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  • Articles  (49,427)
  • Springer  (49,427)
  • MDPI Publishing
  • 1975-1979  (49,427)
  • Chemistry and Pharmacology  (49,427)
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  • Articles  (49,427)
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Polymer bulletin 1 (1979), S. 665-670 
    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 It was found that isotactic polymerization of propylene took place over titanium ion-exchanged Y-zeolite without organometallic compounds. The results obtained have led to the conclusions that Ti4+ species as well as Ti3+ species are active for the polymerization and that neither Ti-alkyl bonds nor Cl ligands are necessarily essential for polymerization of propylene.
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  • 2
    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 new azo monomer (2) was synthesized and copolymerized with styrene. The resulting azo copolymer could be used as an initiator for the acrylonitrile polymerisation yielding grafted copolymers. Quantitative treatment of the grafting experiments leads to the conclusion that the intermediate thiyl radicals show less reactivity towards monomers than phenyl radicals.
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  • 3
    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 Coordination chain polymers of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), zn(II), and Cd(II) with 5,5-(benzidinebisazo)-8-hydroxyquinoline were synthesized by refluxing a mixture of metal acetate hydrates and ligand (1∶1) in DMSO. From analytical data an empirical formula of ML.2H2O is indicated. Ir spectra reveal coordination through O and N of oxine units, thus forming the polymeric chain; presence of coordinated water is also indicated. Magnetic moments and electronic spectra suggest octahedral geometry around the central metal ion. Besides the presence of 2H2O, TGA shows the order of thermal stability as : Cd∼Zn〉 Mn〉 Co∼Ni∼Cu〉Fe.
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  • 4
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    Polymer bulletin 1 (1979), S. 715-722 
    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: Synopsis Several poly(amidine) and poly(guanidine) copolymers and their hydrochloride salts were synthesized by introducing the functional groups into suitable polymers. The properties of the resulting copolymers were investigated by base and acid titration.
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  • 5
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    Polymer bulletin 1 (1979), S. 697-707 
    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 PMMA samples of different molecular weights and degrees of copolymerisation have been tested for their crack-healing behavior. Slightly above Tg, a diffusional interpenetration of chain segments takes place. The fracture toughness in the plane of the interpenetrated interface was measured in short- and longtime experiments. After very short penetration times of only 5 min, full material resistance was regained in short-time experiments, whereas the long-time properties were not restored. A qualitative explanation of these effects, based on structural parameters, is given.
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  • 6
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    Polymer bulletin 1 (1979), S. 727-731 
    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
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  • 7
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    Polymer bulletin 1 (1979), S. 723-725 
    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 Divalent metal salts of mono(hydroxyethyl)phthalate (HEP) were considered to be of interest as difunctional ionic monomers and are useful for the preparation of condensation polymers. Recently, Matsuda1 reported the preparation of Ca, Mg and Zn salts of mono-(hydroxyethyl)phthalate and their polymers2–7. He prepared these salts by the reaction of HEP with the respective divalent metal oxides. But so far there was no report on the preparation of Pb2+ and Mn2+ salts of HEP. Since metal dicarboxylates can be obtained by the reaction of organic dibasic acids and metal acetates8, Pb2+ and Mn2+ acetates can similarly react with HEP to give their respective salts at the optimum temperature. We report here the synthesis and characterisation of Pb2+ and Mn2+ salts of mono(hydroxyethyl)-phthalate (HEP).
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  • 8
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    Polymer bulletin 1 (1979), S. 743-748 
    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 PMMA and PC samples were subjected to several cooling rates from the glass transition temperature. Stress-relaxation data, obtained with these samples under strains larger than the yield strain, were not influenced by the cooling rate previously experienced by the material. This shows that after yielding the effect of previous aging is quickly erased; similar indications, drawn from calorimetric measurements, were already available in (11–12).
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  • 9
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    Polymer bulletin 1 (1979), S. 749-753 
    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 new type of polymer support for immobilizing enzymes, a copolymer grafted onto nylon was investigated. Polyacrylamide was used and successfully coupled to β-galactosidase (from yeast and bacteria) using two different methods to give activities of the order of 5 units/g of polymer for the yeast enzyme, and 156 units/g for the E.coli enzyme. Lactose did not affect the yield. The azide method gave better results than the glutaraldehyde method. β-galactosidase coupled enzyme was fairly stable but not as good as the free enzyme. Papain was also coupled to the polyacrylamide grafted nylon using both methods; the glutaraldehyde gave better results with 1.5mg of enzyme being coupled for each gram of polymer.
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  • 10
    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 present paper describes the terpolymerization involving 2-phenyl-1,3,2-dioxaphospholane, methyl acrylate, and carbon disulfide, which took place without any added initiator in benzonitrile or dimethylformamide. The structure and composition of terpolymer were determined by NMR and IR spectra, as well as by elemental analysis. A reaction scheme proceeding via zwitterion was proposed (Eq. 2–5).
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  • 11
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    Polymer bulletin 1 (1979), S. 253-258 
    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(vinyl chloride-g-isobutylene) has been synthesized using mildly dehydrochlorinated (NaOH treated) PVC in conjunction with BCl3 coinitiator. Treatment of PVC with NaOH increases initial thermal dehydrochlorination rate and renders the polymer suitable for efficient grafting. Untreated PVC produces negligible grafting.
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  • 12
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    Polymer bulletin 1 (1979), S. 347-354 
    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 fragmentation of linear polyethylene of high molecular weight, of normal alkanes, and of other nonbranched poly- α- olefins in a pyrolyzer connected with a gas chromatograph was studied previously. From the evaluation of the fragments longer than C11 or than the respective pentamer random decomposition process was suggested for these polymers. This process was described with characteristic cleavage probabilities for the C-C-bonds in the backbone of the chain. It is not possible to apply this simple model to the decomposition of normal alkanes without consideration of the volatilization. An approach to this problem is presented in this paper.
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  • 13
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    Polymer bulletin 1 (1979), S. 397-402 
    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 By means of a new tensile rheometer for polymer melts, stress-strain curves σ(ε) and the elastic recovery εR(ε) of a low density polyethylene melt were measured up to total strains ε=7, i.e. stretch λ=1097, at 150°C and two strain rates, ε=0.03 and 0.1 s−1. Tensile tests up to very high strains e give relevant results only if the test performance is characterized by quality parameters which are defined and given in this paper. The test results show a maximum in a as well as in εR at about ε=5.5. Hence, in the range of ε investigated, a rheologically steady-state of flow does not exist.
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  • 14
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    Polymer bulletin 1 (1979), S. 517-522 
    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 photochemical and thermal cis-trans isomerization of 4,4 -(diamido)azobenzene derivative built in the polyester segment of a segmented poly(ester urethane) has been investigated. The photoisomerization in bulk proceeds more slowly than in solution and lower fractions of cis-isomers are reached in the photostationary state. The thermal cis-trans isomerization follows first order kinetics in polymers with amorphous soft phase but can only be described by two simultaneous first order processes in annealed samples. This is attributed to restrictions in the chain segmental mobility; it is assumed that the isomerization behaviour reflects different molecular motions in the bulk polymer.
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  • 15
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    Polymer bulletin 1 (1979), S. 523-528 
    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 kinetic theory of crosslinking by step reactions (Kuchanov 1978) may be extended beyond the gel point, and the structure and amount of sol may be described. For random reactions, the kinetic theory yields results identical with the theory of branching processes based on cascade substitution (Gordon 1962, 1975, Dobson 1965). The extension of the kinetic theory may be employed in order to compare deviations between the two theories expected for the dependent reactivities of functional groups.
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  • 16
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    Polymer bulletin 1 (1979), S. 529-534 
    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 mechanism of initiation of polymerization of methyl acrylate by di-t-butyl peroxalate at 60°C, has been investigated using 2,2,6,6-tetramethylpiperidine-1-oxyl as a radical trapping agent and isolation of the resulting products. The following processes were identified: Tail addition of t-butoxy radicals to monomer, hydrogen abstraction from the methyl group of the monomer and fragmentation of the t-butoxy radicals to methyl radicals followed by tail addition of these to the methyl acrylate.
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  • 17
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    Polymer bulletin 1 (1979), S. 647-652 
    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 photostabilizing effect of a hindered piperidine derivative was studied in the photooxidation of polypropylene films by following the formation of carbonyl and hydroperoxide groups, as well as the change of concentration of the stabilizer. This additive — the tetramethylpiperidine sebacate — proved to be more effective than hydroxybenzophenone, hydroxybenztriazole or a sulphur containing nickel complex, since no oxidation products were formed after irradiation with 20O Mlxh dose. Addition of the piperidine derivative together with hydroxybenztriazole or with the organic nickel complex was less effective than with hydroxybenzophenone. In latter case concentration of both stabilizers under irradiation decreased at a slower rate than in the case of separate application. The effect of Cyasorb UV 531 and Tinuvin 770 was additive and the spontaneous rupture of the samples took place only after a long period of irradiation (∼ 250 Mlxh).
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  • 18
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    Polymer bulletin 1 (1979), S. 691-695 
    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 a second example of the functionalization of soluble polymers the conversion of the hydroxyl groups of poly (oxyethylene) into carboxyl groups is reported. As protected carboxyl component, 4-toluenesulfonyl lactic acid ethyl ester was synthesized and was allowed to react with sodium salt of poly(oxyethylene). Polymer-analogous hydrolysis of the di(lactic acid ethyl ester) poly(oxyethylene) yielded the carboxyl derivative of poly (oxyethylene).
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  • 19
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    Polymer bulletin 1 (1979), S. 671-678 
    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 use of a Ce (IV)-thiomalic acid (Ce4+-TMA) redox system as an initiator in the polymerization of acrylamide (M) in an aqueous medium has been investigated. The Ce4+ forms a 1∶1 complex with TMA, decomposing through free radical mechanism in an acid medium. From 5 to 15% conversion the rate equation is $$R_p = - \frac{{d[M]}}{{dt}} = k[M]^{3/2} [Ce^{4 + } ]^x [TMA]$$ where Rp is the rate of polymerization and x is 0.5 or 1.0 depending upon the concentration of monomer. The overall energy of activation has been calculated to be 9.12 k cal. deg−1 mol−1(38.12 kJ/mol) in the investigated range of temperature (25°–40°C) the degree of polymerization (P) of the polymer is directly proportional to [M]. The number of average molecular weight of the polymer remains unaffected at lower concentration of Ce4+ and is found to decrease at higher concentrations. In this investigation the kinetics and mechanism of the Ce(IV)-thiomalic acid (TMA) redox system to initiate the polymerization of acrylamide has been studied. Acrylamide (E. Merck) was purified by usual methods. Thiomalic acid and eerie ammonium sulfate were used without purification. All solutions were p repared in twice distilled water. The polymerization procedure adopted was similar to the one used by MISRA et al. [3, 4]. The polymerization was followed by quantitative estimation of the double bonds in acrylamide as described [8]. A small variable induction period was observed perhaps due tothe residual oxygen in the thiol solution. Curves were plotted after eliminating the induction period. The average molecular weights of the p olymers were determined by viscosity measurements at 30°C in an aqueous medium using the relationship of DAINTON et al. [2]. $$[\eta ] 30^\circ = 6.8 x 10^{ - 4} \bar Mn^{0.66} $$ Where [η]=intrinsic viscosity of the polymer solution and ¯Mn=molecular weight of the sample.
