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  • Polymer and Materials Science  (112,478)
  • Inorganic Chemistry  (83,671)
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  • 201
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The active sites precursors on a MgCl2-supported Ziegler catalyst and the correlation to catalyst stereospecificity were investigated in the initial stage of propene polymerization in terms of the interaction of a variety of ethoxysilanes with the structure (Me)nSi(OEt)4-n. The kinetic study using the stopped-flow technique indicated that the interaction of the catalyst with a variety of ethoxysilanes prevents formation of active sites, and the degree of inhibition depends upon the number of ethoxy groups. It is considered that the values of propagation rate constant on the isospecific active sites are essentially the same regardless of the structure of the ethoxysilane, but the ratio of the isospecific active sites to the total number of active sites depends on the number of ethoxy groups. The same tendency in the variation of the activity, the stereospecificity, and the kinetic parameters depending on the number of ethoxy groups attached to a silane atom was observed regardless of whether the ethoxysilanes were treated with the catalyst or with triethylaluminium before polymerization.
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  • 202
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 199 (1998), S. 625-632 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: For the purpose of grafting conjugated molecules on metal or oxide electrodes (which is an essential step towards a new generation of reliable organic light emitting diodes), we have synthesized soluble oligocyclohexadienes (12 cyclic units) by anionic polymerization and functionalized them by carboxylic acids, thiol and siloxane. Aromatization of the oligomer to oligo(para-phenylene) (OPP) is carried out by dehydrogenation with chloranil. The adsorption of the carboxylic oligo(para-phenylene) derivatives on indium tin oxide powder is investigated by solution equilibration. In tetrahydrofuran (THF) an equilibrium constant of K = 21 500 1 · mol-1 and a maximum surface coverage (Nmax) of 4 μmol/m2 are obtained by using the Langmuir equation. A characteristic area of 40 Å2 per molecule is inferred from the surface density of absorbed oligo(para-phenylene), which indicates that a densely packed monolayer of vertically adsorbed molecules is formed.
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  • 203
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 199 (1998), S. 655-666 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Quinoid thiophene oligomers 6, 7 and 8 were prepared and characterized as model compounds of small bandgap polymers and were shown to have solid state bandgaps in the range of 1.31-2.15 eV and a lowest energy solution optical absorption maximum (λmax) of 480-676 nm. It was found that the bandgap and ionization potential decrease and electron affinity increases with increasing size of the quinoid oligomer. These results of the model compound studies are in agreement with theoretical predictions for the electronic properties of polythiophene with quinoid geometry and suggest that small bandgap polymers can be achieved by direct incorporation of quinoid structure in the polymer backbone.
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  • 204
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of MgCl2-supported Ziegler-Natta type catalysts containing different amounts of ethyl propionate (EP) as internal donor were prepared and tested in the propene polymerization in order to evaluate their activity and stereospecificity. These catalysts were obtained by treating chemically activated MgCl2 supports bearing variable ethyl propionate contents with TiCl4. The supports and the derived catalysts so prepared were characterized by elemental analysis, XRD and FT-IR techniques. The polymerization tests were carried out at 70°C and 7.5 atm using dimethoxydiphenylsilane as external donor and hydrogen as chain transfer reagent. A correlation between the procatalyst structure and composition and their activity as well as stereoselectivity was obtained. On processing the obtained results it was possible to evaluate the trend of both the activity and the stereoselectivity on the simultaneous changes of the Ti/Mg, Ti/EP and EP/Mg molar ratios. Actually, these catalysts show the best performance with a composition corresponding to the following molar ratios: Ti/Mg ≈ 0.03, Ti/EP ≈ 0.14 and EP/Mg ≈ 0.27. Finally, these studies confirm again that the active supports and the procatalysts are essentially based on a Cl-Mg-Cl chain structure model.
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  • 205
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 199 (1998), S. 677-686 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: New director reorientation experiments with a series of different elastomers are presented. Elastomers with a permanent monodomain structure are stretched perpendicular to their initial director alignment. After a threshold strain is exceeded, stripe-domains are formed parallel to the external stress with alternating sense of rotation in each domain. With increasing network density the average spacing of the stripes decreases. The anisotropy of the polymer chains is varied both by changing the reduced temperature and by introducing smectic clusters via copolymerisation with a mesogen forming a smectic-A phase. The anisotropy of the network is analyzed by the isobaric expansion of the sample parallel to the director as a function of temperature. Reorientation experiments at different reduced temperatures show that the interval of strains, where the director rotates, depends on this anisotropy. The experiments on cybotactic-nematic elastomers reveal that smectic fluctuations give a significant contribution to the threshold. The results are compared to the theory of Warner and Terentjev, yielding a good qualitative agreement.
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  • 206
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 13C NMR spectra of the three title polymers have been determined for polymers of different tacticities. Assignments to the various possible HH/HT/TT and m/r dyad structures were made. These were facilitated by the use of optically active monomers in the case of 1 and 3. In the precursor polymers the cis double bonds in the HH dyads were less readily hydrogenated than those in the other types of dyad. Methyl substitution parameters are summarized for the hydrogenated polymers and their unsaturated trans precursors.
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  • 207
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 199 (1998), S. 705-709 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hydrogels consisting of poly(N-isopropylacrylamide-co-N,N-dimethylacrylamide-co-butyl methacrylate) and a novel biodegradable cross-linker were synthesized with different concentrations of ammonium peroxodisulfate (APS) as a free radical initiator by photo-induced radical reaction. The swelling ratio of the hydrogels decreased rapidly in proportion to temperature. In vitro enzymatic degradation of the hydrogels was examined in buffer solution containing papain at different temperatures. The enzymatic degradation of the hydrogel prepared with higher APS concentration was observed to proceed at 30°C, however, the hydrogel was not degraded above 35°C. Such an on-mloff switching degradation in response to temperature was not observed for hydrogels prepared with lower APS concentration. It is considered that modulated degradation of hydrogels with a thermo-responsive network is achieved by controlling the cross-link density and eliminating the entanglement of polymeric main chains.
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  • 208
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An on-line time-resolved fluorescence technique is applied to study local dynamics in polymer particles during an emulsifier-free heterogeneous polymerization. The polymerization of styrene in the aqueous phase, initiated with a polymeric initiator (hydrolyzed propene-maleic acid copolymer with tert-butyl perester groups) was chosen as an illustrative system. To analyze the heterogeneous reaction pyrenyl probes were attached to the backbone of the initiator. Within the end phase of the polymerization an increase of fluorescence lifetime and intensity was observed. Fluorescence quenching experiments of the photo excited pyrene with dibenzoyl peroxide in toluene proved that the perester groups act as quencher. The calculated quenching constant points out that the quenching reaction is diffusion controlled. The also investigated bulk polymerization of styrene with dibenzoyl peroxide as initiator and pyrene as fluorophore showed that a change of the quenching probability at the gel point is responsible for a fluorescence lifetime and intensity enhancement. The emulsion polymerization showed the gel effect, too, although the macro-initiator forms a shell around the polystyrene core. At the gel point the chain mobility is reduced so that the encounter probability of pyrenyl and perester groups is limited. Despite the turbidity of the reaction mixture, fluorescence techniques allow to study the dynamics in the polymerizing particles.
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  • 209
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Enzymatic oxidative polymerization of bisphenol-A was carried out in an aqueous organic solvent using horseradish and soybean peroxidases (HRP and SBP, respectively) as catalysts. The SBP-catalyzed polymerization in an equivolume mixture of methanol and phosphate buffer (pH 7.0) affords a new class of polyphenol quantitatively, which is readily soluble in polar organic solvents such as acetone, methanol, N,N-dimethylformamide, and dimethyl sulfoxide, but insoluble in chloroform, diethyl ether, and water. NMR and IR analyses show that the polymer is mainly composed of a mixture of phenylene and oxyphenylene units. The effects of the type of enzyme and the solvent composition were systematically investigated in respect to the yield and molecular weight of the polymer. The thermal treatment of the polymer produces an insoluble product and the curing temperature and the molecular weight of the starting polymer affect the thermal properties of the product. Crosslinking reaction of the present polyphenol with an epoxide resin affords insoluble polymeric material showing high thermal stability.
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  • 210
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Twenty four cholesteric and telechelic oligoesters were prepared having two maleimide or nadimide end groups. All oligoesters were synthesized by copolycondensation of isosorbide and methyl- or tert-butylhydroquinone with suitable dicarboxylic acid chlorides in 1-chloronaphthalene at 200°C. 4-Maleimidophenol or 4-nadimidophenol was added as terminating reagent. The isolated oligoesters had inherent viscosities in the range of 0,14-0,20 dl/g (CH2Cl2/trifluoroacetic acid) and the presence of the imide end groups was confirmed by 1H and 13C NMR spectroscopy. Most oligoesters were non-crystalline materials with glass transition temperatures in the range of 105-130°C. Most oligoesters were capable of forming a Grandjean texture upon shearing of the cholesteric melt, and thermal crosslinking in the LC phase was possible upon heating to 250°C. In several cases the thermal curve allowed a fixation of the Grandjean texture.
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  • 211
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The cationic isomerization polymerization of bicyclo[2.2.1]hepta-2,5-diene (norbornadiene) was investigated. The synthesis of gel-free poly(3,5-tricyclo[2.2.1.02,6]heptylene) was achieved at a reaction temperature of 0°C. These polymerizations were initiated by AlCl3 in the presence of the weakly donating additives nitrobenzene or nitromethane. NMR spectra show that the polymer contains a small fraction (between 2 and 4 mol-%) of branched structures in addition to a small amount of 5,7-linked bicyclic olefin units (approximately 2%). A reaction mechanism involving non-classical carbocation intermediates is proposed in order to account for the 5,7-enchainment of the bicycloheptenylene units, which contrasts with earlier studies on cationic norbornadiene polymerizations. Further, pentamethylbenzene was utilized as a chain transfer reagent in order to adjust the number average molecular weight Mn to values below 2500.
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  • 212
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    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 199 (1998), S. 869-880 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In this paper we report on the synthesis and characterization of ABC-triblock copolymers poly(N-vinylcarbazole)-block-poly(4-(1-pyrenyl)butyl vinyl ether)-block-poly(2-[4-(2-phenyl-1,3,4-oxdiazolyl)phenyloxy]ethyl vinyl ether) 15. The ABC-triblock copolymers were synthesized by sequential living cationic polymerization of N-vinylcarbazole 11, 4-(1-pyrenyl)butyl vinyl ether 10 and 2-chloroethyl vinyl ether 3. In a second step, the reactive pendant chloro groups of the poly(2-chloroethyl vinyl ether) segment of the block copolymers were substituted with 2-(4-hydroxyphenyl)-5-phenyl-1,3,4-oxadiazole 6 to form fully functionalized ABC'-triblock copolymers. The molecular weight of the block copolymers varied from Mn = 4800 to 14000. The thermal behavior is discussed with respect to the block copolymer composition and compared with corresponding polymer blends. LED characteristics of a single layer device for one of the block copolymers are presented as an example.
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  • 213
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    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 199 (1998), S. 913-921 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Secondary ion mass spectrometry (SIMS) was used to determine the nature of the adhesive bonding which occurs through interchain transesterification (ITR) in thermosetting polyester materials (TS) and in liquid crystalline polyester polymers (LCP). An all aromatic copolyester thermoset was prepared as a deuterated and undeuterated film. These films were cured and then consolidated using heat and pressure to form a good adhesive bond. SIMS produced no direct observation of interdiffusion indicating that the length scale over which it occurred must be less than 500 Å (the resolution of the technique). A similar set of experiments was carried out using a deuterated and non-deuterated film of a liquid crystalline copolyester (LCP) consisting of 73/27 p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid. In this case, the deuterated units diffused throughout the entire undeuterated films within less than one hour at 280°C.
