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  • 1985-1989  (1,426)
  • 1988  (1,426)
  • Chemical Engineering  (691)
  • Engineering  (598)
  • Physical Chemistry  (137)
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Years
  • 1985-1989  (1,426)
Year
  • 1
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 115-117 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A novel oxygen induced reduction of α,β-unsaturated carbonyl compounds is discovered. The reduction of the carbon-carbon double bond of α,β-unsaturated carbonyl compounds by benzeneselenol was caused by an introduction of molecular oxygen into the reaction system. This reduction is likely to proceed via a radical chain pathway involving an SH2 type reaction between a phenylseleno radical and a 1,2-adduct of benzeneselenol to the carbonyl group of the α,β-unsaturated carbonyl compound to give an allylic radical which absracts a hydrogen atom from benzeneselenol to form the reduction product.
    Additional Material: 1 Tab.
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  • 2
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 191-195 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The photochemical reaction of MAQO with various aromatic amines were studied by ESR. The results show that nitroxide radicals are stable productrs of the photooxidation of both diphenylamines and phenylamines. The photolyzed phenothiazine does not yield nitroxide as the final product, instead it gives the neutral radical as the stable final product.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 333-349 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: New series of platinum complexes of cyclopropenylidenes of the types of PtX2(CP)2 and trans-PtX(PBu3)2(CP) have been synthesized, where CP is di-t-butylcyclopropenylidene (BCP) or bis(diisopropylamino)cyclopropenylidene (ACP). The 13C-NMR chemical shifts, and 13C-195Pt coupling constants (1JPtC) for the complexes are discussed in comparison with those values derived from closely related series of compounds, trans-PtCl(PR3)2L; L — —CH3, —C6H5 and —C≡CBu-t. An excellent linear relationship through the origin was obtained between 1JPtC and the formal ‘s’ % character of the carbon directly bonded to Pt for the series trans-PtCl(PR3)2L in which the Pt—C bond is regarded as a pure σ-linkage, whereas 1JPtC deviates largely from this relationship when pπ—dπ bonding interaction possibly exists in the Pt—C bond. The NMR data suggest the strong nmr trans-influence of the cyclopropenylidenes and that in the Pt—CP bond the σ-interaction is appreciable but the π-interaction is negligible.
    Additional Material: 3 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 123-131 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photolysis of N-alkyl-N-(3-aryl-3-butenyl) ureas (1) in acetonitrile gave cyclization products, 3-aryl-3-methyl-pyrrolidines, in good yields, whereas irradiation of 1 in methanol afforded methanol adducts as well as the cyclization products. Both the reactions are singlet reactions, and the cyclization is presumed to proceed via 1,6-hydrogen transfer from exciplexes with charge transfer character.
    Additional Material: 2 Tab.
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  • 6
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 143-151 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dependence of the catalytic efficiencies of sodium carboxymethylamylose (NaCMA) for the hydrolysis of N-lauryl-3-acetoxypyridinium iodide (1) and p-nitrophenyl dodecanoate (3) on its degree of substitution (D. S. = 0·00, 0·12, 0·18, 0·24, 0·29 and 0·35) and on the pH values of the solutions (pH = 7·32, 7·80, 8·10 and 9·30) have been studied. At fixed D. S. values, the observed hydrolysis rates of 1 and 3 increase with increasing concentrations of NaCMA and follow saturation kinetics. At fixed concentration of NaCMA, the rates increase with decreasing D. S. values until they reach maxima at D. S. = 0·00. Furthermore, at any D. S. value the catalytic efficiency increases with increasing pH values of the solutions. All these results indicate that the hydroxyl groups are actually the principal catalyzing groups.
    Additional Material: 5 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 169-178 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The development of positive charge β to silicon in a saturated five-membered ring has been studied in the cis- and trans-2-(trimethylsilyl)cyclopentyl trifluoroacetates. The cis substrate solvolyzes in 97% trifluoroethanol at 25° C about 5 times faster than the analogous six-membered ring, after correction for differences in ring strain. The trans substrate solvolyzes about 360 times more slowly than the analogous six-membered ring. These changes are in agreement with a hyperconjugative mechanism for interaction between the silyl group and the developing positive charge. The expected cosine-squared dependence of hyperconjugation on the Si—C—C—X dihedral angle suggests that the cis dihedral angle is reduced somewhat from the 60° in the six-membered ring, and the trans dihedral angle is reduced substantially from the 180° in the six-membered ring.
    Additional Material: 3 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 209-223 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The equilibrium acidities of phenylacetonitrile, and 20 of its m- and p-substituted derivatives have been measured in Me2SO solution. Their pKa′s plot linearly with those of the corresponding anilines. Combination of the pKa′s of these acids with their oxidation potentials, Eox(HA), and those of their conjugate bases, Eox(A-), provide an estimate of the acidities of the corresponding radical cations. The pKHA+ values for ArCH2CN+., where Ar is Ph, 1- and 2-naphthyl, and 9-anthryl, are -32, -18·5, -17·5, and -11, respectively, compared to 21·9, 20·85, 20·65, and 19·8 for the corresponding ArCH2CN acids. Acidities of PhCH(Me)CN+., Ph2CHCN+., 9-CN-FlH+., and 9-CN-XnH+. are -33, -35, -25, and -27, respectively, compared to 23·0, 17·5, 8·3, and 13·6 for the corresponding acids from which they were derived. The homolytic bond dissociation energies (BDEs) for the benzylic C—H bonds in these arylacetonitriles, estimated by combining pKHA with Eox(A-), fall in the range of 69 kcal/mol for 9-CN-XnH to 82 kcal/mol for PhCH2CN. For GC6H4CH2CN+. radical cations the acidities are decreased, relative to G=H, when G is an electron donor substituent and increased when G is an acceptor. The BDEs of the benzylic C—H bonds in GC6H4CH2CN are weakened by up to 4 kcal/mol by para donors and strengthened by up to 1·2 kcal/mol by m- or p-acceptors. The significance of these changes in BDEs with regard to the use of σ. scales and the ΔAOP method for estimating substituent effects on radical stabilities is discussed.
    Additional Material: 5 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 259-265 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 1-(Phenylazo)-1-(2-pyridyl)ethyl hydroperoxide, 1, 1-(phenylazo)-1-(2-furyl)ethyl hydroperoxide, 2, phenylazo(2-furyl)methyl hydroperoxide, 3, 1-(phenylazo)-1-(4-anisyl)ethyl hydroperoxide, 4, were synthesized in moderate yield by autoxidation of the phenylhydrazones in benzene. The ionic oxidation of benzyl methyl sulfide in benzene by 1-4 yielded the sulfoxide and the metastable α-azo hydroxides in essentially quantitative yield. The reaction was of the first order in α-azo hydroperoxide and sulfide, respectively. The relative reactivity series found was: 1(1.0) 〈4(1.4) 〈 phenylazo(4-anisyl)methyl hydroperoxide 5 (2·9) 〈2 (3·8) 〈 3 (9·6). α-Methyl substitution was found to slow the rate of oxygen-atom trasfer by a factor of 2 to 2.5. The low relative reactivity of 1 was opposite that expected based on electronic effects. Competitive intramolecular hydrogen bonding of the hydroperoxy proton to the pyridyl nitrogen in 1 accounted for the observed result.
