraints. (PsycINFO Database Record (c) 2011 APA, all rights reserved)     

Synergistic bactericidal activity of Ag-TiO₂ nanoparticles in both light and dark conditions

High-throughput screening was employed to evaluate bactericidal activities of hybrid Ag-TiO? nanoparticles comprising variations in TiO? crystalline phase, Ag content, and synthesis method. Hybrid Ag-TiO? nanoparticles were prepared by either wet-impregnation or UV photo deposition onto both Degussa P25 and DuPont R902 TiO? nanoparticles. The presence of Ag was confirmed by ICP, TEM, and XRD analysis. The size of Ag nanoparticles formed on anatase/rutile P25 TiO? nanoparticles was smaller than those formed on pure rutile R902. When activated by UV light, all hybrid Ag-TiO? nanoparticles exhibited stronger bactericidal activity than UV alone, Ag/UV, or UV/TiO?. For experiments conducted in the dark, bactericidal activity of Ag-TiO? nanoparticles was greater than either bare TiO? (inert) or pure Ag nanoparticles, suggesting that the hybrid materials produced a synergistic antibacterial effect unrelated to photoactivity. Moreover, less Ag(+) dissolved from Ag-TiO? nanoparticles than from Ag nanoparticles, indicating the antibacterial activities of Ag-TiO? was not only caused by releasing of toxic metal ions. It is clear that nanotechnology can produce more effective bactericides; however, the challenge remains to identify practical ways to take advantage of these exciting new material properties.     

Unsaturated polyester–poly(ε‐caprolactone) hybrid nanocomposites: Thermal–mechanical properties

This paper reports on the thermal behavior and mechanical properties of nanocomposites based on unsaturated polyester resin (UP) modified with poly(ɛ‐caprolactone) (PCL) and reinforced with an organically modified clay (cloisite 30B). To optimize the dispersion of 30B and the mixing of PCL in the UP resin, two different methods were employed to prepare crosslinked UP–PCL‐30B hybrid nanocomposites. Besides, two samples of poly(ɛ‐caprolactone) of different molecular weight (PCL2: M_n = 2.10³g.mol⁻¹ and PCL50: M_n = 5.10⁴g.mol⁻¹) were used at several concentrations (4, 6, 10 wt%). The 30B concentration was 4 wt% in all the nanocomposites. The morphology of the samples was studied by scanning electron microscopy (SEM). The analysis of X‐ray patterns reveals that intercalated structures have been found for all ternary nanocomposites, independently of the molecular weight, PCL concentration and the preparation method selected. A slight rise of the glass transition temperature, T_g, is observed in UP/PCL/4%30B ternary nanocomposites regarding to neat UP. The analysis of the tensile properties of the ternary (hybrid) systems indicates that UP/4%PCL2/4%30B nanocomposite improves the tensile strength and elongation at break respect to the neat UP while the Young modulus remains constant. POLYM. COMPOS., 35:827–838, 2014. © 2013 Society of Plastics Engineers     

Characterization of a novel protease from Bacillus cereus and evaluation of an eco‐friendly hydrolysis of a brewery byproduct

Proteases and proteolytic enzymes constitute one of the most important groups of enzymes and are attracting worldwide attention in attempts to exploit their physiological and biotechnological applications. In this study, partial purifications and biochemical and antimicrobial characterizations of a protease from Bacillus cereus spp., originally isolated from fermented cabbage, were carried out. The crude extract obtained after purification, involving ammonium sulphate precipitation and dialysis, was designated as a partially purified protease (PPP). The obtained PPP had a specific activity of 0.395–2.539 U/g at 32 °C, with maximum activities for the fractions precipitated at 60 and 80% ammonium sulphate. The PPP activity ranged between 20 and 55 °C, with an optimum temperature at 40 °C. At 60 °C, the PPP retained more than 30% of its activity. The optimum pH for the PPP was achieved at pH 9, indicating the alkaline source of the enzyme. Protease production was specifically dependent on the calcium concentration in the culture medium. Also the robustness of the protease on brewer's spent grain hydrolysis was demonstrated. This suggests a potential eco‐friendly application of the enzyme. Finally, it was found that the PPP inhibited the growth of Escherichia coli O157:H7. This novel property of the PPP liberated by the B. cereus spp. could provide important future benefits to industry. Copyright © 2015 The Institute of Brewing & Distilling