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  • Articles  (39,515)
  • Articles: DFG German National Licenses  (39,515)
  • Springer  (39,515)
  • 1990-1994  (39,515)
  • Chemistry and Pharmacology  (38,358)
  • Nature of Science, Research, Systems of Higher Education, Museum Science  (1,157)
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  • Articles  (39,515)
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  • 1
    Electronic Resource
    Electronic Resource
    Indexed in current contents (1994)
    Springer
    Polymer bulletin 32 (1994), S. A3 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00308550
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  • 2
    Electronic Resource
    Electronic Resource
    Mechanical properties of organosolv-lignin-filled thermoplastics (1994)
    Springer
    Polymer bulletin 32 (1994), S. 361-365 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Organosolv lignin was used as organic filler for polypropylene (PP) and poly(ethene-co-vinylacetate) (EVA) containing 13wt-% vinylacetate. As a function of the lignin content, which was varied between 0 and 30wt-%, mechanical properties such as Young's modulus, yield stress, fracture stress, and elongation at break of the thermoplastic lignin-based compounds were measured. Both lignin-filled thermoplastics exhibit pronounced matrix reinforcement with increasing lignin content. Due to better interfacial adhesion between lignin and EVA, 30wt-% lignin addition to EVA doubles Young's modulus without sacrificing high elongation at break.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00308549
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  • 3
    Electronic Resource
    Electronic Resource
    4-Vinylphthalic anhydride (1994)
    Springer
    Polymer bulletin 32 (1994), S. 373-380 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary 4-Vinylphthalic anhydride can be prepared from phthalic acid via bromination and subsequent olefination (Heck-reaction). Homo- and copolymerization with styrene was accomplished using AIBN as initiator. The copolymer compositions were determined by infrared-spectroscopy. The copolymerization parameters are rs=0,15 and rVPA=3,09, the corresponding Q, e values of 4-vinylphthalic anhydride are estimated as Q=3,34 and e=0.09. Despite the fact that the molecular weights were rather low as a consequence of the reaction contions, the glass transition temperatures rise with increasing VPA content. The homopolymer has a glass transition temperature in the order of 226°C.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00587877
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  • 4
    Electronic Resource
    Electronic Resource
    Homogeneous nucleation of the dispersed crystallisable component of immiscible polymer blends (1994)
    Springer
    Polymer bulletin 32 (1994), S. 471-477 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Immiscible melt mixed blends of a crystallisable polyolefin (isotactic polypropylene, PP) and atactic polystyrene (PS) were prepared in a wide composition range. It was found that when PP is the major component in the blend its crystallisation behaviour is not affected by blending it with PS. However if PP is the minor component, it will be dispersed in the immiscible PS matrix, hence the nucleation mechanism changes from predominantly heterogeneous to predominantly homogeneous as long as the size of the dispersed PP droplets is below a critical value (of the order of 1–2 μm).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00587890
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  • 5
    Electronic Resource
    Electronic Resource
    Synthesis and characterization of glycidyl ethers modified by mesogenic units (1994)
    Springer
    Polymer bulletin 32 (1994), S. 529-536 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary New types of epoxy compounds containing biphenyl and azophenyl groups were synthesized. Model glycidyl ethers with one epoxy group were prepared to study the first reaction steps during the curing process. Diglycidyl ethers with or without a hexamethylene spacer were made to obtain epoxy networks. The structures of some intermediates and of the epoxy compounds synthesized were confirmed by Proton and Carbon-13 NMR spectroscopy.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00973898
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  • 6
    Electronic Resource
    Electronic Resource
    Anionic polymerization and copolymerization of cyclosiloxanes initiated by trimethylsilylmethyllithium (1994)
    Springer
    Polymer bulletin 32 (1994), S. 35-40 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary A novel initiator, i.e. trimethylsilylmethyllithium has been successfully used for the ring opening polymerization of cyclosiloxanes, in toluene or in the bulk, in the presence of the cryptand [211] or DMSO. Suitable conditions have been found in which monomodal distributions of molecular weights are observed for homopolymers of 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane (V4) as well as for copolymers of V4 with D3 or D4.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00297411
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  • 7
    Electronic Resource
    Electronic Resource
    Editorial (1994)
    Springer
    Polymer bulletin 32 (1994), S. 1-2 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00297406
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  • 8
    Electronic Resource
    Electronic Resource
    Stereospecific propene polymerization with rac-[1,2-bis(η5-(9-fluorenyl))-1-phenylethane]zirconium dichloride/methylalumoxane (1994)
    Springer
    Polymer bulletin 32 (1994), S. 41-46 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Methylalumoxane (MAO)-activated rac-[1,2-bis(η5-(9-fluorenyl))-1-phenylethane]zirconium dichloride (1) was used for propene polymerization at 30, 50, and 70°C and constant monomer concentration. The polypropene products are isotactic with stereoregularities depending on the polymerization temperature. The pentad distributions follow “enantiomorphic site statistics”, indicating stereocontrol being conducted by the chiral catalyst site.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00297412
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  • 9
    Electronic Resource
    Electronic Resource
    List of valid recommendations on macromolecular nomenclature (1994)
    Springer
    Polymer bulletin 32 (1994), S. 125-126 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00297424
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  • 10
    Electronic Resource
    Electronic Resource
    Synthesis of a new styrene monomer: the 3-chloro-4-nitrostyrene (1994)
    Springer
    Polymer bulletin 33 (1994), S. 389-395 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary A satisfactory synthesis route to a new monomer, the 3-chloro-4-nitrostyrene (3-CNS) is described. The results of free radical polymerisation experiments (limit of conversion, global kinetics) are reported by comparison with those of the isomer 4-chloro-3-nitrostyrene (4-CNS). They show the great influence of the nitro group position which markedly increases the reactivity of 3-CNS.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00293481
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  • 11
    Electronic Resource
    Electronic Resource
    Preparation of polystyrene poly(β-hydroxy nonanoate) graft copolymers (1994)
    Springer
    Polymer bulletin 33 (1994), S. 431-438 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Poly(β-hydroxy nonanoate)-polystyrene graft copolymers were prepared by the reaction of active polystyrene containing peroxide group with poly(β-hydroxy nonanoate) at 80°C. Graft copolymers with a wide graft composition range depending on the amount of active polystyrene in the original mixture were produced and separated from the grafting product by fractional precipitation. NMR and IR spectra of the graft copolymers were containing the characteristic bands of the corresponding blocks. DSC curves of the graft copolymers had a large endotherm between 50 and 110°C.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00293487
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  • 12
    Electronic Resource
    Electronic Resource
    Real-time small-angle synchrotron study of the crystallization kinetics of isotactic poly(1-hexadecene) (1994)
    Springer
    Polymer bulletin 33 (1994), S. 451-458 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary The isothermal crystallization kinetics of the isotactic content of three poly(1-hexadecene) samples with different tacticity has been studied by real-time small-angle X-ray scattering using synchrotron radiation. The process was analyzed in terms of the Avrami equation. The value of the Avrami exponent was found to be approximately 1, suggesting instantaneous nucleation followed by rod-like growth. The results are compared with those previously obtained by differential scanning calorimetry.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00293490
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  • 13
    Electronic Resource
    Electronic Resource
    Polymerization of styrene with diphenylzinc-butanone systems (1994)
    Springer
    Polymer bulletin 32 (1994), S. 367-371 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary In the present work we report the results of the polymerization of styrene using diphenylzinc-butanone, Ph2Zn-MeCOEt. Our results indicate that these systems induce the polymerization of styrene reaching a larger conversion when the molar ratio MeCOEt/Ph2Zn=1,0. According to size exclusion chromatography, SEC, studies of the polystyrene obtained using the Ph2Zn-MeCOEt showed unimodal curves and have molecular weight distribution narrower than those obtained using the Ph2Zn-H2O system, suggesting a more simple reaction system.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00587876
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  • 14
    Electronic Resource
    Electronic Resource
    Poly(arylenecarbonate)s oligomers by carbonate interchange reaction of dimethyl carbonate with bisphenol-A (1994)
    Springer
    Polymer bulletin 32 (1994), S. 427-432 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Fast atom bombardment mass spectrometry (FAB-MS) has been used to identify oligomers with different end groups obtained by the carbonate interchange reaction of bisphenol-A with dimethyl carbonate and the partial methanolysis of poly(bisphenol-A carbonate)s. Based on the FAB-MS data, a reaction pathway for the formation of compounds in the synthesized oligomers is proposed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00587884
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  • 15
    Electronic Resource
    Electronic Resource
    Semi-interpenetrating polymer networds produced with polyethylene terephthalate oligomer and unsaturated polyester resin (1994)
    Springer
    Polymer bulletin 32 (1994), S. 447-453 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract A series of semi-interpenetrating polymer networks (semi-IPN's) based on different compositions of an acyclic polyethylene terephthalate oligomer and unsaturated polyester resin (UP) were prepared. The oligomer was dissolved in the resin containing styrene crosslinker. Later this mixture was crosslinked at room temperature using methyl ethyl ketone peroxide catalyst and cobalt naphtanate as promoter. The tensile strength of the IPN's decreases as the concentration of oligomer increases, whereas, elongation to break increases. A characterization of the oligomer used is also presented.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00587887
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  • 16
    Electronic Resource
    Electronic Resource
    Compatibilisation of polystyrene-polyolefin blends (1994)
    Springer