    Additional Material: 2 Tab.
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  • 11
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 281-285 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermal and photochemical decompositions of 5 have been studied. Both reactions lead to CBr2 transfer in good to high yields. With the 2-pentenes as substrates, CBr2 transfer is stereospecific in the classical singlet carbene manner.
    Additional Material: 3 Tab.
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  • 12
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 305-308 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Decomposition of the tosylhydrazone salts formed from cubyl carboxaldehyde and homocubanone, potential precursors of cubylcarbene (5) and homocubanylidene (6), leads in each case to products derived from 6. It is suggested that homocub-1(9)-ene (7) is the active ingredient in the formation of 6 from both precursors. The hydrazones formed from N-aziridylamines are useful photochemical sources of 6, and presumably other carbenes. Flash vacuum pyrolysis of the tosyl hydrazone salts and hydrazones at 600°C leads to indene.
    Additional Material: 1 Tab.
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  • 13
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 317-332 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Light- and heat-induced decompositions and reactions with nucleophiles of 6,6,8,8-tetramethyl-2-selena-3,4-diaza-7-oxabicyclo[3.3.0]octa- 1(5),3-diene have been studied. In contrast with the conversion to the cyclopentyne derivative (9), selenium containing intermediates (6a, 6b, and 7) were efficiently trapped using several reagents to give various kinds of organoselenium compounds. Of particular note is the isolation of a stable selenirane derivative (16) obtained by the cycloaddition of the photochemically generated selenirene intermediate (7) with furan. The character and reactivity of the intermediates are also discussed.
    Additional Material: 3 Tab.
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  • 14
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 359-362 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reaction rates for solvolysis of a mustard analogue are accurately correlated by the solvatochromic equation without inclusion of a nucleophilicity term, and thus the equation is shown to reveal mechanistically significant information.
    Additional Material: 1 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 16
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 247-257 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rate of hydrolysis of the aromatic vinyl ether o-carboxy-α-methoxy-β,β-dimethylstyrene was found to be accelerated 25-fold by ionization of its carboxylic acid group, but the effective molarity which may be calculated if all of this rate acceleration is ascribed to intramolecular general acid catalysis is only EM = 1 · 1 m. This is similar to the small effective molarities found before for intramolecular catalysis by carboxylic acid groups of aliphatic vinyl ethers, which shows that, unlike the situation in other intramolecular reactions, e.g. ketone enolization, the extra rigidity of aromatic over aliphatic systems does not improve the efficiency of intramolecular catalysis in vinyl ether hydrolysis.It is suggested that this behaviour is the result of reduced conjugation between the vinyl ether group and the aromatic ring in the transition state of the vinyl ether hydrolysis reaction, which retards the rate and offsets any improvement effected by increased rigidity of the aromatic system.
    Additional Material: 2 Ill.
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  • 17
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 2,2′-Diselenocyanato-1,1′-binaphthyl(1), the first selenium-containing binaphthyl derivative, has been synthesized in optically active form the corresponding diamine by diazotization followed by the reaction with potassium selenocyanate. Its molecular structure is determined by X-ray diffraction method. It is revealed that selenium atoms have hypervalent penta-coordination in the crystal.
    Additional Material: 4 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 287-298 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Ab initio STO-3G and 6-31G minimized geometries of 5-oxo- (9), 6-oxo-7-oxabicyclo[2.2.1]hept-2-yl cation (12) and 7-oxabicyclo[2.2.1]hept-2-yl cation (15) were obtained. The energy barriers for their Wagner-Meerwein rearrangements to the more stable 5-oxo- (11), 6-oxo-3-oxabicyclo[2.2.1]hept-2-yl (13) and 3-oxabicyclo[2.2.1]hept-2-yl (17) cations, respectively, have been evaluated and compared with those calculated for the rearrangement of the 5-oxo (18) and 6-oxobicyclo[2.2.1]hept-2-yl cations (20). In agreement with experimental data, the ‘true migratory aptitude’ of an acyl group is higher than that of β-oxoalkyl group in competitive Wagner-Meerwein rearrangments that are ‘energetically unbiased’. The ease of the acyl group 1,2-shift toward an electron-deficient center is related to the electron-donating ability of the carbonyl group due to favorable n(CO) ↔ σ σ ↔ p(C+) hyperconjugative interaction.
    Additional Material: 1 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 299-303 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Iodide ion promotes the free radical reaction of isopropylmercury idide with bromotrichloromethane to yield isopropyl bromide with rate enhancement in the order of 104. The reaction involves electron transfer from i-PrHgI2- to the trichloromethyl radical in a long kinetic chain process. Iodide ion also promotes the free radical chain conjugate addition of tert-butylmercury chloride to α,β-unsaturated ketones, esters, phosphonate esters and sulfones. Competitive reactivity studies indicate that lithium di-tert-butylcuprates or tri-tert-butylzincates react with 2-cycloalkenones by a mechanism involving attack by tert-butyl radicals. No evidence for radical attack is observed for the corresponding n-butyl ate complexes of copper or zinc.
    Additional Material: 1 Tab.
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  • 20
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 103-114 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of solvent additives on the course of TiO2 photocatalyzed oxygenation of α-methylstyrene has been studied. While the addition of small amounts of nonhalogenated alcohols to TiO2 powders suspended in acetonitrile was found to decrease the rate of photooxygenation, added halogenated alcohols increase the rate of reaction. In addition, the solvent additives affect the observed product distribution.
    Additional Material: 4 Tab.
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  • 21
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 119-121 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Reduction of aromatic aldehydes by benzeneselenol is found to be promoted by molecular oxygen to give corresponding alcohols in good yields. No reduction took place without oxygen.A free radical process involving SH2 reaction at the selenium atom is proposed where the phenylseleno radical attacks the selenium atom of selenohemiacetal, the adduct of benzeneselenol to aldehyde, to give the ketyl radical which then abstracts hydrogen from benzeneselenol. The intermediacy of selenohemiacetal is supported by a quantitative reduction of α-methoxybenzyl phenyl selenide, which is used as a model compound of the intermediate.
    Additional Material: 1 Tab.
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  • 22
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dependency of the wrapping-up capability of sodium carboxymethylamylose (NaCMA) on its degree of substitution (D. S. = 0·00, 0·12, 0·18, 0·24, 0·29, 0·35 and 0·41) have been studied, using two guest species, iodine and cetyl-trimethylammonium bromide (CTAB). The λmax values of NaCMA-iodine helical inclusion complexes decrease with increasing D. S. values and the amounts of encapsulated iodine by NaCMA as measured by amperometric titrations also decrease with increasing D. S. values. With CTAB as the substrate, the largest number of binding sites, n, and the dissociation constants Kd have been determined by the method of surface tension versus the CTAB concentration plots. The results show that n decreases while Kd increases with increasing D. S. values. All these observations point to the fact that the wrapping-up capability of NaCMA decreases with increasing degrees of substitution. The results are discussed in terms of host-guest and host-solvent hydrophobic-lipophilic interactions as well as intramolecular hydrogen-bonding.
    Additional Material: 6 Ill.
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  • 23
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 161-167 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The temperature-dependence of the kinetic isotope effects for branched reactions proceeding via a common intermediate has been simulated by calculations. It is shown that, under certain conditions, anomalously small isotope effects on the Arrhenius preexponential factors, as well as unusually large observed isotope effects, may originate from the branching.
