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161.
Kazukiyo Nagai Lora G. Toy Benny D. Freeman Masahiro Teraguchi Toshio Masuda Ingo Pinnau 《Journal of Polymer Science.Polymer Physics》2000,38(11):1474-1484
The effects of film thickness, physical aging, and methanol conditioning on the solubility and transport properties of glassy poly[1‐phenyl‐2‐[p‐(triisopropylsilyl) phenyl]acetylene] are reported at 35 °C. In general, the gas permeability coefficients are very high, and this polymer is more permeable to larger hydrocarbons (e.g., C3H8 and C4H10) than to light gases such as H2. The gas permeability and solubility coefficients are higher in as‐cast, unaged films than in as‐cast films aged at ambient conditions and increase to a maximum in both unaged and aged as‐cast films after methanol conditioning. For example, the oxygen permeability of a 20‐μm‐thick as‐cast film is initially 100 barrer and decreases to 40 barrer after aging for 1 week at ambient conditions. After methanol treatment, the oxygen permeabilities of unaged and aged films increase to 430 and 460 barrer, respectively. Thicker as‐cast films have higher gas permeabilities than thinner as‐cast films. Propane and n‐butane sorption isotherms suggest significant changes in the nonequilibrium excess free volume in these glassy polymer films due to processing history. For example, the nonequilibrium excess free volume estimated from the sorption data is similar for as‐cast, unaged samples and methanol‐conditioned samples; it is 100% higher in methanol‐conditioned films than in aged, as‐cast films. The sensitivity of permeability to processing history may be due in large measure to the influence of processing history on nonequilibrium excess free volume and free volume distribution. The propane and n‐butane diffusion coefficients are also sensitive to film processing history, presumably because of the dependence of diffusivity on free volume and free volume distribution. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1474–1484, 2000 相似文献
162.
163.
Analyzing methods of Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction analysis (XRD) and X-ray fluorescence spectroscopy (XRF) were used to reveal the adsorption mechanism of Cr(VI) by low-cost adsorbent of rice husk ash. Results of FTIR showed that amide II band, Si--O--Si, and (O--Si--O were important for Cr(VI) removal. SEM micrographs suggested that series of needle-shaped precipitation appeared on cell surface, and inorganic precipitation mechanism and redox mechanism might work in the test. XPS spectra showed that main elements of rice husk ash were C, N, O, P and Si, existing state of C was mainly aldoketones groups, coordi nation reaction existed between C functional groups and Cr(VI); N element, --NH2 in chief, could remove Cr(VI) in the way of physical adsorption based on electrostatic interaction; Si--O might be useful in adsorption process. XRD data suggested representative characteristic adsorption band of SiO2, and the increasing crystallinity of rice husk ash showed metallic compound formed between Cr(VI) and rice husk ash. XRF results indicated that the content of K, Na, Mg and Ca changed, and two new elements were detected, the evidence of ion exchange mechanism. The functional groups played different roles in Cr(VI) adsorption process, and inorganic precipitation mechanism, redox mechanism, surf-complexation mechanism and ion exchange mechanism were important ways in Cr(VI) removal, which could provide theoretical support in further application. 相似文献
164.
Koo CK Lam B Leung SK Lam MH Wong WY 《Journal of the American Chemical Society》2006,128(51):16434-16435
The binuclear cycloplatinated complex {[Pt(L)]2(mu-dppm)}2+ (1), where HL is a new cyclometalating ligand 2-phenyl-6-(1H-pyrazol-3-yl)pyridine, is found to behave as a molecular pivot-hinge in which the closing and opening of the hinge is effected by the reversible formation and cleavage of the Pt-Pt d8-d8 interaction and the intramolecular pi-pi interaction mediated by the protonation/deprotonation of the 1-pyrazolyl-NH on the cyclometalating ligand L. 相似文献
165.
Calculations at B3LYP level predict the existence of three carbon chain oligomers containing HXeC[triple bond]C- branches: C(7)H(8)Xe(2), C(11)H(12)Xe(3), and C(15)H(16)Xe(4). The geometries and NBO charges of the HXeC[triple bond]C- groups in the species are similar to those of the experimental known HXeC[triple bond]CH molecule, and are insensitive to the length of the carbon chain. The structures of the xenon oligomers are very similar to their hydrocarbon precursors. The energetics for C(11)H(12)Xe(3) is calculated to assess the stability of these polymers. Similar to HXeCCH, C(11)H(12)Xe(3) is kinetically stable and protected by a high barrier of 2.47 eV against dissociation to C(11)H(12)Xe(2)+Xe, and is energetically more stable by 1.30 eV than the C(11)H(11)Xe(2)+Xe+H products, which strongly supports the existence of the molecule. Extrapolation of the results for the oligomers suggests the existence of an extended [-CH(2)CH(C[triple bond]CXeH)-](n) polymer. A strategy for preparation is proposed. 相似文献
166.
