Studies of tetrazoles as rubber chemicals. II. Reactivities and antioxidation activities of reactive antioxidants based on tetrazoles

The chemical reactivities of novel reactive antioxidants based on tetrazoles for carbon–carbon double bonds of liquid polybutadiene and their antioxidation activities toward isoprene rubber were evaluated. These antioxidants, i.e., 2-substituted phenyl-5-(3′,5′ -di-tert-butyl-4′-hydroxyphenyl)tetrazoles (PHPT), were pyrolyzed in liquid polybutadiene at 160–170°C for 30 min to attach to rubber in extents of 61–85% of the nitrileimines formed from PHPT by 1,3-dipolar addition reaction. The reactivities of PHPT followed the order p-Cl > m-Cl > H > p-CH₃ > m-CH₃, p-OC₂H₅, suggesting that PHPT reacts with diene rubber in electrophilic reaction and p-derivatives exhibit higher contents of binding than m-derivatives due to steric hindrance. From oxygen absorption data, the antioxidation activities of PHPT for isoprene rubber vulcanizates followed the order m-Cl, m-CH₃ > H, p-Cl, p-Cl, p-CH₃ > p-OC₂H₅. Isoprene rubber vulcanizates, obtained after pretreatment with PHPT by heating, were extracted with acetone, followed by aging to show that there was good retention and appreciable antioxidation activities of PHPT, especially, p-CH₃ and p-Cl substituted PHPT.     

The European,Japanese and US protective helmet,gloves and boots for firefighters: thermoregulatory and psychological evaluations

The purpose of this study was to investigate the physiological and subjective responses of the European, Japanese (JPN) and US firefighters' helmet, gloves and boots for international standardisation. Three experimental conditions were evaluated (clothing mass: 9.4, 8.2 and 10.1 kg for the three conditions, respectively) at the air temperature of 32°C and 60% relative humidity. The results showed that there was no significant difference among the three conditions in oxygen consumption, heart rate, total sweat rate, rectal temperature and mean skin temperature, whereas peripheral temperatures and subjective perceptions were lower in the JPN condition than in the other conditions (P < 0.05). These results indicate that a 0.5-kg reduction in helmet mass and a 1.1-kg reduction in boot mass during exercise resulted in a significant decrease in head and leg temperatures and subjective perceptions, while a 1.9-kg reduction in total clothing mass had insignificant influences on the metabolic burden and overall body temperature.     

Unified reliability estimation and management of NoC based chip multiprocessors

We present a new architecture level unified reliability evaluation methodology for chip multiprocessors (CMPs). The proposed reliability estimation (REST) is based on a Monte Carlo algorithm. What distinguishes REST from the previous work is that both the computational and communication components are considered in a unified manner to compute the reliability of the CMP. We utilize REST tool to develop a new dynamic reliability management (DRM) scheme to address time-dependent dielectric breakdown and negative-bias temperature instability aging mechanisms in network-on-chip (NoC) based CMPs. Designed as a control loop, the proposed DRM scheme uses an effective neural network based reliability estimation module. The neural-network predictor is trained using the REST tool. We investigate how system’s lifetime changes when the NoC as the communication unit of the CMP is considered or not during the reliability evaluation process and find that differences can be as high as 60%. Full-system based simulations using a customized GEM5 simulator show that reliability can be improved by up to 52% using the proposed DRM scheme in a best-effort scenario with 2–9% performance penalty (using a user set target lifetime of 7 years) over the case when no DRM is employed.     

Preparation and characterization of electroplated amorphous gold-nickel alloy film for electrical contact applications

A process for electroplating amorphous gold-nickel alloy with the atomic ratio of unity was developed. The plating bath was prepared by adding potassium cyanoaurate(I) into a known plating bath which produces amorphous nickel-tungsten alloy. At a sufficiently high gold concentration, the alloy deposit did not contain any tungsten. The amorphous nature of the Au-Ni alloy produced in the new bath was confirmed by using TEM and THEED. Hardness, resistivity, and contact resistance of this new alloy were determined, and the results are discussed for applications as an electrical contact material.     