    Additional Material: 2 Ill.
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  • 24
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 153-160 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structures of the allyl anion (1) and two fluoro-substituted derivatives, perfluoro (2) and 1,1-difluoro (3) have been calculated by ab inito molecular orbital theory. Geometries were gradient optimized, and force fields and an MP-2 correlation correction were determined at stationary points. The calculations were done with a double zeta basis set augmented by d functions on carbon (DZ + Dc). Final self-consistent field (SCF) and MP-2 energy calculations were done with the DZ + Dc basis set augmented by diffuse functions. The ground state of 1 is the planar allyl anion (C2v). The rotation barrier in 1 is 21·1 kcal/mol at the MP-2 level. The cyclopropyl carbanion is 27·0 kcal/mol higher in energy at the MP-2 level. The perfluoroallyl anion is not planar, and the rotated structure is 25·7 kcal/mol more stable than the C2v structure at the MP-2 level. The lowest energy structure on the potential energy surface for 2 is the perfluorocyclopropyl carbanion which is 27·8 kcal/mol more stable than the C2v structure at the MP-2 level. The 1,1-difluoroallyl anion is also not planar. Here the most stable structure on the potential energy surface is the rotated allyl anion which is 8·3 kcal/mol more stable than the all-planar allyl anion structure.
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  • 25
    Electronic Resource
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 241-245 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The rates of solvolysis of l-aryl-l-phenyl-2,2-dimethylpropyl(1) p-nitrobenzoates and of aryldiphenylmethyl-p-nitrobenzoates (2) were measured in 80% acetone. An inverse order of reactivity, kp-CF3/km- CF3 〉 l was observed for 1 but not for 2. The X-ray crystallogoraphic study of the parent compounds, l,l-diphenyl-2,2-dimethylpropyl-p-nitrobenzoate (1b) and triphenylemethyl benzoate (3b), and of 2-phenyl-2-propyl-p-nitrobenzoate (4) indicated that in the highly congested system 1 both phenyl rings were nonplanar, whereas the phenyl rings in 3 and 4 were essentially planar.
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  • 26
    Electronic Resource
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 185-190 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: From the 1H-NMR spectra of the various pyrrole compounds, 1-substituted 2,5-dimethylpyrroles having two substituent groups on the carbon adjacent to the nitrogen atom were found to be very much hindered compounds. 1-[(1-Substituted)-2-phenylethyl]-2,5-dimethylpyrroles showed the restricted rotation, and the phenyl group of the most stable conformer was in close proximity to the pyrrole group due to dipole interaction. These NMR observations were supported by force field conformational analysis.
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  • 27
    Electronic Resource
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 197-207 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: ESR spectra of l-cyano-2-(trimethylsilyl)ethyl and related radicals were recorded. Temperature dependent ESR spectra of these radicals revealed that electron-releasing trimethylsilylmethyl and electron-withdrawing cyano groups synergetically functioned to stabilize the radical centers due to σ-π captodative effects.
    Additional Material: 10 Ill.
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  • 28
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The excellent linearity (R2 = 0·997) of a plot of pKa values for 17 m- and p-substituted benzyl phenyl sulfones, GC6H4CH2SO2Ph, vs. those for the corresponding arylacetonitrile, GC6H4CH2CN, demonstrates that substituent solvation and substituent solvation assisted resonance (SSAR) effects for p-CN, p-COPh, and p-SPh are nearly identical in these two substrates. The PhSO2 group in PhCH2SO2Ph increases the BDE of the α-C—H bond by 2 kcal/mol, relative to toluene. The α-C—H bonds in GC6H4CH2SO2Ph sulfones are stabilized by 1-2 kcal/mol by acceptor G′s (m-CN, p-CN, m-CF3, p-CF3), but weakened by 1 and 5 kcal/mol, respectively, by donors (p-OMe and p-NMe2). The GC6H4CH2SO2Ph+. radical cation with G = H has a pKHA+. = -25. Its acidity is increased when G is an acceptor by as much as 9 to 10 kcal/mol (G = 3-CN, 3-CF3, 4-CF3, 4-NO2), but is decreased when G is a donor by as much as 33 kcal/mol (G = NMe2). When G = 4-SPh the radical cation is stabilized, relative to G = H, by a larger amount (25 kcal/mol) than when G = 4-OMe (18 kcal/mol). Structural changes along the series PhCH2SO2Ph, 2-naphthyl-CH2SO2Ph, 9-anthryl CH2SO2Ph cause negligible changes in the acidities of these acids, but sizable decreases in the acidities of the corresponding radical cations. Introduction of a phenylsulfonyl group into the methyl group of 9-methylanthracene or the 9-position of fluorene or xanthene increase the BDEs by 3, 2, and 7 kcal/mol, respectively. These effects of PhSO2 groups are compared and contrasted with those of CN groups.
    Additional Material: 3 Ill.
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  • 29
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 267-273 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The PE spectra of four stable bicyclic triaziridines with trifluoromethyl, methyl, phenyl, spirocyclopentane and spirocyclohexane substituents are measured. From a comparison of these experimental data with MNDO calculations the energies and the interactions of the nitrogen lone-pair orbitals were obtained. The trifluoromethyl group may be reliably simulated by a fluorine atom. The ionization potentials are unexpectedly high and so are the cyclovoltammetric anodic potentials. The MNDO valence electron densities are in agreement with the comparatively small differences in the chemical shifts of the differently substituted nitrogens of the triaziridine rings.
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  • 30
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 275-280 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In order to examine the substituent effect of ethylenedithio and trimethylenedithio groups on electron acceptors, the two title compounds were prepared in one step from the corresponding quinones. These species behave as weak π-electron acceptors owing to the electronic and sterical effects of the fused groups. Only the bis(ethylenedithio) derivative formed a charge-transfer complex with tetrathiotetracene, which showed a moderate electric conductivity of 2·0 × 10-2 S cm-1. In addition, both species oxidized copper, sodium, and potassium iodides to give the corresponding deeply colored metal salts, most of which were semiconductive. The naphtho analogs were similarly studied, but hardly served as electron acceptors.
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  • 31
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988) 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 32
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Photoresponse of the poly(vinyl chloride) membranes, which contain spirobenzopyran and crown ether, covered with a urease layer was studied in the presence and absence of urea. In the absence of urea, UV light irradiation induced more than 160 mV of membrane potential change, whereas the photoresponse decreased with an increase in the concentration of urea in the solution. The effects of such operating variables as crown loading and pH and ionic strength in the aqueous phase on the potentiometric response were also elucidated in the presence of urea. The results were explicated using the fact that the local concentration on NH4+ and H+ ions changed as a result of the urease-catalyzed decomposition reaction of urea.
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  • 33
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 351-357 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The title reaction is an instance of a simple nucleophilic attack of neutral nitrogen on aromatic sp2 carbon. The kinetic data (obtained in dimethyl sulphoxide) are compared to the results reported by the literature for the same reaction of aliphatic amines. Some possible interactions (substrate/nucleophile, substrate/salt) preceding the attack of the nucleophile are discussed.
