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71.
Thixoforming involves heating different types of alloys to the semisolid state at high heating rates and forming in die-casting machines or conventional presses. At temperatures higher than the solidus and lower than the liquidus, the mush metal behaves like a high-viscosity thixotropic material. Therefore, determining the thermodynamic behavior of the solid-to-liquid transition is paramount to control thixoforming processes. This article describes a simple, novel experimental setup based on differential thermal analysis (DTA) for analyzing the phase transitions in an alloy heated using high heating rates typical of industrial applications. A365 alloy was chosen to demonstrate the effectiveness of the method as the phase transformations for this alloy in semisolid materials (SSM) processing are well understood. Samples were heated to 750 °C using constant linear heating rates of 5, 10, 15, 20, 25, 50, 75, 100 and 125 °C min in a Norax 25 kW 8 kHz induction furnace with an Omron E5CK temperature controller. AISI 316 austenitic stainless steel was used as the inert reference. Comparison of the results of DTA using the proposed method and the results of simulation with Thermo-Calc® indicates that the proposed in situ DTA device and its method is suitable for analyzing phase transitions when high heating rates are used.  相似文献   
72.
The primary amino group of 3-(2-aminoethyl)-3-(4-chlorophenyl)-2,3-dihydro-1H-isoindol-1-one ( 1 ) was acylated with acetyl chloride, benzoyl chloride and phenyl acetyl chloride to form the amides 2a -c, respectively. These were cyclized in phosphorus oxychloride to give the 1-substituted-4a-(4-chlorophenyl)-4,4a-dihydropyrimido [6,1-a]isoindol-9(3H)-ones 3a-c . Heating of 1 in formic acid lead to the formation of 4a-(4-chlorophenyl)-4,4a-dihydropyrimido[6,1-a]isoindol-9(3H) -one (3d) . Heating of 1 in the presence of phosgene lead to the formation of 4a-(4-chlorophenyl)-2,3,4,4a-tetrahydropyrimido[6,1-a]isoindole-1, 9-dione (4).  相似文献   
73.
 The dynamic flow behavior of polyamide-6 (PA-6) and a nanocomposite (PNC) based on it was studied. The latter resin contained 2 wt% of organoclay. The two materials were blended in proportions of 0, 25, 50, 75, and 100 wt% PNC. The dynamic shear rheological properties of well-dried specimens were measured under N2 at T=240 °C, frequency ω=0.1–100 rad/s, and strains γ=10 and 40%. At constant T, γ, and ω the time sweeps resulted in significant increases of the shear moduli. The γ and ω scans showed a complex rheological behavior of all clay-containing specimens. At γ=10% the linear viscoelasticity was observed for all compositions only at ω>1 rad/s, while at γ=40% only for 0 and 25 wt% of PNC. However, the effect was moderate, namely decreasing G′ and G′′ (at ω=6.28 rad/s; γ=50%) by 15 and 7.5%, respectively. For compositions containing >25 wt% PNC two types of non-linearity were detected. At ω≤ωc=1.4 ± 0.2 rad/s yield stress provided evidence of a 3-D structure. At ω > ωc, G′ and G′′ were sensitive to shear history – the effect was reversible. From the frequency scans at ω > ωc the zero-shear relative viscosity vs concentration plot was constructed. The initial slope gave the intrinsic viscosity from which the aspect ratio of organoclay particles, p=287 ± 9 was calculated, in agreement with the value calculated from the reduced permeability data, p=286. Received: 24 May 2001 Accepted: 27 August 2001  相似文献   
74.
Large-scale plasma was created in molecular gases (CO, CO2, N2, H2O) and their mixtures by high-power laser-induced dielectric breakdown (LIDB). Compositions of the mixtures used are those suggested for the early earth's atmosphere of neutral and/or mildly reducing character. Time-integrated optical spectra emitted from the laser spark have been measured and analyzed. The spectra of the plasma generated in the CO-containing mixtures are dominated by emission of both C2 and CN radicals. A vibrational temperature of approximately 10(4) K was determined according to an intensity distribution in a vibronic structure of the CN (B2Sigma(+)u-X2Sigma(+)g) violet band. For comparison, the NH3-CH4-H2-H2O mixture has been irradiated as a model of the strongly reducing version of the early earth's atmosphere. In this mixture, excited CN seems to be significantly less abundant than C2. The LIDB experiments were in the molecular gases carried out not only in the static cell but also using a large, double stream pulse jet (gas puff target) placed in the vacuum interaction chamber. The obtained soft X-ray emission spectra indicate the presence of highly charged atomic ions in the hot core of high-power laser sparks.  相似文献   
75.
    
