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  • 1
    ISSN: 1423-0127
    Keywords: Enterovirus type 71 ; Experimental infection ; Mice ; Neutralizing antibody ; Vaccine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract Experimental infection with enterovirus type 71 (EV71) induced death in neonatal mice in an age- and dose-dependent manner. The mortality rate was 100% following intraperitoneal inoculation 1-day-old ICR mice and this gradually decreased as the age at the time of inoculation increased (60% in 3-day-old mice and no deaths occurred in mice older than 6 days of age). A lethal dose greater than 108 PFU was necessary. Lethargy, failure to gain weight, rear limb tremors and paralysis were observed in the infected mice before death. EV71 was isolated from various tissues of the dead mice. Using a reverse transcription polymerase chain reaction technique with a specific primer pair, a 332-bp product was detected in the tissues that produced a culture positive for EV71. Protection against EV71 challenge in neonatal mice was demonstrated following passive transfer of serum from actively immunized adult mice 1 day after inoculation with the virus. Pups from hyperimmune dams were resistant to EV71 challenge. Additionally, maternal immunization with a formalin-inactivated whole-virus vaccine prolonged the survival of pups after EV71 lethal challenge.
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  • 2
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    Springer
    Neuroscience and behavioral physiology 30 (2000), S. 195-200 
    ISSN: 1573-899X
    Keywords: Mice ; dominance ; subordinacy ; stress ; aggression ; locomotor activity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract The behavior of individaals and their responses to external stimuli are controlled by the microsocial environment, which for most mammals is associated with dominant-subordinate relationships. Physiological and behavioral differences between dominant and subordinate individuals may be ‘primary’ (genetically determined) or ‘secondary’ (due to position in the group's hierarchical structure). A series of experiments was conducted to investigate the physiological (pain response threshold), immunological (thymus, spleen weights, primary immune response), and behavioral (motor activity, behavior in a shuttle box test) characteristics of dominant and subordinate individuals in groups of three laboratory mice formed on the basis of linear hierarchy. Assessment of the effects of group conditions was made using a conditioned reflex location preference test. The results showed: 1) there are no statistically significant differences in physiological and behavioral (except for motor activity) parameters between dominant and subordinate mice; 2) co-housing of dominant and subordinate individuals in groups with stable hierarchical relationships was not aversive for them.
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  • 3
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    Springer
    Earth, moon and planets 88 (2000), S. 35-58 
    ISSN: 1573-0794
    Keywords: Chemistry ; interplanetary dust particles (IDPs) ; Leonids ; meteor trails ; meteoroids ; meteors ; structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The cometary Leonid meteoroids represent a size range in between largest carbon-richIDPs and the smallest CI meteorites. Their dustball structure and chemistry offer anopportunity to constrain hierarchical dust accretion inferred from petrologic studies ofaggregate and cluster IDPs. The Leonid shower meteoroids of known ``comet ejection''ages provide an opportunity to study space weathering of cometary dust over periodsof up to several hundred years. The meteors and aggregate and cluster IDPs displaycontinuous thermal modification of organics and volatile element (Na, K-bearing phases), that occur as discrete minerals and amorphous solids each different response during kinetically controlled ablation. Leonid meteoroids are not excessively Na-rich. The occurrences of Leonid meteors can now be accurate predicted and combined withknowledge better models for the settling rates, collections of surviving dust becomea comet nucleus-sampling mission.
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  • 4
    ISSN: 0894-3230
    Keywords: Menschutkin reaction ; duality of SN1, SN2 mechanisms ; benzyl tosylates ; Yukawa-Tsuno equation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate data for the Menschutkin reaction between strongly activated Z-substituted benzyl p-toluenesulfonates and Y-substituted N,N-dimethylanilines in acetonitrile at 35 °C fit the equation, kobs  =  k1 + k2 [DMA], which is consistent with concurrent first- and second-order processes. The k1 and k2 values for each substrate were separated based on the above equation. The SN1 rate constant, k1, is unaffected by the nature of the nucleophile, whereas the SN2 rate constant, k2, increased with the electron-donating substituent of the N,N-dimethylaniline. The substituent effect on the k1 values is linearly correlated by the Yukawa-Tsuno equation with ρ  =  -5.2 and r  =  1.3. The unimolecular reaction can be regarded as a classical SN1 mechanism. In contrast, that on the k2 values shows an upward curvature when analyzed by the Brown σ+ treatment. These results are ascribed to the simultaneous and independent occurrence of SN1 and SN2 mechanisms in the present Menschutkin reaction. © 1998 John Wiley & Sons, Ltd.
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  • 5
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 231-231 
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No Abstract
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  • 6
    ISSN: 0894-3230
    Keywords: calorimetry ; IR spectra ; ketones ; solvation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solution enthalpies of n-hexane, acetone, butan-2-one and octan-2-one in a series of tetrachloromethane-acetonitrile mixtures and the carbonyl stretching absorption frequencies in the IR spectra of these ketones were determined. It was found that over the whole range of concentrations (varying from neat tetrachloromethane up to neat acetonitrile) the solvation enthalpy of these compounds can be obtained additively from the contributions of the alkyl and carbonyl fragments. The solvent effect on the solvation enthalpy of the carbonyl group was found to be satisfactorily correlated with the corresponding IR frequency shifts of the C=O group. It was also found that the sensitivities of the carbonyl IR frequencies to the solvent composition are different for various ketones. From both IR and calorimetric data, the preferential solvation parameters were evaluated. The differences between the IR spectroscopic and calorimetric data are discussed. © 1998 John Wiley & Sons, Ltd.
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  • 7
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    Journal of Physical Organic Chemistry 11 (1998), S. 261-272 
    ISSN: 0894-3230
    Keywords: 1-substituted 2-pyrrolidinones ; C=O stretching frequencies ; solvent effects ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In an effort to model solute-solvent interactions, the C=O stretching frequencies of five 1-substituted 2-pyrrolidinones and four other carbonyl-containing compounds were measured for 30 common solvents. These were then correlated with four empirical parameter sets and one theoretical (computational) parameter set. While an empirical parameter set gave the best correlation equations, the theoretical parameter equations are physically and statistically significant. Solvent volume, polarizability and hydrogen bond donor acidity (capacity) terms are significant in the correlation equations. © 1998 John Wiley & Sons, Ltd.
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  • 8
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    Journal of Physical Organic Chemistry 11 (1998), S. 232-240 
    ISSN: 0894-3230
    Keywords: P - S bond cleavage ; hydroperoxidolysis ; nerve agent VX ; molecular orbital calculations ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The P - S bond cleavage process in the hydroperoxidolysis of a model system for the nerve agent VX was studied using ab initio and semiempirical molecular orbital methods. Aqueous solvation effects were included through single-point calculations using the semiempirical SM5.2PD/A continuum solvation model and geometries optimized at the HF/MIDI! level of theory. The predominant pathway for P - S bond cleavage involves pseudorotation of a low-energy trigonal bipyramidal intermediate followed by apical ligand ejection. In aqueous solution, the free energy barriers for these processes are found to be 14.3 and 4.6 kcal mol-1, respectively, with electronic energies calculated at the MP2/cc-pVDZ//HF/MIDI! level of theory. By comparison with another continuum model of solvation (PCM), it is concluded that the SM5.2PD/A model performs well even for hypervalent phosphorus species, in spite of not having included any such molecules in the model's parameterization set. © 1998 John Wiley & Sons, Ltd.
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  • 9
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    Journal of Physical Organic Chemistry 11 (1998), S. 407-410 
    ISSN: 0894-3230
    Keywords: gas-phase thermolysis ; N-methyl-N-phenyl-tert-butylsulfenamide ; morpholinyl-tert-butylsulfenamide ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: N-Methyl-N-phenyl-tert-butylsulfenamide (MPSA) and morpholinyl-tert-butylsulfenamide (MOSA) were thermolyzed in a stirred-flow reactor at temperatures of 340-390 °C and pressures of 7-13 Torr, using toluene as carrier gas, at residence times of 0.3-1.3 s. Isobutene was formed in 99% yield through first-order reactions having the following Arrhenius parameters (A,s-1, Ea, kJ mol-1): MPSA, log A  =  12.41 ± 0.02, Ea  =  158.8 ± 0.2; MOSA, log A  =  12.91 ± 0.22, Ea  =  159 ± 3. It is proposed that the elimination of isobutene takes place by unimolecular reaction mechanisms involving polar, four-center cyclic transition states, forming S-unsubstituted thiohydroxylamines as co-products. Thermochemical parameters, estimated by semiempirical AM1 calculations, are reported for the latter and for the parent molecules. © 1998 John Wiley & Sons, Ltd.
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  • 10
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    Journal of Physical Organic Chemistry 11 (1998), S. 411-418 
    ISSN: 0894-3230
    Keywords: 2,2′-bisbenzimidazolyl ; tautomerism ; NMR ; semi-empirical calculations ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A dynamic NMR study of the tautomerism of 2,2′-bisbenzimidazolyl in DMSO-d6 and a mechanistic interpretation of the process, based on a stepwise, single-proton transfer and formation of a zwitterionic intermediate, are presented. This interpretation is substantiated by semi-empirical calculations of the postulated intermediate and transition state, that yield results which are compared with previous studies on related aliphatic systems. © 1998 John Wiley & Sons, Ltd.
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  • 11
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    Journal of Physical Organic Chemistry 11 (1998), S. 397-406 
    ISSN: 0894-3230
    Keywords: bond dissociation energy ; acidity ; phenylsulfenylamides ; phenylsulfenylanilides ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Acidities and bond dissociation energies (BDEs) of the N-H bond in two phenylsulfenylamides, PhSNHBz and PhSNH-t-Bu, and four phenylsulfenylanilides, 4-GC6H4NHSPh, where G  =  MeO, H, Br and CN, were measured in order to compare the effects of substituents on acidities and BDEs of N - H bonds with those of C - H bonds. The effects of PhS groups on acidities and BDEs in a series of C - H acids were found to be comparable to those on acidities and BDEs of PhS in a similar series of N - H acids. Comparisons were also made of the effects of changing the oxidation state of sulfur in the series PhS, PhSO and PhSO2 on the acidities and BDEs of adjacent N - H and C - H bonds in weak acids. Hammett-type plots of pKHA values for phenyl benzyl sulfones (4-GC6H4CH2SO2Ph) and phenylsulfenylanilides (4-GC6H4NHSPh) were linear vs σp- values. A linear plot was obtained and explained for a plot of BDE of the N - H bonds in remotely substituted phenylsulfonylanilides with σ+ values. Plots of BDEs vs Eox(A-) were also linear for 4-substituted phenylsulfenylanilides (4-GC6H4NHSPh), phenylsulfonylanilides (4-GC6H4NHSO2Ph) and phenyl benzyl sulfones (4-GC6H4CH2SO2Ph). © 1998 John Wiley & Sons, Ltd.
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  • 12
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    Journal of Physical Organic Chemistry 11 (1998), S. 387-391 
    ISSN: 0894-3230
    Keywords: α-diamides ; 17O NMR ; conformation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 17O NMR spectra of several α-diamides were obtained at natural isotopic abundance in acetonitrile solution in order to study the conformations of these compounds in solution. The 17O NMR shifts vary with the intercarbonyl dihedral angle α in a sense opposite to that observed for α-diketones. © 1998 John Wiley & Sons, Ltd.
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  • 13
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    Journal of Physical Organic Chemistry 11 (1998), S. 392-396 
    ISSN: 0894-3230
    Keywords: 8-azaadenine ; tautomerism ; theoretical study ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The prototropic tautomerism of 8-azaadenine (azaade) was studied theoretically by means of ab initio methods, in both the gas phase and aqueous solution. A number of tautomeric forms were not included in the calculations after applying a stepwise elimination procedure based on both AM1 and HF/6-31G* energy values. The tautomers 9H-azaade, 8H-azaade and 7H-azaade survived to this elimination and their optimized geometries and energies were calculated at the MP2/6-31*//HF/6-31G* level. To include the solvent effects, two self-consistent reaction field method were used: (1) Onsager's SCRF with multipolar expansion up to the hexadecapolar term and (2) the isodensity polarizable continuum method (IPCM). Both methods produce similar results, although the latter represents better the situation in aqueous solution. The stability order in solution, 8H- 〉 9H- 〉 7H-azaade, differs slightly from that found in the gas phase, implying that in general the electrostatic effects in solution are important, but the intrinsic stability of these species in the gas phase overcomes the solvent effect. © 1998 John Wiley & Sons, Ltd.
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  • 14
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    Journal of Physical Organic Chemistry 11 (1998), S. 377-377 
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No abstract.
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  • 15
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    Journal of Physical Organic Chemistry 11 (1998), S. 419-425 
    ISSN: 0894-3230
    Keywords: 5-nitro-5′-dimethylamino-2,2′-bisthiophene ; π* probe dye ; cyclic voltammetry ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cyclic voltamograms of the solvatochromic dye 5-nitro-5′-dimethylamino-2,2′-bisthiophene (1), introduced recently as a sensitive π* probe, were recorded in different solvents. An EPR spectrum of the anionic radical of 1 in DMSO was obtained and compared with other spectra of analogous substituted bisthiophene radicals. It was found that the presence of a donor- acceptor pair of substituents in 1-⋅ reduces significantly the rotational barrier of the radical compared with the unsubstituted bithienyl radical anion 2-⋅. This is the result of an electronic repulsion between the donor ring fragment and the added electron in the coplanar radical, which does not exist in 2-⋅. © 1998 John Wiley & Sons, Ltd.