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  • 34
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    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 115-128 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: An absorbing boundary condition for simple layered media is presented. The method enables the modelling of open space radiation and scattering problems when the source (or scatterer) and a plane interface between two media are both located within the finite-difference or finite-element region. The projection operator method is used to take into account the presence of reflected waves at the media interface. The derivation of the projection operator is presented for one, two and three dimensions. Examples of electromagnetic radiation and scattering in two dimensions are presented to illustrate the numerical implementation and validity of the new absorbing boundary condition.
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  • 35
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    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 129-130 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
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  • 36
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    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 131-136 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: A design method for filters having duobinary signal pulses as impulse response is presented.
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  • 37
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    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 137-151 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Additional Material: 5 Ill.
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  • 38
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    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 153-164 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: Spontaneous emission noise power, although small in magnitude, affects many aspects of the semiconductor laser's operation. An accurate model has been developed for it for use in the transmission-line laser model (TLLM), which is a time-domain, wideband, dynamic, non-adiabatic semiconductor laser model. The effects of approximations used in other dynamic laser models are then investigated by comparison with the results from the TLLM. The study shows that the representation of this noise power has an important bearing on the damping of modelled transient oscillations.
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  • 39
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    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 171-171 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
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  • 40
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    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 165-170 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: A method for analysing the electrical effect of a set of conducting strips is presented. This method is applied to modelling the electrical behaviour of conducting tracks on a printed circuit board (PCB). Unlike most other published work, this analysis is not restricted to the case where the tracks are parallel. The problem is formulated in terms of an admittance matrix. A boundary element method incorporating image theory is used to produce a system of linear equations. These are solved to yield the required admittance matrix, which can then be incorporated into a standard circuit analysis package. Comparisons between measured and predicted circuit performance for a complex layout show close agreement up to at least 1 GHz.
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  • 41
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    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 173-174 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
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  • 42
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    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 175-188 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: The asymptotic form, for high frequencies, of the equations of propagation on a nonuniform N-conductor transmission line is considered. Under the assumption of perfect conditions in uniform, isotropic media, all N propagation velocities are the same, but the characteristic impedance matrix is allowed to vary with position along the line. Closed-form solutions are obtained for some cases of interest.
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  • 43
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    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 19-30 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: The Boltzmann transport equation is used to derive a set of conservation equations which is capable of describing the electron transport phenomena in a single-valley semiconductor. These conservation equations are averaged over the different valleys of the conduction band to develop another set of equations that can be used to describe accurately the electron transport phenomena in a multi-valley semiconductor, such as GaAs, using the equivalent single-electron gas model whose characteristics are the average weighted characteristics of the constituent gases. The nonstationary effects are included by using energy dependent mobility and electron temperature functions. This program is used to simulate a GaAs MESFET with a 0·5 μm gate length and a 0.2 μm thick active layer. The active layer is doped at 1017 cm-3. A travelling Gunn domain is observed between the gate and the drain. The domain oscillation frequency is much higher than the normal operating frequency of the MESFET. The domain formation's dependence on the gate bias and the active layer thickness are also presented.
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  • 44
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    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988) 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
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  • 45
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    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 61-70 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: Two- and three-dimensional electromagnetic resonance calculations have been performed on rising-sun magnetron structures. These calculations have been made using the transmission-line matrix method. Cylindrical coordinates have been used in order to facilitate modelling of the essentially cylindrical device. Recent improvements to the TLM technique, such as the development of the symmetric condensed node for electromagnetics, have been fully exploited. The numerical procedure is described, the modelling process is discussed, and the results obtained are evaluated in comparisons with corresponding empirical data.
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  • 46
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    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 45-59 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: The conventional transverse resonance method, which has been widely used for the approximate characterization of a number of guiding structures and leaky wave antennas, is formulated in a generalized form. The transverse resonance viewpoint combined with the generalized matrix representation of discontinuities yields a rigorous transverse equivalent circuit of the guiding structure.This technique is used to compute the characteristics of both symmetrical and asymmetrical double slot unilateral finlines in terms of phase constant and characteristic impedance of the dominant as well as higher-order modes. Numerical aspects of this method are discussed.In a double-slot finline structure, a coupled-mode regime is established with the onset of the first higher-order mode in addition to the dominant quasi-TEM mode. Symmetrical structures are simply modelled in terms of even and odd mode characteristics, but a more general coupled-line model, in terms of the C-mode and the II-mode must be applied to asymmetrical coupled finlines.
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  • 47
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    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 71-72 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
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  • 48
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    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 85-91 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: Transmission-line models (TLMs) for nonlinear reactive components and mutual inductances are derived. The model for nonlinear reactive components is shown to be an improvement on the previous one. TLM results with the mutual inductance model are compared with the exact solution, and good agreement is found.
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  • 49
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    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 189-206 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: A numerical method using impulse analysis of a transmission-line matrix is used to model the scattering of underwater acoustic waves. The method is demonstrated by observation of plane and curved wavefronts travelling through the medium, and by plane wavefronts being scattered by a reflecting boundary.
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  • 50
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    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 207-220 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: Shooting and bouncing rays (SBR) is a numerical method based on geometric optics developed to compute the electromagnetic scattering from jet inlets and partially open cavity structures. This method is used to study the effects of shaping on the radar cross-section (RCS) of cavities. Two cylindrical cavity structures are analysed: one with a uniform circular cross-section, and the other with a non-uniform cross-section varying from a triangular shape to a circular shape. By bending the longitudinal axis of a cylindrical cavity, a significant reduction in RCS at near axial incidence can be achieved.
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  • 51
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    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988) 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
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  • 52
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    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 1-1 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
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  • 53
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    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 7-17 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: The principal features of the modified TLM method such as the asymmetrical condensed node, graded mesh and dispersion characteristics, are briefly presented. Its general application to multiaxial discontinuities in quasi-planar structures is described, and the modelling of bilateral finline T-junctions is demonstrated in particular.
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  • 54
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    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 3-6 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: The use of models in giving meaning to sense data is described. It is shown that models are essential to human understanding, but that there are no uniquely ‘best’ models. This leads to the discussion of the design of suitable models for engineering use. The role of physical and mathematical models is mentioned, and attention is drawn to geometrical and physical features. It is stated that numerical methods have overriding advantages, one of which is the possibility of numerical experimentation. The modelling of vector fields is discussed and attention is drawn to the ideas of differential geometry which attach the vector field to the space in which it acts. It is shown that variational methods, together with numerical experiments, can be used to derive invariant parameters which give both global and local information about electromagnetic systems in a particularly economical method of computation.
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  • 55
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    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 31-43 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: The coupling between incident electromagnetic fields and lossless multiconductor transmission systems is studied using transmission-line modelling-(TLM) and the impedance parameters of the transmission system. This calculation is a two-stage procedure:firstly, the field problem is solved, with no conductors present, to give the incident fields; secondly, the multiconductor transmission-line problem is solved using equivalent voltage and current sources representing coupling from the incident fields. Comparison of these results with previously published work shows excellent agreement. The numerical model presented is particularly suitable for studying electromagnetic compatibility problems.
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  • 56
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    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 73-83 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: A discrete model is developed to describe the diffusion of dopant/impurity in a single semiconductor crystal during Czochralski growth. The basic diffusion mechanism is assumed to be substitutional-interstitial interchange for the impurity, together with self-diffusion of the host atoms. In particular, the model incorporates the complicated conditions that result from the simultaneous growth and diffusion taking place at the crystal/melt interface. The high temperature dependence of the process is also taken into account, together with possible vacancy production to counteract vacancy depletion. The numerical model is explicit in time, and conditions for convergence and stability are considered. Results are presented for chromium doping of growing gallium arsenide crystals, and compared with published experimental data.
