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  • 1985-1989  (975)
  • 1920-1924
  • 1988  (975)
  • Chemical Engineering  (691)
  • Genetics  (147)
  • Physical Chemistry  (137)
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Cellular and molecular life sciences 44 (1988), S. 491-495 
    ISSN: 1420-9071
    Keywords: Genetics ; stress ; emotionality ; locus ceruleus ; Maudsley strains
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The Maudsley Reactive and Non-Reactive strains have been developed as a model for the study of individual variations in stress-reactivity, and many differences in biobehavioral systems have been found between them. This review discusses limitations of the ‘emotionality’ construct in accounting for differences between the Maudsley strains and offers an alternative, theoretical approach. Amaral and Sinnamon have proposed that the locus ceruleus (LC) plays a stress-attenuating role in mediating behavioral, physiological and neuroendocrine response to prepotent, emergency-provoking stimuli and, building upon this formulation, it is proposed that the LC has been an important focus for gene action in the Maudsley model. It is suggested that the LC of the Non-Reactive strain is more strongly activated by stressful stimuli than the LC of Reactive rats, and is the basis of many of the behavioral and physiological differences between them. Behavioral and biochemical evidence consistent with this proposition is reviewed. Identification of the LC as a target for gene-action in the Maudsley model has an important advantage. It substitutes variations at a specific anatomic location in the brain for a loosely defined construct like emotionality, and the hypothesis is amenable to empirical tests by a variety of experimental approaches.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1432-1440
    Keywords: Genetics ; Hepatitis-B virus ; Immunogenetics ; Vaccination
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The variation in immune responses to standard inoculation of the hepatitis-B virus vaccine suggest that host factors influence response in ways that are not presently understood. We studied 25 low/nonresponding health care workers (anti-HBs titer 〈50 IU/l) after the third inoculation of an experimental hepatitis-B vaccine to determine their immune status (through lymphocyte phenotypes) and HLA type. After application of a fourth inoculation, the seroconverting subjects showed only low anti-HBs levels; three male subjects remained anti-HBs negative. Twelve months after the fourth inoculation only 9 of 25 subjects (36%) maintained anti-HBs titer 〉10 IU/l. Almost all subjects had normal B-cell and CD-4 and CD-8 counts and ratios. Relative to other European populations HLA-A-10 (P〈0.05), B-12 (P〈0.025), CW-5 (P〈0.05), DR-3 (P〈0.025), and DR-5 (P〈0.025) were increased, whereas DR-2 (P〈0.05) was decreased. However, after correction of theP-values for the number of HLA antigens determined, these differences were no longer significant. Furthermore, these HLA types were not the same as those reported in other studies (except for DR-3). We suggest that larger sample sizes or even not yet available immunogenetic markers will be required to prove an “immunogenetic background” in low/nonresponders, if it exists.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 31 (1988), S. 407-414 
    ISSN: 1432-0428
    Keywords: Genetics ; Type 2 (non-insulin-dependent) diabetes ; linkage analysis ; restriction fragment length polymorphism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary In the last five years, genetic markers for a large number of diseases have been localised using linkage analysis of DNA polymorphisms in affected families. The site of the genetic defect or defects leading to Type 2 (non-insulin-dependent) diabetes mellitus, a common illness with a major genetic component, remains unknown. This is due, at least in part, to the lack of large well-defined Type 2 diabetic pedigrees suitable for linkage analysis. There are several features of the disease which make large pedigrees difficult to find. The late age of onset of most probands means that informative older generations are often dead, while there is difficulty in detecting disease in younger generations. The diagnostic criteria for diabetes are, as yet, dependent on an arbitrary cut-off along a continuum of plasma glucose. The high prevalence of the disease may also produce problems as, in any given family, diabetogenic genes may be contributed by more than one parent. Varieties of the disease with a well-defined inheritance, such as maturity onset diabetes of youth, are more suitable for linkage analysis but might be due to defects at a different gene locus. Despite these difficulties, once large well-defined pedigrees have been found, linkage analysis using both candidate genes and random highly polymorphic markers is the strategy most likely to find genetic markers for the disease.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1432-0428
    Keywords: Genetics ; Type 2 (non-insulin-dependent) diabetes ; insulin receptor ; linkage analysis ; maturity onset diabetes of the young