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  • 16
    ISSN: 0894-3230
    Keywords: calix[4]resorcinarenes ; organophosphorus compounds ; solvatophobic interactions ; host-guest complexation ; high-performance liquid chromatography ; x-ray analysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reversed-phase high-performance liquid chromatography [LiChrosorb RP-18,UV detection at 254 nm and acetonitrile-water (86:14,v/v) as mobile phase] was applied to studies of the host-guest complexation of tetraalkylcalix[4]resorcinareneoctols and their upper rim phosphoryl, sulfonyl and dialkylaminomethyl derivatives with some aromatic guests in the mobile phase. It was shown that the formation of the inclusion complexes results in changes in the retention of aromatic guests and improves their separation. Stability constants of the complexes were calculated from the dependences of the l/k′ values of the aromatic guest on the concentration of the calix[4]resorcinarene in the mobile phase. The molecular structure of 4,6,16,18-tetrahydroxy-10,12,22,24-tetrakis(dipropoxyphosphoryloxy)-2,8,14,20-tetramethylcalix[4]resorcinarene (12) was determined. Crystal data for 12 are P21/n, a  =  16.708(9) Å, b  =  18.683(6) Å, c  =  20.243(5) Å, β  =  95.75(3)°, V  =  6287(4) Å3 and Z  =  4. Compound 12 exists in a boat conformation, in which two opposite unsubstituted resorcinol rings of the macrocyclic skeleton lie in the plane formed by four methine bridges and two diphosphorylated rings are perpendicular to the plane. © 1998 John Wiley & Sons, Ltd.
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  • 17
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    Journal of Physical Organic Chemistry 11 (1998), S. 378-386 
    ISSN: 0894-3230
    Keywords: alkylboronic acids ; arylboronic acids ; ab initio ; MM3 ; molecular mechanics ; force field parameters ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The boronic acid functional group has been incorporated into various biologically important compounds. In order to study this class of compounds better with molecular mechanics, five alkyl- and arylboronic acids were calculated using ab initio methods (Spartan) at the RHF/6-31G* level. MM3 force field parameters were developed based on the theoretically calculated geometries, vibrational spectra, and torsional profiles. © 1998 John Wiley & Sons, Ltd.
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  • 18
    ISSN: 0894-3230
    Keywords: γ-lactones ; base-catalysed hydrolysis ; reactivity-structure correlations ; isobenzofuranones ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rate coefficients were measured for the base-catalysed hydrolysis of a series of substituted 3-(phenoxy- or thiophenoxymethylene)-(Z)-1(3H)-isobenzfuranones (3-phenoxy- or thiophenoxymethylenephthalides) in 70% (v/v) aqueous dioxane at 30.0 °C, in addition to the carbonyl stretching frequencies in chloroform and tetrachloromethane following deconvolution and band separation, when required. The Hammett reaction constants for the alkaline hydrolysis of the 3-/4-substituted phenoxy and thiophenoxy series are ca 0.75 and 1.10, respectively. These results are related to electrostatic field and resonance effects. Successful correlations between the carbonyl stretching frequencies and substituent constants and the rates of alkaline hydrolysis were found. Computational studies using the semi-empirical AM1 method correctly model both the details of the mechanistic pathway and the substituent effects. © 1998 John Wiley & Sons, Ltd.
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  • 19
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    Journal of Physical Organic Chemistry 11 (1998), S. 437-447 
    ISSN: 0894-3230
    Keywords: inductive constants ; theoretical estimation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A new model of the inductive effect is proposed, allowing highly accurate theoretical calculations of inductive constants for a diversity of substituents, using a simple and readily available system of mathematics. According to this approach, the inductive effect of a substituent is considered in terms of the additive influence of its constituent atoms. A constant inherent capacity for inductive interaction with a reactive center (with a four-coordinate carbon atom chosen for such a center), represented by an atomic constant σA, is ascribed to each atom. Values of σA for a wide variety of atoms are determined, and their physical meaning is revealed to elucidate to a certain extent the physical nature of the inductive effect. In addition, the proposed model permits the convenient use in calculations of group constants σG characterizing the inductive power of groups. Values of σG are determined for molecular fragments that are most widely dealt with in organic chemistry, and the use of σA or σG constants and of their superposition is shown to have, in most cases, little or no effect on the accuracy and reproducibility of the results obtained. It is also shown that, in terms of the developed approach, the inductive effect of a substituent is closely associated with its conformation. Theoretical inductive constants were calculated for 427 organic, aromatic, organometallic and charged substituents, and they showed perfect correlation with the corresponding experimental values. © 1998 John Wiley & Sons, Ltd.
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  • 20
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    Journal of Physical Organic Chemistry 11 (1998), S. 448-454 
    ISSN: 0894-3230
    Keywords: mandelic acid ; alkaline permanganate ; oxidation ; kinetics ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The kinetics of the oxidation of mandelic acid (MA) by permanganate in aqueous alkaline medium at a constant ionic strength of 1.0 mol dm-3 were studied spectrophotometrically. The reaction shows first-order kinetics in [permanganate ion] and fractional order dependences in [MA] and [alkali]. Addition of products, manganate and aldehyde have no significant effect on the reaction rate. An increase in ionic strength and a decrease in dielectric constant of the medium increase the rate. The oxidation process in alkaline medium under the conditions employed in the present investigation proceeds first by formation of an alkali permanganate complex, which combines with mandelic acid to form another complex. The latter decomposes slowly followed by a fast reaction between the free radical of mandelic acid and another molecule of permanganate to give products. The reaction constants involved in the mechanism were derived. There is good agreement between the observed and calculated rate constants under different experimental conditions. The reaction was studied at different temperatures and activation parameters were computed with respect to the slow step of the proposed mechanism. © 1998 John Wiley & Sons, Ltd.
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  • 21
    ISSN: 0894-3230
    Keywords: Selective arylation ; exocyclic N-position ; 2-pyrimidylnitrenium ion ; tetrazolo[1,5a]pyrimidine ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photo-reactions of tetrazolo[1,5-a]pyrimidine (1) with benzene (2a) and substituted benzenes (2b-f) in the presence of trifluoroacetic acid (TFA) gave 2-(2-, 3- and 4-substituted anilino)pyrimidines (3-5) together with 2-aminopyridine (6) and biphenyl (7) or diarylmethanes (8b, 8c and 8e). From the effect of heavy-atom solvent on the reactions, it is reasonable to assume that 3-5 are formed via a singlet species, but 6-8 via a triplet species. The intermediacy of 2-pyrimidylnitrenium ion is consistent with the evidence derived by the above effect, by a Hammett plot with ρ = -2.9 and by effects of solvent nucleophilicity and counter-anions. The selective exocyclic N-arylation giving 3-5 is discussed. © 1998 John Wiley & Sons, Ltd.
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  • 22
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    Materialwissenschaft und Werkstofftechnik 29 (1998) 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 23
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 153-153 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 24
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. A21 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 25
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 51-56 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Application of Wear Resistant PACVD-Coatings in Aluminium Diecasting under Economical and Ecological AspectsAluminium pressure diecasting is a frequently applied manufacturing process for the near netshape production of precision parts. State of the art production techniques still demand considerable amounts of die lubricants. But the side effects of these lubricants include a decrease in surface quality of the cast part as well as a prolongation of the casting cycle time. The job quality decreases and the waste and exhaust disposal during production and application of lubricants is ecologically risky. In this study different wear resistant coating systems have been developed in order to minimize the use of die lubricants in the casting process while at the same time increasing the service life of the diecasting tools.Nitrides, carbides and borides of titanium were synthesized by means of DC-pulse-PACVD. The influence of the process parameters gas composition, pressure, voltage and pulse/pulse repetition ratio was investigated. Compositional analysis was performed by analytical methods such as XRD, EDS, WDS and SIMS. Hardness, adhesion and friction behaviour of the layers were determined in order to describe their mechanical properties. The wetting angle was determined and the corrosion resistance was evaluated in dip tests in aluminium melt. A selection of the best coatings was then compared in diecasting praxis tests under tightened-up conditions reducing the amount of lubricants.TiN, Ti(B,N), TiC and multilayers of the system Ti-C-N were deposited exhibiting a wide range of stoichiometry. The coatings reached hardness values of up to 4400 HK0.005 and the friction coefficient μ was in the range of 0.3. In the diecasting praxis test the amount of die lubricant could be reduced by 97%. Under most severe conditions all layer types led to a minimum increase in the lifetime of the tool of factor 60 compared to an untreated dummy. A strong dependence on the layer type and on its stoichiometry could be observed. Ti(B,N) as the most successful coating in this study has not yet shown any sign of failure and already achieved an increase in lifetime of 300 times.
    Notes: Der heutige Stand der Technik in Aluminiumdruckguß erfordert den Einsatz von Formtrennmitteln. Zu deren Nebenwirkungen gehört aber eine Verschlechterung der Oberflächenqualität des Gußteils. Formtrennmittel beeinträchtigen die Arbeitsplatzqualität und sind unter ökologischen Gesichtspunkten als bedenklich zu betrachten. Um den Einsatz von Trennmitteln zu vermeiden und gleichzeitig die Standzeit der Druckgußwerkzeuge zu erhöhen, wurden nitridische, karbidische und boridische Schichten auf Titanbasis mittels DC-Plus-PACVD abgeschieden und im Hinblick auf ihren Einsatz im Aluminiumdruckguß optimiert. Durch die Beschichtung konnte bei gleichzeitiger Steigerung der Qualität der abgegossenen Teile die notwendige Trennmittelmenge um 97% reduziert werden. Die Standzeit der beschichteten Druckgußkerne im Vergleich zu unbeschichteten erhöhte sich durch die Beschichtung um über das 300-fache.
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 77-79 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Über die Sinterung mit festen EinlagerungenDas Sintern von porösen Matrixwerkstoffen mit steifen, im speziellen nicht verdichtenden Einlagerungsphasen wird mit Hilfe des sphärischen Verbundwerkstoff-Modells von Scherer diskutiert. Ein neuer Zusammenhang zur Berechnung der Verdichtungsdichte des Verbundwerkstoffs unter Berücksichtigung der durch die nicht-verdichtenden Einlagerungen hervorgerufenen Eigenspannungen, wird vorgeschlagen. Drei Komponenten der Dehnungsrate werden betrachtet: (i) die freie, von den vorhandenen Spannungen unabhängige Verdichtungs-Dehnungsrate, (ii) die sich aus den mikroskopischen Spannungseffekten bei den Sintermechanismen ergebende Dehnungsrate und (iii) die aus der Spannung resultierende makroskopische Dehnungsrate. Die Ergebnisse deuten darauf hin, dass bei steifen Einlagerungen höhere innere Spannungen entstehen, als mit dem originalen Modell von Scherer berechnet.
    Notes: The sintering of porous matrices containing rigid, i.e. non-densifying, inclusions is discussed on the basis of the composite sphere model of Scherer. Recognizing that internal stresses are generated by the presence of the non-densifying inclusions, a new equation for the densification rate of the composite is proposed. It takes into account three contributions: (i) the free densification strain rate, which is independent of the stresses present, (ii) the strain rate due to the microscopic effect of the stresses on the sintering mechanism and (iii) the macroscopic deformation strain rate induced by the stresses. This result indicates that the presence of rigid inclusions may generate higher internal stresses in the densify ing compact than those calculated by the original Scherer's approach.
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. A38 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 97-130 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Valve Materials for Combustion EnginesAn overview is being given on production numbers, requirements and properties of valve materials. Their development from the beginning till today's state of the art is reviewed with a focus on Chromium-Manganese-Nitrogen-alloys. Valve materials are grouped by the criteria of density - heavy, lightweight - and alloying elements. The multiple stresses of the material in the valve are being met with a few standardised grades and specific ways of manufacture. The path of the material from bar stock to the finished valve is being followed. Engine development in the past decades increased the load on the valves which could be met by continuously developing their structural strength. Also the strength of all valve materials could be raised to nominal strength above 1100 Mpa by applying specific methods. Higher strength at the surface is being effectuated by work hardening effects. The technology to increase reliability of hollow valves and new aspects of valve seat facing including residual stress is explicitly discussed. General aspects of alloy utilisation is followed by a discussion of lightweight valve materials as Titanium alloys, intermetallic Titaniumaluminide alloys and ceramic materials, spec. Silicon Nitride, which all have a potential as forthcoming valve materials capable of reducing fuel consumption of the engines.
    Notes: Nach einem Überblick über Produktionszahlen, allgemeine Anforderungen und Eigenschaften von Ventilen für Verbrennungsmotoren, wird in einem Rückblick die Werkstoffentwicklung für die Ventilstähle von den ersten Anfängen bis zum heutigen Stand aufgezeigt. Schwerpunktmäßig wird die Gruppe der Chrom-Mangan-Stickstoff-Stähle behandelt. Daneben werden die Ventilwerkstoffe geordnet nach schweren und leichten und innerhalb dieser Gruppen nach Legierungsmerkmalen beschrieben. Es wird über die vielfältigen Werkstoffanstrengungen am Ventil informiert, die mit wenigen genormten Werkstoffgüten und speziellen Fertigungsverfahren problemlos mit niedrigsten Fehlerraten beherrscht werden. Der Weg des Werkstoffes vom Halbzeug bis zum fertigen Ventil wird in allen Schritten verfolgt. Die in den letzten Dekaden forcierte Motorenentwicklung führte zu verschärften Betriebsbedingungen auch für die Ventile, die mit einer kontinuierlichen Weiterentwicklung bestehender Werkstoffgüten und Verbesserungen der Gestaltsfestigkeit der Ventile aufgefangen wurden. In diesem Zusammenhang werden spezielle Lösungen zur Festigkeitssteigerung aller Ventilwerkstoffe bis in den Bereich von über 1100 MPa erläutert, die nach bekannten metallkundlichen Gesetzen ermöglicht wurden. Als wesentliches Prinzip werden ortsabhängig, besonders an der Oberfläche, erhöhte Festigkeits- und Verschleißeigenschaften zur Optimierung der Gestalts- und Betriebsfestigkeit eingesetzt. Über Entwicklungen zur Technologie der Hohlventile und von erweiterten Lösungen beim Auftragschweißen von Ventilsitzen im Zusammenhang mit Eigenspannungen wird ausführlich berichtet. Einer kurzen allgemeinen Betrachtung zum Legierungsaufwand der wichtigsten Ventilwerkstoffe folgt ein Kapitel über Titan, Intermetallische Verbindungen und Keramik, die möglicherweise als zukünftige leichte Ventilwerkstoffe Verwendung finden können.