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  • 57
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    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 93-102 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: One- and two-dimensional algorithms for the transient simulation of semiconductor devices are presented which incorporate a solenoidal total current. The paper includes results from one-dimensional simulation of a p-n junction, including forward-to-reverse bias switching and also switching and also switch-on into high injection in an asymmetric structure. A discretization scheme for the two-dimensional formulation is described with details on handling voltage driven terminals and the associated boundary conditions.
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  • 58
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    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 103-113 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: This paper describes the application of ASTEC3, a general purpose analogue electronic circuit simulation package, to the analysis of thermal properties of given structures. The modelling of each system is considered for both conduction and convection mechanisms, radiation being assumed to play a very minor role in heat dissipation from most electrical circuits. A procedure is given for the modelling of one-, two- and three-dimensional thermal problems which is then used for the simulation of relatively simple examples. The results obtained with ASTEC3 are compared with results determined by using more traditional and independent techniques.
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  • 59
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    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988) 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
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  • 60
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    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988), S. 221-238 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
    Notes: The development of numerical models to describe physical problems with irregular boundaries frequently involves the use of very fine or variable Cartesian meshes when a more descriptive mesh might be appropriate. This paper describes the application of the transmission line matrix (TLM) technique to the analysis of orthogonal curvilinear mesh problems. Although very high levels of accuracy are possible, the computational efficiency may be reduced owing to the stub admittance factor, S, and the need for an accurate evaluation of the transmission line parameters.
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  • 61
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    Chichester [u.a.] : Wiley-Blackwell
    International Journal of Numerical Modelling: Electronic Networks, Devices and Fields 1 (1988) 
    ISSN: 0894-3370
    Keywords: Engineering ; Electrical and Electronics Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Electrical Engineering, Measurement and Control Technology
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  • 62
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    Journal of Physical Organic Chemistry 1 (1988), S. 21-27 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure of radical intermediates appearing in the reactions of MeMgBr with aromatic monoketones was investigated by using ESR and visible spectroscopy. Stable radical intermediates in the reacting solutions were assigned to the dimeric radical ion pairs.
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  • 63
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    Journal of Physical Organic Chemistry 1 (1988), S. 33-38 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several Cotton effects are developed within absorption bands of trinuclear organotransitionmetal complexes in the presence of acids, diols, amines and aminoalcohols even in the case of bulky substituents on nitrogen; with monohydroxy compounds no circular dichroism could be detected.
    Additional Material: 4 Ill.
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  • 64
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 29-31 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Disparity reaction proposed in a recent application of Marcus-Grunwald theory to nitroalkane ionization is shown to put the reaction's transition state in an energy-diagram region where electronic rearrangement leads proton transfer, contrary to experimental evidence; it is suggested that addition of solvent reorganization to electronic rearrangement as the second reaction progress variable would remedy this situation.
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  • 65
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    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 1 (1988), S. 39-46 
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Triethylsilyl radical was generated by laser flash photolysis of a 1:1 (v/v) solution of triethylsilane and di-tert-butyl peroxide. The silicon centered radical was reacted with sulfides to give carbon centered radicals by displacement at sulfur. The carbon radicals were readily detected by their transient absorption spectra. The absolute rate of reaction of triethylsilyl radical with 9-fluorenylphenylsulfide, di-n-butylsulfide, di-sec-butyl sulfide, di-tert-butyl sulfide and di-n-butyl disulfide are 2.40 ± 0.12 × 108 M-1S-1, 1.1 × 107±0.89×106M-1S-1, 8.79± 0.73×106M-1S-1, 3.29±0.18×106 M-1S-1, and 3.41±0.09×108 M-1S-1, respectively.
    Additional Material: 8 Ill.
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  • 66
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 13-19 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The kinetics of crystallization during anioiiic polymerization of ∊-caprolactam was studied by the adiabatic temperature rise method, A new kinetic model for the non-isothermal crystallization was derived and the possibility of its application was Investigated. By evaluating the parameters in the model for the given adiabatic system, the crystallization behavior during the; polymerization process was analyzed. The experimental and calculated temperature rise showed a very good agreement, which indicated that the model equation was appropriate to describe the non-isothermal reaction-induced crystallization kinetics in this study. The melting temperature of the reaction mixture increased steadily due to the change of the crystal structure with conversion. The equilibrium crystallinity was higher when the crystallization started in the presence of unreacted monomer than when the crystallization occurred after polymerization was completed. At lower conversion, the reaction mixture was less viscous, a condition that made transport to the liquid-crystal interlace easier, and thus the activation energy for transport decreased. On the other hand, the increasing mobility resulted in difficulty in forming stable nuclei arid the free energy of nucleation increased.
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  • 67
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 68
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Investigations of instability of phase morphology of blends of nylons with polyethylenes and polystyrenes and the effects of “compatibilizing” additives or “agents” are described. Annealing coarsens the phase morphology of blends of nylons with polyethylenes and polystyrenes. Phase growth is observed for various periods of annealing time. The addition of compatibilizing agents, specifically maleic anhydride grafted polyolefins to polyethylene-nylon blends and syrene-maleic anhydride copolymers to polystyrene-nylon blends, stabilize the phase dimensions. Styene-maleic anhydride copolymer is found more effective than styrene acrylonitrile copolymer as a compatibilizing agent. The mechanisms of this behavior are critically discussed.
    Additional Material: 14 Ill.
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  • 69
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 70
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 147-156 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This paper discusses a computer control system for ram velocity of an injection molding machine using optimal state feedback based on the linear quadratic control theory. A new approach for the selection of appropriate weighting matrices is presented in this context. The simulation results reveal that the optimal controller has improved performance over the conventional PID controller presently used, having faster speed of response, significantly better tracking performance, and better noise filtering properties. The execution speed and the core storage requirements would allow implementation even on a small online computer.
    Additional Material: 9 Ill.
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  • 71
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    Polymer Engineering and Science 28 (1988), S. 165-169 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Film embossing is a mechanical process in which a flat film is transformed into an embossed product. During the process, thermal and stress fields are applied Lo the polymer, causing changes in the microstructure and physical dimensions of the material. The engineering analysis of the process requires the study of various aspects relating to the characterization of the microstructure before and after embossing, A variety of techniques were employed to characterize the properties and microstructure of the embossed film in relation to: crystallinity, orientation, mechanical properties, and dimensions of the embossed films. The thermal treatment of the polymer film was shown to be the most significant factor in the process. By controlling the thermal treatment of the film, it is possible to manipulate the properties and dimensions of the embossed film. The important aspects: influencing thermal treatment include the radiation heater temperature, preheat roll temperature, line velocity, and film thickness. The initial film orientation and embossing pressure have a minor effect on the final properties of the embossed film. The main effect of the embossing pressure is on the bulk thickness of the embossed film.
    Additional Material: 11 Ill.