    Polymer bulletin 32 (1994), S. 479-485 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary The impact properties of 1:1 polyolefin-polystyrene blends compatibilised with a series of hydrogenated styrene-butadiene block copolymers of various structures have been studied with a view to establishing a structure-property realationship. The most effective compatibiliser in this context appears to be a low molecular weight triblock (Kraton G1652). Addition of only 5% Kraton G1652 affords a ca. three-fold improvement in the impact strength for a 1:1 PP/PS blend over the uncompatibilised blend and leads to near HIPS impact strength for a 1:1 LDPE/PS blend. This compatibiliser is as effective as a high molecular weight tapered diblock and appears to be substantially more effective than either low molecular weight diblocks or a higher molecular weight triblock.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00587891
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  • 17
    Electronic Resource
    Electronic Resource
    Metathesis copolymerization of chlorine-containing acetylenes with NBE catalyzed by MoCl5-n-Bu4Sn (1994)
    Springer
    Polymer bulletin 32 (1994), S. 517-524 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary In the copolymerizations of 1-chloro-1-octyne (ClOc) and 1-chloro-2-phenylacetylene (ClPA) with norbornene (NBE) by MoCl5-n-Bu4Sn in toluene at-20°C, both comonomers were consumed simultaneously. The GPC curves of the copolymerization products were unimodal and identical irrespective of the RI and UV (290 nm) detectors. The13C NMR spectra of the products exhibited the presence of cross-propagating sequences. From these results, it is concluded that the copolymerization products are copolymers and not mixtures of homopolymers. The monomer reactivity ratios were: rClOc=0.69, rNBE=6.4; rClPA=1.0, rNBE=3.1. The more electron-donating the ring substituent of CiPA, the more reactive the ClPA in copolymerization with NBE.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00973896
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  • 18
    Electronic Resource
    Electronic Resource
    Volume contents (1994)
    Springer
    Polymer bulletin 32 (1994), S. A5 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00297426
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  • 19
    Electronic Resource
    Electronic Resource
    Synthesis and properties of poly(diphenylacetylenes) having ether linkages (1994)
    Springer
    Polymer bulletin 32 (1994), S. 133-140 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Polymerization of 1-phenyl-2-(p-phenoxyphenyl)acetylene (p-PhODPA), 1-phenyl-2-(p-methoxyphenyl)acetylene, and 1-phenyl-2-(p-n-butoxyphenyl)acetylene was examined. These monomers polymerized with TaCl5-n-Bu4Sn to give methanol-insoluble polymers in over 60% yields. Poly(p-PhODPA) was a yellow solid completely soluble in toluene, CHCl3, etc., and its weight-average molecular weight was about 1.0x106 or higher. This polymer was thermally very stable (the onset temperature of weight loss in TGA in air was 420 °C). Its oxygen permeability coefficient (P o 2) was 37 barrers (P o 2/P n 2 2.2) and similar to that of natural rubber. In contrast, the other two polymers did not completely dissolve in any organic solvent, and their thermal stability was lower.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00306379
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  • 20
    Electronic Resource
    Electronic Resource
    Homo- and copolymers of methacryloylmalodiethylester, synthesis and behaviour (1994)
    Springer
    Polymer bulletin 32 (1994), S. 141-147 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Chelating polymers obtained by copolymerization of methacryl-oylmalodiethylester (MMDEt) with styrene, methylmethacrylate (MMA), N-vinylpyrrolidone (VPD) and N,N-dimethylacrylamide (DMAM) as well as the homopolymer of methacryloylmalodiethylester (MMDEt) have been investigated. Watersoluble chelating polymers derived from copolymerization with DMAM offer not only the possibility of a very fast removal of metal ions from aqueous solution, but are also insoluble after complexing certain metal ions and can therefore be separated by filtration. As additional investigations on the model acetyloylmalodiethylester (AMDEt) show, preferably hard metal ions such as Mg2+, Ca2+, Al3+ and Cu2+ with an ionic radius up to 1 Å are chelated by the enolic form of the β-ketodiester. The number of ligands for a metal ion corresponds to its valence.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00306380
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  • 21
    Electronic Resource
    Electronic Resource
    An analysis of the 1H- and 13C-NMR spectra of poly(3-bromostyrene) (1994)
    Springer
    Polymer bulletin 32 (1994), S. 207-214 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary The 300 MHz 1H-NMR spectrum of free radical initiated poly(3-bromostyrene) is similar to the 1H-NMR spectra of certain poly(vinyl heterocycles) and can be interpreted in a like manner. The 13C-NMR is typical of spectra for meta-substituted polystyrenes, with some of the carbon resonances showing a sensitivity to polymer stereochemistry. The spectra indicate that poly(3-bromostyrene) synthesized by free radical initiation is an atactic polymer.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00306390
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  • 22
    Electronic Resource
    Electronic Resource
    Effect of thermal molecular motion on pervaporation behavior of comb-shaped polymers with fluorocarbon side groups (1994)
    Springer
    Polymer bulletin 32 (1994), S. 193-200 
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    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Thermal molecular motion of a series of comb-shaped polymers with heptadecafluorodecyl side chains (CF 8C2-) has been studied based on dynamic viscoelastic measurement. The main chain of comb-shaped polymers was poly(fumarate), poly(methacrylate), and poly(acrylate). Poly(fluoroalkylfumarate) with heptadecafluorodecyl group, P(CF 8C2-iPF) was amorphous polymer, whereas poly(acrylate) and poly(methacrylate) with CF 8C2-, P(CF 8C2-Acr) and P(CF 8C2-MAcr) showed mesomorphic behavior. The pervaporation behavior of water/organic mixtures through amorphous polymer, P(CF 8C2-iPF), and mesomorphic one, P(CF 8C2-Acr), were investigated. The distinct increase in permselectivity has been observed at the mesomorphic transition of P(CF 8C2-Acr).
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    URL: http://dx.doi.org/10.1007/BF00306388
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  • 23
    Electronic Resource
    Electronic Resource
    Synthesis of new donor-acceptor diarylacetylene chromophores and preparation of corresponding nonlinear optical side-chain polymers (1994)
    Springer
    Polymer bulletin 32 (1994), S. 265-272 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Sammary New donor-acceptor substituted diarylacetylene hyperpolarizable chromophores bearing an amino group as donor and a methylsulfonyl group as acceptor at each extremities of an azatolane conjugated path have been designed to get a good nonlinearity-transparency trade-off, and synthesized. Corresponding methacrylate esters have been obtained then submitted to free radical polymerization, leading to novel side-chain nonlinear optical polymers and copolymers.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00308536
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  • 24
    Electronic Resource
    Electronic Resource
    Enthalpic interaction of diblock copolymers with immiscible polymer blend components (1994)
    Springer
    Polymer bulletin 32 (1994), S. 241-248 
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    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary An attempt is made to extend the model of Leibler for the emulsifying activity and interfacial properties of A-b-B diblock copolymers in incompatible blends of the homopolymers A and B-which are identical with the respective copolymer components- to enthalpically interacting C-b-D diblock copolymers, the block C being thermodynamically compatible with A and D with B. Due to the attractive enthalpic interaction the A/C-b-D/B compatibilized blends are promising for optimum phase adhesion (bold types for thermodynamically compatible partners). Thus, the extended model for a plane interfacial layer includes the enthalpic interaction of the compatible polymer pairs beside the entropic effects. The approach starts with the equillibrium supposition, not taking into consideration enthalpy driven migration effects of the block copolymer from the bulk to the interface, The model confirms a dominant role of the enthalpic interaction between blocks of the diblock copolymer and the respective homopolymers to the compatibilization of incompatible blend components. It is applicable also for blends compatibilized with block copolymers of unfavourable repulsive type interaction, A/C-b-D/B, and for blend systems with mixed type interactions, e. g. A/C-b-B/B or A/C-b-D/B.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00306395
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  • 25
    Electronic Resource
    Electronic Resource
    A preliminary analysis of the high field 13C-NMR and 1H-NMR spectra of poly(2-thienyl vinyl ketone) (1994)
    Springer
    Polymer bulletin 32 (1994), S. 305-310 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Poly(2-thienyl vinyl ketone) was synthesized via free radical initiation and its 300 H-NMR and 75.5 MHz 13C-NMR spectra were recorded and analyzed. The analysis showed that poly(2-thienyl vinyl ketone) is an atactic polymer.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00308541
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  • 26
    Electronic Resource
    Electronic Resource
    Electrical and third-order nonlinear optical properties of poly(2-fluoro-1,4-phenylenevinylene) and its copolymers (1994)
    Springer
    Polymer bulletin 33 (1994), S. 89-96 
    Details
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Poly(2-fluoro-1,4-phenylenevinylene), PFPV, and its copolymers have been synthesized via water soluble precursor route and their electrical and optical propreties were measured. It seems that electron-withdrawing fluorine substituent on phenylene ring increases the band-gap of PFPV and it affects electrical and optical properties. The conductivity values of FeCl3-doped drawn polymer films ranged from 10-1 to 101 Scm-1 depending on their composition, and were 10 times larger than those of undrawn ones. The χ(3) value for undrawn PFPV, using THG technique at 1907nm fundamental wavelength, was 4.76x10-12 esu.
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    URL: http://dx.doi.org/10.1007/BF00313478
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    A technique to measure the crystallinity of syndiotactic polystyrene using thermal analyses (1994)
    Springer
    Polymer bulletin 33 (1994), S. 109-112 
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    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary A simple method for using differential scanning calorimeters to determine the crystallinity of syndiotactic polystyrene has been developed. Its validity was confirmed by use of infrared and x-ray analysis, as well as comparison to data from the literature. This method will be used to determine the effect of nucleating agents, shear stress, and temperature on the crystallization kinetics of syndiotactic polystyrene.
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    URL: http://dx.doi.org/10.1007/BF00313481
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    Polyether-modified fullerenes (1994)
    Springer
    Polymer bulletin 33 (1994), S. 175-182 
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    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Polyether-modified fullerenes have been prepared under mild conditions by reacting C60 or C70 in toluene with a precursor poly(oxyethylene) or poly(oxypropylene) polymer possessing amino end-groups. In the early stages of the interaction, soluble products are formed. Later, cross-linking proceeds between the polyfunctional fullerenes and the bifunctional polyethers. The non-crosslinked fullerene derivatives are soluble both in toluene and water; by evaporation of toluene, very adhesive films are formed.