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  • 214
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    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 199 (1998), S. 923-935 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The use of nitroxide-mediated ‘living’ free radical procedures as a synthetic tool for obtaining polymers with well defined and complex macromolecular architectures is discussed. The preparation of linear homo, block, and random co-polymers by ‘living’ free radical procedures have been demonstrated for a variety of systems and results in a significant increase in control over the macromolecular structure when compared to traditional free radical polymerization. The factors which affect the success of this novel synthetic approach will be reviewed and the advantages of ‘living’ free radical polymerization over other living polymerization techniques discussed. The synthesis and chemical stability of a wide range of unimolecular alkoxyamine initiators will also be demonstrated and their use in the preparation of complex macromolecular architectures such as hyperbranched polymers and hybrid dendritic-linear polymers illustrated.
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  • 215
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    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 199 (1998), S. 1003-1011 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of hydroxypropyl cellulose (HPC) derivatives with, on the average, 3, 2, 3/2, 1, 1/2, 1/3 alkyl side chains (18 carbons) on each anhydroglucose unit were synthesized. X-ray studies indicate that layered structures prevail in most of these HPC derivatives, even in the sample containing only one alkyl side chain per two rings, i.e. C18(1/6)HPC. The polymers were able to pack in better ordered arrays in the solvent-cast films than in as-made samples obtained by precipitation from a nonsolvent. Side chain melting endotherms were observed for C18(3/3), C18(2/3), C18(1/6), and C18(1/9)HPC's. In C18(1/2) and C18(1/3)HPC's, side chain melting enthalpies were negligible but isotropization enthalpies were unexpectedly large. The isotropization temperatures and the associated enthalpies remained almost constant in differential scanning calorimetry (DSC) heating/cooling cycles. Distinct morphological features were observed under the cross polarized optical microscope (POM) after shearing the samples in the molten state. The degree of side chain substitution has a profound influence on the polymer morphology.
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  • 216
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ring-opening polymerization of the cyclobutane adduct (1) of tetracyanoethylene (TCNE) and ethyl vinyl ether (EVE) was carried out with protonic acid/Lewis acid or EVE-acetic acid adduct (2)/ZnI2 as initiating systems in CH3NO2 at ambient temperature. Poly1s with narrow molecular weight distribution (MWD) were obtained with the systems acetic acid(AcOH)/ZnI2 or 2/ZnI2. In the polymerization with 2/ZnI2, the number-average molecular weight (M̄n) of the polymers decreases with increasing amount of 2/ZnI2, and increases in direct proportion to the monomer conversion. Furthermore, M̄n increases on addition of a fresh feed of monomer at the end of the first-stage polymerization. The MWD remains narrow throughout the reaction. On the basis of the reaction of 1 with an equimolar amount of 2 in the presence of ZnI2 and the diene 5 as a by-product formed by elimination of hydrogen cyanide from 1 in the polymerization, it was proposed that ZnI2 activates both the CH-OAc terminal groups of the growing polymer chain and monomer 1.
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  • 217
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    Macromolecular Chemistry and Physics 199 (1998), S. 1013-1017 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: By using the Lifshitz-Van der Waals-Acid-Base theory, we have determined the surface tensions (γs) of three commercially available liquid crystalline polymers (LCPs) from the measurement of contact angles on thin films. The values obtained are 43.1, 41.1 and 41.5 mJ/m2 (dyn/cm) for Vectra™ A-950, Vectra™ B-950 and Xydar™ SRT-900, respectively. Experimental data suggest that all the three LCPs are monopolar. The strength of Lewis base (tendency to donate a pair of electrons for the formation of a covalent bond) for these three LCPs is as follows: Vectra™ B-950 〉 Xydar™ SRT-900 〉 Vectra™ A-950. We also theoretically estimated γs from both parachor (Ps) and cohesive energy (Ecoh) utilizing the concept of molecular group contribution. It was found that γs's calculated from Hoftyzer & Van Krevelen and Hayes' Ecoh values are close to our experimental results obtained from contact angle measurements. This is especially true for Xydar™ SRT-900 LCP, where γs obtained from contact angle measurements is 41.5 mJ/m2, while from Hoftyzer and Van Krevelen, and Hayes it is 42.4 and 41.8 mJ/m2, respectively. However, more adequate group contributions for naphthalene and amide groups are urgently needed.
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  • 218
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    Weinheim : Wiley-Blackwell
    Macromolecular Chemistry and Physics 199 (1998), S. 1019-1024 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The synthesis of six different aminochalcones, 3-(4-aminophenyl)-1-phenyl-2-propen-1-one (3a), 3-(4-aminophenyl)-1-(4-ethoxyphenyl)-2-propen-1-one (3b), 3-(4-aminophenyl)-1-(4-fluorophenyl)-2-propen-1-one (3c), 3-(4-aminophenyl)-1-(2,3,4,5,6-pentafluorophenyl)-2-propen-1-one (3d), 1-(4-aminophenyl)-3-phenyl-2-propen-1-one (4a), 1-(4-aminophenyl)-3-(9-anthryl)-2-propen-1-one (4b), and a complex 3a/2,6-dimethyl-β-cyclodextrin (3e) is described. Enzymatically catalyzed oxidative polymerization in presence of horseradish peroxidase/H2O2 system was observed in case of 3a and 3b. The oligomeric products were characterized by NMR, IR spectroscopy and thermal analysis.
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  • 219
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The anionic polymerization of isoprene with 2-ethylhexylsodium soluble in hydrocarbons in the absence of electron donor additives has been studied. The kinetics of the propagation reaction is shown to strongly depend on the solvent used. In toluene, the reaction order in initiator appears to be fractional, its value being dependent on the initiator concentration, while in heptane the first order is known to be followed. For polymerization in toluene, a scheme is suggested where monomeric and tetrameric active species are supposed to take part in propagation. With a non-linear regression fit, apparent constants in the equation describing this scheme were evaluated. The kinetics of isoprene polymerization with the mixed 2-ethylhexylsodium/2-ethylhexyllithium initiator, as well as UV spectra of the living polymers obtained, were also studied. Formation of complex active species is suggested.
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  • 220
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cyclohexene oxide and benzoic/substituted benzoic acids were used as model compounds to study the reactivity of cycloaliphatic diepoxides with carboxyl functionalized polymers. A σ-ρ Hammett treatment of cycloaliphatic epoxides with substituted benzoic acids was used to investigate the reaction mechanism(s) of ester formation. The catalytic dependence on the acid strength was obtained via a H0 Hammett-Deyrup acidity function. The σ-ρ Hammett treatment resulted in a positive ρ indicating that the transition state or the activated complex has a developing negative charge. This suggests that only the dissociated benzoic acid (or substituted benozic acids) is the attacking nucleophile.
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  • 221
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymerization rate, glass transition temperature, storage modulus, molecular weight between crosslinks and heterogeneity of the final polymer product were studied as a function of the crosslinking agent concentration for several multifunctional methacrylates. The goal of this study was to determine the effect of crosslinking monomer structure and concentration on the rates of polymerization and mechanical properties of the polymer. A series of copolymers with equal concentrations of crosslinking double bonds was prepared using a monomethacrylate plus a di- or trimethacrylate. The trimethacrylate systems had higher glass transition temperatures, larger storage moduli, and smaller molecular weights between crosslinks than the comparable dimethacrylate systems. However, the heterogeneity of the trimethacrylate systems was found to be much more extensive. Additionally, the maximum rate of polymerization was found to increases with increasing crosslinking agent when octyl methacrylate was used as the monomethacrylate, but passed through a maximum when 2-hydroxyethyl methacrylate was used. The relative rates of polymerization between the trimethacrylate and dimethacrylate systems also depended on the monomethacrylate employed and the concentration of the crosslinking agent.
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  • 222
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    Macromolecular Chemistry and Physics 199 (1998), S. 1057-1062 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The competitive binding of fluorescence-tagged poly(methacrylate) polyanions and poly(phosphate) polyanions with different poly(N-alkyl-4-vinylpyridinium) polycation quenchers (alkyl = methyl, ethyl and propyl) was studied in the region 278÷333 K by fluorescence quenching technique. The equilibrium of this interpolyelectrolyte substitution reaction proved to be temperature sensitive except in the case when the poly(N-methyl-4-vinylpyridinium) polycation was used. Thermodynamic parameters of the reaction were determined. The possibility of effective temperature control of the interpolyelectrolyte reaction might be important for understanding, prediction and utilization of transformation processes of complex particles formed by electrostatically complementary (biological) macromolecules.
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  • 223
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: α,ω-Dihydroxyoligo(alkylene maleate)s with molecular weights ranging from 1 500 to 4 000 were prepared by polycondensation, in 1-methyl-2-pyrrolidone at 105°C, of potassium maleate and 1,4-dibromobutane, 1,6-dibromohexane or 1,8-dibromooctane in the presence of 2-bromoethanol. The structure of oligomers was checked by 1H and 13C NMR spectroscopy. In most cases the mean functionality of oligomers is reasonably close to two.
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  • 224
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The hydrogenation of polystyrene-block-polybutadiene-block-poly(ε-caprolactone) SBC triblock copolymers was performed in the presence of the Wilkinson catalyst RhCl(P(C6H5)3)3. Reaction conditions (hydrogen pressure, temperature and reaction time) were varied to ensure quantitative hydrogenation without detectable side reactions. Gel permeation chromatography showed no broadening of the molecular weight distribution during hydrogenation. The efficiency of the catalyst is markedly influenced by the molecular weight of the copolymer. Due to the presence of the polyethylene (PE) block, the resulting polymers exhibit a reduced solubility in comparison to the starting materials. Using differential scanning calorimetry (DSC), preliminary results about the crystallization and melting behavior of the PE-block were obtained. In the triblock copolymers, the PE-block showed a marked depression of the melting point and crystallinity when compared to pure hydrogenated polybutadiene of equivalent molecular weight and microstructure or to a comparable PE-block within a polyethylene-block-poly(ε-caprolactone) diblock copolymer. A fractionated crystallization process of the PCL-block was observed when the PCL component in the hydrogenated triblock copolymers was present as a minor phase.
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  • 225
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    Macromolecular Chemistry and Physics 199 (1998), S. 1071-1073 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The interaction of a poly(2-methyl-5-vinylpyridine) hydrochloride gel (1 a) with the aqueous solution of a linear sodium poly(vinylsulfonate) (2) was investigated. It was established that the gel collapse takes place as a consequence of the formation of a polyelectrolyte complex (1 a-2) between oppositely charged groups. The binding degree θ of the linear polymer with the gel was determined to be 0,4. The kinetics of the interaction process was examined. With increasing pH and ionic strength value a discrete phase transition both of the gel volume and of the polycomplex is induced. The collapse of the latter has increasingly sharp character.
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    Macromolecular Chemistry and Physics 199 (1998), S. 1075-1079 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymer nanoparticles were prepared from monomers such as styrene (St), butyl methacrylate (BMA), butyl acrylate (BA), methyl methacrylate (MMA), and methyl acrylate (MA) using a modified microemulsion polymerization process. With this process high polymer: surfactant weight ratios (7 : 1 or greater), relatively concentrated (10-30 wt.-%) latexes and small (10-20 nm) particle diameters were attained. Nucleation mechanisms were investigated through observations of the particle size change during the polymerization.
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  • 227
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Copolymerization of glycolide (Glyc) and L-lactide (L-Lac) were conducted at 150°C in bulk to prepare random copolyesters. Four resorbable catalysts were used and compared: ZnCl2, ZnI2, Zn stearate (ZnSte2) and Zn lactate (ZnLac2). Separate time-conversion curves were recorded for glycolide and lactide by means of 1H NMR spectroscopy. Glycolide polymerized faster than L-lactide under all circumstances, but the difference was smallest when ZnLac2 was used as catalyst. Sequence analyses were performed using 13C NMR spectroscopy. Completely random sequences were never obtained, but the sequences resulting from a catalysis with ZnLac2 came closest to the desired randomness. Preparative 1 : 1 (mole ratio) polymerizations were conducted with ZnSte2 and ZnLac2. High yields were obtained with both catalysts, but ZnLac2 yielded far higher molecular weights. Furthermore, ZnLac2-catalyzed copolymerizations were conducted with variation of the Glyc/Lac ratio. It was found that small scale and large scale copolymerizations yield copolyesters having different properties, because the superheating in the early stage of the polymerizations (resulting from glycolide) favors the transesterification. Finally, 1 : 1 copolymerization of ε-caprolactone and L-lactide were studied in bulk at 150°C. Again high yields, high molecular weights and nearly random sequences were obtained.