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  • 72
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 73
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 257-274 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A detailed model for emulsion polymerization is compared with extensive data from continuous stirred tank reactors. Model predictions are compared with both steady-state and dynamic data, for polymerization of styrene, methyl methacrylate, and vinyl acetate. Good agreement between model and experiment is achieved with one set of parameters and without any data fitting. The results show that the model is capable of predicting all of the experimentally observed phenomena including steady-state multiplicity, sustained oscillations, ignition and extinction dynamics, and overshoot during start-up.
    Additional Material: 47 Ill.
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  • 74
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    Polymer Engineering and Science 28 (1988), S. 321-332 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A mathematical model is developed for simulating the pultrusion process of unsaturated polyester resin, using a mechanistic kinetic model based on free radical polymerization. In their previous publications (Refs. 1 and 7), Han and Lee used the mechanistic model to simulate the curing behavior of unsaturated polyester resins under isothermal conditions, employing the differential scanning calorimetry data obtained for a range of single initiators and multiple initiator systems. For the sake of mathematical convenience, a pultrusion die of cylindrical geometry was considered. The mathematical model developed permits one to choose any number of initiators when predicting the distributions of the degree of cure and temperature in both the radial and axial directions of the die. The effects of material variables (e.g., the type and concentration of mixed initiators) and processing conditions (e.g., pulling speed and die temperature distribution) on the performance of the pultrusion are evaluated.
    Additional Material: 22 Ill.
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  • 75
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 189-199 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Post mold thermal processing of epoxy encapsulated semiconductor devices is accomplished in order to optimize the properties of the encapsulating material. Traditionally, such processes were believed to alter solely the state of cure in such systems. We have examined the effects of aging at temperatures close to, but below the molding temperature via dynamic mechanical spectroscopy, Fourier transform infrared spectroscopy, and differential scanning calorimetry as a function of molding temperature. The large property changes observed during aging for samples molded at the lowest temperatures studied were attributed to physical aging phenomena in the presence of low levels of chemical reaction. As the molding temperature was increased chemical aging, phenomena began to precede the volume recovery associated with physical aging, and the overall property shift was altered. It is the intent of this paper to examine in detail the microstructural basis for such observations, as well as the time dependence of the overall property shifts.
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  • 76
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    Polymer Engineering and Science 28 (1988), S. 275-290 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In many operations in polymer processing, such as polymer blending, devolatilization, or incorporation of fillers in a polymeric matrix, continuous mixers are used; e.g., corotating twin-screw extruders (ZSK), Buss Cokneaders and Farrel Continuous Mixers. Theoretical analysis of these machines tends to emphasize the flow in complex geometries rather than generate results that can be directly used (1-5). In this paper, a simple model is developed for the hot melt closely intermeshing corotating twin-screw extruder, analogous to the analysis of the single-screw extruder carried out in 1922 and 1928 (6, 7). With this model, and more specifically with its extension to the complete nonisothermal, non-Newtonian situation, it is possible to understand the extrusion process and to calculate the energy, specific energy, and temperature rise during the process with respect not only to the viscosity of the melt, but also to the screw geometry (location and number of transport elements, kneading sections and blisters, pitch, positive or negative, screw clearance, and flight width) and screw speed. To support the theoretical analysis, model experiments with a Plexiglas-walled twin-screw extruder were performed, in addition to practical experiments with melts on small- and large-scale extruders, with very reasonable results, In Part 2, the Buss Cokneader will be analyzed analogously.
    Additional Material: 15 Ill.
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  • 77
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    Polymer Engineering and Science 28 (1988), S. 434-443 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The radial flow of a chemically reactive fluid between two parallel circular disks during the process of Reactive Injection Molding (RIM) has been simulated in a decelerative, non-isothermal, transient flow environment. The effects of key operating and system parameters (feed temperature, volumetric flow rate, reaction rate, and cavity thickness) on velocity, conversion, and temperature profiles which occur in this decelerative flow environment were determined. A catalyzed, unfilled polyurethane RIM system was modeled by a linear step polymerization scheme using average literature values for the reaction rate, and thermodynamic and constitutive parameters. The numerical solution was achieved using the method of lines and upwind approximations of the spatial derivatives. The geometry studied (two parallel, center gated circular disks) models flow patterns in commercial RIM processes more realistically than the rectangular flow between two parallel surfaces (studied by previous workers) in which the average velocity is constant along the length of the mold. This simulation predicts the accumulation of high polymer near the entrance to the mold and near the outer edge of the cavity in fast reactive systems. The accumulation of material near the gate results in viscous heat generation and a maximum in temperature in the region immediately downstream from the restriction.
    Additional Material: 21 Ill.
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  • 78
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    Polymer Engineering and Science 28 (1988), S. 469-476 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An analysis of a drawing plate test for easily monitoring the low-pressure frictional characteristics of powders is presented. The test is performed by measuring the force required to withdraw a plate from a cylindrical bed of dry powder. The characteristics of the drawing force profile are analyzed using Janssen's classical differential element approach to relate the product μK of powders as a function of packing of powder medium, where μ is the coefficient of friction of the powders against the solid drawing plate, and K is Janssen's constant, an anisotropic pressure distribution factor of a powder bed. The packing arrangement, expressed as the external void fraction, due to tapping, significantly alters the μK value and the effective sustaining strength of a powder bed. Experimental results on spherical glass beads having mono- and bimodal size distributions, and on three different poly (vinyl chloride) (PVC) powders are discussed. A spherical, high bulk density PVC powder has the combination of low μK and high, bulk density desirable for rigid powder compounding applications.
    Additional Material: 11 Ill.
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  • 79
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 80
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    Polymer Engineering and Science 28 (1988), S. 413-420 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This paper presents the development of the boundary element equations for the compression molding process of isothermal Newtonian fluids. It shows the numerical implementation of the boundary element equations and presents a simple method of carrying out the domain integral present in the governing equations. The results and accuracy of a boundary element simulation are discussed, and the numerical results compared to experimental values.
    Additional Material: 14 Ill.
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  • 81
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    Polymer Engineering and Science 28 (1988), S. 444-452 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A numerical method has been developed for simulating fully developed multilayer shear flows of non-Newtonian fluids with arbitrary viscosity functions. Poiseuille and combined Poiseuille/Couette flows in both slits arid annuli may be modeled. The method employs a finite difference system where grid points lie on streamlines and move to their correct positions as the solution procedure converges. Interfaces are easily handled as particular stream lines with the equation of motion replaced by a boundary condition. The method is stable for high interface viscosity ratios and readily handles a large number of layers. Many authors have employed power law models to model multi-layer non-Newtonian flows. We find that the power law is sufficient to predict pressure gradients and interface positions in most cases, but gives unrealistically flat velocity profiles, even when truncated at finite viscosity. Results are presented for the Carreau fluid and for the rubber-like liquid with shear thinning via Wagner's strain functional.
    Additional Material: 9 Ill.
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  • 82
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    Polymer Engineering and Science 28 (1988), S. 477-484 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A computer simulation model was established to analyze the reaction injection molding process of nylon 6. A numerical calculation was carried out to predict the temperature, conversion, and crystallinity profile within a disc type mold. The effects of the feed temperature, wall temperature, and overall reaction constant on the eject time were discussed for searching the optimum processing conditions.
    Additional Material: 14 Ill.