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    URL: http://dx.doi.org/10.1007/BF00297352
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    Polysoap-induced polymerization of methyl methacrylate and styrene by poly(sodium alkyl 2-hydroxy-3-methacryloyloxypropyl phosphate)s in water (1994)
    Springer
    Polymer bulletin 33 (1994), S. 167-173 
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    ISSN: 1436-2449
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Poly(sodium alkyl 2-hydroxy-3-methacryloyloxypropyl phosphate)s as polysoap induced the radical polymerization of methyl methacrylate and styrene in the absence of an added radical initiator in water at 80°C. The polysoap having a C14 alkyl group showed the highest activity of all tested groups. The generalized initiation mechanism of the spontaneous polymerization in which the micellar aggregation state participates is discussed.
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    URL: http://dx.doi.org/10.1007/BF00297351
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    Poly(β-3-methylmalic acid): A new degradable functional polyester with two stereogenic centers in the main chain (1994)
    Springer
    Polymer bulletin 33 (1994), S. 149-158 
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    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Racemic ((3S,4R)-(3R,4S))-3-methyl-4-benzyloxycarbonyl-2-oxetanone has been prepared by a simple and reproductible method starting from a racemic mixture of threo-((2S,3S)-(2R,3R))-3-methylaspartic acid as chiral precursor. This α, β substituted β-lactone has been polymerized anionically, using tetraethylammonium benzoate as initiator, to yield high molecular weight and amorphous racemic threo-poly(β-benzyl-3-methylmalate). The catalytic cleavage of protecting benzyl ester groups has been conducted in different solvents and racemic threo-poly(β-3-methylmalic acid) has been obtained in N-methylpyrrolidone at room temperature. Racemic threo-poly(β-3-methylmalic acid-co-benzyl-β-3-methylmalate) has been prepared by heterogeneous H2/Pd charchoal catalyzed partial hydrogenolysis of the polymer precursor. Solubility of these different materials has been considered. Hydrolysis of threo-poly(β-3-methylmalic acid) has conducted to racemic threo-3-methylmalic acid. High resolution 13C NMR and selective INEPT NMR have been used for resonances assignment of polymers and copolymers. This new poly(β-hydroxy acid) type polyester expands the family of poly(β-malic acid) derivatives by opening the route for tailor making functional polystereoisomers with two stereogenic centers in the main chain and with the presence of an hydrophobic alkyl group and an hydrophilic carboxylic acid group in the macromolecule.
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    URL: http://dx.doi.org/10.1007/BF00297349
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    SERS evidence for existence of a critical concentration for polymer coil shrinking in poly(4-vinyl pyridine) solution (1994)
    Springer
    Polymer bulletin 33 (1994), S. 229-235 
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    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary The dependence of intensity of surface enhanced Raman scattering on the concentration of poly (4-vinyl pyridine) solutions was investigated. The spectral quality and the Raman scattering intensities of the enhanced spectra of poly (4-vinyl pyridine) adsorbed on nitric acid-roughened silver foil were inversely proportional to the concentration when it changed from semi-dilute to very dilute. The band intensity-concentration plot displays a turning point corresponding to the critical concentration for coil shrinkage. The observed phenomena are in accordance with Qian's proposal for the existence of C s for coil shrinkage in dilute solution.
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    Erratum (1994)
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    Polymer bulletin 33 (1994), S. 257-257 
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    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00297364
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    Separation of poly(methyl methacrylate)s according to their tacticity (1994)
    Springer
    Polymer bulletin 32 (1994), S. 629-635 
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    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary The unconventional liquid chromatography of polymers under limiting conditions of their solubility was applied to poly(methyl methacrylate)s differing in their tacticity. The polymers were dissolved in thermodynamically good solvents and injected into an appropriate size exclusion chromatographic (SEC) column flushed with matched, moderately strong nonsolvents. The set of (limiting) conditions was found under which less soluble syndiotactic poly(methyl, methacrylate) moved along the column together with the zone of its initial solvent while better soluble isotactic poly(methyl methacrylate) was eluted according to the SEC mechanism. This indicates the potential of liquid chromatography under limiting conditions to characterize the tacticity of poly(methyl methacrylate)s.
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    URL: http://dx.doi.org/10.1007/BF00973912
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    Viscoelastic relaxations in poly(dimethylphenyl methacrylates) (1994)
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    Polymer bulletin 32 (1994), S. 675-678 
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Dynamic mechanical properties of poly(dimethylphenyl methacrylátes) were studied considering the different positions of the methyl groups on the phenyl ring. In all cases a clear α relaxation can be observed which is associated to the polymer glass transition temperature (Tg). Nevertheless, at lower temperatures, viscoelastic activity is negligible. A correlation between the steric hindrance due to the methyl groups and the temperature at which the relaxation is detected, was established.
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    Relaxation processes in hyperbranched polyesters (1994)
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    Polymer bulletin 32 (1994), S. 679-685 
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    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Dielectric permittivity and loss have been measured over the frequency range 10-2 Hz-10 kHz between 100 K and 350 K for samples of 50/50 mixtures of each of two hyperbranched polyesters, one five-generation hydroxy functional (5G-OH) and one threegeneration alkyl-terminated polymer (3G), with dielectrically inactive linear polyethylene. The thermal transitions of the hyperbranched polymers were studied with differential scanning calorimetry. Three relaxation transitions were found in 5G-OH: α, the glass-rubber transition and two subglass processes denoted β and γ showing Arrhenius temperature dependence both with an activation energy of 96±2kJ mol-1. The low temperature process could be assigned to motions of the terminal hydroxyl groups whereas β is due to reorientation of the ester groups. Sample 3G showed only a glass transition and one subglass process being assigned to reorientation of the ester groups. The high activation energy (202 kJ mol-1) of this process indicates that the ester groups are highly constrained in this polymer.
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    URL: http://dx.doi.org/10.1007/BF00973919
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    An X-ray photoelectron spectroscopy study of poly(methyl methacrylate) surface modified by 193-nm laser radiation (1994)
    Springer
    Polymer bulletin 33 (1994), S. 331-338 
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    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary The chemistry of poly(methyl methacrylate) subjected to 193-nm radiation, emitted by an argon-fluorine excimer laser, was studied by X-ray photoelectron spectroscopy. From the O/C atomic ratios measured at two different sampling depths, it is concluded that the role of depolymerization in the laser ablation process may be less important than previously suggested.
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    URL: http://dx.doi.org/10.1007/BF00314271
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    The application of miscibility parameter to the measurement of polymer-plasticizer compatibility (1994)
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    Polymer bulletin 33 (1994), S. 725-732 
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Poly(vinyl butyral) (PVB)was found to precipitate from a clear plasticizer solution as it was cooled and this unique temperature (TP) (UCST) was noted. Poly(vinyl chloride) (PVC) did not precipitate and in this case the temperature at which it went into solution (TS) was noted. A quantity, referred to previously as the miscibility parameter (MP), is an excellent relative quantitative indicator of the miscibility of poly(vinyl butyral) and poly(vinyl chloride) with plasticizers as demonstrated from a correlation of MP with TP and Ts. Each polymer-plasticizer system is unique. A plot of MP vs. TP or TS for several polymer-plasticizer systems allows additional plasticizers to be evaluated for their plasticizing ability from calculated MP's without resorting to additional experimental measurements. The absolute level of MP acceptability is dictated by the application. For PVB, a copolymer which precipitates from a plasticizer/solvent, the interaction parameter chi(χ) is chi critical ( $$\chi _{cr} $$ ) at the TP of PVB in plasticizer. Since TP approximates the Θ temperature in the limit of molecular weight, the temperature of precipitation or Θ temperature, the solvent volume VS, and the $$\chi _{cr} $$ , define the theoretical MPcr as given by $$\frac{{(\chi _{cr} - 0.35)RT}}{{V_S }}$$ . All MPcr s were≈0.3 which represents the critical MP above which phase separation occurs. The low molecular weight plasticizers were estimated to drastically increase MPcr to about 1 for acceptable application compatibility and this value compares favorably with (PVB) acceptability for a wide range of plasticizer-PVB combinations based on a plasticizer DP of about 20.
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    Anisotropic friction on lamellar crystals of polyethylene by lateral force microscopy (1994)
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    Polymer bulletin 33 (1994), S. 459-464 
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    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary Frictional forces are very sensitive to the interface structure and the chemical and atomic structure of surfaces. It has been shown in the late 80′s (1) that lateral forces due to friction can be measured by atomic force microscopy (AFM) in the contact mode (2,3). This involves measurements which evoke vertical deflection of the AFM probe and observation of lateral forces which twist the AFM force sensor. A simultaneous detection of vertical deflection and twisting of the microcantilever can be done by using a four-sectored positional sensitive photodetector which measures the change in the deflection of a laser light reflected off the top of the microcantilever. The newest generation of SPM (Scanning Probe Microscope) equipment allows for simultaneous AFM and Lateral Force Microscopy (LFM) scans. There is ample evidence in the literature that contact-mode AFM can be used not only to investigate polymer morphology (4,5), but also to study polymer architecture from a true molecular perspective (6).
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    Structure and properties of styrene-divinylbenzene copolymers (1994)
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    Polymer bulletin 33 (1994), S. 487-491 
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    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract The influence of binary mixtures of heptane with different diluents on the porous structure of styrene-divinylbenzene (Sty-DVB) copolymers was investigated. It was found that the porosity produced by the diluent mixtures depends not only on the affinity of each diluent for the copolymer but also on the interaction of the diluent molecules with themselves. In this work it was observed that some polar aromatic solvents when mixed with heptane presented cosolvency effects. In general, the accessible pore volumes were higher than the fixed pore ones, indicating the formation of elastic internuclear chains.