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  • 228
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 1,4-Dioxan-2-one (DOXA) was polymerized by means of Zn L-lactate (ZnLac2) as catalyst in bulk. Upon systematic variation of the temperature, the reaction time and the monomer/catalyst (M/C) mole ratio the highest molecular weights were obtained at 100°C and M/C ratios between 2 000 and 4 000. However, long reaction times (8-14d) were required to obtain optimum results. Zinc chloride proved to be a somewhat less reactive catalyst, whereas zinc bromide proved to be as efficient as ZnLac2. Addition of benzyl alcohol as a coinitiator at a fixed DOXA/ZnLac2 ratio allowed a systematic control of the molecular weight. Furthermore the formation of benzyl ester endgroups was detected. Moreover, ZnLac2 allows the incorporation of various bioactive alcohols or phenols (e.g. testosterone, stigmasterol, ergocalciferol, cortisone, α-tocopherol) in the form of ester endgroups. Finally several properties of polydioxanone are reported and discussed, such as solubilities, IR, 1H NMR and 13C NMR spectroscopic data and thermogravimetric analysis.
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  • 229
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    Macromolecular Chemistry and Physics 199 (1998), S. 1175-1184 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of salt on four model hydrophobically modified alkali-soluble emulsion (HASE) associative polymers were studied. Their reduced viscosities in aqueous solution at different salt concentrations (10-4 to 10-1 M) were measured and the corresponding intrinsic viscosities were determined. The results show that the intrinsic viscosity at any given salt concentration decreases as the hydrophobicity of the hydrophobes (i.e., n in the side chain CnH2n+1) increases. The interpretation is that stronger intra-molecular association of the more hydrophobic macromonomer leads to smaller polymer molecular coils. An increase of salt content in the solution causes the reduced viscosities of all the model polymers to decrease. This is believed to be the result of excess positive ions in solution which have a shielding effect and reduce the mutual repulsion of the charges along the polymer backbone. In dilute solution the hydrophobic associations of the model associative polymers are predominantly intra-molecular. The addition of salt to the polymer solutions hinders the inter-molecular interaction of the model polymers. The increase in salt content also leads to an increase of intra-molecular aggregations of the hydrophobes of the model associative polymers. Stiffness indices such as the stiffness parameter B and the persistence chain length were used to correlate the polymer conformation of the model associative polymers in NaCl solutions.
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    Macromolecular Chemistry and Physics 199 (1998), S. 1185-1192 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(ethylene naphthalene-2,6-dicarboxylate) (PEN) crystallizes in two different modifications depending on the temperature of crystallization. The high resolution solid state 13C NMR spectra of the α modification, β modification and amorphous PEN have been measured by empolying cross polarization with magic angle spinning and high power proton decoupling. By application of both a short contact time pulse sequence and an interrupted decoupling pulse sequence all resonance lines, some of which are overlapped in the original 13C CP/MAS NMR spectra of both amorphous and β modification PEN, are separated. The α modification PEN, β modification PEN, amorphous PEN and PEN in solution show different chemical shifts for each individual carbon atom. The chemical shift difference between amorphous PEN and PEN in solution is much smaller than the difference between either modification crystalline PEN and PEN in solution. The resonance lines of the naphthalene carbon atoms of crystalline PEN have been found to be at a lower field shift than the corresponding lines of PEN in solution. Conversely, the resonance lines of the other carbon atoms on crystalline PEN are shifted upfield from the ones of PEN in solution. A significant difference between of spectra of α and β form PEN can be observed in resonances of the protonated naphthalene carbon atoms C1, C5, C4, and C8. These differ by 1.10 ppm. These chemical shift differences are explained in terms of different conformation and chain packing in the samples.
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  • 231
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    Macromolecular Chemistry and Physics 199 (1998), S. 1323-1327 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyester dendrimers bearing carbazole units at their peripheries were synthesized by attaching 3,5-bis[4-(9-carbazolyl)butoxy]benzoic acid to the peripherical phenoxy groups. The phenoxy-terminated polyester dendrimers were synthesized by hydrogenation of the corresponding benzyloxy-terminated polyester dendrimers. The structure of the synthesized compounds was confirmed with IR, 1H NMR, MALDITOF MS and GPC. The reaction conditions for attaching 3,5-bis[4-(9-carbazolyl)butoxy]benzoic acid to the peripherical phenoxy groups of polyester dendrimers were studied. Fluorescence spectra studies showed that there exist strong intramolecular interactions in the carbazole dendrimer molecules.
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  • 232
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ultrapure diethyl 1,1-cyclopropanedicarboxylate (1) undergoes ring-opening polymerization when placed in the presence of small amounts of sodium thiophenolate (2) at temperatures above 80°C, and leads to the synthesis of a carbon-chain polymer substituted on every third carbon atom by ethyl ester substituents. 1 polymerizes also in the presence of 2 generated in situ from thiophenol and metallic sodium, but does not polymerize in the presence of metallic sodium alone. Polymerizations are slow and require high concentrations in monomer and initiator to obtain reasonable polymerization times. In spite of the high temperatures used in some experiments (up to 130°C), no structural subunit resulting from side reactions was detected, presumably due to the high stability of the propagating malonate carbanion. Polymers of narrow molecular weight distribution were obtained at both 80 and 130°C (M̄w/M̄n 〈 1,14), and absolute degrees of polymerization increased with polymer yields. These results were rationalized on the basic of a quasi-living polymerization mechanism. Thermal properties of poly(1) were determined by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Poly(1) is stable up to 275°C and is a micro-crystalline polymer insoluble in most typical solvents, with the noticeable exception of chloroform and dichloromethane.
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  • 233
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The polymerization behavior of three linear asymmetrically substituted dienes, i.e. 6-phenyl-1,5-hexadiene (A), 7-methyl-1,6-octadiene (B) and R(+)-5,7-dimethyl-1,6-octadiene (isocitronellene, C) is reported in order to study the effect of substitution at one vinylic group. Homopolymerization of these monomers with the catalyst system rac-Et[Ind]2ZrCl2/MAO resulted in no reaction products in the case of monomer A and in polymers with Mw = 3.5 kg/mol and Mw = 14.0 kg/mol with the monomers B and C, respectively. According to NMR analysis, the vinylene end group of isocitronellene remained untouched during polymerization, which excludes the possibility of cyclopolymerization or crosslinking. Copolymerization of isocitronellene with propene resulted in incorporation of the diene (15.6 mol-%) equal to the stoichiometric ratio in the monomer feed, with a relatively high catalyst activity. The degree of incorporated isocitronellene is inversely related to the polymerization temperature, providing control over crystallinity (isotacticity) and molecular weight of the copolymer. The isocitronellene homo- and copolymers could be epoxidized quantitatively and brominated to an extent of 90%. Perfluorohexyl iodide was grafted onto the isocitronellene/propene copolymer by radical reaction (conversion 80%), yielding a poly(α-olefin) with fluorinated side chains.
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  • 234
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: With the aim to investigate the influence of a systematic variation of the length of flexible non-mesogenic main chain segments on the mesomorphic properties a series of new liquid crystalline polyesters with 4-(4-nitrobenzyloxy)biphenyl moieties as mesogenic side groups was prepared. The mesomorphic and dynamic behavior were investigated by means of differential scanning calorimetry (DSC), X-ray measurements, polarization microscopy and dielectric spectroscopy. All polyesters exhibit nematic and different smectic phases. Some of the homologues show “re-entrant” nematic phases. The clearing point decreases at first with increasing main chain spacer length and passes through a minimum. From the results it was possible to propose packing models of the smectic phases with low order.
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  • 235
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    Macromolecular Chemistry and Physics 199 (1998), S. 1547-1554 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Biodegradable hydrogels consisting of gelatin (Gtn) and dextran (Dex) with an interpenetrating polymer network (IPN) structure were prepared by sequential cross-linking reaction below and above the solgel transition temperature (Ttrans) of Gtn, and their enzymatic degradability was examined. IPN-structured hydrogels prepared below Ttrans showed to be homogeneous in terms of phase-contrast microscopic observation and small-angle light scattering measurements. In contrast, IPN-structured hydrogels prepared above Ttrans showed a phase-separated structure. The water content and compression modulus of the IPN-structured hydrogels were almost constant in contrast to the phase morphology, suggesting the existence of physical chain entanglements between Gtn and Dex networks in the hydrogels prepared below Ttrans. Much more bound water was observed in the IPN-structured hydrogel prepared below Ttrans, presumably supporting the above suggestion. The IPN-structured hydrogels prepared below Ttrans exhibited a specific degradation behavior: degradation of the hydrogels by either α-chymotrypsin or dextranase alone was completely hindered whereas the hydrogel was completely degraded in the presence of both enzymes. Such a specific feature of enzymatic degradation was not observed for the IPN-structured hydrogels prepared above Ttrans. It is concluded that the dual-stimuli-responsive degradation can be achieved by enhancing physical chain entanglements of Gtn and Dex networks.
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    Macromolecular Chemistry and Physics 199 (1998), S. 1561-1571 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(diallyldimethylammmonium chloride) samples were prepared in a wide range of molecular weight by radical polymerization at low degree of conversion to realize undisturbed molecular weight distributions. Determination of the molecular and thermodynamic parameters by viscometry, osmometry, light scattering, gel permeation chromatography (GPC) and analytical ultracentrifugation (AUC) give acceptable agreement. The high values of the second virial coefficient would result in a corresponding excluded volume. However, the dependencies of the radius of gyration and the second virial coefficient on molecular weight do not reflect the excluded volume effect. The discrepancy can be explained by a dominating Donnan contribution. Taking into account the polydispersities of the samples, a Kuhn segment length of 5 nm was determined for poly(diallyldimethylammonium chloride) in 0.5 M NaCl solutions. [η]-M relations were obtained for 1 M NaNO3, 1 M NaCl and 0.5 M NaCl solutions.
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    Macromolecular Chemistry and Physics 199 (1998), S. 1581-1587 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The range of ADMET polymerization active catalysts has been expanded to include classical catalytic systems. The acyclic diene metathesis (ADMET) polymerization of hydrocarbon dienes has been performed using the aryloxy-tungsten complexes WCl4(O-2,6-C6H3Ph2)2 (4), W(O)Cl2(O-2,6-C6H3Br2)2 (5), and WCl4(O-2,6-C6H3Br2)2 (6) as the precatalytic species in combination with tetrabutyltin, tetramethyltin and tri-n-butyltin hydride as the cocatalytic entities. High molecular weight polyoctenylene and polyheptenylene are obtained under bulk polymerization conditions. The scope of these classical metathesis catalysts in the polymerization of other hydrocarbon as well as functionalized dienes is studied, revealing significant reactivity differences with respect to the previously studied well-defined metathesis catalysts and providing insights into the identification of suitable classical systems for ADMET polymerization.
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    Macromolecular Chemistry and Physics 199 (1998), S. 1613-1621 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Surface grafting of polymeric materials such as films and fibers improves their reactive surface properties. Poly(propylene) (PP) reactive sites, which should initiate surface postgrafting, can be formed by a nitrogen plasma treatment. It has been shown that grafting of N-vinyl-2-pyrrolidone (NVP) onto different PP plasma-modified surfaces bearing alkyl radicals or hydroperoxides is efficient but the physicochemical properties of the grafted layer are dependent on plasma and grafting conditions. Alkyl radicals are more reactive and initiate the growth of 20 monomer units per radical onto the surface against 12 for hydroperoxide groups. When grafting is initiated with alkoxy radicals, kinetics depend on hydroperoxide decomposition rate and the obtained hydroxyl radicals react with NVP to produce a homopolymer in non negligeable proportion for a duration longer than 25 h.