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  • 20
    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
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  • 21
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    Polymer bulletin 1 (1979), S. 737-741 
    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 The method of stress relaxation has been used to study the effect of ketones on polyethylene as it changes with temperature. From the observation of the stress relaxation in polyethylene under ketones and its temperature dependence, the activation energy of penetrant-enhanced relaxation of polyethylene caused by ketones were obtained and the effect of ketones on polyethylene were discussed.
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  • 22
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    Polymer bulletin 1 (1979), S. 755-761 
    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 β-Galactosidase and glucose oxidase have been immobilized on cellulose-polyacrylamide (C-PAM) graft copolymers, using the azide method or through glutaraldehyde. The original (C-PAM) copolymers were prepared via radiation-induced grafting under controlled conditions by both post-irradiation and simultaneous procedures. The optimum conditions for coupling of the copolymers to the enzymes were established as were the levels of activity of the immobilized enzymes. Grafting by the simultaneous route was seen to be more efficient than postirradiation grafting. Indirect evidence of grafting was found from elemental and thermal analysis. Binding of β-galactoside was found to be more successful than that of glucose oxidase. A relationship between the level of immobilized enzyme activity and the extent of grafting in the copolymer was established for the β-galactosidase system.
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  • 23
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    Polymer bulletin 1 (1979), S. 763-770 
    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 heat of mixing of polyisobutylene with ethylbenzene was measured from 18.2 to 69.2° C with a Tian-Calvet twin micro-calorimeter, and the exchange enthalpy parameter X12 in Flory's theory was estimated. The X12 obtained was discussed also in comparison with the one based on Manzini model. Further combining with osmotic pressure data, temperature dependence of the entropy parameter Q12 was referred.
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  • 24
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    Polymer bulletin 1 (1979), S. 793-799 
    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 Styrene oxide of different enantiomeric compositions was polymerized in bulk using a potassium alkoxide initiator. A preferential consumption of the enantiomer in excess was observed. The magnitude of this effect depends on the enantiomeric composition of the initial monomer: the more unbalanced is the latter, the stronger is the stereoelection observed. The stereoelective effect was almost completely suppressed by addition of complexing agents such as crown-ethers or cryptands. The observed phenomena are explained in terms of polymer-chain effects.
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  • 25
    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 change in the scattering pattern of polyisobutylene fibres following rapid stretching was measured using synchrotron radiation. The half-time for the crystallisation process is approximately 50 seconds. Upon release the crystalline portions disappear immediately.
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  • 26
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    Polymer bulletin 1 (1979), S. 845-848 
    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
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  • 27
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    Polymer bulletin 1 (1979), S. 849-856 
    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 MgCl2 supported TiCl3 catalyst was prepared by grinding the mixture of TiCl3·3Py and MgCl2 in a ball mill. The catalyst was treated either i.vac. at 50–200°C or with alkylaluminum halides to remove the residual pyridine, and propylene polymerization was conducted at 65°C using the resulting catalysts combined with triethylaluminum. The catalyst treated with diethylaluminum chloride showed an extremely high activity for the polymerization.
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  • 28
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    Polymer bulletin 1 (1979), S. 857-864 
    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 The elastic equations of state for 2-component networks are derived from a joint Gaussian distribution function composed of Gaussians for each component. The free energy of elasticity is then applied to the case of uni-directional deformations for compatible systems. The stress-strain equations are shown to be equivalent to those for a single component network except in the case where the macroscopic strain is sufficient to cause the ratio of average chain lengths of the components to change with the strain. The stress-strain equations are developed for both dry and swollen networks.
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  • 29
    ISSN: 1436-2449
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    Notes: Summary The concentration dependence of the elasticity modulus (G) of gels produced by heating soybean globulins (SBG) has been investigated in the concentration range C=7.5–58.4%. The tests included constant rate loading and stress relaxation. The experimental results are presented in the form of a modulus reduction parameter b(C)=G(C) / G(C∘), where C∘=15% corresponds to the standard reference state. Whatever the testing conditions, the results are described by a single smooth curve similar, to a constant factor, to the concentration dependence of the equilibrium elasticity modulus of SBG gels. The experimental relationship b (C) agrees with the theoretical concentration dependence of the equilibrium polymer gel modulus according to Hermanns if it is assumed that the gel-point of SBG, Co=6.6 %. Within an order of magnitude this value of Co is consistent with the experimental data. We have to thank the European Branch Director of Central Soya Intern., Inc., Mr.J.F.Casey for kindly providing us defatted soya flour.
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  • 30
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    Polymer bulletin 1 (1979), S. 897-907 
    ISSN: 1436-2449
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    Notes: Summary This paper describes new fire-resistant bisphenol A and monoalkyl monoalkaline bis(hydroxy-4 phenyl) alkyl phosphonate copolycarbonates. We show that inclusion of minute quantities (in molar percentages of 0.5 to 1%) of monoalkaline potassium salts of bis(hydroxy-4 phenyl)-alkyl phosphonic acid considerably improves the fire-resistant of the bisphenol A polycarbonate. We obtain oxygen indices of 34 to 35.
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  • 31
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    Polymer bulletin 1 (1979), S. 415-420 
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    Notes: Summary Cyclopentadienylation of PVC with alkaline (NaCPD, LiCPD) and acidic (Me2CPDAl) cyclopentadienylating agents has been investigated. In terms of product quality (absence of discoloration, gelation) Me2 CPDAl was found to be a superior cyclopentadienylating agent than NaCPD and LiCPD.
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  • 32
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    Polymer bulletin 1 (1979), S. 427-431 
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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: Summary In a first example of the functionalization of soluble polymers the conversion of the hydroxyl groups of poly(oxyethylene) into primary amino groups has been studied. Starting from poly(oxyethylene), the preparation of the diphthalimido derivative via the disodium salt is described. Prom this regiospecific functionalized polymer the di(aminoethyl) poly(oxyethylene), which exhibits excellent solubility properties, can be obtained by polymeranalogous hydrazinolysis.
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  • 33
    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 It is shown that the probability for the formation of alternating macromolecules by monomer donor-acceptor complexes can be determined from the microtacticity of the copolymers. If the stereoregularity in the alternating copolymerization is described by the Bernoullian trial two other probabilities concerning the meso-diad formation can be determined by this method. If the stereoregularity is described by the first order Markov chain the transition probabilities can be calculated. Thus a more detailed analysis of the propagation mechanism in alternating copolymerization can be carried out.
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  • 34
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    Polymer bulletin 1 (1979), S. 433-436 
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    Source: Springer Online Journal Archives 1860-2000
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    Notes: Summary Cationic copolymerination of α-MS and IBVE was successfully carried out using “H2O”/EtAlCl2 initiator system and CH2Cl2 solvent at −50°C. The effect of monomer feed concentration on the copolymer yield and composition was studied. Small concentrations of IBVE had significant effect on the copolymer yield and composition, while that of α-MS had only marginal effect. Tg of the copolymers was linearly dependent on the α-MS content strongly indicating that the copolymerization was of random nature.
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  • 35
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    Polymer bulletin 1 (1979), S. 459-464 
    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 The Stefan-Winkelmann diffusion technique has been used to determine vapor pressures of high boiling point compound-solvents mixtures. Data are reported at a temperature of 67°C for the mixtures polyphenyl ether (6 rings) — benzene and carbowax 1500 — benzene and at a temperature of 100°C for the mixtures polyphenyl ether (6 rings) — toluene and tricresylphosphate-toluene. The range of concentration is only limited by the appearance of a solid phase, and results are in good agreement with those determined by vapor pressure osmometry.
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    Polymer bulletin 1 (1979), S. 469-473 
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    Notes: Summary 1-isopropenyl anthracene was dimerized by reaction with TiCl4 in CH2Cl2 and the structure of the dimer studied by 1H NMR spectroscopy. The spectrum was assigned and is in agreement with simulation. The structure results from the attack of carbocation on carbon 9.
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    Polymer bulletin 1 (1979), S. 475-479 
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    Notes: Summary 9-isopropenyl phenanthrene was dimerized by reaction with TiCl4, in CH2Cl2 and the structure of the dimer studied by 1H NMR spectroscopy. The structure results from the attack of carbocation on carbon 9.
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    Notes: Summary Radical copolymerisation of MMA(r1) and NVC(r2) yields values of the apparent reactivity ratios r1 = 1.80, r2 = 0.06 (benzene) and r1 = 0.57, r2 = 0.75 (methanol) at 55°C. It is suggested that the apparent increase in reactivity of NVC in methanol arises from high local monomer concentrations due to formation of microphases containing the growing copolymer chains in which NVC is preferentially partitioned. Fluorescence emission and u.v. absorption spectra for copolymers prepared in both solvents are identical and consistent with the occurrence of only very short sequences of NVC units.
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    Polymer bulletin 1 (1979), S. 569-573 
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    Notes: Summary The anionic polymerization of δ-valerolactone in tetrahydrofuran with lithium tert-butoxide was found to give a living ring-chain equilibrium system, in which the cyclic oligomers are produced by back-biting degradation from the initially formed linear polymers. The molar cyclization equilibrium constant for the trimer through hexamer decreased in proportion to −2.5 power of the ring size, in accord with the Jacobson-Stockmayer theory.
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    Notes: Synopsis It was confirmed by EPR that 4-amino-2,2,6,6--tetramethylpiperidine-N-oxyl (TEMP-NH2) is cleaved by chymotrypsin from 4-(N-glycyl-L-phenylalanyl)amino −2,2,6,6-tetramethylpiperidine-N-oxyl attached as a substrate with paramagnetic leaving group to the end of side chains of water soluble hydroxypropyl methacrylamide (HPMA) compolymers.
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    Polymer bulletin 1 (1979), S. 599-602 
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    Notes: Summary γ-Ethyl-L-glutamate derivatives having pendant nucleic acid bases, that is, uracil, adenine and theophylline were synthesized. The γ-ethyl-L-glutamate having theophylline moiety was polymerized by using the N-carboxyamino acid anhydride (NCA) method.