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    Direct measurements of shear-induced particle migration in suspensions of bimodal spheres (1994)
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    Rheologica acta 33 (1994), S. 185-192 
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    ISSN: 1435-1528
    Keywords: Suspension ; particle migration ; demixing ; bimodal ; anisotropy ; concentration gradient
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract A variety of studies reported in the literature have established that initially well mixed suspensions subjected to non-homogeneous shear flows attain an anisotropic particulate structure. It has also been shown that non-homogeneous shearing causes suspensions of unimodal spheres to demix, i.e., gradients in solids concentration are formed. The objective of this study was to determine the effect of non-homogeneous shear flows on suspensions of bimodal particles, and specifically, to determine if the solids concentration gradients which develop are accompanied by size segregation of the coarse with respect to the fine fraction. We used the simplest and most direct methods to determine the relative solids concentrations: visual observation of tracer particles in transparent suspensions and physical separation of the coarse and fine solid fractions. Three different types of non-homogeneous shear flows were examined, and in each case the data support two main conclusions: 1) suspended particles migrate from regions of high shear rate to regions of low shear rate, and 2) the coarse fraction of particles migrates much faster than the fine fraction, leading to size segregation of initially well-mixed suspensions. While the former conclusion is consistent with other studies reported in the literature, to our knowledge this paper provides the first data supporting and, to a limited extent, quantifying the latter conclusion.
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    Boundary conditions for contract lines in coextrusion flows (1994)
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    Rheologica acta 33 (1994), S. 241-241 
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    ISSN: 1435-1528
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
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    URL: http://dx.doi.org/10.1007/BF00437309
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    Fractional complex modulus manifested in asphalts (1994)
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    Rheologica acta 33 (1994), S. 344-354 
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    ISSN: 1435-1528
    Keywords: Complex modulus ; relaxation ; fractional relaxation modes ; asphalts
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract In recent years, a considerable effort has been made to develop a new generation of asphaltic materials based on a combination of polymers and asphalts. Regular and polymer-modified asphalts are studied via fractional relaxation processes, represented here by a fractional rational form of the complex modulus, G *. Basic properties of this complex modulus and the forms of generated constitutive equations are studied. Relaxation times of the model are related via a pseudospectrum to the phase angle lag.
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    Fractional relaxation and the time-temperature superposition principle (1994)
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    Rheologica acta 33 (1994), S. 337-343 
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    Keywords: Rheological models ; viscoelasticity ; fractional differentiation ; non-Debye relaxation ; thermo-rheological simplicity ; projection operator
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract Relaxation processes in complex systems like polymers or other viscoelastic materials can be described by equations containing fractional differential or integral operators. In order to give a physical motivation for fractional order equations, the fractional relaxation is discussed in the framework of statistical mechanics. We show that fractional relaxation represents a special type of a non-Markovian process. Assuming a separation condition and the validity of the thermo-rheological principle, stating that a change of the temperature only influences the time scale but not the rheological functional form, it is shown that a fractional operator equation for the underlying relaxation process results.
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    A domain perturbation study of steady flow in a cone-and-plate rheometer of non-ideal geometry (1994)
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    Rheologica acta 33 (1994), S. 369-384 
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    ISSN: 1435-1528
    Keywords: Cone-and-plate rheometer ; domain perturbation ; viscoelastic fluid ; secondary flow
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract The method of domain perturbation developed by Joseph is used to calculate velocity and stress profiles in a slightly misaligned cone-and-plate rheometer where the cone is spinning and the plate is stationary. Results for a Newtonian fluid, a Criminale-Ericksen-Filbey fluid, an upper-convected Maxwell fluid, and a White-Metzner fluid are presented and compared with earlier results in which the cone is stationary and the plate is spinning (Dudgeon and Wedgewood, 1993). Streamlines calculated for the Newtonian fluid show a very small recirculation region near the stationary plate. Velocity and stress contours are symmetric around the plane of largest gap width. For the elastic fluids studied, streamlines are asymmetric. The fluid response lags where the fluid is dominated by memory effects. Much larger recirculation regions are calculated for fluids dominated by shear thinning. These recirculation regions contain a large fraction of the fluid in the apparatus and have the effect of changing the shape of the flow domain for the remaining fluid that rotates around the cone's axis. Elasticity also has a pronounced effect on the stress profile, indicating that the accuracy of the cone and plate may be compromised even for small mis-alignments.
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    Phase volume and size effects on the terminal relaxation of ABS melts (1994)
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    Rheologica acta 33 (1994), S. 446-453 
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    ISSN: 1435-1528
    Keywords: ABS ; terminal relaxation ; gel point ; particle size ; interparticle distance
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract The dynamical viscoelasticity of ABS melts with different particle size was investigated at various levels of rubbery phase contents. The effects of the rubber are more pronounced in the terminal zone: a transition from viscoelastic liquid to viscoelastic solid behavior was observed which can be interpreted as a physical gelation occurring at a critical rubbery phase content. This critical content resulted in being smaller in the case of smaller particles. A quantitative explanation of the experimental findings was proposed in terms of the average interparticle distance and overlapping of the chains grafted onto the neighboring rubber particles. The gel-like transition appeared to correspond to an approximately constant level of grafted chains overlapping.
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    A terminally anchored polymer chain in shear flow: Self-consistent velocity and segment density profiles (1994)
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    Rheologica acta 33 (1994), S. 485-505 
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    ISSN: 1435-1528
    Keywords: Anchored bead-rod chain ; Brownian dynamics ; simulation ; shear flow ; surface bound polymer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract The behavior of a terminally anchored freely-jointed bead-rod chain, subjected to solvent shear flow, was investigated via Brownian dynamics simulations. Previous calculations have been improved by computing the segment density and fluid velocity profiles self-consistently. The segment density distributions, components of the radius of gyration, and chain attachment shear and normal stresses were found to be sensitive to low values of shear rate. Additionally, it was found that the thickness of a model polymer layer was a strong function of the shear rate, and that the functional dependence on shear rate changed dramatically as the chain length increased. For the longest chains studied, the thickness of the model polymer layer first increased as the shear rate increased, passed through a maximum, and then decreased at high shear rates, in accordance with experimental results in theta solvents. These results suggest that a dilute or semi-dilute layer model may explain hydrodynamic behavior previously thought to be due to the entanglements that occur in dense surface bound polymer layers.
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    Geometry dependence of the viscosity of a thermotropic LC-polymer measured by slit dies (1994)
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    Rheologica acta 33 (1994), S. 542-552 
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    ISSN: 1435-1528
    Keywords: LC-polymers ; capillary rheometry ; slit die wall effect ; ordered texture ; Frank elasticity
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract This paper reports on geometry dependent viscosity curves of the biaxial thermotropic LC-Polymer Vectra B 950 measured with rectangular slit dies. The geometry dependence of the flow behaviour originates from the flow of two layers. The layer near the wall is highly flow oriented and free from defects. The layer in the bulk has an ordered texture. The thickness of the wall layer decreases with wall shear stress. Based on the Frank theory and the assumption that the core of a moving disclination is the smallest radius of distortion, the wall layer thickness is predicted and compared with experimental data.
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    Solidification behavior of the theta system 2-propanol/poly(n-butyl methacrylate) I. Influences of thermoreversible gelation on stationary flow (1994)
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    Rheologica acta 33 (1994), S. 159-164 
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    ISSN: 1435-1528
    Keywords: Zero shear viscosity ; polymer melts ; polymer solutions ; magnetoviscometer ; thermoreversible gelation ; glass transition temperatures ; critical molecular weight ; master curves
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract Zero shear viscosities, η0, were determined by means of a magnetoviscometer for melts of poly(n-butyl methacrylate) (M = 8.7 to 450 kg/mol, T =53.5 to 200°C) and for concentrated solutions of the highest molecular weight sample in isopropanol (T = 34.8 to 131.5 °C). Master curves can be constructed in both cases if the reference temperature is set proportional to the gelation temperature of the particular fluid. Special intersegmental interactions (eventually leading to thermoreversible gelation) can above all be felt in η0 (T) and in M c , the critical molecular weight determined in plots of log η0 vs. log M. As the temperature is lowered, the behavior changes from WLF to Arrhenius, and M c declines considerably. The former observation is explained by analogy to the transition from fragile to hard glasses resulting from increased crosslinking. The latter effect can also be rationalized in terms of a physical network reducing the molecular weight that is required for the formation of entanglements.
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    On the behavior of fine mud suspensions (1994)
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    Rheologica acta 33 (1994), S. 175-184 
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    ISSN: 1435-1528
    Keywords: Yield stress ; rheometry ; suspensions ; mud ; natural clay
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract Flows of natural mud-water mixtures are of great interest for industrial and civil engineering. But there is still no general agreement about the methods for determining the main rheological characteristics of these systems. We propose here an accurate rheological study of some natural mud-water mixtures. We first discuss the possible effects of changing various parameters such as temperature, pH, electrolyte concentration, solid concentration, clay type. The behavior of these muds appears to be very sensitive to most of these parameters and to be hardly predictable from a knowledge of their components. Then, we show that a Herschel-Bulkley model fits very well steady flow experimental data for a very large range of shear rates. We also suggest physical explanations of this model in agreement with our observations of behavior changes when some parameters change. The yield stress value of this model provides a good estimation of real yield stress which is a key parameter for mixture behavior. These considerations are very useful to characterize, predict, and compare various mud flows.