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    Macromolecular Chemistry and Physics 199 (1998), S. 1637-1644 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Amphiphilic poly(ethyleneimine)s prepared by modification with long-chain alkyl halides are described. The amphiphilic range of the polymers can be influenced directly by the degree of alkylation, the n-alkyl chain length and the molecular weight of the poly(ethyleneimine) and indirectly by using additives. The wide range of stabilization properties of the alkylated poly(ethyleneimine)s was demonstrated by microemulsion polymerization of styrene and preparing gold colloids.
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  • 240
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(2-vinyl-4,4-dimethyl-5-oxazolone) (P0) and poly[(2-vinyl-4,4-dimethyl-5-oxazolone)-co-(methyl methacrylate)]s with increasing content of methyl methacrylate units (P1-P4) were synthesized and characterized. NMR spectra were discussed in terms of monomer sequence distribution and tacticity effects. The reaction of 4-methoxy-4′-hydroxybiphenyl (1) with 2-ethyl-2-oxazoline was utilized to prepare 4-methoxy-4′-(β-aminoethoxy)biphenyl (3) through the intermediate 4-methoxy-4′-[(N-propanoyl)-β-aminoethoxy]biphenyl (2). The homopolymer P0 and two copolymers P2 and P3 were functionalized with 4-methoxybiphenyl side groups by reaction with 3 via a ring-opening process in N,N-dimethylformamide (DMF) or 1,2-dichloroethane. The resulting copolymers P5-P8 were characterized by 1H and 13C NMR. The highest degree of functionalized units was obtained in DMF at 80°C.
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    Macromolecular Chemistry and Physics 199 (1998), S. 1167-1173 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conformation of the molecule of diethyl 3,12-diaza-4,11-dioxotetradecanedioate (EtGSGEt) has been investigated in the crystalline state by X-ray analysis. EtGSGEt crystallizes in the monoclinic system, space group P1121/n with a = 4.8174(7) Å, b = 4.9008(5) Å, c = 43.616(5) Å and γ = 112.854(10)°. 965 independent reflections were used in the refinement to the final agreement factor of R = 8.36%. The glycine residues of EtGSGEt are related by an inversion center and adopt a conformation, which slightly deviates from that characteristic of the polyglycine II structure. An all-trans conformation was deduced for the suberamide unit. The packing characteristics of the diamide are similar to that found in the α form of nylons.
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  • 242
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Surface modified poly(ethylene terephthalate) (PET) films with 2-(methacryloyloxy)ethylphosphorylcholine (MPC) and 2-(glucosyloxy)ethyl methacrylate (GEMA) moieties, PMPC-g-PET and PGEMA-g-PET, were prepared by graft copolymerization using an Ar plasma-post polymerization technique. The degrees of polymerization of the grafts PMPC and PGEMA were P̄n ≈ 30 and P̄n ≈ 40, respectively. The contact angle of the modified PET film decreased from θ = 68° (the original PET film) to θ = 26° for PMPC-g-PET and to θ = 43° for PGEMA-g-PET. The modified PET films adsorb less serum proteins than the original PET film. Egg yolk lecithin did not adsorb on PGEMA-g-PET but adsorbed on PMPC-g-PET. PMPC-g-PET showed activity for the inhibition of fibrin formation and no adhesion of mouse fibroblasts (L-929).
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  • 243
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Free-radical polymerizations of methyl methacrylate (MMA) and of butyl acrylate (BA) in fluid CO2 were studied by means of pulsed laser polymerization (PLP) and molecular weight analysis of the resulting polymer using size-exclusion chromatography (SEC). With the PLP-SEC technique propagation rate coefficients, kp, were determined. Depending on the monomer concentration, kp values are up to 40% smaller than corresponding data for bulk polymerizations of MMA and BA.
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    Macromolecular Chemistry and Physics 199 (1998), S. 1217-1220 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A critical analysis is presented of the measurement and interpretation of association phenomena in anionic polymerization in non-polar solvents. In chain initiation, measured differences in reaction order arise because of differences in the way the process is defined. Some also may be caused by the extreme sensitivity of these systems to traces of polar impurities. In chain propagation, differences in measured association numbers of the active centers exist in diene polymerization. These can be caused by problems in the experimental technique. This is illustrated by data on concentrated solution viscosity measurements on linear and regular four-star polystyrenes and polyisoprenes as models for dimeric and tetrameric association.
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    Macromolecular Chemistry and Physics 199 (1998), S. 1233-1239 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The temperature dependences of the associated fraction of PVC units were determined from measurements of integrated intensities of high-resolution 1H NMR spectra in thermoreversible gels of PVC and chemically modified PVC in diethyl oxalate (DEO) and dibutyl oxalate (DBO). The existence of two types of associates of different thermal stability, completely melting at 55°C and 90-130°C, was indicated by these measurements. While the associated fraction and the thermal stability of the associates increase with increasing polymer concentration, a significant reduction in the associated fraction is observed in samples where ≈5% of chlorine atoms are replaced by phenylthio groups or hydrogen. Because the chemical modification takes places only on isotactic and heterotactic triads, this result confirms the important role of these sequences in interactions associated with the gel formation. In DBO gels, the values of the associated fraction are lower than in DEO gels. A complete parallelism was found for temperature dependences of the associated fraction and viscoelastic storage modulus. From measurements of selective and nonselective 1H spin-lattice relaxation times of the solvent, the existence of PVC/DEO complex was confirmed. The life-time of bound solvent molecules which could bridge different chains is shorter than 1 s. Both polymer/solvent complex and polymer-polymer interactions seem to act as physical crosslinks.
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    Macromolecular Chemistry and Physics 199 (1998), S. 1247-1253 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of poly(o-hydroxyamide)s having high molecular weights were synthesized by means of low-temperature solution polycondensation of 4,4′-[isopropylidenebis(1,4-phenylene)dioxy]dibenzoyl chloride (1) and 4,4′-[hexafluoroisopropylidenebis(1,4-phenylene)dioxy]dibenzoyl chloride (2) with three bis(o-aminophenol)s. Subsequent thermal cyclodehydration of the poly(o-hydroxyamide)s afforded polybenzoxazoles. All poly(o-hydroxyamide)s are readily soluble in a variety of solvents, whereas the polybenzoxazoles are insoluble with one exception. The polybenzoxazoles exhibit glass transition temperatures in the range of 218-231°C and are stable up to 500°C in air or nitrogen, with the 10% weight loss temperatures being recorded between 553-607°C in nitrogen.
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    Macromolecular Chemistry and Physics 199 (1998), S. 1263-1270 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two polyimides, PI(BA-TD) and PI(6FDA-TD), based on an aromatic diamine (TD) and two aromatic dianhydrides (BA, 6FDA) were synthesized. They were characterized by viscosity, FT-IR, and X-ray photoelectron spectroscopy (XPS) measurements. XPS results reveal that the binding energy of C1s, N1s, and O1s in PI(BA-TD) is lower than that in PI(6FDA-TD). The synthesized polyimides form stable and homogeneous thin films on an ITO electrode, functioning as good hole transporting materials for organic electroluminescent (EL) devices. The double-layered EL devices consisting of a hole transporting layer of these polyimides and an emitting layer of the tris(8-quinolinolato)aluminium complex exhibit a peak emission wavelength in the bright green at 521-525 nm. Furthermore, a maximum luminance of 97 cd/m2 was achieved at a voltage of 15 V with a current density of 192 mA/cm2 for the EL device using PI(BA-TD) as a hole transporting layer. The phenomenon of an extended luminance of these EL devices was also found when a voltage higher than 15 V was applied.
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    Macromolecular Chemistry and Physics 199 (1998), S. 1291-1300 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(epibromohydrin) (PEBH) was chemically modified using 1,8-diazabicyclo-(5.4.0)-7-undecene to catalyze the substitution of the bromine atom by 4-(propargyloxy)benzoic acid. The linear polyethers obtained showed a degree of substitution from 36 to 82% depending on the PEBH/Nu ratio. A model compound, aryl propargyl ether terminated monomer (II), was synthesized to study the crosslinking. Differential scanning calorimetry (DSC), IR, 1H and 13C NMR analysis showed that this process first involves a sigmatropic rearrangement reaction of the aryl propargyl ether groups to form 2H-1-benzopyran structures which subsequently polymerize. Linear polymers undergo a similar process of crosslinking leading to thermostable polymers. The activation energies are independent of the degree of modification but the final thermal properties depend on the crosslinking density.
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  • 249
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    Macromolecular Chemistry and Physics 199 (1998), S. 1307-1314 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Using modified equations for the free energy of mixing of hydrogen bonded polymer blends that include the effects of intramolecular screening and functional group accessibility, we have been able to predict and duplicate experimentally observed miscibility maps for ethylene-stat-vinyl acetate blends with styrene-stat-4-vinyl phenol and 2,3-dimethylbutadiene-stat-4-vinyl phenol. Moreover, this work suggests that equilibrium constants determined from low molecular weight mixtures may be used to predict the phase behavior of analogous polymer blends, after due consideration is given to intramolecular screening and functional group accessibility, which are a direct consequence of chain connectivity.
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  • 250
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    Macromolecular Chemistry and Physics 199 (1998), S. 1315-1322 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A water-insoluble blue dye was used to study the particle nucleation mechanisms involved in the styrene miniemulsion polymerizations stabilized by sodium dodecyl sulfate (SDS) along with a reactive cosurfactant (e.g., dodecyl methacrylate (DMA) or stearyl methacrylate (SMA)). A mass balance was established to determine the number of latex particles originating from the monomer droplets (Nd) and that of primary particles generated in the aqueous phase (Nw). The accuracy of this method relies on producing a stable miniemulsion during the reaction. About 55% of the monomer droplets initially present in the reaction mixture (Nm,i) can be successfully converted into latex particles for the system stabilized by SDS/DMA. The value of Nd is much smaller than Nw Homogeneous nucleation plays an important role in the reaction kinetics, but it becomes less significant when the DMA concentration is increased. On the other hand, the value of Nm,i is much larger when the more hydrophobic SMA is chosen as the cosurfactant. As a consequence, nucleation of primary particles in the aqueous phase is greatly reduced. Nevertheless, only 49% of the original monomer droplets can be converted into latex particles during polymerization. The value of Nw, is comparable to that of Nd. Thus, the relatively large population of primary particles generated via homogeneous nucleation cannot be neglected for the SMA stabilized system. In addition, increasing the initiator concentration may enhance the degree of homogeneous nucleation during the early stage of polymerization.
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  • 251
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    Macromolecular Chemistry and Physics 199 (1998), S. 1337-1342 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The synthesis of a novel kind of form-retaining liquid crystalline crosslinked metallopolymer is reported. Copper(II) is complexed by Schiff's base units as part of a mesogenic side chain polymer. This leads to remarkable antiferromagnetic exchange interactions between the copper centers that are not present in related monomeric model compounds. IR spectroscopic investigations in the region 4000-200 cm-1, X-ray diffractometry and temperature dependent magnetic susceptibility measurements were carried out to elucidate the structure of this new material. The observed considerably strong antiferromagnetic coupling is assumed to be due to the interactions between the copper centers through oxygen bridges in the polymeric matrix.
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  • 252
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    Macromolecular Chemistry and Physics 199 (1998), S. 1365-1378 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two homologous series of molecularly uniform oligourethanes based on 1,5-naphthylene diisocyanate (NDI) and 1,4-butanediol (BDO) were synthesized and used as model compounds for the investigation of the structure/properties relations regarding the hard segment domains of NDI-based polyurethane (PUR) elastomers. The NDI/BDO oligourethanes show extremely high crystalline melting points and unusually high heats of fusion. This is attributed to strong intermolecular interactions combined with the rigid structure of the naphthalene-butanediol units. Decomposition occurred before the melting was completed. Annealing led to an improved crystal structure and higher softening points as long as decomposition in the amorphous regions was prevented by the choice of sufficiently low annealing temperatures.