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    Polymer bulletin 1 (1979), S. 619-623 
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    Notes: Summary The analytical relationship between the molecular weight averages obtained from an experimental GPC elu tion curve and the true ones is calculated by use of one integration method in order to solve the convolution integral. The knowledge of these relationship signifies an useful tool to carry out critical considerations on the operation of different methods existing for the calculation of the spreading correction and for the elaboration of the calibration function.
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    Polymer bulletin 1 (1979), S. 625-629 
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    Polymer bulletin 1 (1979), S. 653-657 
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    Notes: Summary The polymerization of hexachlorocyclotriphosphazene (trimer) is studied in different solvents. A soluble low molecular weight polymer is obtained when benzene is the solvent, a highly cross-linked polymer when cyclohexane is the solvent, and a mixture of soluble and insoluble polymers results when the solvent is chlorobenzene. The conversion-concentration curve for the trimer shows a dependence of the amount of soluble and insoluble polymer formed on the trimer concentration. No polymerization took place when the solvent was toluene, nitrobenzene or THF, but a reaction between solvent and trimer was detected.
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    Polymer bulletin 1 (1979), S. 659-664 
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    Notes: Summary The effect of radiation on the mechanical behaviour of the crosslinked copolymer of maleic anhydride and styrene containing photochromic azo groups was investigated. The analysis of results of the observed photomechanical conversion proved a considerable influence of the thermal effect in addition to the effect of photoisomerization of the photochrome. The interpretation of some photomechanical experiments described earlier may be obscured by a rise in temperature caused by the absorption of radiation.
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    Colloid & polymer science 257 (1979), S. 977-980 
    ISSN: 1435-1536
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    Notes: Summary Aluminium hydroxide gels were recrystallised in high pH solution for 2–1000 hr to give a series of gibbsite powders of different surface areas, 1`11/2, P11/8, P11/48, P11/360 and P11/X; their average platelet lengths were 30, 60, 130, 260 and 450 nm. The dissolution equilibria of these powders in sodium hydroxide solutions of C=1-8 M were studied at 20° to 80°C. The equilibrium constants (for formation of diaquo-tetrahydroxoaluminate anion) increased with temperature and with increasing surface area; the K value for P11/2 was about four times that of P 11/X at 20 °C and about three times (that for P 11/X) at 80 °C. The dissolutions were endothermic; however, the value over this temperature range increased from −29.5 kJ mol−1 (for P11/X) to −24.7 kJ (for P 11/2). This increase was related to the appreciable surface energies of the high surface-area materials. The (− ΔG°) values increased with increasing temperature and in turn with increasing surface area; the (− ΔG°) values for 1`11/2 dissolution at any temperature were about 4 kJ mol−1 higher than those for P11/X dissolution.
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    Description / Table of Contents: Summary The spherical averaging of the paracrystalline lattice factor for isotropic structures is carried out. These scattering curves differ markedly from the neutron small angle scattering curves from model networks with deuterium labelled crosslinks. A description of the experimental curves with a pair correlation function of the real gas type seems possible.
    Notes: Zusammenfassung Die Rotationsmittelung des parakristallinen Gitterfaktors für vollständig isotrope Strukturen wird durchgeführt. Die Neutronenkleinwinkelstreukurven von Modellnetzwerken mit deuteriummarkierten Netzpunkten können damit nicht beschrieben werden. Hingegen erscheint eine Beschreibung unter Annahme der Paarkorrelationsfunktion eines realen Gases in Übereinstimmung mit dem Experiment zu sein.
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    Colloid & polymer science 257 (1979), S. 1009-1011 
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    Colloid & polymer science 257 (1979), S. 1012-1012 
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    Colloid & polymer science 257 (1979), S. 1013-1013 
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    Colloid & polymer science 257 (1979), S. 1014-1014 
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    Colloid & polymer science 257 (1979), S. 934-941 
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    Description / Table of Contents: Zusammenfassung Es wurde der Einfluß von Schrumpfspannungen auf das mechanische Verhalten von Partikeln mit verstärkten Mischkörpern untersucht. Mittels analytischen Ausdrücken wurden wirkliche Systeme behandelt und der Einfluß der verschiedenen Parameter untersucht. Durch Energiebetrachtungen wurde ein Vergleichsmodul bestimmt, der auch für die Verformungsarbeit maßgebend ist, die durch Schrumpfspannungen in den belasteten Mischkörper eingeführt wird. Dies stellt einen Parameter dar, der nützlich für die Untersuchung der Bedingungen ist, unter denen Reißen oder Bruch des Mischkörpers aus der kombinierten Wirkung von ausgeübten und bleibenden Spannungsfeldern auftreten kann.
    Notes: Summary The effect of shrinkage stresses on the mechanical behaviour of particle composites was investigated. By means of analytical expressions, actual systems were considered, and the effect of the various parameters was studied. Energy considerations were applied to determine an “equivalent” bulk modulus, accounting also for the additional strain energy introduced into the composite upon loading, due to shrinkage. This is a useful parameter for the investigation of the conditions under which cracking or fracture of the composite may occur, as result of the combined action of applied and residual stress fields.
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    Colloid & polymer science 257 (1979), S. 1015-1015 
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  • 56
    ISSN: 1435-1528
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    Description / Table of Contents: Summary The methods to measure red cell flexibility are reviewed and own investigations reported based on red cell aging as a model for a physiological reduction in red cell flexibility. The measurement of this parameter was performed with whole-blood by means of filtration through filters with a pore diameter of 5 µm. The model of red cell aging and the method used for the measurement of red cell flexibility is suitable as a screening system to evaluate whether chemical compounds influence red cell flexibility. In two series of experiments pentoxifylline in concentrations of 10 µg and 20 µg/ml of blood and theophylline and prednisolone in concentrations of 96.6 µg or 20 µg/ml of blood, respectively, were investigated. For pentoxifylline a dose-dependent increase in red cell flexibility was observed, theophylline and prednisolone did not change this parameter in comparison to the control. The effect of pentoxifylline is probably related to an increase in red cell ATP content. Scanning electron microscopy revealed that this compound does not influence the outer membrane of the red cells.
    Notes: Zusammenfassung Es werden die Möglichkeiten der Messung der Erythrozytenverformbarkeit dargestellt und eigene Untersuchungen mit einer Methode beschrieben, welche die Erythrozytenalterung als Modell für eine physiologische Reduzierung der Erythrozytenverformbarkeit benutzt. Die Messung dieser Größe erfolgt in Vollblut mittels Filtration durch Filter mit Poren von 5 µm. Das Erythrozytenalterungsmodell und die Methode zur Messung der Erythrozytenverformbarkeit eignet sich für die routinemäßige Prüfung, ob chemische Substanzen die Erythrozytenverformbarkeit beeinflussen. In zwei Untersuchungsserien wurden Pentoxifyllin in Konzentrationen von 10 µg und 20 µg/ml Blut sowie Theophyllin in einer Konzentration von 96,6 µg/ml Blut und Prednisolon in einer Konzentration von 20 µg/ml Blut untersucht. Für Pentoxifyllin fand sich eine dosisabhängige Erhöhung der Erythrozytenverformbarkeit, unter Theophyllin und Prednisolon fanden sich keine signifikanten Änderungen gegenüber der Kontrolle. Der Effekt von Pentoxifyllin ist wahrscheinlich in einer Erhöhung des erythrozytären ATP-Gehaltes begründet. Rasterelektronenmikroskopische Untersuchungen zeigen, daß die morphologische Struktur der äußeren Erythrozytenmembran durch Pentoxifyllin nicht beeinflußt wird.
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    Rheologica acta 18 (1979), S. 492-504 
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    Description / Table of Contents: Zusammenfassung In Ergänzung früherer Ergebnisse vonMeißner an einem Polyäthylen niedriger Dichte, die im linearen Bereich der Verformung für die zeitabhängige Dehnviskosität das Dreifache der Scherviskosität ergaben, konnte die Gültigkeit der Beziehung $$\mathop D\limits^ \circ (t) = 1/3\mathop J\limits^ \circ (t)$$ gezeigt werden. $$\mathop D\limits^ \circ (t)$$ und $$\mathop J\limits^ \circ (t)$$ sind die Nachgiebigkeiten in Dehnung und Scherung. Im nichtlinearen Bereich steigtJ(t) mit zunehmender Spannung an, währendD(t) abfällt. Die Zeitabhängigkeit der Viskosität, definiert als der Quotient aus Spannung und Geschwindigkeit des viskosen Deformationsanteils, ist in Scherung und Dehnung ebenfalls unterschiedlich. Die Scherviskosität fällt von dem Wert der Nullviskositätη 0 mit wachsender Scherung auf einen stationären Wert ab, die Dehnviskosität dagegen steigt von 3η 0 auf einen höheren stationären Wert an. Die Temperaturabhängigkeit wurde aus Messungen des stationären Wertes der Dehnviskosität bei konstantgehaltener Zugspannung und aus einer Verschiebung der bei unterschiedlichen Temperaturen, aber konstanten Spannungen gemessenen Nachgiebigkeiten in bezug auf die Zeit bestimmt. Sie ist dieselbe wie in Scherung. Dieses Ergebnis konnte indirekt durch Messungen mit konstanter Dehngeschwindigkeit bestätigt werden. Die reversible Dehnung im stationären Zustand wurde bei konstanter Zugspannung als von der Temperatur unabhängig gefunden.
    Notes: Summary In addition to earlier findings ofMeißner on a low density polyethylene that in the linear range of deformation the time-dependent elongational viscosity is three times the shear viscosity the validity of the relationship $$\mathop D\limits^ \circ (t) = 1/3\mathop J\limits^ \circ (t)$$ could be demonstrated where $$\mathop D\limits^ \circ (t)$$ and $$\mathop J\limits^ \circ (t)$$ describe the compliances in elongation and shear, respectively. In the nonlinear rangeJ(t) was found to increase with stress whereasD(t) decreases. The nonlinear viscosity-time behaviour is different in shear and elongation, too. The shear viscosity obtained by relating the stress to the rate of viscous strain decreases with shear from the zero shear viscosity to its steady-state value. The elongational viscosity goes up with time from 3η 0 to a higher steady-state value. The temperature dependence which was determined by measuring the steady-state elongational viscosities at different constant stresses as a function of temperature and by shifting the tensile creep compliancesD(t) measured at constant stress with respect to time, was found to be exactly the same as in shear. This result could indirectly be verified by some constant stretching rate tests. It was shown experimentally that the recoverable strain in the steady-state is independent of temperature if measured at constant stress.