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    A CO2 titration electrode Part I: Theoretical description (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 8-13 
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    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract A novel titration electrode for measuring the concentration of CO2 is described in which OH− is generated electrochemically and the time taken for the OH− to be titrated by the CO2 is measured. A theoretical description of the variation of pH with time is presented. The curve is shown to have two inflection points. The pH at the second point of inflection is close to 8. Hence the time to the second point of inflection is the titration time. Results from experiments with known quantities of OH− are shown to be in good agreement with the theory.
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    A CO2 titration electrode Part II: Development of the sensor (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 14-17 
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    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The construction and operation of a new titration electrode for measuring C02 are described. Typical results are presented including calibration plots and a comparison of results from the new sensor with those from an infrared analyser. Good agreement is found. Results using the sensor to measure CO2 levels in a glasshouse and in the ambient atmosphere of the laboratory are presented.
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    Influence of the composition of zinc-ethyl silicate paints on electrochemical properties (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 1013-1018 
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    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The protection of steel by zinc-ethyl silicate primers is based on the general principle of cathodic protection by metallic zinc in contact with a ferrous substrate. The influence of the zinc content on the paint behaviour has been studied, but little attention has been paid to effects caused by the incorporation of additives, such as extender pigments, to the formulation. The aim of this paper is to study the influence of the whole composition of zinc-ethyl silicate paints on their electrochemical properties. A second purpose is to establish the nature of the anticorrosive action of these paints. Four commercial zinc-ethyl silicate paints were chosen for these investigations. It was found that the incorporation of extender pigments modified the behaviour of these paints. The anticorrosive action was due to the cathodic protection by zinc powder and the inhibition of the electrochemical reactions by corrosion products. The barrier effect, in the sense of ohmic resistance, provided by these paints was of lesser importance.
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    Reduction of chromate in dilute solution using hydrogen in a GBC-cell (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 1028-1036 
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    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Reduction of metal ions in dilute solutions is of great interest for purification of waste waters and process liquids. Hydrogen gas is a very attractive reductant, since its use gives no additional pollution. In this paper the reduction of chromate in a sulphuric acid medium has been studied. A new electrochemical cell, a GBC-cell, which is a combination of a gas-diffusion electrode in direct contact with a packed bed of carbon particles, is introduced. Hydrogen gas flows along the hydrophobic side of the gas-diffusion electrode and a chromate solution is pumped upwards through the bed. Experiments were carried out with H2SO4 solutions initially containing 70 mol m−3 chromate at various temperatures, solution flow rates, H2SO4 concentrations and bed thicknesses. Experimental results for the chromate reduction are described by an empirical relation. It has been found that the reduction of chromate is a first-order reaction in chromate and the apparent rate constant for the chromate reduction increases with decreasing chromate concentration and increasing temperature, H2SO4 concentration and bed thicknesses and is practically independent of the flow rate of the solution. It is concluded that the new GBC-cell is very attractive for the reduction of chromate in dilute solutions and for industrial abnlication on a large scale.
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    Effect of chromate ion on zinc electrowinning from acid sulphate electrolyte (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 1044-1051 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The effect of chromate ion and its interaction with antimony and glue on zinc electrowinning from acid sulphate electrolyte were studied. During electrolysis at 430 A m−2 and 45°C, the chromate ion was found to polarize the cathodic reaction resulting in a refined zinc deposit having a morphology featuring a vertical orientation of the zinc platelets. Although chromium did not codeposit, the current efficiency for zinc deposition was dramatically decreased in the presence of 〉 1000 mg dm−3. This effect became more pronounced when the electrolyte also contained additives such as antimony and glue.
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    Electrical properties of polyaniline films formed in acid with and without Cs+ ions in the electrolyte (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 1059-1065 
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    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The effect of Cs+ ions added to the electrolyte for polyaniline films electrosynthesized in 0.1 m aniline/0.5m H2SO4 was investigated. Some properties of PANI films, such as the capacitance, the ohmic resistance and the charge-transfer resistance were obtained using electrochemical impedance spectroscopy. It was found that Cs+ ions used during PANI synthesis change its morphology, with a consequent increase in capacitance and conductivity, and a decrease in charge-transfer resistance.
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    Calendar (1994)
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    Journal of applied electrochemistry 24 (1994), S. 1073-1075 
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    ISSN: 1572-8838
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
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    Ionic conductivity and lithium electrode stability in Hydrin: LiBF4 elastomers (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 1066-1072 
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    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Three commercial elastomers, Hydrin C, Hydrin H and Hydrin T, which contain ethylene oxide and epichlorohydrin repeat units, have been investigated as polymer electrolytes in contact with lithium electrode. The influence of polyethylene glycol and fine particles of zeolite on ionic conductivity of Hydrin-LiBF4 electrolytes and the exchange current density of the lithium electrode reaction has been studied by using impedance spectroscopy and cyclic voltammetry. The specific conductivity of the elastomeric electrolyte is about 10−5 S cm−1 at room temperature when polyethylene glycol is present. But the mechanical stability of the film is less. The addition of zeolite particles to the elastomers also improves the specific conductivity. When present in low concentrations, the zeolite particles show catalytic effect on the electrochemical reaction at lithium electrode at ambient temperature. The lithium electrode reaction is reversible and the electrolyte possesses good electrochemical stability.
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    Electrochemical polishing of hydrogen sulfide from coal synthesis gas (1994)
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    Journal of applied electrochemistry 24 (1994), S. 1092-1101 
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    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract An advanced process has been developed for the separation of H2S from coal gasification product streams through an electrochemical membrane. This technology is developed for use in coal gasification facilities providing fuel for cogeneration coal fired electrical power facilities and molten carbonate fuel cell (MCFC) electrical power facilities. H2S is removed from the syn-gas by reduction to the sulfide ion and hydrogen gas at the cathode. The sulfide ion migrates to the anode through a molten salt electrolyte suspended in an inert ceramic matrix. Once at the anode it is oxidized to elemental sulfur and swept away for condensation in an inert gas stream. The syn-gas is enriched with the hydrogen. Order of magnitude reductions in H2S have been repeatedly recorded (100 ppm to 10 ppm H2S) on a single pass through the cell. This process allows removal of H2S without cooling the gas stream and with negligible pressure loss through the separator. Since there are no absorbents used, there is no absorption/regeneration step as with conventional technology. Elemental sulfur is produced as a byproduct directly, so there is no need for a Claus process for sulfur recovery. This makes the process economically attractive since it is much less equipment intensive than conventional technology.
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    Fundamental study of the anodic and cathodic reactions during the electrolysis of a lithium carbonate-lithium chloride melt using a carbon anode (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 1102-1108 
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    ISSN: 1572-8838
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Cyclic voltammetry, in conjunction with the chromatographic analysis of the anode product, has been used to elucidate the reactions occurring during the electrolysis of lithium carbonate-lithium chloride melts. At a carbonate ion concentration of 0.033 mole fraction the peak anodic current densities were 3100 A m−2 on vitreous carbon and 6900 A m−2 on graphite with the product being carbon dioxide. The cathodic reduction of carbonate at low concentrations was found to occur at −1.0 V to −1.2 V vs a Ag/Ag(I) reference electrode which is 1.2 V less negative than the potential at which lithium ions were reduced. Voltammetric studies of the reduction of the carbonate ion indicated that the reaction mechanism involved an irreversible charge transfer.
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    Calculation of bypass currents in molten salt bipolar cells (1994)
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    Journal of applied electrochemistry 24 (1994), S. 1124-1132 
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    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract A theoretical model is given for calculation of parasitic currents (bypass currents) for a stack of bipolar cells used in molten salt electrolysis. A simplified bypass current calculation was confirmed by the numerical solution of the Laplace equation for Galvani potentials in the interelectrode space and in the free space of the cell stack for the aluminium cell of the ‘Alcoa Smelting Process’ (AlCl3 electrolysis) with 11 bipolar electrodes. Due to the bypass currents the current efficiency of the electrochemical process was lowered to 82%–94%, depending on the height of the stack, i.e. the thickness of the bipolar electrodes. These values were in a good agreement with values obtained on the basis of the simplified approach. The numerical solution of the Laplace equation allowed a detailed description of the influence of the bypass current flow on the current distribution at the edges of the bipolar electrodes.
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    Corrosion inhibition of amorphous FeBSiC alloy in 1 m HCl by 3-amino-1,2,4-triazole (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 1139-1145 
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    ISSN: 1572-8838
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The mode of corrosion inhibition of amorphous FeBSiC alloy due to 3-amino-1,2,4-triazole (ATA) in molar HCl is studied through weight loss and electrochemical steady-state and transient measurements. From the comparison of results with those obtained using other ‘triazole’ type-organic compounds, it is shown that ATA is the best inhibitor. ATA acts on the cathodic reaction without changing the mechanism of the hydrogen evolution reaction. Impedance studies show that ATA acts by formation of a 3D compact and protective adsorbed inhibition film at the metal surface which is similar to a paint or polymer film. A correlation between the inhibition efficiency of ATA and its molecular structure is established. A schematic representation of surface coverage due to different adsorption modes of ATA is presented. The schematic representation proposed explains why the mechanism of hydrogen reduction is the same in the absence and in the presence of ATA.
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    Electrochemical cell design for in situ measurements in condenser tubes (1994)
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    Journal of applied electrochemistry 24 (1994), S. 1153-1157 
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    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract An electrochemical cell was specifically designed for testing in situ the quality of surface films formed on the cooling water side of condenser tubes in various situations of technical interest. Standard electrochemical techniques can be easily carried out even with the plant in operation, just requiring a half-reduction of the output. Rest potentials and polarization resistance results, together with cyclic voltammograms are presented. The results are in good agreement with those previously obtained by destructive sampling, mounting and using conventional electrochemical cells.