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  • 253
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Novel Pt-containing polymers derived from Zeise salt and polystyrene-polybutadiene diblock (PS-PB) and triblock (SBS) copolymers have been synthesized. The comparison of complex formation peculiarities of Pd-, Rh-, and Pt-containing polymers derived from SBS with 72 wt.-% of PB and PS-PB with 15 wt.-% of PB displayed that a short PB block in PS-PB allows to maintain solubility of organometallic polymers even if intermolecular complexation is probable. Such a solubility was found to be provided by micellization in Pd-, Pt-, and Rh-containing polymers derived from PS-PB. Moreover, crosslinks formed due to complexation were shown to contribute to micellization: iron carbonyl complexes immobilized on PS-PB, where solely intramolecular complexes can be formed, do not provide micellization.
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  • 254
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    Macromolecular Chemistry and Physics 199 (1998), S. 1393-1397 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(styrene-co-divinylbenzene) beads supported rac-Ph2Si(Ind)2ZrCl2 was prepared and tested as a catalyst for ethene polymerization using methylaluminoxane (MAO) as a cocatalyst. At a polymerization temperature below 100°C, the catalyst showed pretty high activity to give polyethene beads replicating the shape of the carrier. With increasing polymerization temperature up to 150°C, the catalyst activity increased drastically but the spherical shape of polyethene disappeared due to the melting. From the plots of apparent activity against polymerization temperature, it was suggested that the polymerization below 100°C is more or less controlled by monomer diffusion through the crystalline polyethene films.
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  • 255
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    Macromolecular Chemistry and Physics 199 (1998), S. 1413-1420 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two new monomers, 3-vinylphenyl selenocyanate and 4-vinylphenyl selenocyanate, were synthesized from 3-and 4-aminoacetophenone as starting materials. Free radical polymerization of the monomers gave poly(3-vinylphenyl selenocyanate) and poly(4-vinylphenyl selenocyanate) as fully soluble and stable materials. The polymers became crosslinked upon 254 nm UV irradiation. The photolysis of phenyl selenocyanate in heptane and cumene solution gave diphenyl diselenide as the main product. The photo-cleavage of SeCN groups into phenylseleno and cyano radicals also occurred in the polymers. Photo-crosslinking data were processed with the Charlesby-Pinner relation. The quantum efficiencies φCL of crosslinking were 0.053 (±0.020) for poly(3-vinylphenyl selenocyanate) and 0.071 (±0.026) for poly(4-vinylphenyl selenocyanate), the quantum efficiencies φCS of chain scission were 85 · 10-4 (±59 · 10-4) and 25 · 10-4 (±25 · 10-4), respectively. A comparison with data on other polystyrene derivatives showed that poly(3-vinylphenyl selenocyanate) and poly(4-vinylphenyl selenocyanate) are highly sensitive negative resists in the polystyrene series.
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    Macromolecular Chemistry and Physics 199 (1998), S. 1427-1433 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two types of new polyurethanes with a highly NLO active chromophore, 2-[4-[4-[bis(2-hydroxyethyl)amino]phenylazo]benzylidene]malonitrile (HAPM), in the polymer side chain were synthesized (PU1-DCN and PU2-DCN) and characterized. The diisocyanate components of the polymers are 2,4-tolylene diisocyanate and 3,3′-dimethoxybiphenyl-4,4′-ylene diisocyanate. The molecular weights of PU1-DCN and PU2-DCN were determined to be M̄w = 23000 (M̄w/M̄n = 2.19) and M̄w = 22000 (M̄w/M̄n = 2.34), respectively. The final products are readily soluble in polar aprotic organic solvents, like tetrahydrofuran, N,N-dimethylformamide, cyclohexanone, etc. Good optical quality films were obtained by spin coating. The glass transition temperatures of both polymers were found to be 158-159°C. They showed no melting points in the DSC curves, suggesting an amorphous phase. It was found that the electro-optic coefficient of PU1-DCN was r33 = 62.7 pm · V-1 at 633 nm wavelength. The macroscopic second-order hyperpolarizability at 1064 nm wavelength was determined to be χ(2) = 136 pm · V-1 for PU1-DCN and χ(2) = 120 pm · V-1 for PU2-DCN.
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    Macromolecular Chemistry and Physics 199 (1998), S. 1445-1450 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new series of water-soluble conjugated aromatic polyimines containing sulfonate groups have been synthesized via polycondensation reaction between diamines and dialdehydes at room temperature. The polymers are soluble in water and N,N-dimethylformamide, giving colored solutions with absorption maxima (λmax) ranging from 400 to 480 nm. One of the polyimines (PIP) showed strong fluorescence in aqueous solution, and concentration dependence of photoluminescence has been investigated. Electrostatic self-assembly of multilayer films consisting of each polyimine as a polyanion and poly(diallyldimethylammonium chloride) as a polycation was successfully carried out by alternate deposition in corresponding aqueous solutions.
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    Macromolecular Chemistry and Physics 199 (1998), S. 1489-1493 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The water retention capacity of methyl, hydroxyethyl and hydroxypropyl celluloses was evaluated through the void ratio and modified consolidation coefficient by the compression method. The void ratio of methyl cellulose increases with decreasing degree of substitution and the modified consolidation coefficient increases with increasing degree of substitution. These results show that methyl cellulose with a low degree of substitution has a high water retention capacity. The water retention capacity of cellulose derivatives estimated from the void ratio is in the order of that of hydroxyethyl, hydroxypropyl and methyl celluloses.
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  • 259
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Various MgCl2-supported Ti(4,4,4-trifluoro-1-phenyl-1,3-butanedionato)2Cl2 catalysts with different Ti contents (0.017 ∼ 0.002 mmol/g) were synthesized and applied to propene polymerization using triethylaluminium and di-i-propyldimethoxysilane (DIPDMS) as the cocatalyst and external donor, respectively. When polymerization was conducted in the absence of DIPDMS, neither the activity nor the isospecificity of catalyst were dependent upon the Ti content. However, the effect of DIPDMS on the catalyst performance was found to be markedly dependent upon the Ti content, i.e., the addition of DIPDMS to the catalyst with low Ti content caused a prominent increase in the activity for isotactic polymerization. As a result, the present catalyst with low Ti content gave a highly isotactic polypropene with Tm = 169.3°C and [mmmm] 〉 99% in high selectivity (I.I. = 97.7%).
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    Macromolecular Chemistry and Physics 199 (1998), S. 1539-1545 
    ISSN: 1022-1352
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(propylene oxide) (PPO) is widely applied for the preparation of thermoplastic elastomers, surfactants and additives. A well-defined polar modification of poly(propylene oxide) was achieved by radical grafting with maleic anhydride (MAn). A protection of hydroxyl end-groups of PPO was realized by acetylation to prevent side-reactions of these groups with MAn. An isolation of highly grafted parts from the reaction products was carried out to obtain suitable samples for a structure characterization. FTIR spectroscopy proved a characteristic shift of the carbonyl valence vibrations of cyclic anhydrides to higher wave numbers due to grafting reactions. It was proven by 13C NMR spectroscopy that the grafting of MAn occurs onto both methine and methylene carbons of the PPO chain. Monosubstituted succinic anhydrides were formed as graft units. Furthermore, in products synthesized with a high initial concentration of MAn (20 wt.-%) beside single units a small amount of oligo(maleic anhydride) grafts was formed.
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    Surface and Interface Analysis 26 (1998), S. 72-91 
    ISSN: 0142-2421
    Keywords: AES ; electron scattering ; data processing ; Auger imaging ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: No Abstract
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    Surface and Interface Analysis 26 (1998), S. 9-16 
    ISSN: 0142-2421
    Keywords: depth profile ; reference material ; thin film ; SIMS ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A delta oxide multilayered thin film is proposed as a new reference material for SIMS depth profiling. This material is composed of seven thick Ta2O5 layers of 18 nm separated by 1 nm SiO2 delta layers. The surface of the thin film was very flat and all the interfaces were sharp according to atomic force microscopy (AFM) and transmission electron microscopy (TEM). In SIMS depth profiling, the dynamic range of the Si+ ion signal at the SiO2 layer was large enough to define the depth resolution. The surface topographic development after ion beam sputtering was negligible under various sputtering conditions, as observed by AFM. This was well correlated with the result that there is no significant deterioration of SIMS interface resolution with sputter depth. This reference material can be useful in SIMS depth profiling analysis to optimize the experimental parameters for a better depth resolution and to calibrate the sputtering rate. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 30-38 
    ISSN: 0142-2421
    Keywords: XPS ; AES ; CoAg granular film ; CoPt alloy ; magnetoresistance ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The chemical state of Co, Ag and Pt in giant magnetoresistive CoAg granular films sandwiched between Pt layers is studied using high-resolution x-ray photoelectron spectroscopy. Measurements were carried out as a function of depth for samples deposited at different temperatures and containing different amounts of Co. In all samples Ag is found to segregate at the surface to form an AgPt alloy. The depth profiles are consistent with the deposited Co concentration modified by preferential sputtering. No variation of the chemical state for Co or Ag in the CoAg layer is found for different deposition conditions. However, small amounts of Pt do affect the Co 3d electrons. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 39-55 
    ISSN: 0142-2421
    Keywords: carbon fiber ; plasma surface treatment ; sizing ; atomic force microscopy ; x-ray photoelectron spectroscopy ; XPS ; AFM ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The objectives of this work were to characterize the surface of commercial carbon fibers, focusing on the effect of polymer sizing and the effect of oxygen radiofrequency plasma treatment. The fiber surface composition was determined by x-ray photoelectron spectroscopy (XPS) and the surface topography was examined by scanning transmission electron microscopy (STEM) and atomic force microscopy (AFM).Voltage-contrast XPS distinguished between unsized and sized carbon fibers, by which the former behaved as a conductive material whereas the latter behaved as a mixture of both conductive and non-conductive materials due to a contribution from a polymeric sizing material. The AFM measurements revealed that oxygen plasma treatment for 30 s roughened the unsized fiber surfaces; however, further treatment smoothed the overall topography. Oxygen plasma treatment for 30 s also increased the surface oxygen content. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 56-61 
    ISSN: 0142-2421
    Keywords: compound semiconductors ; GaAs ; AlAs ; AlGaAs ; wet etching ; reflectivity ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Optical in situ monitoring, exploiting the interference of monochromatic radiation reflected from the surface being chemically etched and from the deeper interfaces of semiconductor layers, was utilized to monitor the etch process of layered AlGaAs/AlAs/GaAs structures. The described method is applicable in controlled etching of heterostructures in order to terminate the etch process precisely and it is also suitable for analysis and diagnostics of epitaxially grown layers and for calibration of etch rates. © 1998 John Wiley & Sons Ltd.
