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61.
Ring strain energies (RSEs) are predicted using homodesmotic reactions at the B3LYP/6-31G* level of theory. Substituents are conserved in the acyclic reference and any difference in energy between the ring and the acyclic reference corresponds exclusively to RSE. Small rings are stabilized by alkyl substituents and this stabilization decreases as the size of the ring increases. There is a destabilization of medium sized rings. Greater stabilization is found upon alkyl substitution at a double bond in an unsaturated ring and this stabilization decreases as ring size increases. The effects of cis-1,2-disubstitution on RSEs have been evaluated and indicate stabilization for both small and medium sized rings. RSEs of saturated and unsaturated polycyclic systems agree well with the RSEs derived from experimental thermochemical data. RSEs are reported for substituted norbornanes, norbornenes, and norbornadienes to complement experimental studies. 相似文献
62.
Tarek M. Madkour Rasha A. Azzam 《Journal of polymer science. Part A, Polymer chemistry》2002,40(14):2526-2536
Polyurethane elastomers of a controlled molecular architecture were synthesized using a two‐step polymerization technique. The building blocks of the elastomeric materials included urea–urethane prepolymers end‐capped with diisocyanate groups and had an exact number of urea groups at both ends. Two‐dimensional bifurcated hydrogen‐bonding networks incorporating the urea groups were, with differential scanning calorimetric and dynamic mechanical thermal analyzer techniques, responsible for the increase in the glass‐transition temperature (Tg) of the hard block and sharp interface morphology between the pure “hard” domains and pure “soft” domains. The higher extent of the phase separation between the two phases contributed to higher elastic moduli for the hard blocks and higher tensile strength for the elastomeric samples. Higher elongation values were attributed to the liberation of the elastomeric chain ends that otherwise would have been constrained in the interface region. The higher Tg values of the hard blocks corresponded to an increase in the hardness values and a decrease in the tear‐strength values. The increase in the amount of urea groups within the hard segments, as a result of the increased amount of water and blowing catalyst, resulted in elastomeric foams with higher open‐cell content. This resulted in lower resilience values as measured using the pendulum rebound test and was attributed to the ability of the open cells to absorb and dissipate energy. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2526–2536, 2002 相似文献
63.
Glucose utilization by lysine-producing fluoroacetate-sensitive mutants ofCorynebacterium glutamicum
A fluoroacetate-sensitive mutant was isolated fromCorynebacterium glutamicum, ATCC 21513, following mutagenesis with NTG. Batch fermentations show that in terms of growth kinetics, glucose utilization,
and lysine formation, there are significant differences between the mutant and the parent. The mutant’s specific growth rate
(0.22/h) is lower than that for the parent (0.34/h). Also, the yield expressed as lysine/glucose consumed does not alter as
a function of the glucose concentration for the mutant, and is about 0.22, whereas for the parent, this coefficient decreases
with increasing glucose concentration. The maximum specific rate of lysine production for the mutant is 1.3 g/L/h that is
about two-fold higher than that for the parent. 相似文献
64.
The standard molar enthalpies of formation
f
H
m
°
(l) at the temperature T = 298.15 K were determined using combustion calorimetry for N-methylpiperidine (A), N-ethylpiperidine (B), N-propylpiperidine (C), N-butylpiperidine (D), N-cyclopentylpiperidine (E), N-cyclohexylpiperidine (F), and N-phenylpiperidine (G). The standard molar enthalpies of vaporization
l
g
H
m
° of these compounds were obtained from the temperature variation of the vapor pressure measured in a flow system. From these data the following standard molar enthalpies of formation in gaseous phase
f
H
m
°
(g) were derived for: A –(61.39 ± 0.88); B –(88.1 ± 1.3); C –(105.81 ± 0.66); D –(126.2 ± 1.3); E ( –88.21 ± 0.75); F –(135.21 ± 0.94); G (70.3 ± 1.4) kJ · mol–1. They are used to determine the strain enthalpies of the cyclic amines A–G. The N-alkylated piperidine rings have been found to be about strainless. 相似文献
65.
A polymer crystal with a noncrystalline surface layer formed by chain loops of different lengths is considered. It is assumed that the length of each loop can be changed by longitudinal diffusion of the molecule through the crystal lattice. From the condition that the free energy of the system is minimum, the loop length distribution and the average loop length as function of temperature are calculated. In contrast to the results for loops of equal length, for the present model, a substantial thickness of the noncrystalline surface layer and a broad melting range is obtained also for the case of adjacent reentry. In order to get this result one has to take into account that even an “ideal fold” consists of at least four rigidly arranged CH2 groups in energetically unfavored conformation. 相似文献
66.