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 141-152 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Hartstoffschichten auf Leichtmetall-Komponenten unter mechanischer OberflächenbeanspruchungIn der vorliegenden Studie wurde das Verhalten von hartstoffbeschichteten Leichtmetallkomponenten unter mechanischer Oberflächenbeanspruchung untersucht. Hierzu wurden drei Leichtmetallegierungen (Ti-6Al-4V, A1Si7Mg und AlMgSi0.5) sowie 100Cr6 - Stahl (als Vergleichsmaterial) mit zwei unterschiedlichen PVD-Verfahren beschichtet: radio frequency magnetron sputtering und electron beam evaporation. Als Schichtmaterialien wurden CrN und TiN verwendet. Um die verschiedenen Substrat/Schicht-Kombinationen hinsichtlich ihres Belastungsvermögens zu beurteilen, wurden Standard-Testmethoden angewendet, die jeweils eine andere Lastsituation simulieren: der Härtetest (der eine statische Normalkraft aufbringt), der Ritztest (der eine statische Normalkraft mit einer statischen Tangentialkraft überlagert) und der Impacttest (der eine dynamische Normalkraft aufbringt).Es wurde beobachtet, daß das Belastungsvermögen beschichteter Materialien von der vorherrschenden Lastsituation abhängt. Die beschichteten Aluminiumlegierungen wiesen unter allen getesteten Lastsituationen ein geringes Belastungsvermögen auf. Allerdings zeigten sie eine höhere Oberflächenhärte als unbeschichteter Stahl. Beschichtetes Ti-6Al-4V wies ein hohes Belastungsvermögen auf, vergleichbar mit beschichtetem Stahl. Bei sämtlichen beschichteten Leichtmetallsubstraten war eine signifikante Verbesserung des Belastungsvermögens mit zunehmender Schichtdicke zu erkennen.An den Ergebnissen des Ritztests, welcher weitverbreitet zur Untersuchung der Haftung dünner Schichten eingesetzt wird, war auf den Aluminiumsubstraten ein sofortiger Durchbruch des Prüfdiamanten durch die Schichten zu beobachten. Es traten keinerlei Abplatzungen auf. Aufgrund dieses Verhaltens erscheint der Ritztest nicht geeignet, um die Schichthaftung auf Leichtmetallsubstraten zu untersuchen. Im Gegensatz dazu wies das Schadensbild des Impacttests auch auf den Aluminiumsubstraten Schichtabplatzungen auf, was auf dessen Eignung zur Beurteilung des Haftungsvermögens dünner Schichten auf sehr weichen Substraten schließen läßt.Die Studie zeigt, daß in bestimmten Anwendungsgebieten eine Substitution des Stahls durch hartstoffbeschichtete Leichtmetallegierungen möglich ist.
    Notes: In this work the behaviour of hard coated light-metal components was investigated when they are mechanically loaded. Three lightmetal alloys, Ti-6Al-4V, AlSi7Mg and AlMgSi0.5 and 100Cr6 steel (as a reference material) were coated by two different physical vapour deposition processes: radio frequency magnetron sputtering and electron beam evaporation. The coating materials utilised were CrN and TiN. Standard test methods with different loading conditions were used to evaluate the substrate/coating-combinations: the hardness test (applying a static normal load), the scratch test (applying a combination of a static normal and a static tangential force) and the impact test (applying a dynamic normal load).It was observed that the load support of coated materials depends on the loading conditions. The coated aluminium alloys showed poor load support under all loading test conditions but produced a higher surface hardness than uncoated steel. Coated Ti-6Al-4V showed very good load support properties, similar to coated steel. All coated light-metal substrates demonstrated significant improvement in load support behaviour with an increase in coating thickness.The results of the scratch test, which is commonly used to asses adhesion properties of thin coatings, showed an immediate indenter-breakthrough on the aluminium alloy substrates, but causing no coating delamination. Due to this behaviour, the scratch test is not suitable to evaluate adhesion properties on coated soft light-metals. Yet the impact test allowed assessment of coating delamination on the aluminium alloys, proving its usefulness for adhesion measurement even on soft substrates.The study indicates that substitution of steel with coated lightmetal alloys is a viable proposition for certain applications.
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 154-162 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: A concept to describe the fatigue lifetime by using statistical methodsIn order to spend time and money, cyclic loading tests have been usually undertaken with a relative small number of specimens. On the other hand, it is well established that fatigue life data, i.e. the cycle number of crack initiation Ni as well as the cycle number of total failure Nf show a scatter for a given load level. Therefore, fatigue live predictions must be undertaken using statistical methods. In this case it has to be taken into account that the quantity Nf consists of two parts, i.e. crack initiation and propagation. The first one has to be calculated in a statistical manner, whereas the second one with deterministic methods. Therefore, a superposition of statistical and deterministic parts has to be taken into account. Up to now it was estimated that in all cases the failure results from the same damage mechanism. In this case a scatter of fatigue life may be described by the Weibull distribution and characterised by the location parameter and the Weibull exponent. By using the correct density function, all fatigue life data Ni can be plotted in a failure probability Pv(Ni) vs. Ni plot. In case of some Al-alloys no linear dependence between Pv and Ni has been found, indicating that more than one type of defect spectrum may initiate the failure. Indeed, in AlMgSi cold worked specimens two types of cracks, e.g. surface as well as corner cracks, have been found that initiate the failure of the specimens. If was possible to correlate each type of crack with an individual Weibull distribution. By using this procedure, fatigue life can be estimated better than before.
    Notes: Zur experimentellen Lebensdauervorhersage an bauteilnahen Proben werden Schwingfestigkeitsuntersuchungen üblicherweise aus Zeit- und Kostengründen mit einer relativ kleinen Anzahl von Proben durchgeführt. Andererseits ist auf einem vorgegebenen Lastniveau grundsätzlich mit einer Streuung der Versuchsergebnisse, d. h. der Anrißlastspielzahl Ni bzw. der Lastspielzahl bis zum Bruch Nf, Zu rechnen. Um Lebensdauervorhersagen auf statistischer Grundlage durchführen zu können, muß beim Merkmalswert Nf in Betracht gezogen werden, daß die Rißausbreitung im Gegensatz zur Rißbildung in vielen Fällen deterministisch bestimmbar ist. Es ist daher abzuschätzen, in wie weit dieser Beitrag die Streuung der Gesamtlebensdauer beeinflußt. Desweiteren wurde bislang vorausgesetzt, daß der Versagensmechanismus immer auf dem selben Schädigungstyp beruht. In diesem Fall kann die Lebensdauer z. B. mit einer zweiparametrigen Weibull-Verteilung durch Angabe des Streu-und Lageparameters statistisch beschrieben werden. Bei der Verwendung einer geeigneten Dichtefunktion lassen sich die Schwingspielzahlen über die Ausfallwahrscheinlichkeiten auftragen. Im Fall von Al-Basislegierungen hat sich gezeigt, daß diese Auftragung keinen linearen Zusammenhang mehr aufweist, was dafür sprechen könnte, daß mindestens zwei unterschiedliche Defektsorten die Anrißbildung im Bauteil einleiten. Dies konnte für AlMgSi-Bleche anhand von Bruchflächenanalysen direkt nachgewiesen werden. Dazu wurden Ermüdungsrisse klassiert, die sich entweder an den Probenkanten oder direkt an Kratzern der Walzhaut bildeten. Die zwei Ereignisse ließen sich bei sonst gleichbleibenden Versuchsbedingungen in einzelne Weibull-Verteilungen zerlegen. Damit läßt sich im Fall von bauteilnahen Proben die Lebensdauer für kleine Ausfallwahrscheinlichkeiten genauer abschätzen als dies bislang der Fall ist.
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 206-214 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: The size effect on the fatigue properties of weldmentsConstant amplitude fatigue tests (R = - 1 and 0)have been carried out in order to investigate the influence of specimen size and manufacturing conditions on the high-cycle fatigue behaviour of large welded I-beams (web height 500 mm, total length 12 and 7 m respectively). The specimens contained transverse butt welds and longitudinal fillet welds, mainly produced by manual metal arc welding. The Δs̰-concept, as proposed in international standards for fatigue related design is supported by the test results as far as transverse butt welds or longitudinal fillet welds in large sections are concerned. The HCF-behaviour of butt joints in large sections, welded under site conditions, are reasonably covered by Eurocode 3 category 90. EC 3-Category 100 does not conservatively cover the HCF-behaviour of longitudinal fillet joints in large sections.
    Notes: Der Einfluß von Bauteilgröße und Fertigungsbedingungen auf die Ermüdungsfestigkeit von Stumpfstößen und Längskehlnähten wurde anhand von Einstufen-Wöhlerversuchen (R = - 1 und 0) mit großen geschweißten I-Blechträgern (Stelghöhe 500 mm, Länge 12 m bzw. 7 m) untersucht. Die Mehrzahl der Schweißnähte wurde im Lichtbogenhandschweißverfahren hergestellt. Das Konzept der Mittelspannungsunabhängigkeit der zulässigen Spannungen, das in den neueren Stahlbauvorschriften propagiert wird, wird für die Nahtformen Stumpfstoß und Längsnaht durch die Ergebnisse der Großbauteilversuche gestüzt. Das HCF-Verhalten von unter Baustellenbedingungen geschweißten Stumpfstößen in großen Bauteilen wird durch die Kerbfallklasse 90 im Eurocode 3 hinreichend abgedeckt. Die im Eurocode 3 für Längskehlnähte vorgesehene Kerbfallklasse 100 deckt die Versuchsergebnisse nicht vollständig ab.
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. A61 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 424-443 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Deficiency and Surplus of Electrons, a Possibility to explain the most different Phenomenons of Materials Science?The dream to explain all phenomenons with a few principles is very old. It has been tried to explain the transformation and the process of destruction with the help of binding ratios between the atoms at the example of iron, iron-alloys and iron-compounds. The binding ratios depend on the mode, the motion and the distribution of the atoms of a material, on the temperature, on the pressure and on the surrounding (mode, distribution and state of aggregate of the surrounding atoms and particles, redox-potential, fields…).The system „Material and surrounding“ is characterized by deficiency and surplus of electrons in a disequilibrium (in the material as well as in the surrounding). Regardless whether a system is in equilibrium or in disequilibrium, there is a steady exchange of electrons (and also of other particles) between material and surrounding. The ratio of binding electrons to non-binding electrons should be suitable for the characterization of the binding ratios in the material.An universal material testing system for material testing corresponding to load is suggested with the aim of estimation of endurance.The UMTS should allow a better valuation of materials and constructional elements and also a better material sampling and constructing corresponding to load on the basis of Load-Energy-Occurence-Graphs and data files as well as the guarantee of endurance of constructional elements, machines, cars, aircrafts as well as constructions.
    Notes: Der Traum, alle Erscheinungen mit wenigen Prinzipien erklären zu können, ist schon recht alt.Am Beispiel von Eisen, Eisenlegierungen und Eisenverbindungen wird versucht, die Modifikationswechsel, Umwandlungsvorgänge und den Zerstörungsprozeß mit den Bindungsverhältnissen zwischen den Atomen zu erklären. Die Bindungsverhältnissen hängen von der Art, Bewegung und Verteilung der Atome eines Stoffes, von der Temperatur, vom Druck und von der Umgebung (Art, Verteilung und Aggregatzustand der umgebenden Atome und Teilchen, Red-Ox-Potential, Felder…) ab.Das System „Stoff und Umgebung“ ist im Ungleichgewicht (sowohl im Stoff als auch in der Umgebung) durch Elektronenmangel bzw. -überschuß gekennzeichnet. Unabhängig davon, ob sich ein System im Gleichgewicht oder im Ungleichgewicht befindet, findet ein ständiger Austausch von Elektronen (und mit Sicherheit auch von anderen Teilchen) zwischen Stoff und Umgebung statt. Zur Charakterisierung der Bindungsverhältnisse im Stoff sollte das Verhältnis „Bindungselektronen zu nicht an der Bindung beteiligten Elektronen“ beitragen können.Ein universelles Werkstoffprüfsystem zur beanspruchungsgerechten Werkstoffprüfung mit dem Ziel der Lebensdauerabschätzung wird vorgeschlagen. Das UMTS sollte eine bessere Werkstoff- und Bauteilbewertung, eine verbesserte Werkstoffauswahl und ein beanspruchungsgerechtes Konstruieren auf der Grundlage von Belastungs-Energie-Ereignis-Schaubildern und -Dateien sowie die Übernahme von Lebensdauergarantien für Bauteile, Maschinen, Fahr- und Flugzeuge sowie Konstruktionen ermöglichen.
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 48-50 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 50-50 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 338-338 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 365-370 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: The corrosion inhibition of mild steel by some naturally occuring substance was evaluated in absence and presence of 600 and 1200 mg H2S/l in 3% NaCl aqueous solution and pH of 3 and temperature of 25 °C. These naturally occurring substance included the water extracts, coumarines and fatty matters extracts of some Egyptian plants. These plants included:(1) Nigella Sativa (Family Ranunculacease) (Extract (1), 2) Coriandrum Sativum (Family Umbelliferea) (Extract II), 3) Ricinus communis (Family Euphorbiaceae) (Extract III). The galvanostatic anodic and cathodic polarization measurements were used for studying the corrosion behavior of mild steel and evaluation of the percentage inhibition of the undertesting extracts of these three plants and also preparation of fatty matters and coumarin fractions were mentioned.