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    Surface and Interface Analysis 26 (1998), S. 134-143 
    ISSN: 0142-2421
    Keywords: Auger parameter ; silicon nitride ; x-ray photoelectron spectroscopy ; XPS ; Auger electron spectroscopy ; AES ; oxidation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Silicon nitride powders have been thermally oxidized between 700 and 1200°C in a high-purity N2-20% O2 gas environment. The powders were subsequently analyzed by x-ray photoelectron and Auger electron spectroscopies for evidence of oxynitride surface states. Measurements were made on the Si 2p, O 1s, N 1s, C 1s, F 1s and Si KLL transitions, the latter being obtained using bremsstrahlung radiation from the Mg x-ray source. As a function of increasing temperature the data show a clear progression of spectral binding energies and peak shapes that are indicative of more advanced surface oxidation. However, definitive analysis of these data rests on the combined use of both Auger and photoelectron data to define the oxidized surface states for a system that involves two electrically insulating end states: silicon nitride and silicon dioxide. Curve fitting the Si 2p and Si KLL transitions as a function of oxidation, coupled with the use of Auger parameters for the starting silicon nitride and final silicon dioxide, reveals no measurable evidence for an interphase oxynitride in the thin oxide scales of this study where the silicon nitride substrate is detectable. Possible incorrect assignment of oxynitride bonding, from shifted Si 2p states in the carbon referenced spectra, is attributable to band bending as the transition is made from incipient to fully formed silicon dioxide. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 124-133 
    ISSN: 0142-2421
    Keywords: plasma etching/processing ; plasma diagnostics ; optical emission spectroscopy ; semiconductor plasma processing ; thin film manufacturing processes ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Sandia National Laboratories has developed a system to monitor plasma processes for the control of industrial applications. The system is designed to act as a fully automated, stand-alone process monitor during printed wiring board and semiconductor production runs. The monitor routinely performs data collection, analysis, process identification and error detection/correction without the need for human intervention. The monitor can also be used in research mode to allow process engineers to gather additional information about plasma processes. Because plasma processes have wide application in thin-film growth, the monitor could also be used to better understand and control myriad thin-film manufacturing processes. Surface interactions, thin-film interfaces, growth and stoichiometry are potential areas of impact.The plasma process monitor/control system consists of a computer running software developed by Sandia National Laboratories, a commercially available spectrophotometer equipped with a charge-coupled device camera, an input/output device and a fiber-optic cable. The tool is designed to be a versatile, multipurpose piece of equipment allowing automated process verification and error detection/correction, as well as a research tool. We have used the monitor for gauging the ‘state-of-health’ of plasma processes. System 1 has been at Texas Instruments in Austin, TX, since February 1996, monitoring the health of printed wiring board plasma desmear and etch-back. System 2 has been at Advanced Micro Devices in Austin, TX, since July 1996, monitoring integrated circuit multivariate oxide etch. These systems and possible benefits derived from in situ monitoring of plasma processes will be discussed. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 177-181 
    ISSN: 0142-2421
    Keywords: InP ; passivation ; alumina ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Alumina was evaporated on InP(100) and InSb/InP(100) substrates. The InSb buffer layer permits thermal and structural protection of the indium phosphide substrate. This layer was obtained by condensation of antimony atoms on the indium-rich InP surface after ionic etching. The evaporation of antimony leads to Sb-In bonds. Modellization of the Auger signal variations during alumina condensation was compared to the experimental results. Auger measurements indicate the improvement of the elaborated structure. This fact has been confirmed by the electrical C(V) characterizations. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 249-269 
    ISSN: 0142-2421
    Keywords: quantitative surface analysis ; XPS ; AES ; nano-structures ; peak shape analysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The accuracy of XPS and AES quantification by peak shape analysis was established from a detailed analysis of a range of model spectra and three sets of experiments. It was found that information on the concentration-depth profile in the surface region up to depths of ∽5λi (where λi is the inelastic electron mean free path) is primarily contained in the spectral energy region up to ∽100 eV below the peak energy and is essentially completely contained by the energy region up to ∽200 eV below the peak. Analysis of a larger energy range than 100 eV does not add much to the information on the details of the structure in the outermost 5λi but gives the possibility to determine additional structural parameters that describe the composition at larger depths. The structural parameters that describe the chemical composition of the outermost 5-10λi of the solid were divided into primary and secondary parameters: the primary parameters are the three most important parameters needed to describe the main characteristics of the distribution of atoms; the secondary parameters are parameters other than the three primary parameters that describe the finer details of the depth distribution of atoms in the outermost 5-10λi of the surface region. The uncertainty in the determined three primary parameters is typically 5-10%. The uncertainty in the determined secondary parameters is typically ≳35%. Different models of depth profiles can be distinguished when they differ significantly over a width of more than ∽1/3λi at any depth ≲5λi. The uncertainty in the total determined amounts of atoms within the surface region is ∽5-10% as long as the depths are within the primary probing depth of the method (i.e. 〈5λi). The absolute quantification of a set of samples where the in-depth distribution varies considerably gives a root-mean-square scatter of 15%. This is reduced to ∽10% when elastic scattering effects are modelled by a simple analytical expression. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 329-334 
    ISSN: 0142-2421
    Keywords: ISS ; ion scattering spectroscopy ; catalysis ; chemisorption ; Mo ; TiO2 ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A series of Mo/TiO2 catalysts was prepared by equilibrium adsorption from aqueous solutions of (NH4)6Mo7O24 by varying the pH of the solution from 9.8 to 4. The Mo loading increases from 0.8 to 3.6 wt.% as the pH of preparation decreases. The surface coverage of the calcined catalysts was monitored by CO2 chemisorption and ion scattering spectroscopy (ISS) measurements. Carbon dioxide uptake was determined in a standard BET system from the adsorption isotherms by extrapolating to zero pressure. Coverage measurements from ISS were obtained by monitoring the changes of the ISS Ti signal with Mo addition. Additional information about the dispersion of the Mo phase of these catalysts was obtained from x-ray photoelectron spectroscopy (XPS) measurements. The XPS results evidenced the presence of a highly dispersed Mo phase. Carbon dioxide chemisorption results for Mo/TiO2 catalysts indicated that the Mo coverage increases linearly from 0.16 to 0.93 with increasing Mo loading from 0.6 to 3.6 wt.%. These results were consistent with those determined by ISS measurements and are in good agreement with the predicted values for monolayer dispersion. These findings are in contrast with those obtained for alumina-supported catalysts, where the CO2 chemisorption method has been shown to overestimate the surface coverage. The origin of the apparent suitability of the CO2 chemisorption method for monitoring the surface coverage of TiO2-based systems is discussed. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 316-328 
    ISSN: 0142-2421
    Keywords: IR ; infrared ; Raman ; XPS ; x-ray photoelectron spectroscopy ; polyimide ; Langmuir-Blodgett ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Ultrathin films of the dimethylhexadecylamine salt of the polyamic acid of pyromellitic dianhydride (PMDA) and oxydianiline (ODA) were deposited onto silver substrates using the Langmuir-Blodgett (LB) technique. These films were transformed to PMDA/ODA polyimide by both thermal and chemical processes. Reflection-absorption infrared spectroscopy (RAIR), surface-enhanced Raman scattering (SERS) and x-ray photoelectron spectroscopy (XPS) indicated that there was no strong interaction between the tertiary amine salt films and the silver substrates and that imidization of these films was quite complete. Both RAIR and SERS were also used to determine the molecular orientation in as-deposited tertiary amine salt films and in films that were imidized. It was concluded that ODA moieties were parallel to the silver surfaces in the as-deposited films. However, both SERS and RAIR indicated that imide formation induced orientation in which the PMDA moieties became more perpendicular to the silver surface while the ODA moieties were more parallel. © 1998 John Wiley & Sons, Ltd.
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  • 272
    ISSN: 0142-2421
    Keywords: RCA clean ; glass ; surface chemistry ; polysilicon ; thin film transistor ; ToF-SIMS ; XPS ; x-ray photoelectron spectroscopy ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The surface chemistry of an alkaline-earth boroaluminosilicate glass is changed by contact with chemical solutions. The present study shows that RCA cleaning creates a silica-rich surface on the glass. This altered surface can be removed by hydrofluoric acid etching. During the RCA cleaning process, glass components can be transferred to a polysilicon film placed in the same alkaline solution. The acidic solution in turn removes most of the contamination from the polysilicon. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 278-289 
    ISSN: 0142-2421
    Keywords: XPS ; x-ray photoelectron spectroscopy ; aliphatic ; hydrocarbon ; high resolution ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Comparison of high-resolution core-level spectra from simple long-chain aliphatic hydrocarbons and hydrocarbon polymers show minor differences between ideal, specially prepared samples and samples of ‘as-received’ materials. Asymmetric peaks whose structure may be attributed to vibrational-level excitation can be resolved easily under conditions that do not cause damage. This asymmetric structure is independent of sample morphology and sampling depth. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 306-315 
    ISSN: 0142-2421
    Keywords: polycarbonate ; SF6 ; plasma ; XPS, SFM ; AFM ; mass spectroscopy ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A systematic investigation was made of the chemical and morphological influences of SF6 plasma on polycarbonate and the influence of plasma treatment on Al metallization. Mass and ion spectroscopy were used for characterization of the plasma and the etching process. X-ray photoelectron spectroscopy (XPS) measurements were applied for the chemical characterization, while atomic force microscopy (AFM) (static and dynamic mode) served to inspect the surface morphology. All analytical techniques were performed in an ultrahigh vacuum system, in order to prevent the polycarbonate sample from being exposed to ambient air after the plasma treatment. During the etching process we used mass difference spectra to demonstrate the removal of masses 19, 28 and 32 corresponding to HF, CO (N2) and CF. Additionally, the inclusion of fluorine was also observed by this technique.The XPS spectra of polycarbonate surfaces show a significant inclusion of fluorine (C-F, C-F2) and a reduction of the oxygen content after the plasma treatment. Aluminium metallization leads to the formation of an Al-F interlayer; metallic growth of Al is only observed when the metallic layers become thicker than a few nanometres.The AFM investigations have shown that even a short plasma treatment causes changes in morphology (structures with an extension of 20-40 nm). After extended plasma exposure the surface becomes very rough, resulting in poor Al adhesion. On untreated polycarbonate, Al grows in the form of weakly bound clusters, which can only be imaged in the dynamic AFM mode. After plasma treatment, Al grows in the form of well-adhering flat layers without clustering. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 337-342 
    ISSN: 0142-2421
    Keywords: ZnS ; degradation ; ageing ; cathodoluminescence ; FED ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The phosphor powder ZnS:Cu,Al,Au has been investigated extensively as a possible green phosphor for field emission displays (FEDs). Phosphor powders of ZnS:Cu,Al,Au have been subjected to electron bombardment (1-5 keV) at oxygen pressures ranging from 1×10-7 to 2×10-6 Torr and different electron current densities (45-58 mA cm-2). Auger electron spectroscopy (AES) and cathodoluminescence (CL), both excited by the same electron beam, were used to monitor changes in surface composition and luminous efficiency during electron bombardment. It was shown that the degradation rate of the CL intensity is a linear function of oxygen pressure. The interactive constant (a measure of the probability of surface reactions) and the burning parameter (a measure of the probability of CL degradation per incident electron) plotted as a function of electron beam energy follow the same trend as the electron impact ionization cross-section for an atom. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 400-411 
    ISSN: 0142-2421
    Keywords: inelastic mean free path ; elastic peak electron spectroscopy ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Theoretical values of the inelastic mean free path (IMFP) and their electron-energy dependence are available in the literature from predictive formulae for various categories of materials, such as elemental solids, inorganic and organic compounds. in contrast, the experimental IMFP values were determined for a more limited number of materials. This refers especially to multicomponent solids.We have measured the IMFP dependence on energy for Cu and two copper oxides, CuO and Cu2O, using elastic peak electron spectroscopy. The experiment consisted of measuring the backscattering probabilities for the investigated materials and an Ni standard in the energy range 400-1600 eV. The IMFP values were determined using a theoretical model describing the phenomenon of elastic backscattering. The IMFP values determined in this work are in reasonable agreement with experimental and theoretical values published in the literature. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 385-399 
    ISSN: 0142-2421