In this paper, we describe a link between Markovian binary trees (MBT) and tree-like quasi-birth-and-death processes (TLQBD) by associating a specific TLQBD to each MBT. The algorithms to compute the matrices Gk in the TLQBD then correspond to the algorithms calculating the extinction probability vector of the MBT. This parallelism leads to a new quadratic algorithm, based on the Newton iteration method, which converges to the extinction probability of an MBT. 相似文献
167.
Elucidating the structure of poly(dopamine) 总被引:3,自引:0,他引:3
Dreyer DR Miller DJ Freeman BD Paul DR Bielawski CW 《Langmuir : the ACS journal of surfaces and colloids》2012,28(15):6428-6435
Herein we propose a new structure for poly(dopamine), a synthetic eumelanin that has found broad utility as an antifouling agent. Commercially available 3-hydroxytyramine hydrochloride (dopamine HCl) was polymerized under aerobic, aqueous conditions using tris(hydroxymethyl)aminomethane (TRIS) as a basic polymerization initiator, affording a darkly colored powder product upon isolation. The polymer was analyzed using a variety of solid state spectroscopic and crystallographic techniques. Collectively, the data showed that in contrast to previously proposed models, poly(dopamine) is not a covalent polymer but instead a supramolecular aggregate of monomers (consisting primarily of 5,6-dihydroxyindoline and its dione derivative) that are held together through a combination of charge transfer, π-stacking, and hydrogen bonding interactions. 相似文献
168.
Epstein SA Shemesh D Tran VT Nizkorodov SA Gerber RB 《The journal of physical chemistry. A》2012,116(24):6068-6077
Methyl peroxide (CH(3)OOH) is commonly found in atmospheric waters and ices in significant concentrations. It is the simplest organic peroxide and an important precursor to hydroxyl radical. Many studies have examined the photochemical behavior of gaseous CH(3)OOH; however, the photochemistry of liquid and frozen water solutions is poorly understood. We present a series of experiments and theoretical calculations designed to elucidate the photochemical behavior of CH(3)OOH dissolved in liquid water and ice over a range of temperatures. The molar extinction coefficients of aqueous CH(3)OOH are different from the gas phase, and they do not change upon freezing. Between -12 and 43 °C, the quantum yield of CH(3)OOH photolysis is described by the following equation: Φ(T) = exp((-2175 ± 448)1/T) + 7.66 ± 1.56). We use on-the-fly ab initio molecular dynamics simulations to model structures and absorption spectra of a bare CH(3)OOH molecule and a CH(3)OOH molecule immersed inside 20 water molecules at 50, 200, and 220 K. The simulations predict large sensitivity in the absorption spectrum of CH(3)OOH to temperature, with the spectrum narrowing and shifting to the blue under cryogenic conditions because of constrained dihedral motion around the O-O bond. The shift in the absorption spectrum is not observed in the experiment when the CH(3)OOH solution is frozen suggesting that CH(3)OOH remains in a liquid layer between the ice grains. Using the extinction coefficients and photolysis quantum yields obtained in this work, we show that under conditions with low temperatures, in the presence of clouds with a high liquid-water content and large solar zenith angles, the loss of CH(3)OOH by aqueous photolysis is responsible for up to 20% of the total loss of CH(3)OOH due to photolysis. Gas phase photolysis of CH(3)OOH dominates under all other conditions. 相似文献
169.
A graph G is said to have bandwidth at most b, if there exists a labeling of the vertices by 1,2,…,n, so that |i−j|?b whenever {i,j} is an edge of G. Recently, Böttcher, Schacht, and Taraz verified a conjecture of Bollobás and Komlós which says that for every positive r, Δ, γ, there exists β such that if H is an n-vertex r-chromatic graph with maximum degree at most Δ which has bandwidth at most βn, then any graph G on n vertices with minimum degree at least (1−1/r+γ)n contains a copy of H for large enough n. In this paper, we extend this theorem to dense random graphs. For bipartite H, this answers an open question of Böttcher, Kohayakawa, and Taraz. It appears that for non-bipartite H the direct extension is not possible, and one needs in addition that some vertices of H have independent neighborhoods. We also obtain an asymptotically tight bound for the maximum number of vertex disjoint copies of a fixed r-chromatic graph H0 which one can find in a spanning subgraph of G(n,p) with minimum degree (1−1/r+γ)np. 相似文献
170.
We study dense colloidal crystals under oscillatory shear using a confocal microscope. At large strains the crystals yield and the suspensions form shear bands. The pure harmonic response exhibited by the suspension rules out the applicability of nonlinear rheology models typically used to describe shear banding in other types of complex fluids. Instead, we show that a model based on the coexistence of linearly responding phases of the colloidal suspension accounts for the observed flows. These results highlight a new use of oscillatory measurements in distinguishing the contribution of linear and nonlinear local rheology to a globally nonlinear material response. 相似文献