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 397-411 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Mechanische und Physikalische Eigenschaften von Vermiculargraphit - Gußeisen GGV
    Notes: The mechanical and physical properties of compacted graphite iron (CGI) have been studied. While it is known that CGI provides at least 70% higher tensile strength, 35% higher elastic modulus and 80% higher fatigue limits than conventional grey cast iron, the objective of this paper was to determine how the properties change with varying nodularity (graphite shape) and pearlite content. Tensile properties, hardness, damping capacity and thermal conductivity were determined over the range 0-90% nodularity and 25-100% pearlite. Compressive properties, wear resistance and fatigue behaviour of CGI are also reported upon. Of greatest importance is the influence of patches of flake graphite in predominantly CGI microstructures. As soon as flake patches appear, which can occur with a loss of as little as 0.001% active magnesium, the mechanical properties of CGI abruptly decrease by 25-40%. Proper foundry control technology and quality procedures are therefore required to ensure the reliable production of this improved material.
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. A1 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 1-8 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Protective coating systems for fasteners in contact with light weight metalsA review of the recent use of fasteners for light weight alloys in automotive car production is given. Mechanical design, materials selection and protective coating concepts for Magnesium- and Aluminum-alloys are presented. The specific problems caused by galvanic corrosion are discussed by the use of electrochemical data of the protective coating systems on fasteners for joining Magnesium. Experience from outdoor exposure in automotive applications up to date are considered.
    Notes: Es wird ein Überblick über die derzeit im Kraftfahrzeugbau verwendeten Verschraubungselemente für Leichtmetallegierungen gegeben. Dabei werden konstruktive Auslegungen, Werkstoffauswahl und Beschichtungskonzepte für Magnesium- und Aluminiumlegierungen vorgestellt. Die spezielle Problematik der Kontaktkorrosion wird anhand elektrochemischer Messungen f ür verschiedene Beschichtungssysteme im Verbau mit Magnesium diskutiert. Bisherige Felderfahrungen im Automobilbereich fließen jeweils in die Betrachtungen mit ein.
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  • 41
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 16-22 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Activation energy of repeated carbide precipitation processes in steelsDispersion microstructures in steels can be formed from the martensitic condition by repeated precipitation and coarsening of M3C (or M6C) particles. The precipitation stage comprehends the nucleation and the growth of one particle generation according to r ∝ t1/2 (r - particle radius, t - time), and already after some minutes it turns into the dominating coarsening according to r ∝ t1/3 (OSTWALD-ripening). The coarsening of the first precipitated particle generation is superposed with the following precipitation of further generations. They can be proved by the coercive field strength, the yield strength, microstructural mean values from scanning electron micrographs and by hardness tests. The occurring maxima of precipitation allow the evaluation of the activation energy for the effective volume diffusion in the α - Fe phase. By including the electronegativity (after L. Pauling ) the covalent bond in the M3C phase is considered. With that is possible to attach the estimated activation energy to the main alloying (and diffusing) element and also to the total composition of the steel.
    Notes: Dispersionsgefüge in Stählen werden aus dem martensitischen Zustand durch wiederholte Ausscheidung und Vergröberung von M3C-Partikeln (oder M6C) gebildet. Das Ausscheidungsstadium umfaßt gemäß r ∝ t1/2 (r - Partikelradius, t - Zeit) die Keimbildung und das Wachstum einer Partikelgeneration und geht schon nach wenigen Minuten in die dominierende Vergröberung gemäß der OSTWALD-Reifung r ∝ t1/3 über. Die Vergröberung zuerst ausgeschiedener Partikelgenerationen überlagert sich mit der nachfolgenden Ausscheidung und Vergröberung weiterer Partikelgenerationen. Sie können mit Hilfe der Koerzitivfeldstärke, der unteren Streckgrenze, mit Gefügemittelwertsdaten rasterelektronenmikroskopischer Abbildungen des Dispersionsgefüges und durch Kleinlasthärteprüfungen nachgewiesen werden. Die auftretenden Ausscheidungsmaxima gestatten die Abschätzung der Aktivierungsenergie für die effektive Volumendiffusion in der α - Fe - Phase. Durch Einbeziehung der Elektronegativitätswerte (hier nach L. PAULING) wird die vorliegende kovalente Bindung der M3C-Partikel berücksichtigt. Durch sie ergibt sich eine Zuordnung der abgeschätzten Aktivierungsenergie zu dem Hauptlegierungselement und darüber hinaus zur Gesamtzusammensetzung eines Stahles.
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  • 42
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. A24 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 43
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 57-65 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: With TiN particles lasermodified Al2O3 ceramic under oscillating sliding contact at different humidities and temperaturesA slightly porous, commercially available alumina ceramic was surface modified up to 170 μm thickness by adding TiN particles. The multiphase surface structure of this laser treated ceramic consisted of about 12 vol.% TiN, 16 vol.% grain boundary phase and 72 vol.% Al2O3. Tribological tests on the modified ceramic and for reference also on a highly dense alumina and titania were carried out in oscillating sliding contact against Al2O3 balls. In these tests, the temperature of the specimens was varied between 28°C and 500°C. At room temperature the relative humidity of the surrounding air was changed between 3% and 70% and additional tests were run by using distilled water as interfacial medium. The resulting multiphase microstructure showed substantially reduced friction and wear at different temperatures and also above relative humidities of about 35% at room temperature compared with the highly dense, commercially available alumina.
    Notes: Über einen zweistufigen Laserprozeß wurde eine handelsübliche Al2O3-Keramik in einer Randschicht von 170 μm Dicke durch Einlagerung von TiN-Partikeln modifiziert. Das entstandene mehrphasige Gefüge setzte sich aus ca 12 Vol.-% TiN, 16 Vol.-% Korngrenzenphase und 72 Vol.-% Aluminiumoxid zusammen. Die tribologische Charakterisierung erfolgte im reversierenden, ungeschmierten Gleitkontakt gegen Al2O3-Gegenkörper. Variiert wurde die Versuchstemperatur zwischen 28°C und 500°C und die relative Luftfeuchte bei Raumtemperatur zwischen 3% und 70%. Zusätzlich wurden Versuche in destilliertem Wasser unter Mischreibung durchgeführt. Als Referenzmaterialien wurden je eine handelsübliche, dichte Al2O3-und TiO2-Keramik mit in die Untersuchungen einbezogen.Die durch Oberflächenmodifizierung entstandenen, mehrphasigen Gefüge zeigten in verschiedenen Temperaturbereichen deutlich reduzierte Reibungszahlen und Verschleißbeträge im Vergleich mit der hochdichten, monolithischen Al2O3-Referenzkeramik. Aus den Untersuchungen zum Einfluß der relativen Luftfeuchte (rF) folgte, daß sich die mit TiN-Partikeln modifizierte Al2O3-Keramik oberhalb von 35 % rF durch niedrigere und von der Feuchte unabhängige Reibungszahlen und Verschleißbeträge auszeichnete.
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  • 44
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 594-594 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 45
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 605-608 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Das Grenzflächenverhalten eines mit Stahlkörnern verfestigten Kupfer-Basis-VerbundwerkstoffesEs wird ein neuer, mit Körnern verstärkter, Guß-Verbundwerkstoff vorgestellt. Zur Verstärkung [VZE]dienen grobe Stahlkörner mit einem Durchmesser von 0.6 bis 1 mm in einer Matrix aus Zinnbronze. Der Verschleißwiderstand dieses Verbundwerkstoffes ist zehnmal besser als der der Matrix, die Zugfestigkeit erreicht einen dreifach höheren Wert. In der vorliegenden Veröffentlichung wird schwerpunktmäßig das Grenzflächenverhalten zwischen den Körnern und der Matrix beschrieben. Als Ergebnis wird die Bildung der Grenzfläche durch Diffusion von Eisen und Kupfer, die zu einer Verfestigung führt, beschrieben.
    Notes: A new type of grain reinforcing cast composite is introduced. The reinforcing component is the coarse steel grain (0.6∼1.0mmφ) with the matrix of tin bronze. The wearing resistance of this material is 10 times as much as the matrix and regarding the tensile strength, 3 times. In this paper, the interface behaviour between grains and the matrix is emphasised. The results show the formation of an interface layer, caused by the diffusion of Fe and Cu, which strengthens the bonding.
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  • 46
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 595-604 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Survival Rate and Reliability of Ceramic Femoral Heads for Total Hip ArthroplastyFemoral heads and sockets made of alumina ceramics are successfully used in total hip replacement. The in vivo fracture rate of Biolox heads is lower than 0.02%. An extremely high load (e. g. accident) can initiate subcritical crack growth causing fracturing.107 retrieved Biolox heads were investigated. When measuring their fracture load no fatigue was detected. This result can be explained by the relation between crack velocity and stress intensity (v-K-diagram). The stress intensity of ceramic heads when loaded with standard conditions (e. g. walking, max. load 3 kN) is in the order of 0.6 MPa m1/2. Stress intensities like that are below alumina's fatigue limit KIo which is in the order on 1 MPa m1/2.Biolox alumina heads are examples for engineering ceramics that are reliable despite tensile stress over very long periods of time.
    Notes: Der totale Ersatz eines Hüftgelenkes mit Kugelköpfen und Pfannen aus Aluminiumoxidkeramik ist klinisch bewährt. Die in vivo Bruchrate eines Biolox Kugelkopfes liegt unter 0,02 %. Ausgelöst durch eine extrem hohe Belastung (z. B. Unfall) kann der Bruch nach unterkritischem Rißwachstum erfolgen.An 107 Biolox Explantaten wurde die Restfestigkeit bestimmt. Es konnte keine Materialermüdung nachgewiesen werden. Dies kann mit Hilfe des Zusammenhanges zwischen der Geschwindigkeit des Rißfortschritts und der Spannungsintensität (v-K-Diagramm)b erklärt werden. Normal belastete keramische Kugelköpfe (z. B. beim Gehen max. 3 kN) haben in vivo Spannungsintensitäten K1 von ca. 0,6 MPa m1/2. Hiermit befindet man sich mit der Spannungsintensität im Bereich unter der Ermüdungsgrenze KIo, für die ca. 1 MPa m1/2 abgeschätzt werden kann.Biolox Kugelköpfe sind ein Beispiel für den Einsatz von Keramik, die trotz Zugspannungen als Dauerbelastung und mit hohen Anforderungen an die Sicherheit über large Zeiten sicher im Einsatz sind.
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  • 47
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Differences in the cyclic deformation behaviour of quenched and tempered steel 42 CrMo 4 (AISI 4140) due to stress- and strain-controlCyclic stress-strain-curves and Manson-Coffin-plots of quenched and tempered steel 42 CrMo 4 (AISI 4140) strongly depend on whether they are determined under stress- or total-strain-control. At total-strain-controlled experiments, this is caused on the one hand by comparatively high initial stress-amplitudes which lead to distinctive cyclic worksoftening. On the other hand, the occurring differences in the evolution of inhomogeneous deformation patterns at both types of loading, which can be recorded by means of photoelasticity and microscopy, lead to differently distributed plastic deformations and to different integral values of plastic strain.
    Notes: Die bei nennspannungs- und totaldehnungskontrollierter Zug-Druck-Wechselverformung von vergütetem 42 CrMo 4 erhaltenen Zyklischen Spannungs-Dehnungs-kurven und Manson-Coffin-Auftragungen hängen stark von der Versuchsführung ab. Ursachen dafür sind einerseits die bei Totaldehnungskontrolle vergleichsweise großen Anfangsspannungsamplituden, die zu ausgeprägten Wechselentfestigungen führen. Andererseits bilden sich bei beiden Beanspruchungsarten, wie sich spannungsoptisch und lichtmikroskopisch nachweisen läßt, unterschiedliche inhomogene Deformationserscheinungen aus, die voneinander abweichende plastische Dehnungsverteilungen und integrale Dehnungswerte ergeben.
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  • 48
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Stress-strain hysteresis measurements of cyclically loaded unidirectional SiC-short-fiber reinforced alkali-lime-silicate-glassFor the technical application of fiber reinforced glasses, the knowledge of their fatigue behavior is important. Therefore, AR-glass specimens and SiC-short-fiber reinforced glass-compound specimens were produced by extrusion and investigated in stress controlled cyclic 3-point bending tests. The cyclic deformation behavior was characterized and the failure mechanisms were evaluated as a function of stress amplitude, number of cycles and fiber volume fraction by hysteresis measurements and microscopical investigations of the specimens surfaces. Selected results are presented and discussed.
    Notes: Im Hinblick auf die technische Anwendung faserverstärkter Gläser ist die Kenntnis des Ermüdungsverhaltens dieser Werkstoffe eine unabdingbare Voraussetzung. Hierzu wurden AR-Glasproben sowie SiC-kurzfaserverstärkte AR-Glas-Verbundproben durch Strangpressen hergestellt und in spannungskontrollierten 3-Punkt-Biegeversuchen im Schwellbereich schwingend beansprucht. Die Charakterisierung des zyklischen Verformungsverhaltens und die Bewertung der Versagensmechanismen in Abhängigkeit von Beanspruchungsamplitude, Beanspruchungsdauer und Faservolumengehalt erfolgte mit Hilfe des Hysteresismeßverfahrens sowie lichtmikroskopischer Strukturuntersuchungen an den Probenoberflächen. Ausgewählte Versuchsergebnisse werden vorgestellt und diskutiert.