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    Rheologica acta 18 (1979), S. 545-548 
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    Rheologica acta 18 (1979), S. 51-61 
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    Description / Table of Contents: Summary Dynamic-mechanical and calorimetric measurements on the polymer system phenolic novolac resin (PF) with styrene-butadiene rubber (SBR), natural rubber (NR) and nitrile-butadiene rubber (NBR) have shown that there only is observed an influence of the mixing ratio on the glass-transition of the rubber. For all compositions the position of the glass-transition of the rubber remains unchanged. From a rubber content of 10 weight-% onwards, a soft phase is being formed beside the rigid matrix phase of the resin. The dominating influence of the rubber on the resin is most evident in the region of rubber elasticity. The mechanical properties in this temperature range are vastly influenced by the rubber phase. The results of the torsional pendulum measurements of the resin-rubber blends at room temperature are compared with the prediction of the elastic properties of polymer blends and composite materials.
    Notes: Zusammenfassung Die mechanisch-dynamischen und kalorimetrischen Untersuchungen an den Polymersystemen Phenolnovolakharz mit SBR, NR und NBR haben gezeigt, daß in diesen Mischsystemen nur ein Einfluß des Mischungsverhältnisses auf den Umwandlungsbereich des Kautschuks, dessen Temperaturlage in allen Konzentrationsbereichen unbeeinflußt bleibt, beobachtet werden kann. Ab einer Kautschukkonzentration von 10 Gew.-% im Harz bildet sich neben der kontinuierlichen Harzphase allmählich eine weiche Phase aus. Der Einfluß des Kautschuks auf das Harz zeigt sich am deutlichsten im kautschukelastischen Bereich. Hier werden die mechanischen Eigenschaften weitgehend von der Kautschukphase bestimmt. Die mit dem Torsionsschwingversuch ermittelten Speichermodulwerte der Mischungen werden mit den theoretischen Überlegungen über den Schubmodul von Polymermischungen und Polymerverbunden verglichen.
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    Rheologica acta 18 (1979), S. 86-95 
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    Description / Table of Contents: Summary The viscosity and the first normal-stress difference as a function of the shear rate ( $$\dot \gamma $$ ) were measured for moderately concentrated (70–150 kg/m3) decahydronaphthalene solutions of a polystyrene sample (M = 2 ⋅ 106). The measurements were carried out in a temperature range of 20–80°C. The results of the measurements are discussed, taking into account the earlier developed theory. The number of temporary junctions are changing in the presence of a shear field and imply changes in the partial entropy and enthalpy of formation of a junction. The changes of these thermodynamical functions were evaluated. The values of the partial entropy, corresponding to $$\dot \gamma $$ ⇒ 0 allow to evaluate the number of junctions. These results are in a qualitative accord with results known from the literature. At a certain critical value of $$\dot \gamma $$ the rate of creation of new temporary junctions is getting to become zero and the probability of their rate of decay equals one. This corresponds to the second Newtonian range. These critical values of the shear rate were evaluated. The probability of the rate of dissociation of temporary junctions should be smaller than one for systems forming a network. This could be understood as a criterion of a system under consideration to form a network.
    Notes: Zusammenfassung Die Viskosität und die erste Normalspannungsdifferenz wurden als Funktion des Schergefälles $$\dot \gamma $$ in mäßig konzentierten (70–150 kg/m3) Dekalin-Lösungen einer Polystyrolprobe (M = 2 ⋅ 106) im Temperaturbereich 20–80°C gemessen. Die Ergebnisse wurden anhand früher entwickelter theoretischer Vorstellungen analysiert. Die Entropie und Enthalpiebeiträge bei Änderung der Verknüpfungszahl als Funktion des Schergefälles wurden ausgewertet. Die Ermittlung der partiellen Entropie bei $$\dot \gamma $$ ⇒ 0 liefert eine Möglichkeit, die Zahl der zeitweiligen Verknüpfungsstellen zu berechnen. Die Ergebnisse stehen im qualitativen Einklang mit den aus der Literatur bekannten Daten. Bei einem kritischem $$\dot \gamma $$ -Wert ist die Geschwindigkeit des Einbaus neuer zeitweiliger Verknüpfungspunkte in das Netzwerk gleich Null und die Wahrscheinlichkeit des Zerfalls dieser Verknüpfungen pro Zeiteinheit gleich Eins. Dieser Zustand entspricht dem zweiten newtonschen Bereich. Diese kritischen Werte der Schergeschwindigkeit wurden ermittelt. Für netzwerkbildende Systeme muß die Wahrscheinlichkeit des Zerfalls der Verknüpfungen pro Zeiteinheit kleiner sein als Eins. Dies kann als Kriterium für ein netzwerkbildendes System betrachtet werden.
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    Rheologica acta 18 (1979), S. 104-107 
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    Description / Table of Contents: Summary Results obtained when a viscoelastic liquid is injected into a Newtonian liquid flowing under turbulent conditions in a straight pipe are reported. Especially, the change in pressure drop along the pipe starting at the injection point were measured as a function of total polymer concentration, concentration of the injected liquid and Reynolds number. If the concentration of the injected liquid is higher the solution remains as a “liquid thread” and is conveyed in the centre region of the pipe. Under these conditions a remarkable drag reduction is also observed, though the polymer has not migrated noticeably into layers near the wall.
    Notes: Zusammenfassung Es wird über Experimente berichtet, bei denen eine viskoelastische Flüssigkeit in der Achse einer ausgebildeten turbulenten Rohrströmung eines newtonschen Fluids injiziert wurde. Insbesondere werden Ergebnisse über die Veränderung des Druckabfalls längs des Rohres in Abhängigkeit von der Gesamtkonzentration des Polymers im Rohr, der Konzentration im injizierten Faden und der Reynolds-Zahl mitgeteilt und diskutiert. Bei der Injektion von höher konzentrierten Polymerlösungen tritt eine deutliche Widerstandsverminderung auch dann auf, wenn die Lösung als elastischer Faden im Kernbereich der turbulenten Strömung mitgeführt wird, d. h. das Polymer noch nicht merklich in die wandnahe Schicht hineindiffundiert ist.
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    Description / Table of Contents: Zusammenfassung Es wurden die Doppelbrechung und der Orientierungswinkel von Polyox-WSR 301-Lösungen im Konzentrationsbereich 50–1350 ppm bis zu Schergeschwindigkeiten von 8000 s−1 gemessen. Dabei wurden einige ausgeprägte Unterschiede gegenüber normalen flexiblen Polymeren gefunden: (i) ein sehr niedriger Wert des Auslöschwinkels, was auf ein ungewöhnlich hohes Molekulargewicht schließen läßt: (ii) die Unabhängigkeit dieses Winkels von der Konzentration, was von einer Änderung der Flexibilität mit der Konzentration herrührt, wie sie durch die Untersuchung der Konzentrationsabhängigkeit der optischen Anisotropie der Segmente aufgezeigt wird; (iii) die Existenz eines Plateaus in der Konzentrationsabhängigkeit der Streckung beic ≳ 150 ppm, welches auf einen konzentrationsabhängigen reversiblen Assoziationsvorgang hindeutet, der auch durch Messung der reduzierten Viskosität nahegelegt wird.
    Notes: Summary Birefringence and orientation angle of solutions of Polyox WSR 301 in the concentration range of 50 to 1350 ppm have been measured up to 8000 s−1. A few marked differences with ordinary flexible polymers have been evidenced: (i) a very low value of the extinction angle at high shear rate, which could be attributed to an unusually high molecular weight; (ii) the independence of this angle on the concentration, which is due to the variation of the flexibility with the concentration, as shown by the study of the concentration dependence of the segmental optical anisotropy; (iii) the concentration dependence of the elongation shows a plateau value forc ≳ 150 ppm, which may come from a concentration dependent and reversible association process, as shown from reduced viscosity measurements.
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    Rheologica acta 18 (1979), S. 289-296 
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    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Zusammenfassung Es wird ein neues Gerät beschrieben, das die Bestimmung der Viskosität von Suspensionen mit Teilchen hoher Dichte in niedrig viskosen Flüssigkeiten ermöglicht. Die an Suspensionen von Teilchen mit niedriger Dichte erhaltenen Ergebnisse stimmen gut mit den mittels eines Weissenberg-Rheogoniometers gewonnenen überein, das entweder mit einer Kegel-Platte- oder einer Koaxial-Zylinder-Meßeinrichtung ausgerüstet war. Als ein überraschendes Ergebnis stellt sich heraus, daß die Eilers-Gleichung, zum Zweck der Erfassung der Teilchenform mit Hilfe des Staudinger-Index in bequemer Weise modifiziert, alle experimentellen Daten gut zu korrelieren imstande ist.
    Notes: Summary A new apparatus is presented which allows the determination of the viscosity of suspensions of high density particles in low viscosity media. Results obtained on suspensions of low density particles compare well with those obtained on a Weissenberg Rheogoniometer equipped with a cone-and-plate and a bob-and-cup. Also, a very interesting observation is that the Eilers equation, conveniently modified to take into account the shape of the particles by means of the intrinsic viscosity, can well correlate all the data.
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    Rheologica acta 18 (1979), S. 308-308 
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    Rheologica acta 18 (1979), S. 303-307 
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    Description / Table of Contents: Zusammenfassung Bei newtonschen Flüssigkeiten weisen die Experimente eine Abweichung vom linearen Zusammenhang zwischen Schubspannung und Schergeschwindigkeit auf. Im Kegel-Platte-Meßsystem ist die Wärmeproduktion durch innere Reibung die wichtigste Ursache der Abweichung. Bei newtonschen Flüssigkeiten, deren dynamische Viskosität sich ungefähr linear mit der Temperatur verändert, ergeben sorgfältig ausgeführte Messungen mit einem Kegel von 10 cm Durchmesser einen linearen Zusammenhang zwischen der Zeit und dem Logarithmus der Temperaturzunahme. Ein aus der Wärmebilanz abgeleitetes Modell vermag dieses Verhalten quantitativ zu beschreiben.
    Notes: Summary At higher shear rates the relation between shear stress and shear rate appears to deviate from the for Newtonian fluids expected linear behaviour. In cone-and-plate rheogoniometry one of the most important causes of that is the effect of viscous heating. Accurate measurements carried out with a 10 cm diameter cone and plate lead to a semi-logarithmic, linear relationship between temperature increase and time for a Newtonian oil which dynamic viscosity varies approximately linearly with time. A simple model based on a heat balance describes this behaviour quantitatively.