Oligomer-Rich Fraction from Polydisperse Sample of Poly(bis(β-phenoxyethoxy)phosphazene)

Poly[bis(-phenoxyethoxy)phosphazene] [PBPEP] had been shown in our previous paper to be a very useful polymer for investigating the crystallization mechanism of polymers, as the crystallization rate of PBPEP is extraordinarily small when isothermally crystallized from the melt. The crystallization of the low molecular weight oligomers of PBPEP was first studied in comparison to the high molecular weight polymers. The oligomer-rich fraction was obtained by fractionation of the as-polymerized sample, which had a broad molecular weight distribution. The fractions thus obtained were characterized by solution viscometry and size exclusion chromatography. The melting temperature and the growth rate of the spherulite from the melt were investigated by differential scanning calorimetry and optical microscopy. The growth rate was one or two orders of magnitude smaller in the oligomer-rich fraction than in the other high molecular weight fractions. A collapsed spherulite appeared in the oligomer-rich fraction at high crystallization temperatures. It is speculated that in the oligomer-rich fraction there is an excess free energy due to defects in the crystal phase. This defect is considerably larger in the oligomer-rich fraction than in the other fractions because a large quantity of short length chains is present.     

Effects of amino acid replacements around the reactive site of chicken ovomucoid domain 3 on the inhibitory activity toward chymotrypsin and trypsin

We have previously shown that replacing the P1-site residue(Ala) of chicken ovomucoid domain 3 (OMCHI3) with a Met or Lysresults in the acquisition of inhibitory activity toward chymotrypsinor trypsin, respectively. However, the inhibitory activitiesthus induced are not strong. In the present study, we introducedadditional amino acid replacements around the reactive siteto try to make the P1-site mutants more effective inhibitorsof chymotrypsin or trypsin. The amino acid replacement AspTyrat the P2' site of OMCHI3(P1Met) resulted in conversion to a35000-fold more effective inhibitor of chymotrypsin with aninhibitor constant (K_i) of 1.17x10^–11 M. The K_i valueof OMCHI3(P1Met, P2'Ala) indicated that the effect on the interactionwith chymotrypsin of removing a negative charge from the P2'site was greater than that of introducing an aromatic ring.Similarly, enhanced inhibition of trypsin was observed whenthe AspTyr replacement was introduced into the P2' site of OMCHI3(P1Lys).Two additional replacements, AspAla at the P4 site and ArgAlaat the P3' site, made the mutant a more effective inhibitorof trypsin with a K_i value of 1.44x10^–9 M. By contrast,ArgAla replacement at the P3' site of OMCHI3(P1Met, P2'Tyr)resulted in a greatly reduced inhibition of chymotrypsin, andAspAla replacement at the P4 site produced only a small changewhen compared with a natural variant of OMCHI3. These resultsclearly indicate that not only the P1-site residue but alsothe characteristics, particularly the electrostatic properties,of the amino acid residues around the reactive site of the proteaseinhibitor determine the strength of its interactions with proteases.Furthermore, amino acids with different characteristics arerequired around the reactive site for strong inhibition of chymotrypsinand trypsin.     

Effect of crosslinkers on the preparation and properties of ETFE‐based radiation‐grafted polymer electrolyte membranes

This study concerns a comparative study of three crosslinkers, divinylbenzene (DVB), 1,2‐bis(p,p‐vinylphenyl)ethane (BVPE), and triallyl cyanurate (TAC) crosslinked poly(ethylene‐co‐tetrafluoroethylene) (ETFE)‐based radiation‐grafted membranes, which were prepared by radiation grafting of p‐methylstyrene onto ETFE films and subsequent sulfonation. The effect of the different types and contents of the crosslinkers on the grafting and sulfonation, and the properties such as water uptake, proton conductivity, and thermal/chemical stability of the resulting polymer electrolyte membranes were investigated in detail. Introducing crosslink structure into the radiation‐grafted membranes leads to a decrease in proton conductivity due to the decrease in water uptake. The thermal stability of the crosslinked radiation‐grafted membranes is also somewhat lower than that of the noncrosslinked one. However, the crosslinked radiation‐grafted membranes show significantly higher chemical stability characterized in the 3% H₂O₂ at 50°C. Among the three crosslinkers, the DVB shows a most pronounced efficiency on the crosslinking of the radiation‐grafted membranes, while the TAC has no significant influence; the BVPE is a mild and effective crosslinker, showing the moderate influence between the DVB and TAC crosslinkers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4565–4574, 2006     