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  • 83
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    Polymer Engineering and Science 28 (1988), S. 497-505 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: With respect to molecular masses, polymers are polydispersive. Since many of their properties depend on the distribution of molecular masses, to study this correlation it is necessary to have samples of narrow molecular mass distribution or samples with accurately defined distribution. In spite of the developmental progress of fast instrumental methods (analytical and preparative gel chromatography) used to determine the molecular mass distribution curve and to obtain higher amounts of fractions of narrow molecular mass distributions, there still exists an interest in classical methods of fractionation. On the basis of a survey of monographs on polymer fractionation, numerous publications and personal experience, this review describes primarily what is an efficient fractionation. Afterwards, factors that affect fractionation efficiency according to the type of effects arc given and causes of their action are described. Conditions under which efficient fractional precipitation and fractional solution methods are applied are considered separately. At the end of the review, criteria on the basis of which fractionation efficiency is evaluated are considered in detail.
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  • 84
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    Polymer Engineering and Science 28 (1988), S. 538-543 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The relationship between the relaxation time spectrum H(τ) in the terminal zone and the volume-fraction differential molecular-weight-distribution function P(M) is derived by considering binary chain contacts for stress transmission, where β and λ are constants for a given chemical type. This is used to determine the molecular-weight-distribution curves from the stress relaxation modulus spectrum (above the crystal melting point) at 370°C for a number of commercial and experimental poly(tetrafluoroethylenes) (PTFEs). It is found that PTFEs typically have bimodal molecular-weight distributions. The lower-molecular-weight peak conforms essentially to the “most-probable” distribution, and the higher-molecular-weight peak to the binary coupling distribution. The entanglement molecular weight Me is 5490, and the number of main-chain atoms between entanglement points is 110, consistent with a flexible chain. The zero-shear melt viscosity at 370°C is η0 = 1.79 × 10-13 Mw2.94±0.13, where η0 is in Pa.s and Mw/Me = 2,000 to 12,000. The monomeric friction coefficient is also determined.
    Additional Material: 8 Ill.
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  • 85
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    Polymer Engineering and Science 28 (1988), S. 81-89 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A method to obtain the tenacity and Young's modulus of nonwoven webs without direct measurement of web thickness is proposed. This has been tested with several series of samples with different basis weight. It was found that these properties were nearly Independent of the sample gage length, and both tenacity and modulus generally decreased with increase in the die temperature, the air pressure at the die, or the die to collector distance [DCD]. The web stiffness as measured by bending rigidity followed similar trends. The elongation Lo break also decreased as die temperature and air pressure at The die increased, but it increased with increasing DCD. The average filament diameter in the web decreased with increasing die temperature or air pressure at the die. The single filament strength was measured and compared with strength properties of web and of high-speed melt spun filament prepared from the same resins. The strength of single filaments in the web lie in between those of the web and high-speed spun filaments. The mechanical properties of melt blown web were interpreted in terms of the changes in Fiber diameter, the level of interfilament bonding, the molecular orientation developed in the filament, the diameter uniformity along the individual filaments in the web, and the presence of voids in the filament.
    Additional Material: 20 Ill.
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  • 86
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    Polymer Engineering and Science 28 (1988), S. 113-119 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A computer simulation model for the latent skin growth inside a hollow fiber polymeric membrane Is developed. The evaporation step is studied using a solvent evaporation Law and a concentration-dependent diffusion coefficient, both derived from data. The solvent concentration profiles inside the fiber are obtained as a function of the evaporation time for different sets of the parameters governing the internal diffusion and the surface evaporation of the solvent. The computer model enables estimation of the role of the parameters in the growth of the asymmetric latent skin.
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  • 87
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    Polymer Engineering and Science 28 (1988), S. 136-142 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A series of thermotropic liquid crystalline polyesters based on p-acetoxybenzoic acid, naphthalene dicarboxylic acid, hydroquinone diacetate, and poly(ethylene terephthalate) were prepared via melt polycondensation. The anisotropic melts were studied by means of thermal optical testing, differential scanning calorimetry, scanning electron microscopy. X-ray diffraction, and rheological methods. It was found that the copolyesters in the mesomorphic state exhibit drastic shear-thinning and the experimental results indicate that the non-Newtonian Index n is in the range of 0.17 to 0.50, the flow-activation energies ΔEη are 297.1 to 182.0 KJ/mol over the shear rate of 10 to 1000 S-1 at temperature 225 to 270°C; and the mesomorphic copolymers are readily oriented during processing, resulting in highly oriented as-spun fibers.
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  • 88
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    Polymer Engineering and Science 28 (1988), S. 170-180 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Results of experimental and modeling studies of the peroxide promoted degradation of polypropylene (PP) are presented. Experiments were carried out, in glass ampoules and in a plasticating extruder. The initiator, 2.5-dimethyl-2,5-bis(tert-butylperoxy)hexane was used as a radical generator. The extruder used had a 38 mm diameter and 24:1 L/D single-screw. In these experiments, the effect of peroxide concentration and screw speed on the molecular weight distribution (MWD) of the polypropylene resin was studied. Samples collected from the experimental runs were analyzed for melt flow index (MFI), flow curve, extrudate swell, and MWD. The measured data are presented and correlations among various parameters are considered. Generally, it can be concluded that controlled-rheology (CR) resins with lower molecular weight, narrower MWD, and reduced viscosity and elasticity, can be produced, A kinetic model for the peroxide Initiated degradation of PP is proposed. Simulations based on this model are compared with experimental data for the production of CR resins. The experimental data were obtained from three sources: (i) industry, (ii) literature, and (iii) present experimental work. The comparison was done in terms of average molecular weights of the resin. Agreement between model predictions and experimental results is quite satisfactory suggesting that this model should find use in commercial practice.
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  • 89
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    Polymer Engineering and Science 28 (1988), S. 181-187 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This study examines the effects of crystallinity and temperature on the mechanical properties of PEEK. Crystallinity in PEEK Increases with annealing temperature up to a maximum of 28 percent with a melting point at 335°C. A minor melting peak also occurs about 10°C above the annealing temperature. In cold drawing the samples exhibited a yield stress and necking followed by homogeneous drawing. The yield stress increases with crystallinity, but there is no change in the modulus. The extension in the necking process also increases with crystallinity, however there is only a slight increase in extension-to-break since necking is compensated by the final amount of homogeneous drawing. The yield stress of PEEK when drawn at Tg (145°C) is significantly lower than at room temperature indicating a reduction in mechanical properties at temperatures approaching Tg. After mechanical drawing the minor melting peak disappears and on heating the material undergoes cold crystallization near the onset of Tg. There is evidence that this minor crystalline component might contribute to the yield stress changes with annealing history. Cold drawing induces crystallization of amorphous PEEK but decreases crystallinity and generates microscopic voids in crystalline PEEK, The various effects of crystallinity on mechanical properties could be important in determining the stress response of PEEK as the matrix in composites.
    Additional Material: 5 Ill.