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    Rheologica acta 18 (1979), S. 311-322 
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    Description / Table of Contents: Zusammenfassung Eine inkompressible nicht-newtonsche Flüssigkeit fließt unter der Einwirkung eines gleichförmigen konstanten longitudinalen Druckgradienten durch einen von zwei exzentrischen Kreiszylindern begrenzten Ringspalt. Die Strömung wird als so langsam angenommen, daß das Stoffgesetz einer Rivlin-Ericksen-Flüssigkeit zweiter Ordnung angewandt werden kann. Die von der Flüssigkeit auf die beiden Zylinder ausgeübten resultierenden Kräfte werden berechnet.
    Notes: Summary An incompressible non-Newtonian fluid flows in the annular region between two eccentric circular cylinders under a uniform constant longitudinal pressure gradient. The flow is assumed to be sufficiently slow, so that the second-order Rivlin-Ericksen constitutive equation is applicable. The resultant forces exerted by the fluid on the cylinders are calculated.
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    Rheologica acta 18 (1979), S. 335-338 
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    Description / Table of Contents: Zusammenfassung Es werden longitudinale Instabilitäten beim Ausströmen aus einem Parallelspalt analysiert. Dabei wird eine Theorie in Ansatz gebracht, welche diese auf die Oberflächenspannung zurückführt. Sie sagt ein Größerwerden der kritischen Wellenlänge mit wachsender Oberflächenspannung, abnehmender Viskosität und zunehmender Spaltweite voraus. Es wird gezeigt, daß dieser Effekt nicht nur, wie früher schon berichtet, in viskoelastischen, sondern auch in newtonschen Flüssigkeiten beobachtet werden kann. Die Theorie sagt weiter voraus, daß derartige longitudinale Instabilitäten nicht beobachtet werden können, solange die mit der halben Spaltweitea gebildete Ohnesorge-Zahl kleiner als 0.945 ausfällt. Schließlich folgt noch, daß die beobachteten Störungen Wellenlängen besitzen, die kleiner als 1,91/a sind.
    Notes: Summary Longitudinal instabilities in exit flow from a slit have been analysed. A theory which shows them to be of surface tension origin has been proposed. It predicts an increase in critical wave length with increasing surface tension, decreasing viscosity, and increasing slit opening. This effect is shown experimentally to be observable in the flow of Newtonian fluids besides the observations in viscoelastic fluids reported previously. The theory predicts that these longitudinal instabilities will not be observed if the Ohnesorge number based on half slit widtha is less than 0.945. Also, the observed disturbances will have wave lengths corresponding to wave numbers less than 1.91/a.
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    Rheologica acta 18 (1979), S. 339-344 
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    Description / Table of Contents: Summary The mathematical effort needed for the description of the strain answer of a viscoelastic material is, in general, very high. Prony-Dirichlet series enable here-with good approximations, where the constants of the series are computed from simple experiments, as for instance creep tests. Possibilities of simulation, based on the mechanical-electrical analogy, as for example the use of passive electrical elements, analog computer circuits or of a process computer, are discussed. Practical examples, obtained with an analog computer for the simulation of material behaviour built in the frame of this work, are presented.
    Notes: Zusammenfassung Der für die Beschreibung der Dehnantwort eines viskoelastischen Körpers benötigte mathematische Aufwand ist im allgemeinen sehr groß. Hierfür ermöglichen Prony-Dirichlet-Reihen gute Approximationen, wobei die Konstanten der Reihen aus einfachen Versuchen, wie z. B. dem Kriechversuch, berechnet werden können. Simulationsmöglichkeiten, die auf der mechanischelektrischen Analogie basieren, wie z. B. der Einsatz passiver elektrischer Bauteile, elektrischer Analogrechnerschaltungen oder eines Prozeßrechners werden diskutiert. Vorgestellt werden praktische Beispiele, die mit Hilfe eines im Rahmen dieser Untersuchung gebauten Analogrechners für Werkstoffsimulation erzielt werden.
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    Rheologica acta 18 (1979), S. 369-373 
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    Description / Table of Contents: Zusammenfassung Es werden verschiedene neue Meßergebnisse mitgeteilt, die in Scherströmungen an den beiden kommerziellen Polyisobutylen-Typen Vistanex LMMH und L 100 gewonnen worden sind. Außer einigen Messungen unter stationären Bedingungen werden insbesondere Untersuchungen betreffend den Aufbau der Tangentialspannungen nach einer ruckartigen Ingangsetzung der Schergeschwindigkeit sowie deren Abklingen nach Anhalten der stationären Scherströmung durchgeführt. Die Ergebnisse werden zur Prüfung eines rheologischen Stoffgesetzes verwendet, das schon von verschiedenen anderen Autoren untersucht worden ist. Der Vergleich scheint die Eignung des vorgeschlagenen Modells zu bestätigen, wobei dessen einziger Anpassungsparameter sich als unabhängig vom Molekulargewicht erweist.
    Notes: Summary Some new data in shear flow are presented for two commercial polyisobutylene samples, namely Vistanex LMMH and L 100. In particular beyond a few steady state results, the tangential stress build-up after a sudden imposition of a shear rate and the decay after cessation of steady shear flow have been collected. The data are used to further test a constitutive equation already advanced by some of the authors. The comparison seems to confirm the validity of the proposed model, whose single adjustable parameter is shown to be independent of molecular weight.
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    Description / Table of Contents: Zusammenfassung Das rheologische Verhalten wäßriger Polymerlösungen von Separan AP-30 und Polyox WSR-301 wird in einem Konzentrationsgebiet von 10–10000 wppm in einem Kegel-Platte-Rheogoniometer untersucht. Der Zusammenhang zwischen Schubspannung und Schergeschwindigkeit wird für niedrige Schergeschwindigkeiten durch eine konzentrationsabhängige Zeitt 0 gekennzeichnet. Für Schergeschwindigkeiten 4000 s−1 〈 $$\dot \gamma $$ 〈 10000 s−1 zeigen beide Polymere ein genähert binghamsches Verhalten, gekennzeichnet durch eine dynamische Viskositätη 0 und eine scheinbare Fließgrenzeτ 0, welche ebenfalls konzentrationsabhängig sind. Die Trägheitskräfte werden für Wasser und einige newtonsche Öle bestimmt. Die Abweichung der experimentellen Ergebnisse vom theoretischen Modell wird durch die Abhängigkeit der Gestalt der Flüssigkeitsoberfläche von der Schergeschwindigkeit erklärt. Um die Werte der ersten Normalspannungsdifferenz zu erhalten, muß man bezüglich der Trägheitskräfte, der Oberflächenspannung und der Auftriebskräfte korrigieren. Die Normalspannungen für Separan AP-30, gemessen für 350 s−1 〈 $$\dot \gamma $$ 〈 3300 s−1, zeigen eine lineare Abhängigkeit von der Schergeschwindigkeit.
    Notes: Summary The rheological behaviour of aqueous solutions of Separan AP-30 and Polyox WSR-301 in a concentration range of 10–10000 wppm is investigated by means of a cone-and-plate rheogoniometer. The relation between the shear stress and the shear rate is for lower shear rates characterized by a timet 0, which is concentration dependent. Both polymers show for 4000 s−1 〈 $$\dot \gamma $$ 〈 10000 s−1 a behaviour similar to that of a Bingham material, characterized by a dynamic viscosityη 0 and an “apparent yield stress”τ 0, which also depend on the concentration. The inertial forces are measured for water and some other Newtonian liquids. An explanation is given why the theoretical model developed for these forces does not match the experimental values; the shape of the liquid surface is shear rate dependent. To obtain the first normal stress difference, we have to correct for these inertial forces, the surface tension and the buoyancy. The normal forces, measured for Separan AP-30, appear to be a linear function of the shear rate for 350 s−1 〈 $$\dot \gamma $$ 〈 3300 s−1.
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    Rheologica acta 18 (1979), S. 429-429 
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    Rheologica acta 18 (1979), S. 442-450 
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    Description / Table of Contents: Zusammenfassung Es wird eine probabilistische Theorie vernetzter Polymersysteme entwickelt, die auf einer einzigen physikalischen Konstanten, der Häufigkeit der Netzpunkteα, sowie deren Verteilung zwischen den primären Makromolekülen basiert. Diese Theorie ermöglicht das Auffinden struktureller und physikalischer Kenngrößen des Systems in ähnlicher Weise wie in einer früher vom Verfasser zusammen mitA. Ziabicki entwickelten thermodynamischen Theorie, ist jedoch viel einfacher und kann auch auf Systeme angewendet werden, die nicht notwendigerweise zufallsverteilt sind und sich nicht im thermodynamischen Gleichgewicht befinden. Als Beispiel wird die Anwendung auf die Theorie eines monodispersen Systems diskutiert, doch ist die Verallgemeinerung für eine beliebige Massenverteilung der Primärmoleküle ohne besondere Problematik durchführbar. Neue Konzepte betreffend die gel-effektiven Bindungen, die gel-effektiven Makromoleküle und eine reduzierte Vernetzungsdichte werden eingeführt. Ein neues Kriterium für den Gelpunkt wird vorgeschlagen und diskutiert, wobei die reduzierte Vernetzungsdichte den genauen Wert 2 annimmt. Gelpunkt, Gelanteil und Elastizitätsmodul werden berechnet.
    Notes: Summary The probabilistic theory of crosslinked polymer systems is developed. The theory is based on a single physical characteristic — the fraction of reacted groups (functionalities),α, and on the distribution of reacted groups between primary macromolecules. The theory enables to find structural and physical characteristics of the system as the previous thermodynamic theory developed by the author together withA. Ziabicki but is much simpler and may be applicable to systems not necessarily random and not necessarily in thermodynamic equilibrium. An example of an application of the theory to a monodisperse system is discussed but the generalization for any primary molecular mass distribution is straightforward. New concepts of gel-effective junctions, gel-effective macromolecules and of reduced crosslinking density are introduced. The new criterion for the gel-point — the reduced crosslinking density is exactly equal to 2 — is proposed and discussed. Gel-point, gelfraction and modulus of elasticity are evaluated.
