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61.
G. Dlubek J. Stejny Th. Lüpke D. Bamford K. Petters Ch. Hübner M. A. Alam M. J. Hill 《Journal of Polymer Science.Polymer Physics》2002,40(1):65-81
High‐quality positron lifetime measurements (70 million total counts) are reported for polyethylenes (PEs) of different crystallinities (Xc = 3–82%). The specific volumes of the crystalline and amorphous phases (Vc and Va, respectively) were estimated from density and wide‐angle X‐ray scattering (WAXS) experiments. Some samples (those with low values of Xc) were branched PEs, and those with high values of Xc were linear PEs for which Xc was varied with changes in the crystallization temperature. Both Vc and Va increase with decreasing Xc in the range 0% ≤ Xc ≤ 56% (the branched PEs) but are constant for Xc ≥ 56% (the linear PEs). The lifetime spectra were analyzed with the MELT and LIFSPECFIT routines. Artifacts that can appear in the spectrum analysis were checked via an analysis of computer‐generated spectra. Four lifetime components appeared in all of the PEs; the two long‐lived ones are attributed to pick‐off annihilation of ortho‐positronium (o‐Ps) in crystalline regions (τ3) and in holes of the amorphous phase (τ4). With increasing Xc, τ3 decreases from about 1.2 to 1 ns, τ4 decreases from 3.0 to 2.5 ns, and the intensity I4 decreases from 29 to 0%. An increase in I3 from 6 to 12% was observed. A comparison with simulations shows that the true I3 value approaches 0 for Xc → 0%. The decrease in I4 is weaker than the increase in Xc; this leads to the conclusion that the apparent specific o‐Ps yield in the amorphous phase I4Xc increases with Xc. Possible reasons for this surprising results are discussed. The fractional free hole volume [h = (Va ? Vocc)/Va, where Vocc is the crystalline occupied volume] was estimated from density and WAXS results. Between Xc = 0 and 56%, h decreases from 0.151 to 0.090, but it does not change further above Xc = 56%. The mean size (v) of the local free volumes (holes) estimated from τ4 decreases from 200 to 150 Å3. The number density of holes (Nh) calculated from these values (Nh = h/v) also decreases from 0.8 to 0.6 nm?3 in the range 0% ≤ Xc ≤ 56%. The values of Va, Vc, h, and Nh increase with an increasing degree of branching but do not vary for linear PEs. The possible influence of a crystalline–amorphous interfacial phase (three‐phase model) on the observed lifetime parameters is also discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 65–81, 2002 相似文献
62.
Tommaso R.I. Cataldi Ian G. Blackham G.Andrew D. Briggs John B. Pethica H.Alien O. Hill 《Journal of Electroanalytical Chemistry》1990,290(1-2)
The successful expansion which the scanning tunneling microscopy (STM) has had is dependent on its ability to examine surfaces on a sub-nanometric scale and on providing in situ (i.e. in the presence of bulk electrolyte) sample examination. In addition to the ability to study metals and semiconductors in vacuo, the application of the technique to surfaces in contact with an electrolytic solution has prompted increased interest amongst electrochemists. We discuss herein the technique, with particular reference to advances in electrochemical applications. A new scanning tunneling microscope for operation in electrolytic environments is described. Atomic force microscopy, scanning electrochemical microscopy and scanning ion-conducting microscopy are compared with the STM. 相似文献
63.
Self-assembly of aqueous solutions of molybdate and vanadate under reducing, mildly acidic conditions results in a polyoxomolybdate-based {Mo72V30} cluster compound Na8K16(VO)(H2O)5[K10 subset{(Mo)Mo5O21(H2O)3(SO4)}12(VO)30(H2O)20].150H2O, 1, a quantum spin-based Keplerate structure. 相似文献
64.
A. J. Hill P. L. Jones J. H. Lind G. W. Pearsall 《Journal of polymer science. Part A, Polymer chemistry》1988,26(6):1541-1552
Positron annihilation lifetime spectroscopy has been used to study the isothermal relaxation response of compression molded bisphenol-A polycarbonate at temperatures of 263, 273, and 303 K. The temperature dependence of both the lifetime and intensity of the ortho-Positronium (o-Ps) pickoff component is discussed in terms of ductile-to-brittle transition behavior and free volume theory. An additive exponential model and the Williams–Watt model were used to analyze the relaxation as a function of temperature and provided results consistent with the anticipated molecular mobility of polycarbonate at sub-Tg temperatures. 相似文献
65.
