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1.
Scott T. Knauert Jack F. Douglas Francis W. Starr 《Journal of Polymer Science.Polymer Physics》2007,45(14):1882-1897
Nanoparticles can influence the properties of polymer materials by a variety of mechanisms. With fullerene, carbon nanotube, and clay or graphene sheet nanocomposites in mind, we investigate how particle shape influences the melt shear viscosity η and the tensile strength τ, which we determine via molecular dynamics simulations. Our simulations of compact (icosahedral), tube or rod‐like, and sheet‐like model nanoparticles, all at a volume fraction ? ≈ 0.05, indicate an order of magnitude increase in the viscosity η relative to the pure melt. This finding evidently can not be explained by continuum hydrodynamics and we provide evidence that the η increase in our model nanocomposites has its origin in chain bridging between the nanoparticles. We find that this increase is the largest for the rod‐like nanoparticles and least for the sheet‐like nanoparticles. Curiously, the enhancements of η and τ exhibit opposite trends with increasing chain length N and with particle shape anisotropy. Evidently, the concept of bridging chains alone cannot account for the increase in τ and we suggest that the deformability or flexibility of the sheet nanoparticles contributes to nanocomposite strength and toughness by reducing the relative value of the Poisson ratio of the composite. The molecular dynamics simulations in the present work focus on the reference case where the modification of the melt structure associated with glass‐formation and entanglement interactions should not be an issue. Since many applications require good particle dispersion, we also focus on the case where the polymer‐particle interactions favor nanoparticle dispersion. Our simulations point to a substantial contribution of nanoparticle shape to both mechanical and processing properties of polymer nanocomposites. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1882–1897, 2007 相似文献
2.
3.
Mingyang Zhao Warren T. Ford Stefan H. J. Idziak Nicholas C. Maliszewskyj Paul A. Heiney 《Liquid crystals》1994,16(4):583-599
The hexa-4-dodecyloxybenzoyl derivative 1 of azacrown [18]-N6 was originally reported to have a 'tubular' mesophase on the basis of its large central ring and 6-fold symmetry. Starting in the mesophase, annealing of 1 under a cover slip results in formation of a new crystalline phase that melts directly to an isotropic liquid at the temperature previously observed for the mesophase to isotropic transition. Thus the phase behaviour of 1 is kinetically controlled. The analogous hexa-3,4-bisdodecyloxybenzoyl derivative 2 of azacrown [18]-N6 has no kinetic limitations to its phase changes and has an enantiotropic columnar liquid crystalline phase. We have synthesized side chain copolysiloxanes with a (CH2)11 spacer and 75-84 per cent by weight of the same 4-dodecyloxybenzoyl-[18]-N6 mesogen. The polysiloxanes also display a liquid crystalline phase. 相似文献
4.
Three fixtures for conducting laboratory fretting fatigue tests are described and their respective testing methods and the
results of the analysis are compared. Each of these fixtures has been used to investigate the effects of various parameters
of interest in fretting fatigue. These fixtures include a unique apparatus in which all load applied to the specimen is transferred
to the fretting pads, an apparatus similar to many found in the literature where partial load transfer occurs across the pads,
and a simplified dovetail fixture in which the clamping load, P, and the shear load, Q, are varied in phase. Select test conditions from prior experiments performed on identical material and resulting in similar
lives ranging from one to ten million cycles from these fixtures are identified. The various testing conditions were used
to compute the unique stress field for each case. The resulting contact stresses were used to calculate crack initiation based
criteria, and to calculate stress intensity factors. The three fixtures were shown to be able to accommodate a range of loads,
fretting pad contours, and specimen geometries that produced a variety of stress fields. A crack-initiation-based criterion
was shown to predict the failure lives of thinner specimens accurately. The stress intensity factor calculations showed the
possibility of a crack arresting for a stress field that decays rapidly and the possibility of a local minimum for K as a function of depth. The fixtures are shown to be complementary in generating data for development of robust fretting
fatigue models that use these criteria. 相似文献
5.
Nicholas W. DeLuca Yossef A. Elabd 《Journal of Polymer Science.Polymer Physics》2006,44(16):2201-2225
The direct methanol fuel cell (DMFC) has the potential to replace lithium‐ion rechargeable batteries in portable electronic devices, but currently experiences significant power density and efficiency losses due to high methanol crossover through polymer electrolyte membranes (PEMs). Numerous publications document the synthesis and characterization of new PEMs for the DMFC. This article reviews this research, transport phenomena in PEMs, and experimental techniques used to evaluate new PEMs for the DMFC. Although many PEMs do not show significant improvements over Nafion®, the benchmark PEM in DMFCs, experimental results show that several new PEMs exhibit lower methanol crossover at similar proton conductivities and/or higher DMFC power densities. These results and recommendations for future research are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Parts B: Polym Phys 44: 2201–2225, 2006 相似文献
6.