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    Electrocatalytic behaviour of a poly(N-methylaniline) filmed electrode to hydroquinone (1994)
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    Journal of applied electrochemistry 24 (1994), S. 1164-1169 
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    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Poly(N-methylaniline) (PNMA) was prepared on a bare platinum electrode by electrooxidation of N-methylaniline in 1.0 mol dm−3 HCl. The PNMA film was more stable to anodic treatment than the polyaniline film. The electric conductivity of the PNMA film was potential dependent. High conductivity appeared only within the potential region where PNMA itself was redox-active. The PNMA filmed electrode showed redox response to dissolved hydroquinone whose redox current was evident within the potential region. Furthermore, the PNMA film behaved as an electrocatalyst for the electrode reaction of hydroquinone. The kinetics of the electrocatalytic reaction were investigated mainly using a rotating disc electrode. The experimental results obtained were analysed by the theory of Albery and Hillman, and the rate constant of the electron cross-exchange transfer between hydroquinone and the redox-active sites in the film (k) was determined and found to be 6.4 × 103 m −1 s−1 at 20° C.
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    Preparation and electrochemical characteristics of a new Li-Mn-V-O system formed from heat-treatment of a MnO2, NH4VO3 and LiNO3 mixture (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 1176-1181 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract New quarternary oxides (Li2O) x · MnO2 · yV2O5 (x = 0.125 ∼ 0.25, y = 0.125 ∼ 0.25), formed by heating mixtures of MnO2, NH4VO3 and LiNO3 at various Li/Mn and V/Mn atomic ratios and at different temperatures (300 ∼ 400 °C in air, have been characterized by X-ray diffraction, X-ray photoelectron spectroscopy (ESCA) and infrared spectroscopy. The quarternary oxide with x = 0.25 and y = 0.25 showed a discharge capacity of 220 A h (kg oxide)−1 and an energy density of ca. 600 W h (kg oxide)−1 at a current density of 0.20 mA cm−1 in 1 m LiClO4-propylene carbonate at 25 °C. When charge-discharge cycling with the (Li2O) · MnO2 · 0.25V2O5 electrode was performed at a constant capacity of 30 A h (kg oxide)−1 and at a constant current density of 0.10 0.20 mA cm−2, the electrode sustained over 100 cycles at a high mean discharge potential of ca. 3 V vs Li/Li+.
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    Electrochemical synthesis of erythrosin from fluorescein (1994)
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    Journal of applied electrochemistry 24 (1994), S. 1188-1190 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
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    Book reviews (1994)
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    Journal of applied electrochemistry 24 (1994), S. 1194-1195 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
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    Electrochemical treatment of bisphenol-A containing wastewaters (1994)
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    Journal of applied electrochemistry 24 (1994), S. 1052-1058 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The effectiveness of electrochemical methods in purification of synthetic wastewaters containing bisphenol-A has been tested. The role of electrode material and electrolysis parameters have been considered. The kinetics of bisphenol oxidation have been followed using different analytical techniques and a degradation mechanism has been proposed.
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    Photoelectrochemical properties of bismuth-doped titanium oxide electrodes (1994)
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    Journal of applied electrochemistry 24 (1994), S. 1133-1138 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract With the aim of obtaining TiO2 films with increased photoresponse titanium metal was alloyed with bismuth and then directly oxidized. The free energy efficiencies of the Ti-Bi oxide increased four times by increasing the bismuth content up to 10 wt %. The spectral response of the Ti -Bi oxides was slightly shifted toward the visible region with respect to the response of TiO2, and their E g were observed to be in the range 2.87–3.0 eV.
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    Electrochemistry and the environment (1994)
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    Journal of applied electrochemistry 24 (1994), S. 1077-1091 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Advances in electrochemical methods for pollutant remediation, recycling and sensing are reviewed. Additionally, applications of these methods in the drinking water industry, and for disinfection scenarios are discussed. Lastly, new electrode materials for environmental applications are described. In a companion review, photoelectrochemical methods will be discussed.
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    Effect of operating conditions on anode passivation in the electrorefining of copper (1994)
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    Journal of applied electrochemistry 24 (1994), S. 1109-1115 
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    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The effect of various process variables on anode passivation in copper electrorefining was investigated by combining conventional electrochemical techniques, laser-based visualization, and digital image processing in a laboratory scale copper electrorefining cell. High current density operation causes early anode passivation; in the range of 0.23 to 1.50 kA m−2, the effect of current density on the onset of passivation was found to be constant. The higher the temperature the longer the time required for the onset of anode passivation. When the electrolyte is circulated, anode passivation occurs earlier than in the absence of circulation, but the effect also depends on the direction of circulation.
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    Optimal time-varying cell-voltage control of a parallel-plate reactor (1994)
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    Journal of applied electrochemistry 24 (1994), S. 1116-1123 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract As a means to illustrate the calculation of an optimal cell-voltage control for a parallel-plate reactor, we determine the time-varying cell voltage that maximizes p-aminophenol produced from the electroreduction of nitrobenzene in a differential-conversion reactor operated in a batch mode; that is, the electrolyte is continuously recirculated from a batch holding tank through the reactor in which a low conversion per pass occurs. A rationale is given for restricting the search for the optimal control for this particular reaction network to a chattering-cell voltage that switches between a priori chosen minimum and maximum values. The optimal, time-varying duty cycle is computed using a gradient-search technique. The predicted concentrations are dependent upon the reaction time; for the conditions examined here, an improvement of twenty-five percent in the production and nine-hundred percent in the selectivity of p-aminophenol may be achieved by using the optimal, time-varying voltage in comparison to the best steady value. Since a chattering control is a mathematical construct, we illustrate that a rectangular, high-frequency waveform may be applied to yield results which are indistinguishable from those effected by a chattering cell voltage. The period of the waveform must be short enough so that surface concentrations are time invariant over it and yet, simultaneously, must be long enough so that double-layer charging does not account for a significant passage of coulombs.
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    Electrochemical production of lead chromate and sodium hydroxide in a two-compartment cell (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 1146-1152 
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    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract This paper describes the application of an anode-support system (AS) and a cationic permselective membrane to the electrolytic production of yellow lead chromate pigment and sodium hydroxide solution in a two-compartment cell. The authors have determined that it is possible to utilize in the process an AISI-316 stainless steel or a titanium mesh basket loaded with lead granules. Under the operating conditions used both the AISI-316 stainless steel and the titanium remain passive and act only as electrical contact between the lead anodic pieces and the external current source. A Nafion® 901 bimembrane (Dupont, USA) is utilized to separate both compartments. Good quality yellow lead chromate and sodium hydroxide solution (50–150 g dm−3) are obtained, with a power requirement of 0.41 kWh (kg PbCrO4)−1.
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    Inhibition of aluminium corrosion in chloride media: an impedance study (1994)
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    Journal of applied electrochemistry 24 (1994), S. 1158-1163 
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    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Inhibition of the corrosion of pure aluminium by nitrite and chromate anions in near neutral aqueous chloride solution has been studied by electrochemical impedance spectroscopy, keeping the ionic strength constant by addition of potassium sulphate electrolyte. Negative of the chloride pitting potential impedance spectra show that both anions are successful in reducing corrosion through adsorption, nitrite more than chromate. Positive of this value, nitrite becomes ineffective, whereas chromate remains adsorbed and continues to prevent pitting corrosion, probably through its ability to repair defects in the oxide film. Impedance techniques successfully show the qualitative and quantitative differences between the two inhibitors.
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    Electroreduction of molecular oxygen on preferentially oriented platinum electrodes in acid solution (1994)
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    Journal of applied electrochemistry 24 (1994), S. 119-125 
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    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The oxygen electroreduction reaction was studied on two different preferentially oriented ((111)-type and (100)-type and on a conventional polycrystalline (PC) platinum rotating disc electrodes in acid solutions at 30 °C. At low overpotentials, Tafel lines of −0.060 V decade−1 were obtained on the three electrodes in oxygen-saturated 1.0m H2SO4 and 1.0m H2SO4 + y m K2SO4 (0 ⩽y ⩽ 1). At high over-potentials the usual Tafel slope of -0.120V decade−1 was observed on both (111)-type and PC platinum electrodes in 1.0m H2SO4, whereas a slope of −0.165V decade−1 was found on (100)-type platinum. In oxygen-saturated 1.0m H2SO4 the surface coverage by O-containing adsorbates on (100)-type platinum was greater than on both (111)-type and PC platinum. Rotating ring-disc electrode data showed that a higher amount of H2O2 was produced on (100)-type platinum than on the other platinum surfaces. The overpotential against current density plots are influenced by the anion concentration depending on the type of preferentially oriented platinum.
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    Mass transfer at rough gas-sparged electrodes (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 139-144 
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    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Rates of mass transfer were measured by the limiting current technique at a smooth and rough inner surface of an annular gas sparged cell in the bubbly regime. Roughness was created by cutting 55°V-threads in the electrode normal to the flow. Mass transfer data at the smooth surface were correlated according to the expression j = 0.126(Fr Re)−0.226 Surface roughness of peak to valley height ranging from 0.25 to 1.5 mm was found to have a negligible effect on the mass transfer coefficient calculated using the true electrode area. The presence of surface active agent (triton) in the solution was found to decrease the mass transfer coefficient by an amount ranging from 5% to 30% depending on triton concentration and superficial air velocity. The reduction in the mass transfer coefficient increased with surfactant concentration and decreased with increasing superficial gas velocity.