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    Rheologica acta 18 (1979), S. 392-423 
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    Description / Table of Contents: Summary In this paper, the flow of Newtonian and non-Newtonian fluids in channels with varying diameter along the longitudinal axis is investigated. The contures of these channels are calculated by means of the analysis of systematical packings of spheres. The investigated channels are similar to the appointed packings as their circular cross-sections vary in the same way as the cross-sections of the pores in the corresponding types of packings. In search of appropriate characteristic numbers for the flow problem of Newtonian fluids different kinds of representation of the friction factor — Reynolds number correlation,ψ = f(NRe) are discussed. If the characteristic numbersψ andN Re are built analogously to the hydraulic diameter and the flow rate in pores, according toDupuit's definition the models show the same pressure-drop characteristics as the corresponding types of packing, in creeping flow as well as in fully developed turbulent flow. In contrast to the flow through packed beds, where the transition from laminar to turbulent flow occurs continuously, the flow through the channels shows a remarkably different transition behaviour forN Re ≈ 600. By means of an appropriately defined characteristic diameter which is to be calculated theoretically from the channel geometry, and by means of a characteristic flow rate, which depends on this diameter, the flow characteristics of all channels can be described by the well known Hagen-Poiseuille equation, for creeping flows of Newtonian as well as non-Newtonian liquids. For the determination of the shear-rate dependent viscosity of non-Newtonian fluids, a modified method, proposed byChmiel andSchümmer, is used, i.e. the shear rateD rep is defined with the above specified exoressions of the diameter and the characteristic flow rate. Furthermore, the friction factor — Reynolds number correlation for Newtonian and inelastic or slightly elastic non-Newtonian liquids can be desribed in the rangeN Re ≤ 30 andN Re ≥ 1200 by the equationψ = 64/NRe + Ct/N Re 0.1 where the factorC t, for which a semi-empiric equation is given, depends only on the geometry of the channels, with values of 0.39 ≤C t ≥ 1.7. In contrast to this liquids with strong viscoelastic properties show atN Re 〉 1 a pronounced excess pressure drop, which depends on the concentration of the polymer solution and the channel geometry. Based on experimental results it is demonstrated by theoretical arguments that up toN Re ≈ 600 the flow characteristics depending on viscoelastic phenomena can be described with the characteristic numberN De = Θfl D rep, in addition toψ andN Re. HereΘ fl signifies the relaxation time of the polymer solution.
    Notes: Zusammenfassung Es wird das Strömungsverhalten newtonscher und nicht-newtonscher Fluide in Kanälen mit variierendem Querschnitt untersucht, deren Konturen aus einer analytischen Betrachtung geordneter Kugelpackungen hergeleitet werden. Die untersuchten Kanäle sind den zugeordneten Kugelpackungen insofern ähnlich, als sich deren kreisförmige Strömungsquerschnitte in Fließrichtung in der gleichen Weise ändern wie die Porenquerschnitte entsprechender Packungstypen. Auf der Suche nach geeigneten Kennzahlen zur Beschreibung des Strömungsproblems für newtonsche Fluide werden verschiedene Darstellungsarten der Widerstandskennlinienψ = f(Re) diskutiert. Hierbei zeigen die Modellkanäle im Bereich der schleichenden und der turbulenten Strömung das gleiche Widerstandsverhalten wie die entsprechenden Packungsarten, wenn die Kennzahlenψ undRe analog mit dem hydraulischen Durchmesser und der nachDupuit definierten mittleren Kanalgeschwindigkeit gebildet werden. Während sich bei der Durchströmung von Kugelpackungen der Übergang von der schleichenden zur turbulenten Strömung allmählich vollzieht, ist jedoch bei der untersuchten Kanalströmung ein charakteristisches Übergangsverhalten festzustellen. Mit Hilfe einer geeignet definierten Durchmesserkenngröße, die sich theoretisch aus der Kanalgeometrie berechnen läßt und einer von diesem Durchmesserparameter abhängig gewählten Kanalgeschwindigkeit kann das Widerstandsverhalten aller Kanäle für newtonsche und nicht-newtonsche Fluide im Bereich der schleichenden Strömung durch die bekannte Hagen-Poiseuille-Gleichung beschrieben werden. Zur Bestimmung der scherabhängigen Viskosität nicht-newtonscher Fluide wird ein modifiziertes vonChmiel undSchlümmer vorgeschlagenes Berechnungsverfahren herangezogen, wobei die oben angeführten Geschwindigkeits- und Durchmesserparameter zur Definition einer charakteristischen SchergeschwindigkeitD rep verwendet werden. Darüber hinaus lassen sich die Widerstandskennlinien für newtonsche und wenig elastische nichtnewtonsche Fluide im BereichRe ≤ 30 undRe ≥ 1200 durch die Gleichungψ = 64/Re + Ct/Re0,1 beschreiben; hierbei hängt der FaktorC t, für den eine halbempirische Berechnungsgleichung angegeben wird, mit 0,39 ≤C t ≤ 1,7 allein von der Kanalgeometrie ab. Demgegenüber zeigen Fluide mit ausgeprägten viskoelastischen Eigenschaften fürRe 〉 1 ein deutlich überhöhtes Druckverlustverhalten, das von der Lösungskonzentration und von der Kanalgeometrie beeinflußt wird. Gestützt auf die experimentellen Ergebnisse kann an Hand theoretischer Überlegungen gezeigt werden, daß bis zuRe ≈ 300 das auf viskoelastischen Phänomenen beruhende Widerstandsverhalten neben den genannten Kennzahlenψ undRe durch eine ÄhnlichkeitskennzahlDe = Θ fl D rep charakterisiert werden kann, wobeiΘ fl eine fluidspezifische Relaxationszeit bedeutet.
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    Rheologica acta 18 (1979), S. 629-634 
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    Description / Table of Contents: Zusammenfassung Diese Untersuchung enthält eine analytische Berechnung der Relaxations- und Retardationsspektren von Polymeren mit enger Verteilung, binären Polymermischungen und gewöhnlichen Polymeren. Das Retardationsspektrum weist zwei Maxima auf, wobei das eine vom Molekulargewicht unabhängig ist (Übergangsbereich), das andere hingegen sich zu längeren Zeiten verschiebt, wenn das Molekulargewicht anwächst (Endbereich). Das aus dem analytischen Ausdruck für das Retardationsspektrum abgeleitete Relaxationsspektrum bricht zu langen Zeiten hin abrupt ab, doch wird dieses Abbrechen ausgeglättet, wenn die konventionellen Methoden zur Bestimmung vonH(τ) aus experimentellen Daten angewandt werden. — Solche analytischen Ausdrücke für das Retardationsspektrum sowie für das daraus durch Integration gewonnene Relaxationsspektrum sollten für die Prüfung von theoretischen Stoffgesetzen nützlich sein.
    Notes: Summary This paper presents an analytical calculation of the relaxation and retardation spectra for narrow distribution polymers, binary blends and whole polymers. The retardation spectrum exhibits two peaks, one independent of molecular weight (transition region), and one shifting toward long times as the molecular weight increases (terminal region). The relaxation spectrum derived from this analytical retardation spectrum is shown to have a sharp cut-off at large times, this cutoff being smoothened when using conventional approximation methods to deriveH(τ) from the experimental data. — The analytical retardation spectra of integrated relaxation spectra (from the retardation spectra) should be useful in the tests of constitutive equations.
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    Rheologica acta 18 (1979), S. 657-661 
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    Description / Table of Contents: Zusammenfassung Messungen bei stationärer Scherung (Viskosität und erste Normalspannungsdifferenz), harmonischperiodischer Scherbeanspruchung (dynamische Viskosität und Speichermodul), sowie rheo-optische Messungen (Mikrophotographien unter polarisiertem Licht während der Scherung mit stroboskopischer Beleuchtung) wurden an einem konzentrierten Poly-β-Benzyl-Aspartat-Gel durchgeführt. Die Eigenschaften erwiesen sich in ausgeprägter Weise als von der Scherungsvorgeschichte abhängig. Die Ergebnisse deuten auf die Existenz einer scherempfindlichen, heilbaren Netzwerkstruktur hin.
    Notes: Summary Steady shear (viscosity and first normal stress difference), dynamic (viscosity and storage modulus), and rheo-optical measurements (polarized light micrographs taken during shear with stroboscopic illumination) were all made on a concentrated gel of poly-β-benzyl-aspartate. The properties were found to be strongly dependent on prior shear history. Results are consistent with the existence of a shear-sensitive and healable network.
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    Rheologica acta 18 (1979), S. 679-679 
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    Rheologica acta 18 (1979), S. 673-678 
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    Description / Table of Contents: Zusammenfassung Die vom Verfasser entwickelte probabilistische Theorie der vernetzten Polymersysteme wird so verallgemeinert, daß Systeme mit Zyklen eingeschlossen sind. Man findet topologische Kenngrößen solcher Systeme, die von den beiden Parametern Vernetzungsdichtel (bzw. Häufigkeit der Netzstellenα) und Häufigkeit der Zyklen bildenden Bindungenβ abhängen. Es wird gezeigt, daß durch das Vorhandensein von Zyklen der kritische Wert der Vernetzungsdichte erhöht wird, wohingegen die reduzierte Vernetzungsdichte den kritischen Wert 2 behalten sollte. Weiter wird mittels des eingeführten Prinzips der makroskopischen Einheitlichkeit abgeleitet, daßβ eine Funktion der Vernetzungsdichte sein muß.
    Notes: Summary The probabilistic theory of crosslinked polymer systems developed by the author is generalized to allow for application to systems with cycles. Based on the two parameters — the crosslinking densityl (or the fraction of reacted functionalitiesα) and the fraction of junctions closing cyclesβ — topological characteristics of such a system are found. It is shown that the presence of cycles increases the critical value of the crosslinking density, whereas the critical value of the reduced crosslinking density ought to remain equal to 2. Then from the introduced principle of macroscopical uniformity,β is found to be a function of crosslinking densityl.
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    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Zusammenfassung Die Ausziehfähigkeit von Polymer-Schmelzen ist von großer Bedeutung für viele Prozesse der Kunststoffverarbeitung. Ausgehend von einer Zustandsgleichung vom Integraltyp mit einem deformationsabhängigen Gedächtnisfunktional, deren Gültigkeit für zwei ähnliche wohldefinierte Polyäthylen-Schmelzen niedriger Dichte nachgewiesen werden konnte, werden Aussagen gemacht über das Materialverhalten bei uniaxialer Dehnung. Dabei werden die folgenden Fälle betrachtet: Versuche bei konstanter Dehngeschwindigkeit, konstanter Zugspannung und konstanter Zugkraft. Es zeigt sich, daß Experimente bei konstanter Zugkraft besser beschrieben werden, wenn man ein rein viskoses Verhalten der Polymer-Schmelzen voraussetzt, als wenn man die Gültigkeit eines Maxwell-Modells annimmt.
    Notes: Summary The extensibility of polymer melts is of great practical importance for polymer processing. On the basis of a single-integral constitutive equation with a straindepent memory functional verified for two similar well-characterized LDPE melts, predictions are made on material behaviour in uniaxial extension under constant strain-rate, tensile stress, and tensile force conditions. It is found that experiments at constant tensile force are more adequately described by assuming purely viscous response of the polymer melts than by assuming Maxwell-model type of behaviour.