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  • 49
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    Materialwissenschaft und Werkstofftechnik 29 (1998) 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 50
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 339-344 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Zerstörungsfreie Zustandsermittlung von GasturbinenschaufelnDie Restlebensdauer von sich in Einsatz befindenden Gasturbinenschaufeln wird durch die Bestimmung von Gefügeveränderungen des Grundwerkstoffes während der Betriebszeit ermittelt. Da man versucht Turbinenschaufelstufen in kompletten Sätzen zu halten, ist die Zerstörungsfreie Untersuchung (ZfU) sehr attraktiv. Ziel dieser Untersuchung war es deshalb, die Möglichkeiten eines ZfU Verfahrens zur Bestimmung von Strukturveränderungen im Basismaterial zu bewerten.Das einstufige Oberflächenabdruckverfahren (kombiniert mit REM-Untersuchungen) zeigt sich als relativ einfaches Verfahren, das allen Anforderungen entspricht. Auf unbeschichteten Turbinenschaufeln ist dieses Verfahren direkt anwendbar. Um es auf beschichteten Turbinenschaufeln anzuwenden, muß die Beschichtung lokal entfernt werden.
    Notes: In order to determine the remaining life of service exposed turbine blades it is necessary to characterize the degeneration of the microstructure of the base metal during service. Since turbine blades of industrial gas turbines are kept in complete stages, non-destructive inspection (NDI) is very attractive. Hence the goal of the investigation reported here was to evaluate a NDI technique able to detect microstructural changes of the base metal. It was found that single-stage replication (in combination with investigation in a Scanning Electron Microscope) is a relatively simple technique that fulfils all requirements. This technique can be used in-situ on uncoated buckets. For coated turbine blades local removal of the coating is necessary to perform base metal replication.
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. A97 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. A77 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 53
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 389-396 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Plasma Pretreatment and Coating of Polymer Films. Part 3: Analysis of the Experimental Results and DiscussionThe food packaging industry demands cheap polymer films possessing a high barrier against permeation of gases, moisture and flavour. Candidates for the most successful materials fulfilling these requirements are vacuum web coated biaxial oriented polypropylene (BOPP) films containing a thin inorganic barrier layer. For a good adhesion of the barrier layer on the BOPP films, the polymer film must be pretreated. The industry uses the Corona atmosphere plasma. This work is separated in three parts. The first part describes the experimental setup and the properties of vacuum web coated layers on polymer films[1] The next part contains the results of the systematic modification of polymer surface by atmosphere and low pressure plasmas[2]. The influence of the surface properties on the final functionality of the coated films is given. In the last part, the discussion of the results of the first and second part reveals systematic relations between the production parameters of the high barrier films and their final functionality. These results firstly reveal the adhesion mechanism of the inorganic barrier layers of the polymer films and the necessary surface properties of the polymer films, in order to get cheap high barrier films by vacuum web coating.
    Notes: Die lebensmittelverpackende Industrie verlangt nach immer billigeren Kunststoffolien mit immer höheren Barrieren gegenüber Gasen, Wasserdampf und Aromastoffen. Ein sehr erfolgreicher Schritt, um diese Anforderungen zu erfüllen, besteht in der vakuumtechnischen Beschichtung mit dünnen anorganischen Schichten von biaxial orientierten Polypropylenfolien (BOPP). UM gute Haftungen der aufgedampften Aluminiumschichten zu erzielen, müssen die BOPP-Folie vorbehandelt werden. Industriell steht dafür das Corona-Atmosphärendruckplasma zur Verfügung. In dieser Arbeit aufgeteilt in drei Abschnitte wird zuerst der Versuchsaufbau und die Eigenschaften beschichteter Kunststoffolien allgemein dargestellt[1]. Im nächsten Schritt erfolgt die systematische Modifikation der Folienoberfläche mittels verschiedener Atmosphärendruck- und Niederdruckplasmen [2]. Die Plasmen werden mittels Langmuir-Sonde und Quadrupolmassenspektrometer charakterisiert. Nach Beschichtung der mittels verschiedener Plasmen modifizierten Kunststoffolien zeigen Haftung und Permeabilitätsmessungen den Einfluß der Vorbehandlung auf die Funktionalität der Folie/Schicht-Systeme. Im letzten Abschnitt werden aus den Ergebnissen der Analysen der unbeschichteten und beschichteten Folien systematische Zusammenhänge zwischen Herstellungsparametern und funktionellen Eigenschaften der beschichteten Folien hergestellt. Daraus lassen sich erstmals die zu einer guten Schichthaftung führenden Mechanismen aufzeigen und die notwendigen Oberflächeneigenschaften der unbeschichteten Folie identifizieren, so daß durch die vakuumtechnische Beschichtung preisgünstige Hochbarrierefolien produziert werden können.
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 336-338 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Es wird die Präparation und die temperaturabhängige Lichtdurchlässigkeit thermotroper Gelnetzwerke in Abhängigkeit von ihrer Zusammensetzung auf der Basis von Polyvinylalkohol (PVA), ethoxyliertem Polydimethyl-siloxan (ePS) und Wasser beschrieben. Diese thermotropen Materialien sind für den Einsatz in sogenannten „intelligenten“ Fenstern geeignet.
    Notes: The aim of this study has been to examine the possibility of preparing thermotropic aqueous gel networks that exhibit multiphase transitions in connection with changing the transparency of the system depending on temperature variation. As polymers polyvinyl alcohol (PVA) and ethoxylated polydimethylsiloxane (ePS) were chosen. Thermotropic materials can be used as intelligent shadegivers.
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  • 55
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 345-364 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Plasma Pretreatement and Coating of Polymer Films. Part 2: Experimental Results of the Plasma Pretreatment of Polymer FilmsThe food packaging industry demands cheap polymer films possessing a high barrier against permeation of gases, moisture and flavor. Candidates for the most successful materials fulfilling these requirements are vacuum web coated biaxial oriented polypropylene (BOPP) films containing a thin inorganic barrier layer. For a good adhesion of the barrier layer on the BOPP films, the polymer film must be pretreated. The industry uses the Corona atmosphere plasma. This work is separated in three parts. The first part describes the experimental setup and the properties of vacuum web coated layers on polymer films [1]. The next part contains the results of the systematic modification of po } ymer surface by atmosphere and low pressure plasmas. The influence of the surface properties on the final functionality of the coated films is given. In the last part, the discussion of the results of the first and second part reveals systematic relations between the production parameters of the high barrier films and their final functionality. These results firstly reveal the adhesion mechanism of the inorganic barrier layers of the polymer films and the necessary surface properties of the polymer films, in order to get cheap high barrier films by vacuum web coating.
    Notes: Die lebensmittelverpackende Industrie verlangt nach immer billigeren Kunststoffolien mit immer höheren Barrieren gegenüber Gasen, Wasserdampf und Aromastoffen. Ein sehr erfolgreicher Schritt, um diese Anforderungen zu erfüllen, besteht in der vakuumtechnischen Beschichtung mit dünnen anorganischen Schichten von biaxial orientierten Polypropylenfolien (BOPP). Um gute Haftungen der aufgedampften Aluminiumschichten zu erzielen, müssen die BOPP-Folie vorbehandelt werden. Industriell steht dafür das Corona-Atmosphärendruckplasma zur Verfügung. In dieser Arbeit aufgeteilt in drei Abschnitte wird zuerst der Versuchsaufbau und die Eigenschaften beschichteter Kunststoffolien allgemein dargestellt [1]. Im nächsten Schritt erfolgt die systematische Modifikation der Folienoberfläche mittels verschiedener Atmosphärendruck- und Niederdruckplasmen. Die Plasmen werden mittels Langmuir-Sonde und Quadrupolmassenspektrometer charakterisiert. Nach Beschichtung der mittels verschiedener Plasmen modifizierten Kunststoffolien zeigen Haftung und Permeabilitätsmessungen den Einfluß der Vorbehandlung auf die Funktionalität der Folie/Schicht-Systeme. Im letzte Abschnitt werden aus den Ergebnissen der Analysen der unbeschichteten und beschichten Folien systematische Zusammenhänge zwischen Herstellungsparametern und funktionellen Eigenschaften der beschichteten Folien hergestellt. Daraus lassen sich erstmals die zu einer guten Schichthaftung führenden Mechanismen aufzeigen und die notwendigen Oberflächeneigenschaften der unbeschichteten Folie identifizieren, so daß durch die vakuumtechnischen Beschichtung preisgünstige Hochbarrierefolien produziert werden können.
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 412-423 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Weldability of Aluminium and Al AlloysAluminium is behind steel the most used metal. Advantages of Al-materials are the low weight, the favourable strength and deformation properties, the good corrosion resistance and the good electrical and thermal conductivity. Welding of aluminium encounters difficulties due to high melting oxide layer at the surface, the strong heat dissipation from the welding region, the tendency to form craters or pores and the high heat extension. This contribution describes the basic facts and special features of arc welding and weld properties of aluminium and Al-alloys during welding.
    Notes: Aluminium ist das nach dem Stahl am häufigsten eingesetzte Metall. Vorteile der Aluminiumwerkstoffe sind das geringe Gewicht, günstige Festigkeits- und Verformungseigenschaften, der hohe Korrosionswiderstand sowie die hohe elektrische und Wärmeleitfähigkeit. Beim Schweißen ergeben sich vielfach Schwierigkeiten, die u. a. durch die hochschmelzende Oxidhaut, die starke Wärmeableitung, die Neigung zur Riß- oder Porenbildung sowie durch die große Wärmedehnung verursacht werden. Im vorliegenden Beitrag werden die Grundlagen und Besonderheiten von Reinaluminium und unterschiedlicher Legierungen hinsichtlich der Lichtbogen-Schweißtechnologie und der Nahteigenschaften dargestellt.
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 447-450 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 451-451 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 59
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 466-475 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Low energy IBAD: correlation between process parameters ans film properties for ion beam assisted evaporation and sputter depositionBinary nitride films with Al, Cr and Ti as metal components have been deposited with ion beam assisted evaporation and sputtering (IBAD) and the film properties are investigated in terms of the individual deposition parameters.In the case of ion beam assisted evaporation the flux ratio between the film forming metal atoms and the nitrogen ions from the ion source was shown to enable a quantitative control of the composition and the chemical phases of the films. Detailed studies for TiN reveal the possibilities to manipulate texture and stress, the average grain size and the morphology of the films. Such results are discussed with an extended structure zone model, introducing the energy input per film forming particle as the relevant parameter. Also, the structural film properties and the deposition parameters are quantitatively correlated with the hardness and the beginning of TiN deposition on stainless steel resulted in distinctly improved adhesion properties.For the deposition of TiN with a dual ion beam arrangement in which one beam bundle was directed onto a Ti-target and an other onto the substrate with the growing film, a strong influence of the particle energies and the incidence angles on the film texture and its directional orientation was found. Such effects are quantitatively related to the minimization of the free energy of the films and the influence of preferential re-sputtering effects. For ion beam sputter deposition without simultaneous ion bombardment of the growing film, the texture and the film stress are found to be controlled by energetic particles resulting from elastic backscattering at the target surface.
    Notes: Mittels ionenstrahlunterstütztem Aufdampfen und Aufsputtern (IBAD)wurden binäre Nitridschichten mit Al, Cr und Ti als Metallkomponente deponiert und hinsichtlich ihrer Eigenschaften in Abhängigkeit von den Depositionsparametern Charakterisiert.Beim ionenstrahlunterstützten Aufdampfen konnten durch Variation des Flußratenverhältnisses zwischen den schichtbildenden Metallatomen und den aus der Ionenquelle extrahierten Stickstoffionen die Schichtzusammensetzung und die chemischen Phasenverhältnisse kontrolliert eingestellt werden. Ausführliche Untersuchungen an den TiN-Schichten zeigen, daß auch Textur, Eigenspannungen, mittlere Korngröße und Morphologie der Schichten in weiten Grenzen manipuliert werden können. Ausgehend vom Energieeintrag pro schichtbildendem Teilchen werden die Ergebnisse anhand eines erweiterten Strukturzonenmodells diskutiert. Weiter lassen sich die strukturellen Schichteigenschaften und die Depositionsparameter mit der Härte und der Haftfestigkeit der Schichten quantitativ korrelieren. Durch dynamische Prozeßführung in der Anfangsphase des Schichtwachstums konnte eine deutliche Verbesserung der Haftung von TiN auf Werkzeugstahl erzielt werden.Für die Deposition von TiN mit einer Zweistrahlanordung, bei der ein Ionenstrahlbündel auf ein Ti-Target und ein weiteres auf das Substrat mit der aufwachsenden Schicht trifft, ergibt sich ein deutlicher Einfluß der Teilchenenergien und -auftreffwinkel auf die Schichttextur und deren Ausrichtung. Betrachtungen zur Minimierung der freien Energie in den Schichten und zum Einfluß von präferentiellen Rücksputtereffekten liefern ein quantitatives Verständnis der Effekte bei der Texturbildung. Bei der Ionenstrahl-Sputterdeposition ohne simultanem Substratbeschuß werden Textur und Schichtspannungen durch die vom Sputtertarget kommenden energiereichen Rückstreuteilchen bestimmt.