ABSTRACT

In this work, a tunable dual-band near-infrared perfect metamaterial absorber formed by combining a highly birefringent nematic liquid crystal with a nanoscale metamaterial cavity arranged in mirror symmetry is designed and numerically investigated. Electromagnetic simulations indicate that the absorbance greater than 99.4% may be achieved at 328 THz and 364 THz. Perfect absorbance results both form the use of highly lossy metal and the optimization of the metamaterial structure. In addition, absorbance of the metamaterial device can be substantially tuned both in terms of its magnitude and wavelength with the spectral tunability up to 8 THz by switching of liquid crystal alignment. The soft-matter-based metamaterial absorbers may pave a crucial role towards various active multifunctional systems working in the near-infrared range.  相似文献   
76.
    
Bacteriochlorophyll (BChl) derivatives (with central Mg replaced by metal \"M\") ([M]-BChl with M = 2H, Mg, Zn, Pd, Cu) have been investigated for their photodynamic capacity and stability toward photodegradation in organic solvents and aqueous micellar solution. A protocol has been developed for screening new sensitizers. BChl and [Zn]-BChl are efficient sensitizers, but they are also quickly degraded by the reactive oxygen species (ROS) produced by autosensitization, as well as by hetero-sensitization with 17(4)-methyl-13(2)-demethoxycarbonyl-pheophorbide a (MPP). Photostable [Cu]-BChl is a poor sensitizer, whereas [Pd]-BChl and bacteriopheophytin a are not only very efficient sensitizers but are also very stable toward ROS. beta-Carotene is no efficient physical quencher of ROS in the system; rather, it acts as a photochemical quencher that competes with [M]-BChl and undergoes photooxygenation at high rates. Photolability seems to depend on the pigment oxidation potential and, in parallel, on the presence of central metals preferring coordination numbers higher than 4, whereas photodynamic capacity depends on long excited state life-times of the pigment or efficient intersystem crossing (or both).  相似文献   
77.
    
Characterization of the surface layer of starch powder, originated from potato or maize, was carried out applying various experimental techniques: Fourier-transformed infrared internal reflection spectroscopy (FTIR-IRS), inverse gas chromatography (IGC) and scanning electron microscopy (SEM). The main kinds of starch were studied as potential fillers for rubber and results discussed in terms of factors requiring modification to improve starch miscibility and activity towards rubber. Starch of high amylopectine content shows surface enrichment with amylose what makes crystallinity of the surface layer higher than in bulk of the material. Particles of the both kinds of starch have very smooth surface (morphological index, Im = 0.995), highly resistant to its geometrical development. Dispersive component of the surface energy of starch was found to be similar to that of low energy polymers (γsd = 32.5 mJ/m2 at 23°C) and its surface to be of electron-donor character.  相似文献   
78.
79.
    
1H, 13C and 15N NMR studies of iron(II), ruthenium(II) and osmium(II) tris‐chelated cationic complexes with 2,2′‐bipyridine and 1,10‐phenanthroline of the general formula [M(LL)3]2+ (M = Fe, Ru, Os; LL = bpy, phen) were performed. Inconsistent literature 1H signal assignments were corrected. Significant shielding of nitrogen‐adjacent protons [H(6) in bpy, H(2) in phen] and metal‐bonded nitrogens was observed, being enhanced in the series Ru(II) → Os(II) → Fe(II) for 1H, Fe(II) → Ru(II) → Os(II) for 15N and bpy → phen for both nuclei. The carbons are deshielded, the effect increasing in the order Ru(II) → Os(II) → Fe(II). Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   
80.
    
Unimolecular phototautomeric reactions in 4-thiouracil, 1-methyl-4-thiouracil and 6-aza-4-thiouracil were studied using the matrix-isolation technique combined with infrared absorption spectroscopy. For monomers of these compounds, isolated in solid argon at 10 K, an intramolecular proton-transfer photoreaction was observed. Upon UV (lambda > 345 nm) irradiation, the initial oxo-thione forms of 4-thiouracils were converted into the corresponding oxo-thiol tautomers. The photogenerated oxo-thiol isomers were identified by comparing their experimental IR spectra with the spectra theoretically calculated at the DFT(B3LYP)/6-311++G(2d,p) level. Good agreement between the observed and predicted pattern of spectral bands allowed a reliable identification. This is the first report on experimental observation of isomeric forms of 4-thiouracils other than the canonical oxo-thione tautomers.  相似文献   
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