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  • 79
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    Rheologica acta 18 (1979), S. 702-710 
    ISSN: 1435-1528
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Zusammenfassung Die Arbeit beschreibt eine phänomenologische Methode zur rheologischen Charakterisierung einer unelastischen thixotropen Flüssigkeit in einer viskometrischen Strömung. Diese Flüssigkeit wurde als Flüssigkeit vom „rate“-Typ behandelt, und es wurde ein Strukturparameterκ definiert, der den inneren Zustand der Flüssigkeit beschreibt. Damit wurde eine Definition der positiven und negativen Thixotropie gegeben. Anschließend wurde eine Prozedur vorgeschlagen, die das Modell der thixotropen Flüssigkeit durch eine Zustandsgleichung und eine Geschwindigkeitsgleichung beschreibt. Unter Benutzung der einfachsten Abhängigkeit, d. h. einer Potenzgleichung, wurde das Modell in expliziter Form konstruiert. Schließlich wurde gezeigt, daß ein Experiment vom Typ einer sprunghaften Änderung der Schergeschwindigkeit die Bestimmung der fünf rheologischen Parameter ermöglicht, die in diesem Modell auftreten.
    Notes: Summary The paper presents a phenomenological method of rheological characterization of inelastic thixotropic fluid in viscometric flow. The fluid was regarded as a material of the rate type and a structural parameterκ was defined as one of the variables describing the fluid state. A definition of positive and negative thixotropy was also given. A procedure leading to the construction of a model of thixotropic fluid in the form of an equation of state and a rate equation was proposed. Using the simplest dependence of power law, the model was constructed in an explicite form. It was proved that the experiment of the type “step-change of the shear rate” enables the determination of the five rheological parameters occurring in this model.
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  • 80
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    Rheologica acta 18 (1979), S. 717-723 
    ISSN: 1435-1528
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Summary Solutions of polyacrylonitrile (PAN) in dimethylformamide (DMF) with concentrations 0.05 to 0.175 kg/l were studied in two cylinder viscometers at 22°C. The overshoot measurements in a newly designed version of the elastoviscometer according toLederer andSchurz showed an increase of the shear modulus at rest with the fourth power of the concentration above 0.08 kg/l. Recoil measurements with the Rotovisco device (Fa. Haake; with improved design for a time constant 〈0.1s) showed recoverable shear elasticity at shear gradients above 10s−1 andc ≥ 0.1 kg/l. For solutions of PAN/DMF, the transition from complete particle solution to network solution has to be assumed around 0.08 kg/l.
    Notes: Zusammenfassung Lösungen von Polyacrylnitril (PAN) in Dimethylformamid (DMF) mit Konzentrationen von 0,05 bis 0,175 kg/l wurden in zwei Zylinder-Viskosimetern bei 22°C untersucht. Die Anlaufmessungen im Elastoviskosimeter nachLederer undSchurz, das durch einen Neubau betriebssicher gemacht wurde, ergaben eine Zunahme des Ruheschermoduls mit der vierten Potenz der Konzentration oberhalb 0,08 kg/l. Die Rückfederungsmessungen am Rotovisko mit Elastizitätsmeßzusatz der Firma Haake (wofür konstruktive Verbesserungen vorgeschlagen werden, um auch Vorgänge, die in weniger als 0,1 s ablaufen, erfassen zu können) zeigen gespeicherte Scherungen bei Deformationsgeschwindigkeiten über 10s−1 und Konzentrationen ab 0,1 kg/l. Für Lösungen von PAN in DMF kann der Übergang vom nicht vollständig ausgeprägten Partikeltyp zum Netzwerktyp im Konzentrationsbereich um 0,08 kg/l angenommen werden.
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  • 81
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    Rheologica acta 18 (1979), S. 740-748 
    ISSN: 1435-1528
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Zusammenfassung Die Verteilung eines gelösten Stoffes in nicht-newtonschen Flüssigkeiten, die durch Kanäle und Rohre fließen, wird unter Zugrundelegung einer homogenen chemischen Reaktion erster Ordnung untersucht. Es wird gezeigt, daß bei gleicher mittlerer Strömungsgeschwindigkeit der äquivalente Verteilungskoeffizient abnimmt, wenn die Reaktionsgeschwindigkeit zunimmt. Diese Abnahme wird bei nicht-newtonschen Flüssigkeiten noch verstärkt.
    Notes: Summary The dispersion of a solute in non-Newtonian fluids flowing through channels and pipes has been studied by taking into account the homogeneous first-order chemical reaction. It is shown that for the same mean velocity of the flow the equivalent dispersion coefficient decreases as the rate of the chemical reaction increases. This decrease is enhanced due to non-Newtonian nature of the fluid.
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  • 82
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    Rheologica acta 18 (1979), S. 730-739 
    ISSN: 1435-1528
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Zusammenfassung Diese Arbeit betrifft laminare Strömungen von Potenzgesetzflüssigkeiten durch Kornschüttungen. Eine kritische Prüfung der Annahmen, die von verschiedenen Autoren für das Kapillar-Modell der Schüttung gemacht worden sind, führt uns zu der Folgerung, daß die Herleitung der Korrelationsgleichung [13] nachChristopher undMiddleman auf einem übervereinfachten Modell der Kornschüttung basiert. Unter Nutzbarmachung der Annahmen, die in den klassischen Arbeiten vonKozeny undCarman dargestellt worden sind (sie wurden sowohl von manchen anderen Autoren als auch in unseren früheren Arbeiten nicht beachtet), werden nun eine modifizierte Korrelationsgleichung für die Potenzgesetzflüssigkeiten [21], eine korrigierte Formel für die Schergeschwindigkeit in der Schüttung [29], eine korrigierte Formel für die Deborah-Zahl [32] und eine korrigierte Korrelationsgleichung für Flüssigkeiten, die Gedächtnis-Effekte zeigen [34], angegeben.
    Notes: Summary The paper deals with laminar flow of power law fluids through granular beds. A critical review of the assumptions concerning the capillary model of the bed, applied by various authors, led us to the conclusion that the derivation of the correlation eq. [13] given byChristopher andMiddleman was based on a too simplified model of the granular bed. Taking advantage of the approach presented in the classical works ofKozeny andCarman (which seems to be partly overlooked by some authors, including our own previous works) a modified correlation equation for power law fluids [21], a corrected formula for shear rate in the bed [29] and for Deborah number [32], as well as corrected correlation equation for fluids exhibiting memory effects [34] were presented.
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  • 83
    ISSN: 1435-1528
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Summary A very sensitive method has recently been developed for the study in vitro of the rheological properties of blood in transient flow at low shear rate. By this method the blood viscoelasticity and thixotropy can be evidenced accurately from the recording of four rheograms corresponding to four different flow conditions, and obtained in well defined and invariable experimental process with the same small blood sample. Thus a given blood can be characterized by means of a small number of mechanical parameters. This method has been used to show that human blood samples, considered as normal from hematological point of view, may exhibit large and reproducible differences of rheological behaviour, which is important for the hemodynamical consequences. On the other hand, it has been demonstrated, on several examples, that viscosity, viscoelasticity and thixotropy of blood frequently show considerable variations when the blood samples are artificially modified. This emphasizes the major role the use of the proposed method may play in the domain of normal and pathological hematology.
    Abstract: Zusammenfassung Vor kurzem wurde eine sehr empfindliche Methode entwickelt, um die rheologischen Eigenschaften von Blut unter nicht-stationären Bedingungen bei niedrigen Schergeschwindigkeiten in vitro zu untersuchen. Hiermit lassen sich die Viskoelastizität und die Thixotropie des Blutes anhand von vier Rheogrammen genau bestimmen, wobei vier verschiedene Fließvorgänge gemäß einem exakt reproduzierbaren Versuchsprogramm an ein und derselben kleinen Blutprobe realisiert werden. Auf diese Weise ist das vorgegebene Blut mittels einer kleinen Anzahl mechanischer Parameter charakterisierbar. Diese Methode wurde angewandt, um zu zeigen, daß vom hämatologischen Standpunkt normales Humanblut bezüglich seines rheologischen Verhaltens erhebliche und reproduzierbare Unterschiede aufweisen kann, die wichtige hämodynamische Folgen haben. Weiterhin wurde an verschiedenen Beispielen nachgewiesen, daß die Viskosität, Elastizität und Thixotropie von Blut durch künstlich vorgenommene Modifikationen wesentlich verändert werden kann. Dies macht die wichtige Rolle deutlich, die derartige vorgeschlagene Methoden für die normale und pathologische Hämatologie zu spielen imstande sein dürften.
    Notes: Résumé Une méthode très sensible d'étude in vitro des propriétés rhéologiques du sang en régime d'écoulement transitoire à faible vitesse de cisaillement développée récemment permet de mettre en évidence avec précision la viscoélasticité et la thixotropie du sang à partir de l'enregistrement de quatre rhéogrammes obtenus en quelques minutes, dans des conditions mécaniques différentes et selon un protocole expérimental standard bien défini, sur un même échantillon de sang de quelques cm3. On peut ainsi caractériser un sang donné au moyen d'un petit nombre de paramètres mécaniques. Cette technique a été utilisée pour montrer que des sangs humains considérés comme normaux du point de vue hématologique peuvent présenter des différences notables de comportement rhéologique, ce qui a des conséquences au niveau de l'hémodynamique. D'autre part il est prouvé sur plusieurs exemples que la viscosité, la viscoélasticité et la thixotropie du sang présentent souvent des variations considérables dans le cas de sangs artificiellement modifiés. Ceci montre l'importance du rôle que pourrait jouer l'utilisation de la technique proposée dans le domaine de l'hématologie normale et pathologique.
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  • 84
    ISSN: 1572-8927
    Keywords: Enthalpies of solution ; hydrophobic hydration ; quaternary ammonium bromides ; solvent mixtures ; water and DMF
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Enthalpies of solution of methyltributylammonium bromide, tetraethanolammonium bromide, and three azoniaspiroalkane bromides in binary solvent mixtures of water and N,N-dimethylformamide have been measured calorimetrically at 298.15oK over the whole mole fraction range. The results are interpreted in terms of a simple hydration model with two parameters and compared with those of the corresponding tetraalkylammonium bromides. Enthalpic studies with different types of quaternary ammonium bromides are useful in reexamining the assumptions and limitations of the hydration model.