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 518-524 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Custom-Tailored Coating-Interface Systems by Means of lon Beam Assisted DepositionA coated sample represents in its most simple form a threefold junction consisting of substrate interface and top layer. In many cases the top layer consists again of several sublayers or the interface contains a modified substrate surface and an interconnection between top layer and interface. An ideal coating technique is evaporation under simultaneous ion bombardment with an ion source it is possible because of several free parameters to come close to an ideal system.For the coating Al/Al2O3 on steel it is shown that the width of a composition gradient between the sublayers Al and Al2O3 can be optimized with respect to excellent corrosion resistance.The example CrxN coating on steel or corrosion and wear resistence demonstrate the ability to optimize the corrosion and wear resistence by modifying the microstructure via variation of the parameters ion energy, ion impact angle, ion to atom ratio and process temperature.Finally, TiN layers on steel were chosen to show that the ion beam parameters influence the porosity and the crystal structure of the coatings. This fact can be used to optimize the corrosion protection or wear reduction obtained by the coating. Especially the multilayer Ti/TiO2/TiN exhibits very interesting properties.
    Notes: Ein beschichtetes Bauteil stellt in seiner einfachsten Form einen Dreierverbund aus Substrat, Interface und Schicht dar, in vielen Fällen kann die Schicht aus mehreren Untersystemen bzw. das Interface aus der modifizierten Substatrandschicht und einem Zwischenbereich zur Schicht bestehen. Eine ideale Beschichtungsmethode sollte es daher erlauben, alle diese Schichten bzw. Schichtbereiche in kontrollierter und aufeinander abgestimmter Form zu erzeugen.Mittels des IBAd-Verfahrens, bei dem Aufdampfschichten während ihrer Abscheidung mit Ionen aus einer Ionenquelle beschossen werden, ist es möglich, infolge der zahlreichen frei wählbaren Parameter sich an das ideale System heranzutasten.Anhand des Verbunds Stahl/Al/Al2O3 wird erlätert, wie durch einen in der Ausdehnung optimierten Zusammensetzungsgradienten das Interface zwischen den Subschichten Al und Al2O3 bezüglich des Korrosionsschutzvermögens der Schicht verbessert werden kann.An CrxN-Schichten wird demonstriert, daß durch die Wahl der Parameter Ionenenergie, Ioneneinfallswinkel, Ionen/Atom-Verhältnis und Prozeßtemperatur über die Mikrostruktur von Schicht und Oberfläche das Verschleiß-und Korrosionsverhalten sowie die Härte angepaßt werden können.Am Beispiel TIN auf Stahl zeigt sich, daß je nach Ionenstrahlparameter die Porosität und damit das Korrosionsverhalten bzw. die Kristallinität und damit Härte und Verschleißverhalten optimiert werden können. Besonders Mehrlagenschichten Ti/TiO2/TiN zeigen interessante Eigenschaften.
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    Materialwissenschaft und Werkstofftechnik 29 (1998) 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
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  • 62
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Coatings in polymer processingCrxN coatings produced by PVD-magnetron sputtering (MSPVD) open unitsFor several years hard coatings have been used in plastic processing. The reduction of adhesion and contamination effects play a more and more important role besides the wear protection of injection moulds and extrusion tools. Applications of hard coatings in the field of highly stressed screws and barrels of plastification units are very seldom. In these cases the tribological effects are very intense so that the demanded wear resistance of hard coatings in the range 10μm is not sufficient. Different hard coatings based on titanium and chromium were tested according to their applicability for wear protection of screws in plastification units. Thickness, hardness, internal stresses and adhesion of the coatings were studied.Afterwards tribological tests in a model testing unit were investigated. Here the coatings were studied under tribological conditions, similar to those in a real plastification unit. The CrxN multilayer coatings showed extremely better wear resistance than the titanium based coatings. For this reason the CrxN coatings were optimized by help of the deposition parameters. These optimized coatings have been investigated according to their applicability for different polymers in comparison to other coating systems. First tests of CrCN/TiCN coated screw elements in practice showed very pleasing results. The test in practice with the optimized CrxN multilayer coating has yet to take place, but in the model tests the CrxN coatings showed excellent results.
    Notes: Hartstoffschichten werden bereits seit langem in der Kunststoffverarbeitung eingesetzt. Neben dem Verschleißschutz von Spritzguß-und Extrusionswerkzeugen stehen häufig auch die Verringerung von Klebneigungen und Formverschmutzungen im Vordergrund. Anwendungen im Bereich der hochbeanspruchten Schnecken und Zylinder von Plastifizieraggregaten sind noch selten. Die Verschleißeffekte sind hier so heftig, daß in der Praxis eine große Verschleißreserve gefordert wird, die Hartstoffschichten mit maximal 10 μm Schichtdicke naturgemäß nicht mitbringen. Verschiedene Hartstoffschichten auf Titan- und Chrombasis wurden hinsichtlich ihrer Eignung für den Verschleißschutz von Schnecken für Plastifizieraggregate untersucht. Schichtdicke, Härte, Eigenspannungen und Haftfestigkeit der Schichten wurden bestimmt.Anschließend wurden Verschleißversuche mit Hilfe einer Modellprüfapparatur, die die Schichten ähnlichen tribologischen Belastungen aussetzt, wie sie in einer Plastifiziereinheit auftreten, durchgeführt. Die CrxN-Mehrlagenschichten waren hierbei den auf Titan basierenden Schichten deutlich überlegen. Deshalb wurden für die CrxN-Schichten optimale Beschichtungsparameter bestimmt. Diese optimierten Schichten wurden mit verschiedenen anderen Schichtsystemen im Hinblick auf Ihre Eignung für unterschiedliche Kunststoffmaterialien verglichen. Erste Praxisversuche mit CrCN/TiCN-beschichteten Schneckenlementen sind sehr vielversprechend. Ein Praxistest der optimierten CrxN-Mehrlagenschichten steht zwar noch aus, jedoch konnten die guten Ergebnisse der CrxN-Schichten bei den Modellversuchen stets bestätigt werden.
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 569-572 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Predicting the fatigue strength of fillet-rolled crankshaftsSince three years Darmstadt University of Technology uses finite element method for simulation of fillet rolling process. Now, together with Daimler-Benz AG, a fracture mechanics based concept has been successfully applied predicting the fatigue strength of fillet-rolled crankshafts. For these parts conventional assessment of fatigue behaviour shows several disadvantages. The new concept reduces time and costs for development and design. It consists of three parts: calculation of residual stresses induced by fillet rolling and affected by crankshaft and roller geometry, rolling load and work hardening data of materialsimulation of residual stress redistribution due to cyclic loadassessment of fatigue cracks starting from notch root and propagating under compressive residual stresses by means of linearelastic fracture mechanics.
    Notes: Nachdem vor drei Jahren an der TU Darmstadt erstmals das Festwalzen erfolgreich mit Finite-Elemente-Methoden simuliert wurde [1], gelang nun in Zusammenarbeit mit der Daimler-Benz AG die rechnerische Abschätzung der Schwingfestigkeit festgewalzter Kurbelwellen mit Methoden der Bruchmechanik. Mit dem auch in der Vorentwicklung einsetzbaren Berechnungskonzept - hier zeigen die klassischen Berechnungsmöglichkeiten für festgewalzte Bauteile deutliche Defizite - können sowohl Entwicklungszeiten als auch Kosten der Versuchserprobung reduziert werden. Die Berechnung erfolgt dabei in drei Stufen: Berechnung der beim Festwalzen induzierten Eigenspannungen mit Hilfe der geometrischen Daten von Kurbelwelle und Festwalzrolle bei vorgegebener Werkstofffließkurve und Festwalzkräften.Berücksichtigung der Umlagerung der Eigenspannungen aufgrund der zyklischen Beanspruchung des Bauteils.Bruchmechanische Bewertung der sich im Radiusbereich der Kurbelwelle bildenden Anrisse und deren Verhalten in der druckeigenspannungsbehafteten Zone.
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 629-631 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. A132 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Keywords: Chemistry ; Polymer and Materials Science
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    Description / Table of Contents: Influence of mean stresses and mean strains on the cyclic deformation behavior and the plasticity-induced martensite formation of X6CrNiTi1810 stainless steelThis paper describes some aspects of the fatigue behavior of the metastable austenitic stainless steel X6CrNiTi1810 (German material number 1.4541). The aim of the present investigation is to determine the influence of plasticity-induced martensite formation on the cyclic deformation behaviour at room temperature and T = 300°C. Several specimen batches were tested under stress and total strain control with different R-values, a frequency of 5 Hz and triangular load-time functions, s̰-hysteresis and nondestructive magnetic measurements are used to characterize the fatigue behavior. Characteristic results are presented and discussed.
    Notes: Anhand von einstufigen spannungs- und totaldehnungskontrollierten Versuchen werden Zusammenhänge zwischen dem zyklischen Verformungsverhalten und der verformungsinduzierten Martensitbildung des metastabilen austenitischen Stahls X6CrNiTi1810 (Werkstoff-Nr. 1.4541) bei Raumtemperatur und T = 300°C untersucht. Besondere Beachtung findet hierbei der Einfluß von Mittelbeanspruchungen. Alle Versuche wurden mit einem dreieckförmigen Beanspruchung-Zeit-Verlauf und einer Frequenz von 5 Hz durchgeführt. Zur Charakterisierung des Wechselverformungsverhaltens dient neben den aus σ-Hysteresen ermittelten mechanischen Kennwerten, der on-line mittels eines Wirbelstromsensors gemessene magnetische Phasenanteil. Ausgewählte Versuchsergebnisse werden vorgestellt und diskutiert.
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    Keywords: Chemistry ; Polymer and Materials Science
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 713-713 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
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  • 69
    ISSN: 0894-3230
    Keywords: 3-methyl-2, 4-diphenyl-3-azabicyclo[3.3.1]nonan-9α-ol esters ; analgesics ; synthesis ; structure ; conformation ; pharmacological assays ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of esters derived from 3-methyl-2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9α-ol (1) was synthesized and studied by 1H and 13C NMR spectroscopy, and the crystal structure of 3-methyl-2,4-diphenyl-9α-(3,5-dimethylbenzoyloxy)-3-azabicyclo[3.3.1]nonane (2) was determined by x-ray diffraction. The compounds studied display in CDCl3 a preferred flattened chair-chair conformation. This bicycle conformation is similar to that found for 2 in the crystal state. Pharmacological assays on mice were performed to evaluate drug-induced behavioral alteration, peripheral or central acute toxicity and analgesic activity. © 1998 John Wiley & Sons, Ltd.
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    Journal of Physical Organic Chemistry 11 (1998), S. 101-108 
    ISSN: 0894-3230
    Keywords: encounter complexes ; 1-cyanonaphthalene ; norbornadiene ; stereospecific ; nucleophilic trapping ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photo-induced electron donor-acceptor reactions between 1-cyanonaphthalene (CNN) and norbornadiene (N) generate products of several structure types. Methanol adducts (1-3) formed in polar solvents are rationalized via the radical cation, N+·, and stereospecific (exo-) nucleophilic attack by methanol. In less polar solvents, CNN and N form [2 + 2]-cycloadducts, exclusively on the exo-face of N. In non-polar solvents containing methanol, CNN, N and methanol combine to form 1:1:1 adducts, containing the sensitizer on the endo- and the methoxy groups on the exo-face. The formation of these products is rationalized via the trapping of encounter complexes of different geometries. Any rearrangement of the norbornenyl system can be eliminated, since neither tricyclyl nor 7-methoxynorbornenyl structures are formed. Apparently, the alcohol captures an endo-encounter complex of CNN and N by attack from the exo-face, similar to the attack of methanol on N+·. © 1998 John Wiley & Sons, Ltd.
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    ISSN: 0894-3230
    Keywords: aromaticity ; Diels-Alder transition states ; Diels-Alder adducts ; reaction mechanism ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Semiempirical, ab initio and DFT investigations on the mechanism of the Diels-Alder reactions of a set of masked dienes (ring-fused dienes), viz. o-quinodimethane, anthracene and α-vinylnaphthalene, with ethylene, and reactions of α-vinylnaphthalene with maleic anhydride and p-benzoquinone were performed with a view to understanding the role of masking factors on the activation and reaction energies. The reactions were found to occur in a concerted fashion through synchronous transition states (TSs) in the first two reactions and through asynchronous TS in the other case. Of the compounds studied, o-quinodimethane is the most reactive diene both in a kinetic and a thermodynamic sense. α-Vinylnaphthalene reacts faster with maleic anhydride than p-benzoquinone, as expected, and two possible stereoselective TSs, one endo and the other exo, have been located for the reactions of α-vinylnaphthalene with the above dienophiles. Calculations show that the relative gain or loss of aromatic stabilization of the benzonoid ring in the transition state and in the product seems to play a major role in the kinetic and thermodynamic control of these reactions. © 1998 John Wiley & Sons, Ltd.
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    ISSN: 0894-3230
    Keywords: methylbenzoic acids ; infrared spectra ; conformation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Infrared spectra of all isomers of polymethyl-substituted benzoic acids were recorded in the carbonyl and hydroxyl regions in tetrachloromethane at various concentrations and interpreted in terms of conformation. According to a plot of ν(C=O) of the monomeric form vs Hammett substituent constants σ, these compounds may be classified into two classes. Derivatives with none or only one methyl group in the ortho position are concluded to exist in an equilibrium of two planar conformations, unless the equilibrium is degenerate. Derivatives with two ortho-situated methyl groups are concluded to take up one non-planar conformation. These findings are supported by the shape of the hydroxyl and carbonyl bands, which are unsymmetrical in the former class, although they could not be reliably separated into bands pertinent to the individual conformers. This conclusion is at variance with the common interpretation which has invariably ascribed to these and similar ortho derivatives non-planar conformations with a variable torsional angle. © 1998 John Wiley & Sons, Ltd.