Yong-Dong Li Hao Zhao Nan Zhang 《International Journal of Solids and Structures》2013,50(22-23):3610-3617
The purpose of the present work is to study the mixed mode fracture of a piezoelectric–piezomagnetic composite with two un-coaxial cracks parallel to the interface and each in a layer. Methods of generalized dislocation simulation, Green’s function, Cauchy singular integral equation and Lobatto–Chebyshev collocation are combined together to get the numerical results of mechanical strain energy release rate (MSERR). Three kinds of effects are revealed by parametric studies, i.e., the free-surface effect, the shielding effect and the interference effect, and they are used to interpret the characteristics of COD and MSERR curves. In addition, the effects of shear loading, magnetic loading and electric loading on MSERR are also disclosed, respectively, by varying the corresponding loading factor. 相似文献
67.
68.
This work extends our previous understanding concerning the nonlinear responses of entangled polymer solutions and melts to large external deformation in both simple shear and uniaxial extension. Many similarities have recently been identified for both step strain and startup continuous deformation, including elastic yielding, i.e., chain disentanglement after cessation of shear or extension, and emergence of a yield point during startup deformation that involves a deformation rate in excess of the dominant molecular relaxation rate. At a sufficiently high constant Hencky rate, uniaxial extension of an entangled melt is known to produce window-glass-like rupture. The present study provides evidence against the speculation that chain entanglements tie up into "dead knots" in constant-rate extension because of the exponentially growing chain stretching with time. In particular, it is shown that even Instron-style tensile stretching, i.e., extending a specimen by applying a constant velocity on both ends, results in rupture. Yet, in the same rate range, the same entangled melt only yields in simple shear, and the resulting shear banding is clearly not a characteristic of rupture. Thus, we conclude that chain entanglements respond to simple shear in the manner of yielding whereas uniaxial extension is rather effective in causing some entanglements to lock up, making it impossible for the entanglement network to yield at high rates. 相似文献
69.
An investigation into the bulk properties, elastic properties and Debye temperature under pressure, and deformation mode under tension of Al8Cu4Y and Al8Cr4Y compounds was investigated by using first principles calculations based on density functional theory. The calculated lattice constants for the ternary compounds (Al8Cu4Y and Al8Cr4Y) are in good agreement with the experimental data. It can be seen from interatomic distances that the bonding between Al1 atom and Cr, Y, and Al2 atoms in Al8Cr4Y are stronger than Al8Cu4Y. The results of cohesive energy show that Al8Cr4Y should be easier to be formed and much stronger chemical bonds than Al8Cu4Y. The bulk modulus B, shear modulus G, Young's modulus E and Poisson's ratio ν can be obtained by using the Voigt–Reuss–Hill averaging scheme. From the results of elastic properties, Al8Cr4Y has the stronger mechanical behavior than Al8Cu4Y. Our calculations also show that pressure has a greater effect on mechanical behavior for both compounds. The ideal tensile strength are obtained by stress-strain relationships under [001](001) uniaxial tensile deformation, which are 15.4 and 23.4 GPa for Al8Cu4Y and Al8Cr4Y, respectively. The total and partial density of states and electron charge density under uniaxial tensile deformations for Al8Cu4Y and Al8Cr4Y compounds are also calculated and discussed in this work. 相似文献
70.
Christina Schmidt A. M. Sarwaruddin Chowdhury† Klaus Neuking Gunther Eggeler 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(3):204-210
Thermomechanical cycles including programming, cooling, unloading and heating to trigger the 1WE were examined for a shape memory polymer (SMP), Tecoflex® (TFX EG-72D). Cycles were performed at 60°C with 50% and 225% strains and the recovery time of 10 min. Strains evolving with time were estimated during the thermomechanical treatments for the total 44 cycles using 50% strains and the total 50 cycles using 225% strains. Recovery ratios for 50% strains and 225% were also estimated. It turns out that programming, cooling, unloading and heating to trigger the 1WE causes an increase of irreversible strain and is associated with a corresponding decrease of the intensity of the 1WE in particular during the first thermomechanical cycles. In parallel scanning electron microscopic study using secondary electron imaging shows a very slight wavy surface structure evolved during cycling. 相似文献