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    Design of a dome-shaped aluminium water battery (1994)
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    Journal of applied electrochemistry 24 (1994), S. 145-148 
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    ISSN: 1572-8838
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Aluminium/water batteries using hydrogen evolving cathodes are one of the candidate batteries for sub-sea application. However, it is impractical to use parallel plate construction because the significant increase in the anode-cathode gap during long term anodic discharge leads to unacceptable iR losses. A conceptual design, using a dome-shaped configuration, is presented and preliminary tests on a prototype show that such a battery can ensure constant anode-cathode gap and uniform anode dissolution. The energy density of such a battery for a two year period is estimated to be 855 Wh kg−1.
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    Electrochemical stripping of gold from Au-Ni-Cu electronic connector scrap in an aqueous solution of thiourea (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 157-165 
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    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The electrochemical behaviour of a gold-plated connector from electronic scrap in aqueous thiourea solution has been investigated. An attempt was made to recover gold from scrap in a nontoxic thiourea medium by an electrochemical method rather than the traditional cyanide process. Linear sweep voltammetry indicated that thiourea extraction of gold is more efficient in acidic solution than in neutral and alkaline. Hydrochloric acid is preferable to control the pH of the solutions; the optimum concentration of thiourea is 2.5% (0.33 m). Analysis of voltammetric data yielded a critical potential (0.40 V vs SCE), which is the upper limit for significant extraction of gold from scrap. Higher potentials should be avoided in practice to prevent decomposition of thiourea and its passivation of the scrap. Electrolysis at constant potential indicated that gold was extracted selectively in the range 0.20–0.30 V vs SCE. Electrolysis at potentials either less than 0.15 V vs SCE or greater than 0.40 V vs SCE is not recommended, because of slow dissolution in the former and severe passivation in the latter.
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    Inhibition effect of sodium boro-gluconate on mild steel with and without nitrite ions in low chloride containing water (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 179-183 
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    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract As an alternative for the replacement of chromate containing corrosion inhibitors for mild steel in cooling water systems, sodium borogluconate (SBG) has been evaluated by gravimetric and electrochemical methods in water containing 100 p.p.m. Cl− in an open system at ambient temperature. An inhibitor efficiency of 90% has been obtained in the presence of optimum concentration (50 p.p.m.) of SBG alone. However, the inhibition efficiency tends to decrease after 48 h of immersion due to the formation of soluble iron gluconate complexes. The formation of the complex is evident from the shift of the u.v. absorption peaks of Fe(II) and Fe(III) in the presence of gluconate ions. To stabilize the inhibitive action of SBG, NO 2 − ions were added in an equal mass ratio and their combined effect was found to be very effective in maintaining inhibition efficiency up to 100 h of immersion.
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    Origin of ohmic losses at Co3O4/Ti electrodes (1994)
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    Journal of applied electrochemistry 24 (1994), S. 189-194 
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    ISSN: 1572-8838
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Co3O4/Ti and NiCo2O4/Ti electrodes were prepared in different ways to investigate the origin of the ohmic losses observed experimentally. In particular, titanium was pretreated in various ways including etching with a HF mixture, and reduction by cathodic hydrogen discharge prior to coating. Different types of commercial titanium and different concentrations of the precursors in solution were also tried. Some electrodes were prepared with a RuO2 interlayer. Nickel and mild steel were also used as supports. Parameters to quantify the ohmic losses were the peak distance in voltammetric curves, and the initial slope and the deviation from linearity of current vs sweep rate plots. The experimental picture corroborates the view that the main component of the ohmic drop comes from the insulating barrier which forms at the support/oxide layer interface. The intrinsic conductivity of spinels does not appear to represent the main problem for thermal layers as usually prepared.
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    Comparative evaluation of electroreduction of nitrobenzene and m-dinitrobenzene on Ti/TiO2 electrodes in H2SO4 (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 1256-1261 
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    ISSN: 1572-8838
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Cyclic voltammetric studies of nitrobenzene and m-dinitrobenzene in 1M H2SO4 on thermally coated Ti/TiO2 electrodes indicate heterogeneous redox catalysis for both these compounds. Significant adsorption and blocking effect of these compounds are noticed at higher concentrations. m-Dinitrobenzene (MDNB) exhibits greater inhibitive adsorption when compared to nitrobenzene. These effects, however, do not significantly influence the yield and current efficiency of the reduction of these two nitro compounds to their corresponding amines. Under optimum experimental conditions yields of over 87% nitrobenzene reduction and over 83% m-dinitrobenzene reduction could be achieved. The electrolyte could also be reused by recovering the amines as their sulphates at lower temperatures.
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    Effects of diffusion-limited mass transfer on metal underpotential deposition voltammograms (1994)
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    Journal of applied electrochemistry 24 (1994), S. 1276-1278 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Summary A simple method is presented to separate the DLMT effects from those of the actual adsorption isotherm in UPD experiments. The DLMT features of UPD are resolved explicitly in terms of C b, D, and v. The latter quantities are known variables of an experiment, and hence, the surface effects can be analysed by independently fitting f with the experimental voltammograms. This procedure of data analysis including DLMT can simplify tha task of choosing adsorption isotherms in UPD studies.
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    Surface finishing CD (1994)
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    Journal of applied electrochemistry 24 (1994), S. 1279-1280 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
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    Mechanism of the solid state battery: magnesium/ poly(thionaphtheneindole/gold) (1994)
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    Journal of applied electrochemistry 24 (1994), S. 114-118 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The mechanism of a battery, that was assembled by including poly(thionaphtheneindole) (pTNI) pressed pellets between a gold cathode and a magnesium or zinc anode, was investigated. The importance of the water content of the pTNI in assuring proton migration in the polymer was established. Electrochemical reactions for magnesium oxidation at the anode and H+ reduction at the cathode are proposed.
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    Oxidation of iodide to iodate concurrently with evolution of oxygen at Kelgraf composite electrodes (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 107-113 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The oxidation of I− to IO 3 − in acidic media occurs at numerous electrode materials at potential values corresponding to the anodic discharge of H2O with simultaneous evolution of oxygen. In the study reported here the anodic current density for IO 3 − production was measured by difference voltammetry at rotated disc electrodes (r.d.e.'s) constucted from pure glassy carbon (GC) and Kelgraf (graphite plus Kel-F) composite materials. These signal values (S) were normalized relative to the background current (B) for oxygen evolution measured at 1.75 V vs SCE, a potential corresponding to the transport-limited production of IO 3 − at GC. Despite a small positive shift in E 1/2 with decreasing fractional active area, the signal-to-background ratio (S/B) at the Kelgraf electrodes was enhanced relative to that for the GC electrode. For example, SIB at a 2% Kelgraf r.d.e. was nine times larger than at a GC r.d.e. This corresponds to an increase in current efficiency (S/(S + B)) for IO 3 − production from about 50% at the GC r.d.e. to about 90% at 2% Kelgraf r.d.e. This is explained on the basis of (i) a significant decrease in total background current as a result of the decreased fraction of the Kelgraf surface that corresponds to carbon, and (ii) a larger flux density of I− at the carbon microelectrodes in the Kelgraf r.d.e., as compared to the GC r.d.e., as a result of radial diffusion, i.e. the so-called ‘edge effect’.
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    Recycling of carbon dioxide using a proton conductor as a solid electrolyte (1994)
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    Journal of applied electrochemistry 24 (1994), S. 126-130 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Using a proton conductor based on SrZrO3 or CaZrO3 as a solid electrolyte, three attempts have been made to react CH4 with CO2 efficiently. When the mixture of CH4 and CO2 was used as a fuel gas for a SOFC, the cell provided stable electric power. Furthermore, the electrochemical hydrogen pump accelerated both the reforming of CH4 with CO2 and the oxidative coupling of CH4 with CO2.
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    Local structure and concentration in Al-Mn alloy electrodeposits (1994)
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    Journal of applied electrochemistry 24 (1994), S. 131-138 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The structures of f.c.c. crystalline and amorphous phases coexisting in Al-Mn alloy electrodeposits containing 11–30 wt% were examined by using the grazing-incidence X-ray diffraction (GIXD) method, high-resolution transmission electron microscopy combined with energy dispersive X-ray spectrometry (HRTEM/EDS), and the manganese K-edge extended X-ray absorption fine-structure (EXAFS) technique. The amorphous and f.c.c. phases were homogeneously distributed in the through-thickness direction of the electrodeposits, although the amorphous phase increased and the f.c.c. phase decreased with increasing manganese total concentration. The decrease of Mn-content in the f.c.c. crystalline phases with increasing manganese total concentration was revealed by the lattice constant measurement of the f.c.c. crystalline phase. This result was also supported by the microarea elemental analysis by HRTEM/EDS. The EXAFS result has indicated that the manganese local structures in the amorphous phases are almost identical in different manganese total concentration electrodeposits. This suggests that the Mn-content in the amorphous phases hardly changes with increasing manganese total concentration. These results have revealed that a peculiar elemental partition occurs in the amorphous and crystalline phases of Al-Mn alloy electrodeposits.
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    Preparation and characterization of thin films of LaNiO3 for anode application in alkaline water electrolysis (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 149-156 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract LaNiO3 electrodes were prepared, in the form of thin films on platinum by the methods of spray pyrolysis and sequential coating of mixed metal nitrate solutions followed by thermal decomposition. The films were adherent and of p-type semiconducting. Cyclic voltammetric studies indicated the formation of a quasireversible surface redox couple, Ni(iii)/Ni(ii), on these films before the onset of oxygen evolution in 1 m KOH. The anodic Tafel slopes were ∼40 and ∼65 mV decade−1, on the sprayed LaNiO3 film and on the film obtained by a layer method, respectively. The reaction order with respect to OH− was found to be 2.2 on the sprayed oxide film and 1.2 on the layer film. The sprayed oxide film was found to be electrocatalytically more active. It is suggested that the oxygen evolution reaction proceeds on both the film electrodes via the formation of the physisorbed H2O2 as an intermediate in the rate determining step.