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  • 90
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    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 91
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 367-371 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A negative-acting dry-film photoresist was examined via both photocalorimetry and conventional calorimetry. The photo reaction of the resist was investigated as a function of temperature, and two distinct regimes with different activation energies have been identified. Possible reaction mechanisms were discussed in terms of termination reactions of the polymerization as well as effects of vitrification. The thermal reactivity of this particular resist was studied as well. It was possible to use Kissinger's equations to predict thermal aging effects. Finally, the utility of photocalorimetry as a tool to examine quickly the reactivity of monomers and initiator systems was demonstrated.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 92
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 381-384 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The applicable range of the regression equation proposed by Yamada, et al. expressing oligomer melting point by oligomer characteristics and relations derivable from the equation correlating each oligomer characteristic and melting point were studied. It was confirmed that the equation is applicable not only to poly(ethylene terephthalate) (PET) oligomer but also to the extent of polymerization. As number-average degree of polymerization (Pn) increases, the influence of end groups on melting point becomes weak, and when Pn exceeds 50, the influence of end groups becomes negligibly small. On the other hand, when Pn is below 2, It was confirmed that the influence of end groups on melting point is very strong.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 93
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 405-412 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Means of improving the deep drawability of thermoplastic sheets were explored by introducing temperature gradients in the deforming material during deep drawing of initially flat sheets. The specific experimental procedure consisted of either limiting the heating to the flange section of the deforming sheet or exposing the entire material to higher temperatures. At the same time, the initial blank size and the clamping force at the flange section were varied systematically. Both polypropylene and polypropylene with 40 percent calcium carbonate in the form of sheet were tested up to 130°C. It is demonstrated that the draw-ability increases markedly with increasing temperature gradient between the flange and punch sections. The results of measured strain distribution in the deformed part indicate that the magnitude of temperature difference between the flange and punch sections determines the relative amount of deep drawing and stretching in the wall of the formed part, which in turn dictates the drawability of the material.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 94
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    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 333-339 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Injection molding can be used to fabricate fiber-reinforced polymer composites by impregnating a continuous fabric mat preplaced in a mold cavity with a polymer resin. The mold-filling time is dependent on the flow and heat transfer behavior in the mold. A model is proposed that considers the non-Newtonian How through the porous fabric mat and the heat transfer between mold, fabric mat, and flowing fluid. The model was simulated for the mold filling of a carbon fiber mat with a pseudoplastic polymer solution. The results from the simulation provide Information for optimizing mold-filling parameters through proper selection of inlet fluid pressure, heat source temperature, and type of polymer-solvent system.
    Additional Material: 8 Ill.
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  • 95
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 291-310 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The wire-coating process was analyzed numerically making use of a particular die design employed in highspeed industrial operations. Both the lubrication approximation theory and a fully two-dimensional finite element analysis were applied under isothermal and nonisothermal conditions, respectively. Particular emphasis has been given to the heat transfer effects between the melt arid the solid and free boundaries. A variety of thermal boundary conditions was studied, ranging from adiabatic to constant temperature walls. The influence of dimension less groups such as Peclet, Nahme, and Biot numbers is examined. Oscillation-free solutions are obtained for the temperature field by using a standard finite element Streamline-Upwind/Petrov-Galerkin technique. Rheological data for a wire-coating low-density polyethylene (LDPE) resin (Alathon-3535) were used in the analysis. The predictions include pressure and temperature distributions, shear stresses and shear rates both at the die wall and the wire, and wire tension for different wire speeds. The numerical results are compared with a set of experimental data for LDPE in a typical die used by Du Pont Co. It is found that the isothermal lubrication approximation for power-law fluids overestimates pressure distributions when applied at die operating temperature. The nonisothermal finite element analysis gives better predictions, especially when realistic thermal boundary conditions are imposed, with the experimental results lying between those found from simulations assuming isothermal walls (upper limit) and adiabatic walls (lower limit).
    Additional Material: 26 Ill.
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  • 96
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 393-402 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Using three series of sodium carboxymethylcellulose (NaCMC) in the range of the degree of substitution (the average number of carboxymethyl groups/glucose unit) from 0.5 to 1.3, weight-average molecular weight Mw was determined by light scattering in solution of triethylenediamine cadmium hydroxide (cadoxene). It was found that the relation between Mw and the limiting viscosity number [η] in 0.1 N sodium chloride (NaCl) aqueous solution can be represented by Staudinger's equation. Dynamic viscoelasticity of aqueous disperse systems of NaCMC with various added salts was measured by means of a cone-and-plate rheometer. If the concentration of added salt is less than the concentration at which polymer begins to salt out, frequency dependence curves of the dynamic modulus, which is measured at various salt concentrations, can be superposed into a master curve by horizontal shift only. The shift factor depends on the salt concentration and the kind of salt.
    Additional Material: 11 Ill.
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  • 97
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    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 385-392 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: To study the effect of potassium titanium oxyoxalate on the esterification reaction of terephthalic acid (TPA) and ethylene glycol (EG) in the first tank reactor of TPA/EG continuous esterification, experiments at various addition rates of potassium titanium oxyoxalate were made in the pilot plant. Potassium titanium oxyoxalate accelerated the esterification reaction of TPA and EG. Also, reaction rate constants of the reaction scheme reported in a previous report were fitted with the experimental results, and the calculated values of physical properties of oligomers obtained from these reaction rate constants showed relatively good agreement with experimentally obtained physical properties of the oligomers. The effect of potassium titanium oxyoxalate on the reaction rate constants was expressed by a set of seven equations: Using the resultant reaction rate constants, the esterification reaction at various addition rates of potassium titanium oxyoxalate were stimulated and the following conclusions drawn: 1Under low pressure close to atmospheric, when the amount of water in the reaction mixture is very low, the decomposition of potassium titanium oxyoxalate proceeds slowly and decomposition can be practically neglected.2Potassium titanium oxyoxalate accelerates the esterification reaction.2Potassium titanium oxyoxalate mainly accelerates the main reactions and its effects on side reactions are rather weak. As a result, the higher the addition rate of potassium titanium oxyoxalate, the lower the values of AV and DEG, as is preferable.
    Additional Material: 12 Ill.
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  • 98
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988) 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Type of Medium: Electronic Resource
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  • 99
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 1-5 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Physical aging of a thermoset system based on bisphenol-A epoxy (DERTrademark of The Dow Chemical Company. 383) and tetrabromobisphenol-A cured with sulfanilamide and diaminodiphenylsulfone was studied as a function of cure history. Changes in the dynamic mechanical spectra for the thermoset system were correlated to changes in relative toughness associated with physical aging as determined by plane-strain biaxial tension-compression yield measurements. It was found that master curves, generated by using tan δ data obtained in the β relaxation temperature regime, are well related to the corresponding changes in mechanical properties and, hence, have predictive value. Relative toughness decreases and compressive yield increases with decreasing tan 5 because of decreased molecular segmental mobility. The relative extent of physical aging for the as-cast thermosets was shown to be linearly related to the cure time.
    Additional Material: 9 Ill.
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  • 100
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    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 6-12 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Strain-induced crystallization of poly(ether ether ketone) (PEEK) was studied by the use of a parallel plate rheometer. The experimental variables included preheating time, crystallization temperature, and shear rate. The crystallization kinetics were characterized by means of an induction time defined as the time elapsed from the start of shearing to the onset of crystallization. The experimental results showed that the induction time for strain-induced crystallization of PEEK was significantly shorter than that for crystallization under quiescent condition, and that strain-induced crystallization was much less temperature dependent than quiescent crystallization. The activation energy for strain-induced crystallization was found to be 0.035kcal/mole, which was considerably smaller than the reported activation energy for quiescent crystallization. Photomicrographs of the sheared specimens indicated that PEEK crystallites orient along the flow direction.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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