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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 29 (1991), S. 669-676 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Charge transfer (CT) interactions between poly[[o-(trimethylsilyl)phenyl]acetylene] or poly(o-Me3SiPA) and some electron acceptors were studied by ultraviolet-visible and infrared absorption spectroscopy and by x-ray photoelectron spectroscopy, (XPS). The electron acceptors used included iodine, bromine, o-chloranil, o-bromanil, 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), and tetracyanoethylene (TCNE). Varying degrees of CT interactions were observed in all of the polymer/acceptor complexes studied. The electrical conductivities σ of the organic acceptor complexes exhibited a strong acceptor concentration dependence at low acceptor levels, with the DDQ complex exhibiting the highest σ. The extent of CT and the redistribution of charges resulting from the CT in all the complexes were revealed by XPS. The poly (o-Me3SiPA)/I2 complex film lost iodine spontaneously while more than half of the bromine in the poly (o-Me3SiPA)/Br2 complex existed as covalently bonded bromine, even at low halogen loading.
    Additional Material: 10 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 33 (1995), S. 833-839 
    ISSN: 0887-6266
    Keywords: spectroscopy ; polyaniline ; Donnan effect ; protonation/deprotonation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Emeraldine base films were treated with HClO4 solutions of various concentrations, with and without the addition of NaClO4. The protonation of the films was studied using angle-resolved x-ray photoelectron spectroscopy (XPS), Fourier transform infra-red (FTIR) absorption spectroscopy, and ultraviolet (UV)-visible absorption spectroscopy. The protonation level can be substantially increased by the presence of salt if sufficient time is allowed for the anions to migrate into the bulk of the film. Conversely, in the partial deprotonation of emeraldine salt films, a higher retention of anions is observed in the presence of salt, even though the effect is not as pronounced as in the protonation process. © 1995 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Surface and Interface Analysis 20 (1993), S. 645-650 
    ISSN: 0142-2421
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: A calculation method for the secondary ion mass spectrometry (SIMS) analysis of the reaction of a pure metal with gas mixtures of water and oxygen is introduced. Equation systems are to be solved, each expressed as: Y = A × X, where Y is an amplitude column measured from the SIMS spectrum, A is a matrix constructed from the relative abundances of isotopes of the metal and X is an unknown amplitude column of the relevant species MeaOHb±(a = 1, 2; b = 0, 1, 2 and 3). The applicability of the calculation method has been tested in SIMS analysis of ex situ-grown iron oxides with different and known 18O contents. In in situ oxidation, measurement of the ratio of H216O/H218O in the metal-water-oxygen reaction allows fractions of O in the species MeaOHb+ that originate from water to be calculated. Data from such calculations have been used to study the initial stage of the reaction of Fe and Cr in H216O/H218O/16O2 gas mixtures. The results are interpreted in terms of coupled/uncoupled reaction type, reactivity of metal to water relative to oxygen in the mixed gas and degree of dissociation of water.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Surface and Interface Analysis 19 (1992), S. 33-37 
    ISSN: 0142-2421
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: X-ray photoelectron spectroscopy provides a useful tool for the critical comparison of the chemical nature of the nitrogens corresponding to the various intrinsic redox states of electroactive polypyrrole (PPY) and polyaniline (PAN) and their N-substituted derivatives. Proton modifications of the PPY nitrogens can give rise to a number of intrinsic redox states corresponding to various proportions of the imine-like (=N—) and amine-like (—NH) nitrogens, similar to those observed in PAN. For complexes prepared from oxidative polymerizations, the intrinsic oxidation level of PAN is always about twice that of PPY (50% vs. 25%). The behaviours of the nitrogens of the corresponding redox states in both polymers towards oxidation, reduction, protonation and charge transfer interactions are grossly similar. However, the amine nitrogens in the emeraldine (EM) oxidation state of PAN (50% =N— structure) are more susceptible to protonation in the presence of excess protonic acids than those of the 25% deprotonated PPY (DP-PPY). Finally, the doping level in poly(N-methylaniline) (PMAN) is twice that of poly(N-methylpyrrole) (PMPY). The base polymers of PMAN and PMPY exist only in the fully reduced state and are susceptible to reoxidation. The nitrogens of PMAN, but not PMPY, are also susceptible to protonation.
    Additional Material: 5 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Surface and Interface Analysis 24 (1996), S. 51-58 
    ISSN: 0142-2421
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Surface modification of polypyrrole (PPY), polyaniline (PAN) and poly(3-alkylthiophene) films by ozone was studied by angle-resolved x-ray photoelectron spectroscopy (XPS). In the case of the N-containing polymers, oxidation occurs readily and mainly at the carbon atoms, resulting in the formation of CνO, CξO, COOH and even OνCOOH (especially for PAN) species. The carbon atoms of doped PPY and PAN films are significantly more resistant to ozone oxidation, but the samples suffer some loss of the dopant in the surface region. Ozone treatment does not involve the direct oxidation of the nitrogen heteroatoms to form theνNOx species, even at high extent of carbon oxidation. In addition, a substantial decrease in the intrinsic oxidation state ([ξNν]/[νNHν] ratio) was observed in the 25% deprotonated PPY (DP-PPY) base, the 50% intrinsically oxidized emeraldine (EM) base and the 75% intrinsically oxidized nigraniline (NA) base after ozone treatment and subsequent atmospheric exposure. In the case of the S-containing polymers, ozone treatment results predominantly in the oxidation of sulphur heteroatoms to give rise to the sulphone and peroxide species. The oxidized sulphur species, however, are readily reduced or consumed in a photochemical reaction.