    Keywords: oxygen plasma ; surface treatment ; styrene-butadiene rubber ; adhesion ; T-peel strength ; XPS ; IR-ATR spectroscopy ; contact angle measurements ; SEM ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The surface of a synthetic vulcanized styrene-butadiene rubber (R2) was treated in an oxygen plasma to improve adhesion in joints prepared with a one-component solvent-based polyester-urethane adhesive. The modifications produced on the rubber surface by plasma treatment were assessed using advancing and receding contact angle measurements, x-ray photoelectron spectroscopy, (XPS), infrared-attenuated total reflection spectroscopy and scanning electron microscopy. Adhesion was obtained from T-peel tests of treated R2 rubber/polyurethane adhesive joints. Several experimental variables were considered, such as the radio-frequency power and the length and lifetime of the plasma treatment. The treatment in the oxygen plasma produced a noticeable decrease in contact angle, which can be mainly ascribed to the creation of C—O and C=O moieties on the rubber surface. Advancing and receding contact angles only differed by ∽10°. Depending on the experimental conditions used, some ablation was produced on the surface, which was more noticeable as the length and power of the treatment increased. An adequate performance of adhesive joints was obtained using a power of 50 W and a time for oxygen plasma treatment of 〈10 min. The changes in the rubber surface remained for 2 h after plasma treatment, as indicated by the variation in peel strength and XPS data. Although improved adhesion was obtained by treating the rubber in an oxygen plasma, the T-peel strength values are not sufficient to assure technical use, probably due to the migration of waxes and zinc stearate to the surface once the treatment was carried out. Finally, sulfur oxidation was produced by the plasma treatment, and for severe conditions solid crystals of a sodium salt of an oxidized sulfur compound (sodium sulphate or an organic sulphate) appeared on the treated rubber surface. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 415-419 
    ISSN: 0142-2421
    Keywords: WO3/ZrO2 catalysts ; surface coverage ; ion scattering spectroscopy ; CO adsorption ; ISS ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A series of WO3/ZrO2 catalysts with tungsten (W) loadings varying from 0.5 to 11.4 wt.% WO3 was prepared by incipient wetness impregnation. The surface coverage of these catalysts was monitored by ion scattering spectroscopy (ISS) and low-temperature CO adsorption.Comparable values for the surface coverage were obtained from ISS and CO adsorption. The surface coverage as determined by these two independent techniques increased from zero to 51±3% as the W loading increased from zero to 4.5 wt% WO3, and leveled off at ∽54±3% with further increases in W loadings. For catalysts with W loadings 〈3.0 wt.% WO3, the surface coverage values were in reasonable agreement with those predicted assuming a monolayer dispersion. For higher W loadings, the results were consistent with multilayer or WO3 formation. This study gives further support for the proposed methodology for monitoring the surface coverage of supported catalyst systems. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 490-497 
    ISSN: 0142-2421
    Keywords: XPS ; surface charging ; insulators ; organic overlayers ; differential charging ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Electrical charging of insulating samples during XPS is of direct concern for referencing the binding energy scale. Results are presented on charging of composite insulating samples that consist of an organic overlayer of polystyrene (PS) or polydimethylsiloxane (PDMS) deposited on NaCl particles. The samples were analysed using small-spot monochromatized radiation, the surface charge being stabilized with an electron flood gun. The charging shift of the NaCl substrate is influenced by three different factors: the total photoelectron flux, the energy of the electrons produced by the flood gun and the flux of electrons originating from the overlayer. The overlayer is acting as an additional electron source, which makes the substrate more negative and reduces inhomogeneities of the local potential affecting the peak full width at half-maximum. Comparison of substrate peak intensities with computed values showed that PS overlayers were less uniform compared to PDMS overlayers. The overlayer thickness and uniformity affect both the total photoelectron flux and the flux of electrons from the overlayer to the substrate. Overlayer charging, like substrate charging, is probably determined by the balance of electron fluxes in the phase considered. The kinetic energy of the photoelectron is determined by the electrical potential in the phase where photoemission occurs and not with respect to the sample surface. This was demonstrated by differential charging between the NaCl substrate and PS overlayer. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 498-511 
    ISSN: 0142-2421
    Keywords: plasma polymers ; fluorocarbons ; oxidation ; ageing ; surface restructuring ; XPS ; FTIR ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Plasma polymer coatings were deposited from perfluoro-1,3-dimethylcyclohexane (PFDMCH) and their composition and surface properties studied by XPS, grazing-angle Fourier transform infrared spectroscopy and contact angle measurements as a function of time after fabrication as they were stored under ambient conditions for more than 2 years. The spontaneous ambient oxidation of PFDMCH plasma polymers was found to be a multi-step process. The rapid initial oxygen uptake, assigned to reaction between carbon-centred radicals incorporated into the coating during deposition and in-diffusing atmospheric O2, was similar to that of plasma polymers deposited from hydrocarbon-based monomers (alkanes, alkylamines, alcohols), suggesting that the density of radicals incorporated during deposition was similar. Subsequently, however, the extent of oxidation was much lower for PFDMCH coatings. This can be attributed to the lack of availability of hydrogen abstraction reactions, which are important for radical propagation in hydrocarbon-based plasma polymers. While XPS recorded a continuous incorporation of oxygen for more than 2 years, the air/water contact angles decreased only during the first 2 months and on further storage remained stable. There appeared to be only a small extent of surface restructuring as assessed from the small depth variations of compositions. The surface was enriched in CF3 groups at all times. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 518-523 
    ISSN: 0142-2421
    Keywords: x-ray photoelectron spectroscopy ; polymeric adsorption ; mineral surfaces ; kaolinite ; quartz ; hydrolysed polyacrylamide ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: This study describes results in which mineral surfaces, treated with partially hydrolysed polyacrylamide (HPAM), were analysed in both standard and imaging XPS instruments. The adsorption of HPAM, as a function of mineral surface, solution concentration and solution pH, has been followed using XPS. Imaging XPS was used to show that HPAM adsorbed preferentially on kaolinite, demonstrating its applicability to measurements of polymeric adsorption at mineral surfaces. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 512-517 
    ISSN: 0142-2421
    Keywords: sputtering ; sputter profiling ; mixing ; isotope sputtering ; balance equation ; binary-collision simulation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A recent experiment by Wittmaack demonstrated that simultaneous sputter profiling by ion scattering and secondary ion mass spectrometry of a two-component target yields information on the depth of origin of sputtered atoms. We have studied the relation between the two signals and the depth of origin theoretically. The main features emerge from just considering stoichiometric mixing and sputtering, but even weakly preferential behaviour affects the difference between the two signals noticeably. The quantitative analysis hinges on material parameters characterizing the low-energy behaviour of collision cascades. We have determined such parameters from a computer simulation code under conditions pertaining to Wittmaack's experiment. The sensitivity to details of the simulational model has been studied extensively. While the resulting sputter depth is only slightly greater than the one emerging from the original analysis, the apparent scatter in the measured values is asserted to be a systematic feature resulting from preferential sputtering. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 524-530 
    ISSN: 0142-2421
    Keywords: corrosion ; aluminium matrix composite ; chloride solutions ; XPS ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: An XPS study of corrosion products formed in seawater and in NaCl solutions on the surface of Al 6061 T6 alloy-10% Al2O3 (v/v) composite was carried out in order to investigate the influence of chloride and magnesium ions (coming from corrosive solutions) and inhomogeneity of the metallic matrix due to the presence of inter-metallic compounds segregated at the grain boundaries.Potentiodynamic polarization tests were carried out to evaluate Al composite resistance to both general and localized attack.Large- and small-area XPS analyses were performed to obtain qualitative and quantitative characterization of corrosion layers. The distribution of the most interesting components of corrosion layers was observed with the Auger technique.The results of electrochemical tests, indicating that specimens immersed in NaCl solutions have a lower pitting corrosion resistance, were correlated with the composition of the corrosion layers, showing higher content in Cl compounds where localized corrosion takes place and higher resistance to corrosion where magnesium compounds are co-precipitated with aluminium corrosion compounds. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 597-605 
    ISSN: 0142-2421
    Keywords: SIMS ; LEIS ; secondary ion mass spectrometry ; low-energy ion scattering ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Kinetic energy distributions of the secondary ions and scattered ions of O+, Cs+ and Ar+ (bombardment with primary ions of O-, O2+, Cs+ and Ar+ was utilized) were obtained from the elemental surfaces of Mg, Al, Si, Ag and Pb using a modified Cameca IMS-3f magnetic sector mass spectrometer. In addition, the distributions of O+ were acquired for O2+ ion surface bombardment of several standard reference materials (Ti-base alloys of SRM648 and SRM649) and geological samples [pyrrhotite (Fe(1-x)S) and arsenopyrite (FeAsS)]. Distinct features attributable to elastic binary projectile/target backscattering collisions were found to be superimposed in the data. Hence, a full characterization of these kinetic ion energy distributions could be made. As a result it is possible to identify both the secondary ion and scattered ion contributions present in the collected kinetic energy distributions and to perform low-energy primary ion surface scattering (LEIS) experiments combined with in situ secondary ion mass spectrometry (SIMS) analysis, albeit to a reduced sensitivity and resolution compared to those possible on dedicated LEIS instruments. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 565-568 
    ISSN: 0142-2421
    Keywords: diamond-like carbon ; photoemission ; electronic structure ; valence band ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The widely differing properties of amorphous carbon films originate from the different s-p hybridization schemes possibly occurring in the C-C bond. For the study of such systems, an approach is suggested that provides direct access to these different types of s-p hybridization via a separate mapping of the s and p partial density of states (DOS) contributing to the total valence band (VB) DOS in carbon materials. Both x-ray and UV-excited VB spectra are needed to this end: the dependence of photoionization cross-sections on photon energy in fact makes x-ray-excited VB photoemission essentially a probe of the s-DOS, and UV-excited VB photoemission essentially a probe of the p-DOS. © 1998 John Wiley & Sons, Ltd.
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  • 286
    ISSN: 0142-2421
    Keywords: ellipsometry ; elastic recoil detection ; x-ray photoelectron spectroscopy ; oxidation ; iron ; single-crystal surfaces ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Thin oxide films play an important role in the corrosion of metals. Using XPS it is possible in principle to obtain information on the chemical state of near-surface atoms, the stoichiometry of the surface layer and its thickness. A problem is the quantification of XPS spectra, due to the large uncertainty in the value of both electron attenuation lengths as well as sensitivity factors. By applying the Tougaard background subtraction method and comparing only peak intensities of the Fe 2p and O 1s peaks with those of Fe, FeO and Fe2O3 reference samples, we determined the stoichiometry of the oxide layer grown on Fe(100) and Fe(110) at 200°C and room temperature to be Fe0.90±0.05O. We combined XPS with the high-energy ion-beam technique of elastic recoil detection (ERD). By comparing the absolute coverages of oxygen determined by ERD with the intensities of different XPS peaks, we were able to determine the attenuation lengths for kinetic energies of 776 eV (Fe 2p) and 957 eV (O 1s) to be 9.3×1015 and 9.9×1015 Fe0.9O molecules cm-2, respectively. © 1998 John Wiley & Sons, Ltd.
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    Keywords: XPS spectra ; overlapping peaks ; oxidation ; film thickness ; composition accuracy ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The composition and thickness of thin iron oxide films on polycrystalline pure iron were evaluated from Fe 2p spectra as measured by x-ray photoelectron spectroscopy. To this end the experimental spectra were reconstructed from reference spectra of the constituents Fe0, Fe2+ and Fe3+. The background contributions in the spectra owing to inelastic scattering of signal electrons were calculated from the depth distributions of these constituents and their reference spectra. In the reconstruction procedure the film thickness and the concentrations of Fe2+ and Fe3+ in the oxide film were used as fit parameters. The values obtained for the oxide film thickness were compared with thickness values determined from the intensity of the corresponding O 1s spectra and with thickness values resulting from ellipsometric analysis. The sensitivity of the reconstruction procedure with regard to film thickness and film composition was tested. © 1998 John Wiley & Sons, Ltd.
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  • 288
    ISSN: 0142-2421
    Keywords: ToF-SIMS ; XPS ; biomaterials ; biomolecules ; surface modification ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and x-ray photoelectron spectroscopy (XPS) are used to characterize the grafting of the reagent N-(m-(3-(trifluoromethyl)diazirine-3-yl)phenyl)-4-maleimido-butyramide (MAD) to various substrates: silicon, silicon nitride and diamond. MAD carries a maleimide function for thermochemical modification of thiolated molecules and a diazirine function that is lost during light activation (350 nm light). Photoactivation leads to carbene-mediated grafting to solid supports. X-ray photoelectron spectroscopy atomic constituents and chemical shifts, as well as ToF-SIMS molecular peaks and characteristic fragments of the photoimmobilized molecule, are identified. Extended interpretation of surface analysis data suggests that diamond is the substrate with the highest MAD grafting efficiency and that the formation of C-O bonds upon diazirine photoactivation is involved. The difference in grafting extent for the three substrates leads to the conclusion that other reaction sites could be involved but they are not identified. © 1998 John Wiley & Sons, Ltd.