The preparations of the new complexes [AsBr(3)[MeS(CH(2))(2)SMe]], [AsX(3)([9]aneS(3))] (X = Cl, Br or I; [9]aneS(3) = 1,4,7-trithiacyclononane), [AsCl(3)([14]aneS(4))] ([14]aneS(4) = 1,4,8,11-tetrathiacyclotetradecane), [AsX(3)([8]aneSe(2))] ([8]aneSe(2) = 1,5-diselenacyclooctane), [(AsX(3))(2)([16]aneSe(4))] ([16]aneSe(4) = 1,5,9,13-tetraselenacyclohexadecane), and [(AsBr(3))(2)([24]aneSe(6))] ([24]aneSe(6) = 1,5,9,13,17,21-hexaselenacyclotetracosane) are described. These are obtained from direct reaction of the appropriate AsX(3) and 1 mol equiv of the thio- or selenoether ligand in anhydrous CH(2)Cl(2) (or thf for X = I) solution. The products have been characterized by microanalysis and IR and (1)H NMR spectroscopy. In solution they are extensively dissociated, reflecting the weak Lewis acidity of AsX(3). Reaction of AsX(3) with MeSe(CH(2))(2)SeMe or MeC(CH(2)EMe)(3) (E = S or Se) gave only oils. Treatment of PCl(3) or PBr(3) with Me(2)S, MeE(CH(2))(2)EMe, or [9]aneS(3) failed to give solid complexes, and there was no evidence from NMR spectroscopy for any adduct formation in solution. The crystal structures of the first series of thioether and selenoether complexes of As(III) are described: [AsBr(3)[MeS(CH(2))(2)SMe]], C(4)H(10)AsBr(3)S(2), a = 10.2818(6) A, b = 7.8014(5) A, c = 14.503(1) A, beta = 102.9330(2) degrees, monoclinic, P2(1)/c, Z = 4; [AsI(3)[MeS(CH(2))(2)SMe]], C(4)H(10)AsI(3)S(2), a = 9.1528(1) A, b = 11.5622(2) A, c = 12.0939(2) A, beta = 93.863(1) degrees, monoclinic, P2(1)()/n, Z = 4; [AsCl(3)([9]aneS(3))], C(6)H(12)AsCl(3)S(3), a = 17.520(4) A, b = 17.520(4) A, c = 16.790(7) A, tetragonal, I4(1)cd, Z = 16; [AsCl(3)([14]aneS(4))], C(10)H(20)AsCl(3)S(4), a = 13.5942(2) A, b = 7.7007(1) A, c = 18.1270(3) A, beta = 111.1662(5) degrees, monoclinic, P2(1)()/n, Z = 4; [(AsCl(3))(2)([16]aneSe(4))], C(12)H(24)As(2)Cl(6)Se(4), a = 9.764(3) A, b = 13.164(1) A, c = 10.627(2) A, beta = 114.90(1) degrees, monoclinic, P2(1)()/n, Z = 2; [(AsBr(3))(2)([16]aneSe(4))], C(12)H(24)As(2)Br(6)Se(4), a = 10.1220(1) A, b = 13.4494(2) A, c = 10.5125(2) A, beta = 113.49(2) degrees, monoclinic, P2(1)()/n, Z = 2. [AsBr(3)[MeS(CH(2))(2)SMe]] and [AsI(3)[MeS(CH(2))(2)SMe]] reveal discrete mu(2)-halo As(2)X(6) dimeric structures involving distorted octahedral As(III), with the dithioether ligand chelating. [AsCl(3)([9]aneS(3))] adopts a discrete molecular distorted octahedral geometry with the thioether behaving as a weakly coordinated fac-capping ligand. [AsCl(3)([14]aneS(4))] forms an infinite sheet involving two mu(2)-chloro ligands on each As but bridging to two distinct As centers. Each macrocycle coordinates to two adjacent As centers via one S atom, giving a cis-octahedral Cl(4)S(2) donor set at As(III). The structures of [(AsCl(3))(2)([16]aneSe(4))] and [(AsBr(3))(2)([16]aneSe(4))] adopt 2-dimensional sheet structures with mu(2)-dihalo As(2)X(6) dimers cross-linked by mu(4)-tetraselenoether macrocycles, giving a disorted cis-X(4)Se(2) donor set at each As center. These species are compared with their antimony(III) and bismuth(III) analogues where appropriate. 相似文献
66.