    Additional Material: 9 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 43 (1991), S. 573-579 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The thermogravimetric behavior of polypyrrole (PPY), polybithiophene (PBT), and poly-aniline (PAN) perchlorate complexes and their corresponding base polymers have been studied. The PBT-perchlorate complex and base polymer decompose at significantly lower temperatures than do the PPY and PAN counterparts. All three perchlorate complexes retain half or more of their original conductivities with no changes in the doping levels after one cycle of heating to 150°C in air and cooling to room temperature. However, after heating at 150°C for 24 h, only the PAN-perchlorate complex shows no significant change in the doping level, although its conductivity decreases by more than two orders of magnitude. X-ray photoelectron spectroscopy analyses of the perchlorate complexes reveal the presence of at least two distinct chlorine species. The thermal decomposition of the perchlorate anions results in the formation of volatile chlorine species as well in chlorine covalently bonded to the polymer. The thermal decomposition of the PPY-perchlorate complex also results in the conversion of positively charged nitrogens to iminelike structures.
    Additional Material: 4 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 38 (1989), S. 2009-2017 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Simultaneous chemical copolymerization and oxidation of pyrrole and N-methylpyrrole by bromine an iodine has been carried out. The composition of the copolymes can be effectvely controlled by varying the monomer feed ratio. From elemental analysis the copolymer composition and the monomer reactivity ratios have been determined. As the copolymer composition changes, the IR absorption spectra show changes in the intensity of certain bands. In bromineinduced polymerization, the electrical conductivity, the electrical conductivity, thermal stability, and bromine content of the copolymer complex decrease with increase in N-mthylpyrrole fraction. X-ray photoelectron spectroscopy data suggest that a fixed fraction of bromine is incroporated as covalent bromide in the copolymer complex. When iodine is used the halogen content do not show substantial differences among the copolymers but the electricdal conductivity and thermal stability of the copolymers also decrease with increase in N-methylpyrrole fraction.
    Additional Material: 5 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 3107-3114 
    ISSN: 0887-624X
    Keywords: PTFE ; auto-adhesion ; surface grafting ; amphoteric monomer ; Ar plasma ; XPS ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The surfaces of Ar plasma-pretreated polytetrafluoroethylene (PTFE) films are further functionalized via UV-induced graft copolymerization with amphoteric N,N′-dimethyl(methacryloylethyl)ammonium propansulfonate (DMAPS) either in Ar atmosphere, or under atmospheric conditions and in the absence of a polymerization initiator. The so-modified PTFE films from either process are capable of exhibiting adhesive-free adhesion or auto-adhesion with one another when brought into intimate contact in the presence of a small quantity of water. The lap shear adhesion strength increases with increasing graft concentration and can readily exceed the yield strength of the PTFE substrate. Two plasma-pretreated PTFE films also readily undergo thermal graft copolymerization with concurrent lamination when lapped together in the presence of a small quantity of the DMAPS monomer solution at elevated temperature in the atmosphere. The surface compositions of the graft-copolymerized PTFE films and the delaminated surfaces were characterized by X-ray photoelectron spectroscopy (XPS). In most cases, adhesional failure occurred near the graft-substrate interphase. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3107-3114, 1998
    Additional Material: 9 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 27 (1989), S. 4365-4374 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polyaniline-tetracyanoethylene (TCNE) complexes can be synthesized either from emeraldine base or emeraldine hydrochloride by a relatively simple method. The complexes demonstrate greater stability than the emeraldine hydrochloride at elevated temperatures and under high current densities. The electrical conductivity of the complexes synthesized from emeraldine base can be varied from 〈 10-6 to 0.2 S/cm by varying the amount of TCNE incorporated. The complexes synthesized from emeraldine hydrochloride are slightly more conductive than the starting emeraldine hydrochloride. In both types of complexes, it appears that electron transfer between the polyaniline and TCNE has occurred resulting in the formation of some positively charged polyaniline nitrogen and TCNE anions.
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  • 10
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 357-366 
    ISSN: 0887-624X
    Keywords: surface graft copolymerization ; adhesive-free adhesion ; polycarbonate ; XPS ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The surfaces of ozone-pretreated polycarbonate films were subjected to further modification by thermally induced graft copolymerization with acrylic acid (AAc), sodium salt of styrene sulfonic acid (NaSS), N,N-dimethylacrylamide (DMAA), N,N-(dimethylamino)ethyl methacrylate (DMAEMA) and 3-dimethyl(methacryloyl ethyl)-ammonium propanesulfonate (DMAPS) monomers. The structure and composition at the copolymer interface were studied by angle-resolved X-ray photoelectron spectroscopy (XPS). For polycarbonate films with a substantial amount of grafted polymer, the hydrophilic graft penetrates or becomes partially submerged beneath a thin surface layer of dense substrate chains. This microstructure was further supported by the water contact angle measurements. Adhesive-free adhesion studies revealed that the AAc, DMAA or DMAPS graft copolymerized polycarbonate film surface adhered strongly to another similarly modified surface (homo-interface) when brought into direct contact in the presence of water and subsequently dried. The development of the lap shear strength is dependent on the concentration of the surface graft, the microstructure of the grafted surface, the adhesion (drying) time, and the nature of the interfacial interaction. The simultaneous presence of chain entanglement and electrostatic interaction readily results in substantially enhanced adhesion strengths between two DMAPS graft copolymerized surfaces or between an AAc and a DMAA graft copolymerized surface (hetero-interface). XPS analyses of the delaminated surfaces suggest that failure occurred cohesively below the graft-substrate interface. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 357-366, 1998
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