Fractionation and enrichment of CLA isomers by selective esterification with Candida rugosa lipase

A commercial product of CLA contains almost equal amounts of cis-9,trans-11 (c9,t11)-CLA and trans-10,cis-12 (t10,c12)-CLA. We attempted to enrich the two isomers by a two-step selective esterification using Candida rugosa lipase that acted on c9,t11-CLA more strongly than on t10,c12-CLA. An FFA mixture containing CLA isomers was esterified with an equimolar amount of lauryl alcohol in a mixture of 20% water and the lipase. When the esterification of total FA reached 50%, two isomers were fractionated in a good yield: t10,c12-CLA was enriched in FFA, and c9,t11-CLA was recovered in lauryl esters. The FFA were esterified again to enrich t10,c12-CLA. At 27.3% esterification of total FA, the t10,c12-CLA content in FFA increased to 64.8 wt% with 89.3% recovery: The ratio of the content of t10,c12-CLA to that of two isomers was 95.9%. Lauryl esters obtained by the single esterification were employed for enrichment of c9,t11-CLA. After the esters were hydrolyzed, the resulting FFA were esterified again with lauryl alcohol. At 62.0% esterification of total FA, the c9,t11-CLA content in lauryl esters increased to 73.3 wt% with 79.4% recovery: The ratio of the content of c9,t11-CLA to that of two isomers was 95.6%. In a 600-g-scale purification, molecular distillation was effective in separating the reaction mixture into lauryl alcohol, FFA, and lauryl ester fractions.     

Preparation of π-conjugated polymers consisting of 2-decylbenzimidazole and thiophene units and chemical properties of the polymers

Polycondensation by Stille coupling of 2-decyl-4,7-dibromobenzimidazoles and N-methyl-2-decyl-4,7-dibromobenzimidazole with 2,5-bis(trimethylstannyl)thiophene and 5,5′-bis(trimethylstannyl)-2,2′-bithiophene gave the corresponding π-conjugated polymers, poly(2-decylbenzimidazole-4,7-diyl-thiophene-2,5-diyl) 1b, poly(2-decylbenzimidazole-4,7-diyl-bithiophene-2,5-diyl) 1c and poly(N-methyl-2-decylbenzimidazole-4,7-diyl-thiophene-2,5-diyl) 2b, in 98-99% yields. The polymers 1b and 2b were fully soluble in CF₃COOH, and partially soluble in DMF (about 60 and 40% for 1b and 2b, respectively) and NMP (about 70 and 40%, respectively). The NMP soluble part of 1b and DMF soluble part of 2b gave values of 0.36 and 0.24 dl g⁻¹ in NMP and DMF, respectively. The DMF soluble part of 1b, 1c and 2b showed absorption peaks at about 458, 465 and 388 nm, respectively, in DMF. In an alkaline medium the absorption peaks of 1b and 1c are shifted to a longer wavelength by 92-101 nm; the observed shifts in the acidic medium and alkaline medium were much larger than those observed with usual benzimidazoles with low molecular weights. Packing structures of 1b, 1c and 2b are discussed based on their XRD patterns.     

Effect of vanadium and chromium on the microstructural features of V–Cr–Mn–Ni spheroidal carbide cast irons

The objective of this investigation is to study the influence of vanadium（5.0wt%–10.0wt%） and chromium（0–9.0wt%） on the microstructure and hardness of Cr-V-Mn-Ni white cast irons with spheroidal vanadium carbides. The alloys＇ microstructural features are presented and discussed with regard to the distribution of phase elements. The structural constituents of the alloys are spheroidal VC, proeutectoid cementite, ledeburite eutectic, rosette-shaped carbide eutectic（based on M7C3）, pearlite, martensite, and austenite. Their combinations and area fraction（AF） ratios are reported to be influenced by the alloys＇ chemical composition. Spheroidized VC particles are found to be sites for the nucleation of carbide eutectics. Cr and V are shown to substitute each other in the VC and M7C3 carbides, respectively. Chromium alloying leads to the formation of a eutectic（γ-Fe ＋ М7С3）, preventing the appearance of proeutectoid cementite in the structure. Vanadium and chromium are revealed to increase the total carbide fraction and the amount of austenite in the matrix. Cr is observed to play a key role in controlling the metallic matrix microstructure.