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    Journal of Physical Organic Chemistry 11 (1998), S. 149-154 
    ISSN: 0894-3230
    Keywords: P - C bond cleavage ; phosphoranyl radicals ; organophosphonate biodegradation ; ab initio calculations ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Barrier heights for P - C bond homolysis in P-hydroxy-P-methyl-P,P-dioxophosphoranyl and P,P,P-trihydroxy-P-methylphosphoranyl were calculated using well correlated levels of electronic structure theory. The best estimate for the difference in barriers between the two indicates that homolysis is more facile for P,P,P-trihydroxy-P-methylphosphoranyl by roughly 9 kcal mol-1. This result suggests that bacterial pathways leading to P - C bond cleavage in organophosphonate derivatives will preferentially proceed via initial one-electron reduction of substrates rather than oxidation. © 1998 John Wiley & Sons, Ltd.
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    Journal of Physical Organic Chemistry 11 (1998), S. 201-208 
    ISSN: 0894-3230
    Keywords: indolizines ; cycloaddition ; reaction mechanism ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The peculiarities of [8+2] cycloaddition reactions of indolizines with dienophiles are reviewed. Quantum chemical SINDO1, AM1 and ab initio calculations of transition states were performed for [8+2] cycloaddition reactions of indolizine and 6-nitroindolizine with a series of alkenes with donor and acceptor groups. The calculations predict a dipolar cycloaddition mechanism (electrophilic addition and ring closure) for reactions of indolizine and 6-nitroindolizine with nitroethylene. For the reaction of 6-nitroindolizine with N,N-dimethylaminoethylene, the predicted mechanism corresponds to a previously unknown ‘inverse’ dipolar cycloaddition (nucleophilic addition and ring closure). © 1998 John Wiley & Sons, Ltd.
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    Journal of Physical Organic Chemistry 11 (1998), S. 115-124 
    ISSN: 0894-3230
    Keywords: cross-interaction constants ; gas-phase nucleophilic substitution reactions ; PM3 MO ; benzyl chlorides ; phenoxides ; thiophenoxides ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gas-phase nucleophilic substitution reactions of Y-benzyl chlorides with X-phenoxide and X-thiophenoxide nucleophiles were investigated theoretically using the PM3 semi-empirical MO method. The Leffler-Grunwald rate-equilibrium and Brønsted correlations predict that the degree of bond formation in the transition state (TS) is approximately 45 and 40% on the reaction coordinate for the phenoxides and thiophenoxides, respectively. For a weaker nucleophile, a later TS is obtained with an increased bond making and breaking. The variation of the TS structure with substituents in the nucleophile is thermodynamically controlled and is well correlated by rate-equilibrium relationships. In contrast, the TS variation (a tighter TS) with substituent (for a stronger acceptor Y) in the substrate is dependent only on variations of the intrinsic barrier and so cannot be correlated by such thermodynamically based rate-equilibrium relationships. The gas phase ρX and ρY values are much greater in magnitude than those in solution. A similar gas-phase theoretical cross-interaction constant, ρXY (ca -0.60), is obtained for both phenoxides and thiophenoxides, which is in good agreement with the experimental value (-0.62) for the thiophenoxide reactions in MeOH at 20.0 °C. The oxy and sulfur anion bases lead to a similar TS structure, but a lower reactivity for the former is due to a greater endothermicity of the reaction. A relatively wide range variation of the reaction energies, ΔG°, can be ascribed to the loss of resonance stabilization of anion nucleophiles upon product formation. © 1998 John Wiley & Sons, Ltd.
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  • 76
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    Journal of Physical Organic Chemistry 11 (1998), S. 171-176 
    ISSN: 0894-3230
    Keywords: acetaldehyde ; oxidation ; periodate ; osmium (VIII) catalysis ; ruthenium (III) catalysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Os(VIII) and Ru(III) catalysis of the periodate oxidation of acetaldehyde in aqueous alkaline medium was investigated. The catalytic efficiency is Ru(III)〈Os(VIII). The product of oxidation in both cases is acetate and IO3-. The stoichiometry is the same in both catalyzed reactions, i.e. [IO4-]:[CH3CHO] = 1:1. Probable mechanisms are proposed and discussed. The reaction constants involved in the mechanisms are derived. © 1998 John Wiley & Sons, Ltd.
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  • 77
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    Journal of Physical Organic Chemistry 11 (1998), S. 223-229 
    ISSN: 0894-3230
    Keywords: Solvolysis ; Grunwald-Winstein-type analysis ; Hammett-type analysis ; YxBnCl scale ; 1-aryl-1-phenylmethyl cations ; Mulliken population analysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Rate constants of solvolysis of α-tert-butyl(2-naphthyl)methyl chloride (1), 9-fluorenyl chloride (2) and a series of monosubstituted benzhydryl chlorides (3) in a wide range of solvents were measured. Grunwald-Winstein-type correlation analysis of log k for 2 and 3 against YBnCl, with or without nucleophilicity N, yielded less satisfactory linear correlations than that against log k(1). A new scale of solvent ionizing power, YxBnCl, for the correlation of solvolytic reactivities of benzylic chlorides with extended charge delocalization based on log k(1) was developed. Application to the mechanistic study suggested the solvolysis of 2 and 4-nitrobenzhydryl chloride were non-limiting. Hammett plots against σ+ constants exhibited more negative ρ values in less nucleophilic solvents. In a benzhydryl chloride containing a strong deactivating substituent, such as 4-nitro, the positive charge delocalizes mainly over the unsubstituted ring in the cationic transition state. The uneven charge distribution was also confirmed by Mulliken population analysis at the level of the RHF/6-31G*//RHF/3-21G(*) basis set for cations. Comparison of the results of correlation analysis using the equation log(k/k0) = mY vs the equation log(k/k0) = mY+hI, and using the equation log(k/k0) = mY+lN vs the equation log(k/k0) = mY+lN+hI indicated the use of YBnCl or YxBnCl could give a better understanding of solvolytic mechanisms than the combinatorial use of YCl and I. © 1998 John Wiley & Sons, Ltd.
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  • 78
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    Keywords: Solvent-solute interactions ; β-carotene ; electronic absorption spectrum ; solvent effects ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvent effects on the wavenumber of the maximum of the longest wavelength electronic absorption band of all-trans-β-carotene were determined in 34 solvents. Together with results from previous studies, a data set for 51 solvents, mostly non-hydrogen bond donors, was constructed. This information was analyzed in terms of reaction field models and also showed its value for correlation purposes when used either alone or in combination with standard empirical solvent polarity-polarizability scales. © 1998 John Wiley & Sons, Ltd.
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  • 79
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    Journal of Physical Organic Chemistry 11 (1998), S. 177-184 
    ISSN: 0894-3230
    Keywords: nitro derivatives of phenols ; pyrolysis initiation reactions ; impact sensitivity ; UHF-SCF-AM1 MO method ; activation energy. ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The UHF-SCF-AM1 MO method was applied to the study of two kinds of pyrolysis reactions of six nitro derivatives of phenols (homolysis reaction by rupture of the C - NO2 bond into radicals and isomerization reaction involving phenolic hydrogen transferring to oxygen on the NO2 group). The molecular geometries of reactants, transition states and products were fully optimized. The potential energy curves and activation energies were first obtained. The results show that this category of compounds is more easily initiated via isomerization reactions than by homolysis reactions. The parallel relationship among the Wiberg bond order of the pyrolysis-initiation H - O bond in the molecule of a reactant, the activation energy of the isomerization reaction breaking the H - O bond and impact sensitivity of the reactant gives ‘the principle of the smallest bond order’ (PSBO) powerful support. The sensitizing effect of a phenol group was elucidated based on calculation results. The different influences of OH and NO2 groups on the heat of formation of a molecule are discussed. © 1998 John Wiley & Sons, Ltd.
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  • 80
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    Journal of Physical Organic Chemistry 11 (1998), S. 216-222 
    ISSN: 0894-3230
    Keywords: o-carboxybenzohydroxamic acid ; phthalic anhydride ; phthalic acid ; hydrolysis ; intramolecular acid catalysis ; kinetics ; activation parameters ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Phthalic anhydride was detected spectrophotometrically in the hydrolysis of o-carboxybenzohydroxamic acid (OCBA) in CH3CN-H2O solvent containing 0.03 mol dm-3 HCl. Pseudo-first-order rate constants (k1) for hydrolysis of OCBA are almost independent of the change in CH3CN content from 10 to 80% (v/v) in mixed aqueous solvents. The rate constants k1 are more than 10-fold larger than the corresponding rate constants for hydrolysis of phthalamic acid. These observations are explained in terms of a mechanism slightly different from the mechanism for hydrolysis of phthalamic acid. The activation parameters, ΔH* and ΔS*, are not affected appreciably by an increase in CH3CN content from 10 to 80% in mixed aqueous solvents. © 1998 John Wiley & Sons, Ltd.
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  • 81
    ISSN: 0894-3230
    Keywords: solute-solvent interactions ; solvent-solvent interactions ; binary solvents ; alcohol-water mixtures ; water structure ; solvatochromic indicators ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A preferential solvation model that takes into account the enhancement of the structure of water when small amounts of alcohol are added was applied to solvatochromic data for binary mixtures of water with 2-methylpropan-2-ol, propan-2-ol, ethanol and methanol. Application of the model allows the calculation of the effect of the enhancement of the water structure on solvatochromic solvent properties. It is demonstrated that the enhancement of water structure increases the solvent dipolarity/polarizability and hydrogen-bond donor acidity and decreases the solvent hydrogen-bond acceptor basicity. The effect decreases in the order 2-methylpropan-2-ol-water, propan-2-ol-water, ethanol-water and methanol-water. © 1998 John Wiley & Sons, Ltd.
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  • 82
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    Journal of Physical Organic Chemistry 11 (1998), S. 157-170 
    ISSN: 0894-3230
    Keywords: heterolytic bond dissociation energy ; carbon-carbon σ bonds ; hydrocarbons ; structural dependence ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The coordination of a resonance-stabilized hydrocarbon cation and anion yielded a series of unprecedented hydrocarbons, which are susceptible to thermal heterolytic cleavage of carbon-carbon σ bonds in polar media, generating the original ions under reversible conditions. When the component ions were sufficiently stabilized, some ion pairs were even isolated as solids, thus providing the first examples of hydrocarbon salts. The direct observation of the heterolysis by means of spectroscopy permitted reliable thermodynamic treatments of the observed degree of ionic dissociation. Correlation of the free energy of heterolysis with solvent dielectric constants and parameters of ion stabilities such as pKHA, pKR+ and redox potentials revealed the importance of the thermodynamic stabilities of ions, the degree of solvation and steric congestion in the starting molecule as major controlling factors in the heterolysis. © 1998 John Wiley & Sons, Ltd.
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  • 83
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    Journal of Physical Organic Chemistry 11 (1998), S. 273-276 
    ISSN: 0894-3230
    Keywords: N,N-diphenylcarbamoylpyridinium ion ; solvolysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Solvolyses of the N,N-diphenylcarbamoylpyridinium ion are subject to specific and/or general base catalysis, which can be eliminated by addition of perchloric acid or increased, especially in fluoroalcohol-containing solvents, by addition of pyridine. The uncatalyzed solvolyses in aqueous methanol and aqueous ethanol involve a weakly nucleophilically assisted (l  =  0.22) heterolysis and the solvolyses in the pure alcohols are anomalously slow. © 1998 John Wiley & Sons, Ltd.
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  • 84
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    Journal of Physical Organic Chemistry 11 (1998), S. 209-215 
    ISSN: 0894-3230
    Keywords: securinine ; cationic micelles ; anionic micelle ; non-ionic micelle ; alkaline hydrolysis ; kinetics ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of micelles of cetyltrimethylammonium bromide (CTABr), tetradecyltrimethylammonium bromide (TTABr), sodium dodecyl sulfate (SDS) and polyoxyethylene 10 lauryl ether (C12E10) on the rates of alkaline hydrolysis of securinine were studied at a constant [-OH] (0.05 M). An increase in the total concentrations of CTABr, TTABr, SDS and C12E10 from 0.0 to 0.2 M causes a decrease in the observed pseudo-first-order rate constants (kobs) by factors of ca 2.5, 3, 7 and 4, respectively. The observed data are explained in terms of pseudophase and pseudophase ion-exchange (PIE) models of micelle. The binding constants, KS, of securinine with SDS, C12E10, CTABr and TTABr micelles are 32.4, 14.8, 22.1, and 9.1 M-1, respectively. The magnitudes of the second-order rate constants, kM, for the reactions in the micellar pseudophase are negligible compared with the corresponding rate constant, kW, for the reaction occurring in the aqueous pseudophase for CTABr, TTABr, SDS and C12E10. © 1998 John Wiley & Sons, Ltd.
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  • 85
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    Journal of Physical Organic Chemistry 11 (1998), S. 277-282 
    ISSN: 0894-3230
    Keywords: colloidal CdS-induced photochemical reactions ; photocatalytic reactions ; photooxidation ; 2-methylindole ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2-Methylindole (2-MI) is adsorbed on the surface of colloidal CdS particles with an adsorption intensity of 0.6 × 103 dm3 mol-1. A new emission band at 530 nm is produced by forming an exciplex between excited CdS and 2-MI and the red emission due to CdS is simultaneously quenched. The emission maxima of green bands for different indoles increase in the order indole 〈 tryptophan 〈 2-MI 〈 3-MI and are observed at 508, 520, 530 and 540 nm, respectively. The shift in emission maxima is related to the oxidation potential of these substrates. The irradiation of an aerated reaction mixture containing CdS and 2-MI with visible light induces the oxidation of adsorbed 2-MI by photogenerated holes to produce 2-methyl-3-indolinone and 2-acetamidobenzaldehyde. The latter product is formed due to oxidative C - C bond cleavage of the pyrrole ring. The reactivity of trapped holes towards the adsorbed 2-MI is evidenced by a decrease in the lifetime of the red emission of CdS in the presence of 2-MI. In this reaction the possibility of the participation of singlet oxygen is ruled out. A general mechanism of CdS-induced oxidation of indoles is discussed. © 1998 John Wiley & Sons, Ltd.
