Rubber materials filled with reinforcing fillers display nonlinear rheological behavior at small strain amplitudes below γ0 < 0.1. Nevertheless, rheological data are analyzed mostly in terms of linear parameters, such as shear moduli (G′, G″), which loose their physical meaning in the nonlinear regime. In this work styrene butadiene rubber filled with carbon black (CB) under large amplitude oscillatory shear (LAOS) is analyzed in terms of the nonlinear parameter I3/1. Three different CB grades are used and the filler load is varied between 0 and 70 phr. It is found that I3/1(φ) is most sensitive to changes of the total accessible filler surface area at low strain amplitudes (γ0 = 0.32). The addition of up to 70 phr CB leads to an increase of I3/1(φ) by a factor of more than ten. The influence of the measurement temperature on I3/1 is pronounced for CB levels above the percolation threshold.
Demand for biodiesel has increased due to being a more environmentally-friendly fuel. Cold weather operation of biodiesel is challenging due to fatty acid methyl ester (FAME) content in biodiesel. Saturated FAMEs crystallize at relatively high temperatures, increase the viscosity of biodiesel, and can clog fuel lines. Here, several factors altered crystallization temperature (CT) of FAMEs, including composition, shear rate, and cooling rate. The crystallization of pure and binary mixtures of methyl palmitate, methyl myristate, and methyl stearate were studied under shear flow and static conditions. Static phase CTs of pure methyl palmitate, methyl myristate, and methyl stearate were 26, 14, and 35°C, respectively. In binary mixtures, CTs were depressed up to 7°C, which agreed with freezing point depression theory. Increasing shear rate up to 100 s−1 decreased CT by 2°C compared to static conditions. Decreasing cooling rate from 1 to 0.1°C/min increased CT less than 2°C. Overall, FAME composition altered CT more than shear flow or cooling rate for pure and binary mixtures of three FAMEs. 相似文献
The majority of plant defenses against insect herbivores are coordinated by jasmonate (jasmonic acid, JA; (+)-7-iso-jasmonoyl-L-isoleucine, JA-Ile)-dependent signaling cascades. Insect feeding and mimicking herbivory by application of oral secretions (OS) from the insect induced both cytosolic Ca2+ and jasmonate-phytohormone elevation in plants. Here it is shown that in Arabidopsis thaliana upon treatment with OS from lepidopteran Spodoptera littoralis larvae, the antibiotic neomycin selectively blocked the accumulation of OS-induced Ca2+ elevation and level of the bioactive JA-Ile, in contrast to JA level. Furthermore, neomycin treatment affected the downstream expression of JA-Ile-responsive genes, VSP2 and LOX2, in Arabidopsis. The neomycin-dependent reduced JA-Ile level is partially due to increased CYP94B3 expression and subsequent JA-Ile turn-over to12-hydroxy-JA-Ile. It is neither due to the inhibition of the enzymatic conjugation process nor to substrate availability. Thus, blocking Ca2+ elevation specifically controls JA-Ile accumulation and signaling, offering an insight into role of calcium in defense against insect herbivory. 相似文献
Phenylacetylene is oxidized slowly by molecular oxygen at 110°C. The main oxidation products are benzoic acid, benzoic anhydride, and benzaldehyde. Besides the oxidation, thermal dimerization, oligomerization, and polymerization processes also take place. As individual products 1,4-diphenylbut-1-yn-3-ene and 1,3,5-triphenylbenzene were identified. About 80% of the phenylacetylene consumed are converted into products of low volatility which could not be detected by gas chromatography. The autoxidation of acetylenic hydrocarbones [1] preferably yields products of the attack at C H bonds in α-position to the CC triple bond. An attack at the CC riple bond was a first proved in the case of phenylacetylene, which besides polymeric products yielded benzaldehyde, acetophenone, and organic acids [2]. Later, in the causes of the isomeric octynes [3] and of various 1-Phenylalk-1-ynes [4] an attack at the CC triple bond was also proved. As the primary products of the oxidative attack at the CC triple bond short-lived oxirenes or their valence isomers, the corresponding ketocarbenes are to be expected. Indeed, their rearrangement products were found in the oxidation mixtures of both the isomeric ocytnes [3] and the 1-phenylalk-1-ynes [4]. Other products of the oxidative attack at the CC triple bond are lower carboxylic acids, formally produced by oxidative cleavage of the CC triple bond [3, 4]. 相似文献
The title compounds were prepared from 2,4-dioxohexahydro-triazine (DHT) and the corresponding acid chlorides in the presence of sulphuric acid. They are active acylating agents against piperidine in dioxane as the solvent. Only the diacyl derivatives of DHT with acyl chain lengths up to C6 react with aqueous solutions of sodium perborate forming the corresponding peroxy acids. 相似文献
Products of the reaction of propane-2-sulphonic acid p-cresylester with sodium butoxide in butanol are the sodium salt of propan-2-sulphonic acid, di-n-butyl ether, p-cresyl-n-butyl ether and p-cresol. The reaction proceeds via propane-2-sulphonic acid n-butylester which is formed from the starting compound by an elimination-addition (sulphene) mechanism. The elimination step is an E1-cB reaction. 相似文献
Materials exhibiting exceptional mechanical properties can be fabricated from rigid polymers. In a spinning process, an oriented solution is solidified by the action of a nonsolvent, which induces crystallization of an oriented rigid polymer. Drying and heat treatment result in the final material having the desired properties. The effect of heat treatment on the morphology of poly(p-phenylene benzobisthiazole) (PBZT) films was studied by measurements of small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD). Films were formed by coagulation in water. The wet films were dried with supercritical CO2 to maintain an open network structure. Coagulation in water resulted in formation of microfibrils having diameter of ∼9 nm. Heat-treatment at 600°C caused significant coalescence of microfibrils. The crystallite size was increased by heat treatment from a value that is smaller than the microfibrillar diameter indicating defects in chain packing, to a value comparable to the microfibrillar diameter. 相似文献
The products of the autoxidation of phenyl cyclopropane ( I ), phenyl cyclobutane ( II ), phenyl cyclopentane ( III ), phenyl cyclohexane ( IV ), phenyl cycloheptane ( V ) and phenyl cyclooctane ( VI ) were analyzed after reduction of the reaction mixtures with LiAlH4. As products of the attack on the α-C H bonds the corresponding 1-phenyl cycloalkanols and 1-phenyl alkan-1-ols were found. In the case of phenyl cyclopropane some SR2 ring opening probably takes place. The oxidabilities $ {\rm k}_{\rm p} /\sqrt {{\rm k}_{\rm t}} $, the chain termination constants kt, the absolute chain propagation constants kp and the relative chain propagation constant (kp)rel were determined for the phenyl cycloalkanes I — VI . As it is to be expected on the basis of the I-strain concept the autoxidation rate of phenyl cyclopentane ( III ) is considerably higher than that of phenyl cyclobutane ( II ) and phenyl cyclohexane ( IV ). 相似文献