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    Calendar (1994)
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    Journal of applied electrochemistry 24 (1994), S. 184-188 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
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    Electrochemical copolymerization of aniline and para-phenylenediamine on IrO2-coated titanium electrode (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 166-178 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Copolymerization of aniline (AN) and para-phenylenediamine (PPDA) was electrochemically performed by cyclic voltammetry on IrO2-coated titanium electrodes in 0.5m H2SO4. The cyclic voltammograms, with and without a middle peak at about 580 mV, can be produced by controlling the PPDA concentration in the aniline solution during polymer preparation. The peak at about 580 mV corresponds to the para-aminophenol/benzoquinoneimine (PAP/QI) redox couple and crosslinking sites. The mass of polymer deposited on an IrO2-coated titanium electrode is correlated with the polymer anodic peak current, which allows the rates of polymer deposition to be monitored by increases in the anodic peak current at various PPDA concentrations. SEM photographs show that the morphology of the polymer film depends dramatically on PPDA concentration. Stability test information can be used in generating an effective index to discern between the crosslinking and the PAP/QI reactions induced by PPDA. The linear relationship between the second redox process potential (E 1/2), corresponding to the oxidation and reduction between polaronic emeraldine and pernigraniline in PPDA-modified PANI films, and pH, possesses a slope of about -120 mV/pH.
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    Nucleation and growth of nickel by electrodeposition under galvanostatic conditions (1994)
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    Journal of applied electrochemistry 24 (1994), S. 201-205 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The first stages of nickel electrodeposition on amorphous carbon and polycrystalline silver substrates have been studied under galvanostatic conditions. An island growth mode is observed on the two types of substrate. For equivalent conditions the cluster density is higher on silver substrates than on carbon substrates. Dissolution of some nickel clusters is observed a short time after the onset of electrolysis on carbon substrates. This is confirmed by the evolution of the current efficiency and the evolution of the metal surface cluster density as a function of the quantity of electricity.
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    Direct electrorefining of copper scrap using a titanium anode-support system in a monopolar cell (1994)
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    Journal of applied electrochemistry 24 (1994), S. 206-211 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract This paper describes the application of an anode-support system to the direct electrorefining of copper scrap (〉 95%) in sulphuric acid medium. The authors have established that it is possible to utilize a basket of titanium mesh as the anode-support, with chopped scrap inside the basket. It is feasible to utilize this system under the same operational conditions used for the industrial electrorefining of copper with conventional cast anodes. The proposed system avoids all the pyrometallurgical stages needed to produce the traditional cast anodes used in copper electrorefining and acts only as electrical contact between the anodic copper mass and the external current. Cathodes of good quality (〉 99.98% Cu) were obtained after 14-day electrolyses, with a current yield of 98.5–99.0% and inventory savings of 48–57% referred to the conventional process using casting anodes.
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    Electrocatalytic oxidation of methanol and C1 molecules on highly dispersed electrodes Part 1: Platinum in polyaniline (1994)
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    Journal of applied electrochemistry 24 (1994), S. 219-226 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The oxidation of methanol and C1 molecules was investigated on platinum-modified polyaniline electrodes. It was found that such electrodes are conducting even at 0.0 V vs RHE. They were found to have a higher electrocatalytic activity than bulk platinum electrodes. Moreover, the poisoning effect is drastically decreased as proved by in situ EMIRS studies which show no significant COads signal. Finally, kinetic results show that the methanol electrooxidation is first order with respect to methanol and that the main oxidation product is formaldehyde.
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    Sulphur content and the hydrogen evolving activity of NiS x deposits using statistical experimental strategies (1994)
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    Journal of applied electrochemistry 24 (1994), S. 233-238 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The effect of such electroplating conditions as current density, thiourea (TU) concentration, temperature and pH on the sulphur content of NiS x deposited electrodes has been systematically studied using fractional factorial design and response surface methodology. Fractional factorial analysis indicates that the main and interaction effects of TU concentration and current density are the key variables influencing sulphur content in a NiS x deposit. Empirical models for sulphur content and hydrogen evolution overpotential are fitted and plotted, using central composite experimental design, as contour diagrams in order to facilitate comparison with experimental sulphur content trends and hydrogen evolving activity. The results show that, for deposits containing 〉 12 wt % sulphur content, hydrogen evolving activity increases with increasing sulphur content, while for those possessing 〈 12 wt% sulphur content, hydrogen evolution overpotential decreases with increasing electroplating current density.
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    Electrochemical reduction of silver thiosulphate complexes Part I: Thermodynamic aspects of solution composition (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 239-244 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Deposition of silver from electrolyte solutions is of major importance in the industrial applications of photographic development and electroplating. Prior to the kinetic study of the reduction of silver thiosulphate complexes, the concentrations, activities and activity coefficients of all components formed in AgNO3-Na2S2O3-NaNO3 solutions are calculated, starting from the measurement of the equilibrium potential. In view of the high ionic strength of the solutions (greater than 0.1 mol kg−1), the ion interaction model is applied for the estimation of the activity coefficients, inevitably imposing the use of an iterative calculation routine. The activity coefficients are shown to comply with known thermodynamic laws, supporting the appropriateness of the model, together with the approximations.
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    Corrosion behaviour of Ti-6Al-4V in phosphoric acid (1994)
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    Journal of applied electrochemistry 24 (1994), S. 250-255 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Ti-6A1-4V shows distinct active-passive behaviour in phosphoric acid over a wide concentration range. The cathodic polarization curves are similar over a wide range of acid concentration and temperatures. The alloy undergoes active dissolution and turns passive in the negative potential region followed by a wide range of passivity at all acid concentrations at different temperatures. Increasing acid concentration up to 11 M results in an increase in critical current density (i cr). The passive current density (i p) increases up to an acid concentration of 9 M while at 13 M i cr and i p decrease appreciably. A significant increase in both i cr and i p occurs with increase in solution temperature. The passive specimen remained stable for a long time when exposed to phosphoric acid under open circuit conditions.
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    A boundary element method for transient diffusion (1994)
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    Journal of applied electrochemistry 24 (1994), S. 261-267 
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Transient diffusion in two-dimensional geometries is considered. It is shown how the spatial variation of the mass transfer-limited flux of a minor species varies with time from initially uniform to the non-uniform, steady-state distribution. Flux distributions on sinusoidal electrode and on a line electrode embedded in an otherwise insulating plane are considered. A boundary-element method is used to solve the problem in Laplace transform space, and the results are subsequently inverted into the time domain.
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    Anodic behaviour of copper during electrorefining using a rotating ring-disc electrode (1994)
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    Journal of applied electrochemistry 24 (1994), S. 420-425 
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    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The anodic dissolution of copper during electrorefining has been studied by a rotating ring-disc electrode technique. The influence of temperature, some additives (Cl− ions and polyethylene glycol) and the anode-alloying element (phosphorus) on the polarization curves was examined. It was shown that at certain conditions the concentration of Cu+ ions on the ring electrode decreased. As a result, a reduction of powdered copper in the electrolyte due to the disproportionation of cuprous ions may be expected.
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    Synergistic effects of benzalacetone and benzophenone on the electrocrystallization of tin from acid stannous sulphate solutions (1994)
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    Journal of applied electrochemistry 24 (1994), S. 404-410 
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    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The synergistic effects of two kinds of aromatic ketones (benzalacetone (BA), benzophenone(BP)) and N,N-bis(polyoxyethylene)octadecylamines (POOA) on the surface morphology and the crystal orientation of electrodeposited tin from acid stannous sulphate solutions have been studied by electrochemical methods, scanning electron microscopy and X-ray diffractometry. BA itself had no effect on the reduction of tin (II) ions, but the reduction product of BA had a strong inhibitory effect on the reduction of tin (II) ions. However, the inhibitory effect of BP was stronger than that of the reduction product of BP. POOA induced a uniform deposition of tin over the whole surface, but the crystal grain size and the surface roughness of electrodeposited tin were relatively large. On the other hand, fine-grained and smooth electrodeposited tin, which had a preferred orientation with the (10 0) plane parallel to the surface, were obtained from acid stannous sulphate solutions containing POOA, BA and BP due to the synergistic effects of the three kinds of adsorbed species. It was found that BA has a levelling action and BP has a grain refinement action.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00254152
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    Electrochemical reduction of benzaldehyde using Pt-Pb/Nafion® as electrode (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 434-438 
    Details
    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The electrochemical reduction of benzaldehyde using Pt-Pb/Nafion® as electrode without supporting electrolyte in the liquid organic phase was investigated. A novel Pt-Pb/Nafion® electrode was prepared for the electrolysis of the organic compound in this solid polymer electrolyte (SPEO) system. A reaction mechanism is proposed. No benzyl alcohol was produced using fresh Nafion® as electrode. The selectivity of benzyl alcohol using Pt-Pb/Nafion® as an electrode was almost 100% and only a trace of hydrobenzoin byproduct was found in the catholyte. The optimum faradic yield of benzyl alcohol was 18.70 g F−1. The primary factors affecting the current efficiency or faradic yield of the cathodic reduction of benzaldehyde to benzyl alcohol were cell voltage, solvent and temperature. The use of a Pt-Pb/Nafion® electrode in a SPE® system for the electrochemical reduction of benzaldehyde was found to be a feasible technique.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00254156
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  • 100
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    Performance characteristics of a certain class of electrolysers (1994)
    Springer
    Journal of applied electrochemistry 24 (1994), S. 316-320 
    Details
    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The performance properties of a continuous-flow electrolyser are analysed under plug-flow and parabolic-flow conditions. The duty of the electrolyser is to produce a species via anodic oxidation or cathodic reduction, upon which the product undergoes a first-order irreversible chemical decomposition (without net electron transfer). The effect of various parameters on electrolyser performance is also discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00242059
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