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  • 86
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    Keywords: crown dithioether ; conformational analysis ; multicomponent equilibrium ; Chemistry ; Theoretical, Physical and Computational Chemistry
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The solid-state molecular structure and the conformational behaviour in solution of the 12-membered crown dithioether 8-methyl-1,4-dioxa-7,10-dithiacyclododecane-5,12-dione were studied by x-ray crystallography, 1H and 13C NMR spectroscopy and molecular mechanics. The conformational rigidity of some constituent structural fragments allowed a detailed analysis of the structure and distribution of the conformers. A protocol for studies of multiconformational equilibrium was developed by means of the combined use of structure calculations and dynamic NMR measurements. © 1998 John Wiley & Sons, Ltd.
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  • 87
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    Journal of Physical Organic Chemistry 11 (1998), S. 321-333 
    ISSN: 0894-3230
    Keywords: metal-catalyzed carbenoid reactions ; iodonium ylides ; sulfonium ylides ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transition metal-catalyzed decomposition of phenyliodonium and diphenylsulfonium ylides was investigated with regard to application in asymmetric carbenoid reactions. Phenyliodonium ylides react in the presence of Rh(II) catalysts with the same selectivity in inter- and intramolecular cyclopropanations as the corresponding diazo compounds, and intramolecular CH insertions proceed with identical enantioselectivities. With diphenylsulfonium ethoxycarbonylmethylide the Cu(I)-catalyzed cyclopropanation of olefins affords trans/cis ratios and asymmetric inductions identical with those of diazo compounds, but with Rh(II) catalysts some small, although significant, selectivity variations occur, which are ascribed to coordination of diphenyl sulfide to one of the coordination sites of the catalyst. © 1998 John Wiley & Sons, Ltd.
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  • 88
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    Journal of Physical Organic Chemistry 11 (1998), S. 299-304 
    ISSN: 0894-3230
    Keywords: molecular architecture ; molecule-based magnets ; biopolymers ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Application of the principles of physical organic chemistry to the construction of molecule-based magnets is discussed. Not only the magnetic structures of conventional magnets but also secondary and tertiary structures of biopolymers are instrumental in the molecular design. © 1998 John Wiley & Sons, Ltd.
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  • 89
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    Journal of Physical Organic Chemistry 11 (1998), S. 350-355 
    ISSN: 0894-3230
    Keywords: 1,3-dipoles ; cumulenes ; infrared spectroscopy ; mass spectrometry ; flash vacuum thermolysis ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the direct investigation of reactive intermediates it is particularly valuable to use a combination of several spectroscopic techniques. This commentary highlights recent examples, using primarily flash vacuum thermolysis for the generation of the intermediates, and matrix IR spectroscopy in conjunction with gas-phase mass spectrometric methods for their identification. The examples include nitrile imines, nitrile ylides, nitrile sulfides and selenides, dinitrogen sulfide and several novel cumulenes (X=C=C=Y, RN=C=C=C=X). © 1998 John Wiley & Sons, Ltd.
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  • 90
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    Journal of Physical Organic Chemistry 11 (1998), S. 305-320 
    ISSN: 0894-3230
    Keywords: poly(alkylmethyldiallylammonium halides) ; aggregation behavior ; polyelectrolytes ; polysoaps ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hydrophobically modified polyelectrolytes (polysoaps) are a unique class of water-soluble polymers containing distinct hydrophobic and hydrophilic regions. Above a certain concentration, polysoaps form intramolecular and intermolecular aggregates in aqueous solution. They have attracted much attention not only for their ability to mimic some functions demonstrated by biopolymers but also for their important industrial applications. This review highlights some interesting features of novel non-cross-linked and cross-linked poly(alkylmethyldiallylammonium halides) that have been described in recent years. © 1998 John Wiley & Sons, Ltd.
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  • 91
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    Journal of Physical Organic Chemistry 11 (1998), S. 334-340 
    ISSN: 0894-3230
    Keywords: brain chemistry ; membrane proteins ; molecular neurobiology ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Efforts to developed detailed insights into the structure and function of the molecules of memory, thought and sensory perception - physical organic chemistry on the brain - are described. By combining more conventional chemical tools with a number of techniques adapted from modern biology, it is now possible to perform systematic structure-function studies on the integral membrane proteins that play a central role in molecular neurobiology. There are substantial challenges associated with such studies, but we believe the potential payoff is considerable. © 1998 John Wiley & Sons, Ltd.
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  • 92
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    Journal of Physical Organic Chemistry 11 (1998), S. 341-349 
    ISSN: 0894-3230
    Keywords: vicarious nucleophilic substitution ; hydrogen ; mechanism ; orientation ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Hydrogens located at activated positions in electrophilic arenes, e.g. ortho and para hydrogens in nitrobenzenes, can be replaced with a nucleophile moiety provided there is at least one nucleofuge X connected to the nucleophilic centre. As the group really leaving in this hydrogen substitution process is not the hydride anion but X, the reaction has been named vicarious nucleophilic substitution of hydrogen (VNS). The concepts on the mechanism of the reaction and their experimental background are presented. Reactivity and orientation - the fundamental questions concerning synthetical applications of VNS - are discussed in light of the supposed mechanistic picture.
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  • 93
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    Journal of Physical Organic Chemistry 11 (1998), S. 291-291 
    ISSN: 0894-3230
    Keywords: Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 94
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    Journal of Physical Organic Chemistry 11 (1998), S. 362-376 
    ISSN: 0894-3230
    Keywords: highly strained cyclophanes ; reactivity ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An essential feature of the concept of aromaticity has been the stability and lack of reactivity of aromatics relative to that of other unsaturated compounds. Contrary to this general experience, high and unusual reactivity is encountered when simple, monocyclic benzene rings are bent by short bridges into a boat-shaped conformation, as is the case in small [n] paracyclophanes (n ≤ 8) and [n]metacyclophanes (n ≤ 7). This is illustrated, mostly with examples taken from the authors' own work, for thermal and photochemical behavior and reactions with electrophiles, nucleophiles and dienophiles. © 1998 John Wiley & Sons, Ltd.
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  • 95
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    Journal of Physical Organic Chemistry 11 (1998), S. 356-361 
    ISSN: 0894-3230
    Keywords: heterogeneous catalysis ; organic reactions ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A decade's worth of work is reviewed: building on the demonstrated prowess of heterogeneous catalysis in industrial organic chemistry, the author's laboratory devised efficient catalysts for a number of organic reactions, based on aluminosilicates such as clays and zeolites. This review also spells out, at a time when creative research is overshadowed by imitative research, some of the methodological musts that also happen to characterize physical organic chemistry: the devising of experiments so that accurate numerical data can be obtained; the importance of remote, interdisciplinary connections; the need for estrangement from stereotypic preconceptions that may obscure the true explanations for the phenomena; and the over-riding need for concerning oneself only, or at least predominantly, with the important facts that nature tells, if one cares to listen. © 1998 John Wiley & Sons, Ltd.
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    Journal of Physical Organic Chemistry 11 (1998), S. 292-298 
    ISSN: 0894-3230
    Keywords: flash-photolysis ; short-lived reaction intermediates ; mandelic acid ; keto-enol tautomers ; enzyme-catalyzed racemization ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The advantage of adding more structure-diagnostic information to the simple detection of flash photolytically generated transient species by changes in UV-visible light absorbance is illustrated by a case study involving the mandelic acid keto-enol system. An early report based on preliminary evidence proposed that flash photolysis of phenyldiazoacetic acid produces the enol of mandelic acid by hydration of phenylhydroxyketene, itself generated by a photo-Wolff reaction of the diazo acid. Further examination, however, shows that this is only a minor route, and that the major pathway is a new enol-forming reaction involving what appears to be hydration of a carboxycarbene formed by dediazotization of the diazo compound. Hydration of phenylhydroxyketene is nevertheless the reaction by which mandelic acid enol is generated when esters of benzoylformic acid are the flash photolysis substrates. These mechanisms, and also identification of the enol as a tranisent species, are supported by detailed arguments involving acid-base catalysis, solvent isotope effects, and the use of oxygen-18 as a tracer. The work produces a keto-enol equilibrium constant for the mandelic acid system, pKE  =  16.19, and also acidity constants of the enol ionizing as an oxygen acid, pKEa  =  6.39, and the keto isomer ionizing as a carbon acid, pKKa  =  22.57. The bearing of these results on the enzyme-catalyzed racemization of mandelic acid is discussed. © 1998 John Wiley & Sons, Ltd.
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  • 97
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 152-152 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 98
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 300-311 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Fiber composites of raw renewable materials for the ecological lightweight designDue to their low density natural fibers have the potential to be outstanding reinforcements in lightweight structures. Since most natural fibers are hollow they also bear great potentials in offering an increased bending resistance and buckling strength.By imbedding natural fibers in organic polymers instead of in conventional petroleumbased polymers a unique completely renewable and if wanted biodegradable composite can be created. Structural components made up of this new composite material cannot only be recycled or burned (in this case even CO2-neutral), but also be reintegrated in the cycle of natural decomposition.Presently e.g. car door linings or instrument panels have no supporting function in the car structure. In the future generation of cars weight reduction can be achieved giving these elements reinforcing functions by integrating hollow natural fibers aligned in the main loading directions. Furthermore critical regions in therms of stiffness and strength where loads are applied, like e.g. fastenings for side airbags, can be realised in the the same material without addition of metals. This can also be achieved for any other application.In this paper the potential of hallow natural fibers for reinforcements of lightweight structures, the renewable and (if wanted) biodegradable composites and their application in technical constructions will be discussed.
    Notes: Naturfasern weisen aufgrund ihrer niedrigen Dichte ein hohes Leichtbaupotential auf. Da viele Naturfasern zudem auch hohl sind, kann dieses Potential hinsichtlich Biege-, Knick- und Beulsteifigkeit verstärkt genutzt werden.Werden Naturfasern statt in herkömmlichen Polymeren auf petrochemischer Basis in neuartigen Biopolymeren auf der Basis nachwachsender Rohstoffe zu Faserverbundwerkstoffen verarbeitet, so können entsprechende Strukturen sogar die Eigenschaft der Bioabbaubarkeit haben. D. h., Faserverbundbauteile könnten nicht nur rezykliert oder verbrannt (hier sogar CO2-neutral) werden, sondern bieten zusätzlich über die Kompostierung die Möglichkeit der geschlossenen Kreislaufwirtschaft.Während heute z. B. Türinnenverkleidungen oder Armaturenbretter im Fahrzeugbau im wesentlichen verkleidenden Charakter aufweisen, kann im Zuge konsequenten Leichtbaus für zukünftige Automobilgenerationen auch an mittragende Strukturen gedacht werden, indem gerichtet hohle Naturfasern in die Kraftpfade eingearbeitet werden. Zudem können auch steifigkeits- und festigkeitskritische Lasteinleitungen z. B. für die Aufnahme von (Seiten-) Airbags aus gleichem Material ohne zusätzliche Metallinserts realisiert werden. Gleiches läßt sich auch auf beliebige andere Ingenieursanwendungen übertragen.Im Rahmen des Aufsatzes soll über das Leichtbaupotential hohler Naturfasern, über nachwachsende und biologisch abbaubare Faserverbundwerkstoffe und deren Anwendung berichtet werden.
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  • 99
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    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 39-47 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: The growth of the oxide protective layer on different Ni-Cr-Fe-alloys with variation of oxygen partial pressureHigh temperature alloys e.g. Incoloy 800 H, Hastelloy X and Ni75Cr25 model alloy are in-situ oxidized with variation potentials oxidation of PO2 = 4,41 × 10-19 bar, PO2 = 4,41 × 10-17 bar and PO2 = 176 × 10-16 bar by temperature, 800°. The behaviour of the scales which are oxidized at different oxidizing atmospheres has been investigated in this work, with deuterium permeation. The test of scales as corrosion barrier had been done in sulfidizing atmospheres with PS2 = 1,82 × 10-7 bar. The microstructure of the oxide layers has been investigated with Light Microscopy (LM), Scanning Electron Microscopy (SEM), Analytical Transmission Electron Microscopy (ATEM) and High Resolution Transmission Electron Microscopy (HRTEM). It is found that the deuterium permeation measurement can be correlated as a method for characterization corrosion layer at high temperature alloys. The structure of the oxide layer, the influence of sulfidizing atmospheres, additions of small amounts of reactive elements such as Ti before oxidation, the interface structure between oxide layers and matrix, as well as crystal defects and grain boundaries is explainable.
    Notes: Hochtemperaturlegieungen wie Incoloy 800 H, Hastelloy X und die pulvermetallurgisch hergestellte Modellegierung Ni-Cr/75-25 wurden mit ihren Oxiddeckschichten, die in verschiedenen Oxidationspotentialen mit Sauerstoffpartialdrucken von PO2 = 4.41 × 10-19 bis PO2 = 1.76 × 10-16 bar und bei einer Betriebstemperatur von T = 800° gewachsen sind, untersucht. Während der Oxidation wurde die Deuterium-Permeation gemessen. Gefügeuntersuchungen mit Hilfe der Lichtmikroskopie, der Rasterelektronenmikroskopie und vor allem der Transmissionselektronenmikroskopie unterstützen dabei die Aussagefähigkeit der Permeationsmessungen. Insbesondere werden Aufbau der Oxidschicht, der Einfluß von Schwefel, eine zusätzliche Titanbeschichtung vor der Oxidation, eine eventuell vorhandene Korngrenzenkorrosion und die Struktur der Grenzfläche Werkstoff-Oxidschicht vorgestellt und diskutiert.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 100
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Materialwissenschaft und Werkstofftechnik 29 (1998), S. 66a 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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