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    Keywords: ToF-SIMS ; XPS ; biomaterials ; carbohydrates ; galactose ; patterning ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and x-ray photoelectron spectroscopy (XPS) are used to characterize a newly synthesized glycosylated photoactivatable reagent designed for surface glycoengineering. The glycoaryldiazirine reagent MAD-Gal (N-[m-(3-(trifluoromethyl)diazirine-3-yl)phenyl]-4-(-3-thio(-1-D- galactopyrannosyl)-maleimidyl)butyramide) is immobilized with 350 nm light on diamond surfaces. The XPS atomic constituents and chemical shifts, as well as ToF-SIMS-specific characteristic fragments of the photoimmobilized molecule, are identified. The grafting on oxygen-containing sites previously observed for N-(m-(3-(trifluoromethyl)diazirine-3-yl)phenyl)-4-maleimido-butyramide (MAD) is confirmed. The difference in grafting efficiency for fresh and aged substrates indicates that other still unidentified reaction sites could be involved. The ToF-SIMS imaging is used to exhibit the ability to pattern the surface with the glycosylated aryldiazirine. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 800-805 
    ISSN: 0142-2421
    Keywords: anisotropy ; entropy ; grain boundaries ; solute segregation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: From the viewpoint of existence of linear dependence between entropy and enthalpy of grain boundary segregation, the meaning of the entropy term is discussed. It is suggested that negative values of segregation entropy for silicon segregation at individual grain boundaries in α-iron reflect an ‘ordering’ tendency of the interfaces due to the presence of silicon. On the other hand, positive values of segregation entropy suggest a ‘disordering’ of the structure of these grain boundaries by segregation of carbon and mainly of phosphorus. The effect of ‘disordering’ is especially high for special grain boundaries with compact intrinsic structure, resulting in high values of segregation entropy. The slope of the dependence of enthalpy on entropy of solute segregation at different grain boundaries can be considered as a compensation temperature. Its existence implies that an anisotropy of grain boundary chemical composition will possess a qualitatively different character above and under this temperature. This anisotropy measured above the compensation temperature will be characterized by high values of grain boundary concentration for special boundaries as compared to general boundaries. © 1998 John Wiley & Sons, Ltd.
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  • 291
    ISSN: 0142-2421
    Keywords: multilayers ; ZrN ; BN ; AES ; RBS ; depth profiling ; factor analysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Multilayers of ZrN/BN have been deposited on Si(100) using a double ion beam sputtering system. The multilayers have been characterized by transmission electron microscopy, Rutherford backscattering spectroscopy and Auger electron spectroscopy (AES) depth profiles in order to get a quantitative analysis of the components and contaminants in the different layers and at their respective interfaces. Factor analysis is used to deconvolute the different chemical states of the components and to identify secondary phases and compounds that determine the quality of the multilayer. Two secondary phases have been observed at the different interfaces: one is associated with the incorporation of oxygen, mainly in the zirconium layer, and leads to the formation of ZrNxOy. In addition we have observed that Ar bombardment during the AES depth profile leads to the formation of ZrBxNy in all the interfaces. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 939-956 
    ISSN: 0142-2421
    Keywords: XPS ; reference data ; x-ray photoelectron spectroscopy ; peak fitting ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Standard test data (STD) are simulations of analytical instrument responses that help to determine the veracity of computer-based, data analysis procedures that are typically used with instruments. The STD were developed for determining errors in peak parameters obtained from data analysis algorithms used in x-ray photoelectron spectroscopy (XPS). The STD were mainly C 1s doublet spectra constructed from spline polynomial models of measured C 1s polymer spectra. Different spectra were created based on a replicated factorial design with three factors: peak separation; relative intensity of the component peaks; and fractional Poisson noise. These doublet spectra simulated XPS measurements made on different two-component specimens. Single-peak C 1s spectra for individual polymers were also simulated, to provide the null case for identification of the doublet spectra. Twenty analysts used a variety of data analysis programs and a variety of curve-fitting approaches to determine peak binding energies. Results indicate that data analysis of doublet spectra may be problematic, because up to 50% of the STD doublets were assigned incorrectly as singlets. For spectra that were correctly identified as doublets, bias and random error in peak binding energies depended on the amount of separation between the component peaks and on their relative intensities. Biases ranged from -0.055 eV to 0.34 eV, while random errors ranged from 0.012 eV to 0.13 eV. Use of the Gaussian-Lorentzian function fitted to spectra resulted in smaller biases than the use of a Gaussian function alone. As a guide to evaluating peak energy uncertainties in their own analyses, analysts may find it useful to analyze the STD themselves and then compare their results with those reported here. The spectra may be obtained at http://www.acg.nist.gov/std/main.html. © 1998 John Wiley & Sons, Ltd.
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    Surface and Interface Analysis 26 (1998), S. 17-29 
    ISSN: 0142-2421
    Keywords: Elastic scattering ; peak attenuation ; quantitative surface analysis ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: We define a new parameter to describe the effects of elastic electron scattering in XPS and AES. The parameter is the ratio of emitted intensity from a layer of atoms located at a given depth in a solid calculated from theories that take into account and neglect elastic electron scattering. We have found that the correction parameter can be expressed by a simple formula. This formula is of general validity for typical experimental geometries applied in practical XPS and AES. The formula was determined by fitting an analytical expression to the results of extensive Monte Carlo calculations made under variation in the full relevant range of electron energy, matrix atomic number, depth of origin of emitted electrons and angular emission anisotropy. The formula depends on the inelastic (λi) and the transport (λtr) mean free path for electron scattering. Three assumptions were made in the calculations, namely that the geometry is close to normal emission, that the angle between x-ray source and analyser axis is close to the magic angle (54°) and that the ratio λtr/λi is approximately constant over the analysed depth. However, the result is expected to vary only slightly when these assumptions are not strictly fulfilled. © 1998 John Wiley & Sons, Ltd.
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    Fire and Materials 22 (1998), S. 39-42 
    ISSN: 0308-0501
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Architecture, Civil Engineering, Surveying , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Heat Release Rates of organic materials are studied in many countries, but there is no mathematical formula to represent their shape. We considered a mathematical expression of the Heat Release Rate Curve by a simple equation. And we also derived the index of degree of combustibility, named ‘Burning Index (BI)’. The Heat Release Rate Curve is expressed by the derivative of a probability function of maximum value and has three parameters; an amplitude coefficient, a time width coefficient and an ignition index. BI is in proportion to an amplitude and a time width and in inverse proportion to an ignition index. BI values of cable plastic compounds with flame-retardant material had good relations with the quantity of non-organic ingredients. © 1998 John Wiley & Sons, Ltd.
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  • 295
    ISSN: 0308-0501
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Architecture, Civil Engineering, Surveying , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Additional Material: 1 Ill.
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  • 296
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    New York, NY [u.a.] : Wiley-Blackwell
    Fire and Materials 22 (1998), S. 213-218 
    ISSN: 0308-0501
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Architecture, Civil Engineering, Surveying , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: The paper describes results of investigations of conveyor belt flammability in full scale, using the large-scale gallery method and using cone calorimeter. On the basis of oxygen consumption calorimetry, the amounts of heat release during burning of conveyor belts were calculated. A correlation was found between results of conveyor belt flammability obtained using both methods. Criteria for conveyor belt flammability assessment were established for the cone calorimeter method, which define a level that would be equivalent to that for the large-scale gallery test. © 1998 John Wiley & Sons, Ltd.
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  • 297
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    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Fire and Materials 22 (1998), S. 239-252 
    ISSN: 0308-0501
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Architecture, Civil Engineering, Surveying , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: The gasification behavior for a wide range of polydimethylsiloxane fluids in a nitrogen atmosphere was investigated. Part 1 of this study addressed the measurement of the energy (global heat of gasification) required for the gasification of a wide range of dimenthylsiloxanes. Several significant corrections were required to reconcile measured gasification energy(s) with calculated heat(s) of gasification based on fundamental thermochemical data. The identification of the dominant mode(s) of gasification via the characterization of pyrolysis products provided a firm basis and rationale for understanding and directing efforts at quantifying these correction factors. In Part 2, the gasification products were identified and quantified at various stages of the gasification process corresponding to ignition, fire growth, and steady-state burning. Pyrolysis of methylated siloxanes occurs via two modes: (1) the volatilization of short chain and intermediate chain length species native to the polymer, and (2) the volatilization of short chain and intermediate chain length species resulting from thermal degradation via siloxane rearrangement. The former process is the dominant gasification mechanism for short chain oligomers and low viscosity fluids (η〈10 cS) and the latter process is dominant in all higher molecular weight polymers (η〉100 cS). Both gasification mechanisms are evident in all polymers (η〉20 cS); the dominant mechanism is dependent upon polymer size and distribution thereof, the gasification stage, and the presence of trace catalysts in the polymer. Because of their structural similarity, the combustion of all gasification products emanating from PDMS regardless of the stage of the pyrolysis process or the dominant mode of gasification will result in virtually identical combustion products, i.e. SiO2, CO2, and H2O. Copyright © 1998 John Wiley & Sons, Ltd. This paper was written under the auspices of the US Government and is therefore not subject to copyright in the US.
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  • 298
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Fire and Materials 22 (1998), S. 47-54 
    ISSN: 0308-0501
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Architecture, Civil Engineering, Surveying , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: High-temperature pyrolysis of various classes of polymers have been discussed. For the non-carbonizing polymers it was shown that polymer structure can affect the pyrolysis characteristics. Data on the high-temperature pyrolysis of some polypropylene samples with different crystallinity have been presented. Modification of the standard method allowing one to obtain kinetic data from the single experiment was discussed. A kinetic model for the degradation of char-forming polymers in conditions of high-temperature pyrolysis has been suggested. It has been supposed that pyrolysis of carbonizing polymers proceeds in some (two in present work) parallel stages with different activation energies, temperatures and pyrolysis rates. Questions of the applicability of the suggested model to describe the various types of charring systems have been discussed. High-temperature pyrolysis for a number of epoxy resin-based polymeric compositions have been investigated. Kinetic parameters of the pyrolysis have been computed. © 1998 John Wiley & Sons Ltd.
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  • 299
    ISSN: 0308-0501
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Architecture, Civil Engineering, Surveying , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: The oxygen index (OI) of poly(butylene terephthalate) (PBT) tends to decrease when it is combined with milled-glass fibres either with or without the sizing treatment. This shows that the previously found apparent increase of flammability of PBT glass fibre composites (GFPBT) as compared to PBT is not due to the introduction of the flammable sizing together with the glass fibres in the polymer which was one suggested explanation in the literature, but rather to the wick and anti-dripping effects of glass fibres. The effectiveness of a typical brominated organic compound-antimony trioxide fire retardant system (FR), as measured by OI, is found to be larger in GFPBT as compared to PBT. A linear increase of the temperature index (TI) of PBT and of GFPBT is observed with increasing concentration of the FR. The fire retardant increases the time to ignite while it decreases the maximum rate of heat release and increases the smoke optical density and CO evolution on burning in the cone calorimeter. The dependence of fire risk and hazard assessement on the combustion model of the combustion test method is discussed for OI and cone calorimeter in the case of PBT, GFPBT and FR corresponding materials. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 7 Ill.
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  • 300
    ISSN: 0308-0501
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Architecture, Civil Engineering, Surveying , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: The study presented addresses the fire behaviour of polypropylene compounded with six classes of flame retardants. The application of cone calorimetry for the assessment of the thermal characteristics of the tested materials and their comparison with thermogravimetry are the central point of this research. This study only presents data for 25 kW/m2 of incident heat flux exposure and includes five tests for polypropylene with no additives and five tests for polypropylene with flame retardants based on triglycidylisocyanurate and lignin. The data collected include the rate of heat release, mass loss rate, char yield, time to ignition and time of total combustion. Results represent meaningful comparison between the behaviour of the materials under simulated fire conditions, using the cone calorimeter, and in the slow dynamic environment utilized in thermogravimetric analysis. © 1998 John Wiley & Sons Ltd.
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