It has been found that cobalt(II, III) oxide, Co3O4, lowers the thermal decomposition temperature of Na2S2O8 and K2S2O8 by about 25°C by catalysis, and it therefore acts as a P-type semiconductor at high temperature and atmospheric (air) pressure. Also, this oxide reacts at high temperature with sodium or potassium pyrosulfates to form thermally stable sodium cobalt disulfate, Na2Co(SO4)2 and potassium cobalt trisulfate, K2Co2(SO4)3, respectively. Binary systems, consisting of a 1 : 3 mole ratio (oxide : persulfate), are established as representing the solid state stoichiometric reaction. X-Ray diffractometry is employed to identify intermediate and final reaction products in general. All calculations are based on data obtained from TG, DTG and DTA curves. 相似文献
67.
We have used a flow calorimeter and a flow densimeter for measurements leading to apparent molar heat capacities and apparent molar volumes of dilute aqueous solutions of NaIO3, KMnO4, and MnCl2 at 25°C. These apparent molar quantities have been extrapolated to infinite dilution to obtain the corresponding standard state apparent and partial molar heat capacities and volumes. which have then been used for the calculation of conventional ionic heat capacities and volumes. 相似文献
68.
Marcus RK Davis WC Knippel BC LaMotte L Hill TA Perahia D Jenkins JD 《Journal of chromatography. A》2003,986(1):17-31
A method utilizing capillary-channeled polymer (C-CP) fibers as stationary phases in high-performance liquid chromatographic separations has been investigated. Polymeric fibers of differing backbones (polypropylene and polyester) having nominal diameters of approximately 50 and approximately 35 microm and a channeled structure on their periphery were packed into stainless steel tubing (305 x 4.6 mm I.D.) for use in reversed-phase separations of various mixtures. The fibers have eight channels running continuously along the axis which exhibit very high surface activity. As such, solvent transport is affected through the channels through wicking action. Bundles of 1000-3000 fibers are loaded co-linearly into the tubing, providing flow channels extending the entire length of the columns. As a result, backing pressures are significantly lowered (approximately 50% reduction) in comparison to packed-sphere columns. In addition, the capital costs of the fiber material (< US$0.25 per column) are very attractive. Flow-rates of up to 5 ml/min can be used to achieve near baseline separation of related compounds in reasonable run times, indicating very fast mobile phase mass transfer (C-terms). The polymer stationary phases demonstrate high selectivity for a wide variety of analytes with gradient elution employed successfully in many instances. Specifically, separations of three polyaromatic hydrocarbons (benzo[a]pyrene, chrysene, pyrene), mixtures of both organic and inorganic lead compounds [chlorotriethyllead, chlorotriphenyllead, lead nitrate, lead(II) phthalocyanine], and a lipid standard of triglycerides were accomplished on the polymeric stationary phases. Other species of biological interest, including groups of aliphatic and aromatic amino acids have also been effectively separated. The reversed-phase nature of the fiber surfaces is supported through atomic force microscopy measurements using hydrophilic and hydrophobic functionalized polystyrene beads as the probe tips. Separations of the various analytes demonstrate the feasibility of utilizing C-CP fibers as stationary phases in reversed-phase LC. It is envisioned that columns of this nature would be particularly useful in prep-scale separations as well as for immobilization matrices for organic constituents in aqueous environments. 相似文献
69.
Hughes D Dailianis AE Hill L McIntyre DA Anderson A 《Journal of AOAC International》2001,84(2):416-429
The TECRA Unique Salmonella test uses the principle of immunoenrichment to allow rapid detection of Salmonellae in food. A collaborative study was conducted to compare the TECRA Salmonella Unique test with the reference culture method given in the U.S. Food and Drug Administration's Bacteriological Analytical Manual. Three food types (milk powder, pepper, and soy flour) were analyzed in Australia and 2 food types (milk chocolate and dried egg) were analyzed in the United States. Forty-one collaborators participated in the study. For each of the 5 foods at each of the 3 levels, a comparison showed no significant differences (p > or = 0.05) in the proportion of positive test samples for Unique and that for the reference method using the Chi-square test for independence with continuity correction. 相似文献
70.
The interaction of optically active ethyl(1-naphthyl)phenylgermyllithium, R′3-Ge*Li, with alkyl halides, RX, to give optically active R′3Ge*R compounds, occurs with predominant retention of configuration at germanium in the case of MeBr, i-PrCl, i-PrBr, n-BuCl, n-BuBr, t-BuCl, t-BuBr, CH2CHCH2Cl, CH2CHCH2Br and PhCH2Cl, but with predominant inversion in the case of MeI, i-PrI, CH2CHCH2I, PhCH2I, and PhCH2Br. It is suggested that the retention reactions involve direct coupling between R′3Ge*Li and RX, in a four-centre process, while the inversion reactions involve halogen—lithium exchange, to give R′3GeX and RLi, also in a four-centre retentive process, followed by coupling between R′3GeX and RLi in an invertive process. 相似文献