An enzymatic solution to the problem of obtaining 13C/15N-labeled nucleotides that are deuterated uniquely at the H2' ' position within the ribose ring is presented. Selective deuteration occurs with an overall yield of >80%. The deuteron at the H2' ' position allows measurement of the scalar and residual dipolar couplings for the bond vectors attached to the C2' carbon of each ribose sugar. These data allow the accurate determination of sugar conformation. Interesting DNA double helices of 2-3 turns are now within the reach of solution NMR spectroscopy. As an example, these labeled nucleotides are incorporated uniquely at positions 6-14 in a 20-bp DNA sequence containing the adenovirus major late promoter. 相似文献
7.
Eckhard Spohr Andrij Trokhymchuk Douglas Henderson 《Journal of Electroanalytical Chemistry》1998,450(2):211
We report molecular dynamics (MD) simulations on the adsorption of water in attractive and repulsive slit pores, where the slit and a bulk region are in contact with each other. Water structure, surface force and adsorption behavior are investigated as a function of the overall density in the bulk region. The gas–liquid transition in both types of pores occurs at similar densities of the bulk region. 相似文献
8.
A simple and versatile method for the synthesis of acetals from aldehydes and ketones using bismuth triflate 总被引:1,自引:0,他引:1
Leonard NM Oswald MC Freiberg DA Nattier BA Smith RC Mohan RS 《The Journal of organic chemistry》2002,67(15):5202-5207
Acetals are obtained in good yields by treatment of aldehydes and ketones with trialkyl orthoformate and the corresponding alcohol in the presence of 0.1 mol % Bi(OTf)3.4H2O. A simple procedure for the formation of acetals of diaryl ketones has also been developed. The conversion of carbonyl compounds to the corresponding 1,3-dioxolane using ethylene glycol is also catalyzed by Bi(OTf)3.4H2O (1 mol %). Two methods, both of which avoid the use of benzene, have been developed. 相似文献
9.
Chester M. Mikulski William Henry Louis L. Pytlewski Nicholas M. Karayannis 《Transition Metal Chemistry》1977,2(1):135-140
Summary Complexes (2 : 1) of diethyl benzoylphosphonate (debp) with 3d metal perchlorates were synthesized and characterized by means of i.r. and electronic spectral, magnetic susceptibility and conductance measurements. In new complexes of the types [M(debp)2(OClO3)(OH2)](ClO4) (M = Fe, Co, Zn) and [Fe(debp)2(OClO3)(OH2)](ClO4)2, both debp ligands function as bidentate chelating agents, coordinating through the P=O and C=O oxygens. In contrast, in the manganese(II) and nickel(II) complexes, which are of the [M(debp)2(OClO3)(OH2)2](ClO4) type, one debp acts as a bidentate chelating ligand, while the second debp is unidentate, coordinating only through the P=O oxygen. Hexacoordination in the new cationic complexes is completed by coordination of aqua and unidentate perchlorato ligands, which are in competition for sites in the inner coordination sphere of the central metal ion with the weak debp ligand. On the other hand, debp, owing to its bulkiness, and especially the presence of the benzoyl substituent, introduces sufficiently severe steric hindrance during coordination. As a result of this, the formation of [M(debp)3]n+ tris-chelate cationic complexes with the 3 d metal ions under study does not seem to be possible. 相似文献
10.
Copper(II) halides, CuX2 (X = Br?, Cl?), have been combined in non-aqueous medium with various α,-β-dione dioxime (α,β-dodoH) ligands to produce new 1:1 adducts, the di-μ-halo-bis[halo(α,β-dodoH)copper(II)] dimers. These are: Di-μ-bromo-bis[bromo(ethanedialdioxime)copper(II)]; di-μ-bromo-bis[bromo(diphenylethanedione dioxime)copper(II)]; di-μ-bromo-bis-[bromo(9,10phenanthrenedione dioxime)copper(II)]; di-μ-chloro-bis-[chloro(9,10-phenanthrenedione dioxime)copper(II)]. The materials were characterized by conventional methods. The results clearly indicate that the compounds crystallize in discrete dimers, quite consistent with the results of closely related dimers studied earlier. 相似文献