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  • 85
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    Journal of solution chemistry 8 (1979), S. 83-95 
    ISSN: 1572-8927
    Keywords: Monensin ; alkali metal complex ; silver complex ; thallium complex ; potentiometry ; enthalpy of complexation ; entropy of complexation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The acid-base and complexing properties of a naturally occurring antibiotic ionophore-monensin (MonH)-were studied in anhydrous methanol solutions primarily by potentiometric measurements. The pK a of the acid was found to be 10.30±0.05 at 25°C. Complexes of silver, thallium, and alkali ions with the undissociated ligand were also studied, and their stability constants were determined. The acid dissociation constant of MonH as well as the stability constants of Mon− Na+ and MonH·NaClO4 complexes were determined in the 5–45°C temperature range, and the enthalpy and entropy of the acidity and stability constants were determined from van't Hoff's plots. The formation of MonH and Mon−Na+ species are both enthalpy and entropy stabilized, but the formation of the MonH·NaClO4 complex is enthalpy stabilized but entropy destabilized.
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  • 86
    ISSN: 1572-8838
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    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Limiting currents were measured for the electropolishing of horizontal copper electrodes facing downwards in phosphoric acid solution under natural convection conditions. The electrode diameter was varied from 1–6 cm and the phosphoric acid concentration between 8–12 M. The limiting current was found initially to decrease with electrode diameter and then to remain constant with further increase. Within the concentration range of phosphoric acid used, the limiting current was found to decrease with phosphoric acid concentration. Mass transfer data was found to agree closely with the equation $$(Sh) = 0 \cdot 18[(Sc)(Gr)]^{0 \cdot 33} for 1 \cdot 1 \times 10^9〈 (Sc)(Gr)〈 2 \cdot 46 \times 10^{11} .$$
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    Journal of applied electrochemistry 9 (1979), S. 7-13 
    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract An experimental programme in which aluminium-copper alloys were electroplated from alkyl benzene/ AlBr3 electrolytes is described. The investigation showed that Al-Cu alloys (0–3.5 wt% Cu) can be plated onto steel and that the resulting coatings are bright, adherent and less porous than equivalent coatings of pure aluminium. The composition of the cathode deposits can be readily controlled by using Al-Cu anodes of specified copper content. About half the copper dissolved from the anodes is transferred to the cathode, the remainder being precipitated from the electrolyte as CuBr. Coating composition varies with current density and this parameter can also be used to control the process. In a parallel investigation, potential differences between aluminium and a number of other metals (Zn, Pb, Cd, Sn, Cu, Ag) were measured. Potential differences in the alkyl benzene electrolytes were found to be 10–30 times less than in aqueous electrolytes which indicates that the alkyl benzenes should be useful for plating other alloys in addition to those of aluminium and copper.
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    Journal of applied electrochemistry 9 (1979), S. 29-35 
    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The investigation is concerned with the drop of current efficiency (CE) of copper deposition under pulsed current conditions. A mathematical model which is based on different charge transfer rates between the following two reactions, (1) $$Cu^{2 + } + e \to Cu^ + $$ and (2) $$Cu^ + + e \to Cu$$ has been formulated to describe the behaviour of a Cu/CuSO4 system under pulsed current conditions on a rotating disc electrode. The results indicate that the CE drops continuously as the difference between the exchange current densities of the two reactions increases. The exchange current densities of Reactions 1 and 2 were estimated to be 0.034 mA cm−2 and 0.024 mA cm−2, respectively. Prediction of CE using the mathematical model agreed to within 3.5% with experimental data over a range 80.4–93.7%.
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    Journal of applied electrochemistry 9 (1979), S. 37-41 
    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 for the cathodic reduction of potassium ferricyanide at a particulate bed of graphite supported on a horizontal nickel disc were studied under H2-evolving conditions. Variables studied were: H2 discharge rate, particle size and bed height. The rate of mass transfer was found to increase to a maximum in the presence of the bed which was about 4.5 times compared to that of the supporting disc. The rate of mass transfer was found to increase with H2 discharge rate, particle size and bed height. Polarization was measured for beds of different particle size and it was found that the presence of the bed increased polarization especially at relatively high current densities, the increase in polarization was independent of particle size of the bed. Comparison with an O2-evolving particulate electrode was made and possible practical applications were pointed out.
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  • 90
    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Zinc deposits contaminated with lead were found to have characteristic morphologies and orientations which were dependent on the amount of lead present in the zinc deposits and to a lesser extent on the presence of other impurities such as antimony and glue in the deposits. Increasing lead in the zinc deposits progressively changed the orientations from (1 1 2) to (1 0 1) to (1 0 0) to finally a poorly crystalline (0 0 2) structure. The lead content of the zinc deposits was dependent on both the concentration and chemical composition of lead added to the electrolyte, the current density and also on the presence of antimony or glue in the electrolyte. A relationship was shown to exist between the effect of lead contamination on zinc deposit morphology and orientation and on the overpotentials associated with zinc electrodeposition in the presence of lead.
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  • 91
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    Journal of applied electrochemistry 9 (1979), S. 15-20 
    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract A comparison of calculated and experimental parameters for the packed-bed reactor working with recirculation of the electrolyte is given. A simple mathematical model was applied and the applicability of the relation $$c = c^0 {\text{ exp(}} - k_1 At/V{\text{) for }}V_c \ll V_R $$ was tested. For the investigated reactor a dimensionless relation has been established from experimentalI-E curves for the single pass mode $$(Sh) = 0 \cdot 5(Re)^{0 \cdot 7} (Sc)^{0 \cdot 33} .$$ For pure practical engineering requirements these two equations together give us a satisfactory way of predicting the concentration-time dependence.
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  • 92
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    Journal of applied electrochemistry 9 (1979), S. 21-27 
    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The voltage drop and current distribution in a chlorine-caustic cell using an anode with a titanium substrate was estimated for several geometric arrangements of the titanium mesh and associated supports and conducting elements. The cell was modelled with a three-dimensional grid network and Kirchoff's law applied to each node. Results were applied to the design of anodes for a full-scale cell which was put in operation and showed the anticipated voltage improvement.
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    Journal of applied electrochemistry 9 (1979), S. 43-53 
    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The electrode kinetics of spongy and dendritic zinc deposition were studied in the presence of three inhibitors (lead acetate, tetrabutylammonium bromide and benzalacetone). It was shown that these additives increase the cathodic overvoltage, decrease the current efficiency, eliminate multiple steady states in acid electrolytes, and modify the impedance diagrams. Such changes in electrode kinetics were interpreted in terms of weaker autocatalytic adsorption of metal cations and enhanced hydrogen adsorption. It was also shown that a pH decrease had a similar effect on these reaction rates. It was concluded from very low frequency impedance measurements that the additives give rise to an accelerated nucleation rate ensuring a faster renewal of active growth sites.
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  • 94
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    Journal of applied electrochemistry 9 (1979), S. 147-153 
    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Poly(4-vinyl pyridine-co-methyl methacrylate), which is soluble in water in its protonated form and insoluble as a neutral molecule, has been synthesized and introduced into an acid bath for copper deposition. Potential-sweep investigations have shown that the copolymer affects the electrocrystallization of copper on graphite by delaying nucleation even before conditions for codeposition of the polymer are reached. At overpotentials at which the diffusion limiting current of copper is reached and hydrogen evolution starts, alkalinity at the electrode surface causes precipitation of the polymer. This is found to affect the resistivity of the deposit. Electron microscopy revealed that under such conditions copper is deposited in the form of globular particles, the size of the globules being in the micron range and decreasing with increasing overpotential.
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    Journal of applied electrochemistry 9 (1979), S. 171-181 
    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The influence of HCl on the anodic behaviour of Fe and Ni in DMSO/1 M H2SO4 depends on the water content of the solution. In completely anhydrous solutions the current density at the same voltage is in no case enlarged and pittings are certainly not observed. At water contents in the range 2–50% the two metals show pitting corrosion, but the current density at the same voltage is much lower than in aqueous solutions. The true anodic polarization measured with an interrupting potentiostat is very high and probably caused by a salt layer. It may be the source of the inhibition effect of DMSO. Fe in DMF/1 M H2SO4 has a similar anodic behaviour depending on the HCl concentration, but the polarization in this anhydrous solvent is much lower. The inhibition effect also seems to be lower.
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  • 96
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    Journal of applied electrochemistry 9 (1979), S. 191-199 
    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Available data are assembled on the critical potentials for various metal-environment systems below which stress corrosion cracking (SCC) does not occur. Such data can be used practically to avoid SCC by use of cathodic polarization, inhibiting ions or by employing galvanic couples. The slow drift of the corrosion potential before coincidence with the critical potential explains in part the observed induction times for SCC. The relative positions of the two potentials with respect to each other explains the susceptibility or resistance to SCC of various metals in a variety of chemical media. Several models proposed to explain the SCC mechanism are reviewed in the light of the present evidence.
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    Journal of applied electrochemistry 9 (1979), S. 141-141 
    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
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    Journal of applied electrochemistry 9 (1979), S. 117-123 
    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract A trickle bed electrochemical reactor has been developed for the production of dilute alkaline peroxide solutions by reduction of oxygen. Oxygen gas and sodium hydroxide flow concurrently downward through a cell which consists of a thin packed cathode bed of graphite particles separated from the anode plate by a porous diphragm. Current flows perpendicular to the flow of electrolyte. The effects of current density, oxygen pressure and flow rate, electrolyte concentration and flow rate, graphite particle size, bed thickness and length were investigated. In 2 M NaOH peroxide solutions of 0.8 M have been produced at 60% efficiency with current densities of 1200 A m−2 and cell voltages of 1.8 V. A bipolar cell stack consisting of five cells has been tested.
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    Journal of applied electrochemistry 9 (1979), S. 155-160 
    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The quantitative analysis of the morphology of dislocation-free {211} iron surfaces during electrochemical dissolution and measurements of distances and directions of monatomic steps provide information about the rates and potential dependences of three different elementary processes involving iron atoms bound to the lattice in three geometrically and energetically different states. The interaction of the three elementary processes explains the well-known anomalies of the kinetics of the iron electrode. A statistical analysis of the step distances is given.
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    Journal of applied electrochemistry 9 (1979), S. 161-169 
    ISSN: 1572-8838
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract The influence of underpotential Pb- and Tl-adsorbates at rotating disc silver single crystal surfaces (111), (100), and (110) on the kinetics of ‘outer-sphere’ and ‘inner-sphere’ redox reactions was studied in 0.5 M NaClO4 and 0.5 M Na2SO4 solutions (2 〈 pH 〈 4) containing Fe3+, Ce4+ or NO 3 − ions. While the reduction of Fe3+ and Ce4+ under limiting diffusion conditions was not affected by the metal adsorbates, a strong inhibition effect correlated to the degree of Pb- or Tl-adsorbate coverages was observed in the case of the reduction process in the presence of NO 3 − ions. The results are interpreted in terms of a strong chemical interaction between the reactant or a reaction intermediate and the silver substrate, taking into account the previously proposed superlattice structures of the metal adsorbates, depending on the orientation of the silver single crystal surfaces and on the underpotential range.
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