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary The possibility of linkage between the human insulin receptor gene locus and diabetes was examined in three Type 2 (non-insulin-dependent) diabetic families and one family with maturity onset diabetes of the young. Insulin receptor gene haplotypes were established using BglII, Rsal and Sstl restriction enzyme digests of genomic DNA from all available family members. The digested DNA was subjected to agarose gel electrophoresis, Southern blotted, and hybridised to 32P-labelled human insulin receptor gene cDNA. In the pedigree with maturity onset diabetes of the young, formal linkage analysis allowed exclusion of close linkage between the insulin receptor locus and diabetes (logarithm of the odds for linkage versus non-linkage was −5.35 at recombination fraction of 0.01). This confirms the absence of linkage between insulin receptor and diabetes which has been reported in two similar pedigrees. In the three Type 2 diabetic families there were a minimum of 4 recombinants between the insulin receptor locus and diabetes, which makes a direct role for insulin receptor defects unlikely. The importance of using realistic estimates of penetrance when performing linkage analysis in a disease with a late age of onset is emphasised. In contrast to the one previous linkage analysis study of the insulin receptor gene, no specific association of diabetes with the rare Sstl Sl(-) allele was observed in either the maturity onset diabetes of the young or the Type 2 diabetic families.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Pediatric nephrology 2 (1988), S. 239-243 
    ISSN: 1432-198X
    Keywords: Cockayne syndrome ; Renal histology ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Two siblings with typical features of the Cockayne syndrome were studied at autopsy. Many glomeruli revealed a paucity of capillary loops and had thickened capillary walls. Some glomeruli with advanced lesions showed collapse of the glomerular tufts or complete hyalinization. Atrophy of tubules and interstitial fibrosis were also observed. There were no significant arteriosclerotic changes in the vessels. Ultrastructural studies demonstrated thickened glomerular basement membranes with bends and folds. These histopathological findings are different to those previously reported with the exception of the 1966 report by Ohno and Hirooka.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    European journal of pediatrics 147 (1988), S. 550-552 
    ISSN: 1432-1076
    Keywords: Pterygium syndrome ; Congenital malformations ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract We present two brothers with Multiple Pterygium Syndrome type Escobar. Characteristic findings in this autosomal recessively inherited pterygium syndrome are, in addition to multiple pterygia, short stature, cleft palate, vertebral fusion defects and minor facial anomalies. The adult height in the two male siblings was below the third centile. Secondary sexual development and testicular size were normal, in contrast with the cryptorchidism and pubertal delay documented in most young patients.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Journal of neurology 235 (1988), S. 366-367 
    ISSN: 1432-1459
    Keywords: Gilles de la Tourette's syndrome ; Twin study ; Computed tomography ; Clinical neurophysiology ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A 19-year-old male twin pair were concordant for suffering from Gilles de la Tourette's syndrome in different forms and severity. CT revealed ventricular asymmetries of varying degree within the normal range and there were no neurophysiological abnormalities. The interrelationship of genetic and environmental factors in phenotyping the syndrome is discussed.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Psychopharmacology 95 (1988), S. 237-244 
    ISSN: 1432-2072
    Keywords: Morphine ; Etonitazene ; Genetics ; Mice ; Taste ; Saccharine ; Gender
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract C57BL/6J and DBA/2J mouse strains have been characterized as morphine preferrers and avoiders, respectively (Horowitz et al. 1977). Previously, sweetened morphine solutions were presented with a water alternative, primarily with male subjects. Because sweetness may affect the endogenous opioid system and rodents have shown strain and sex differences in taste preferences, this study looked for strain- and gender-related taste preferences that might have affected opiate consumption. Preference for sweetened and unsweetened morphine and etonitazene was compared across gender and strain. In all choice tests, the control was a similar tasting quinine sulphate solution. Under these conditions, C57BL/6J mice continued to show strong preference for morphine. However, DBA/2J mice drank approximately equal amounts of morphine and quinine solutions, rather than avoiding morphine as when water was the alternative. Both strains appeared surprisingly indifferent to the synthetic opioid etonitazene, compared because it is potent at concentrations having barely perceptible bitterness. This raises the possibility of unexpected differences in post-ingestional effects between morphine and etonitazene. Contrary to reports of gender differences in sweet preference in rats, none were found in either strain of mouse. Neither were there any significant sex differences in opiate preference in either strain. C57 mice preferred sweetness more than did DBA mice.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Psychopharmacology 94 (1988), S. 428-430 
    ISSN: 1432-2072
    Keywords: Lithium ; Clonidine ; alpha2-Adrenoceptor ; Locomotor activity ; Genetics ; Mice
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Four strains of mice (C57, BALB, DBA, C3H) were used to determine whether genetic factors influence the effects of lithium on hypoactivity induced by a low dose of the alpha2-adrenoceptor agonist clonidine (0.2 mg/kg). Lithium was administered in the diet for 3–4 weeks at a dosage that produced average serum lithium levels of 0.58–0.66 mmol/l. Locomotor activity was reduced by either clonidine or by lithium given alone. When combined, however, lithium attenuated the activity-suppressant effects of clonidine, and that action was influenced by genetic factors. The findings suggest that genetic differences in alpha2-adrenoceptors play a role in behavioural effects of lithium.
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 1432-2072
    Keywords: Selective breeding ; Mouse ; Ethanol-stimulated activity ; Genetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Abstract Low doses of ethanol (EtOH) stimulate activity in an open field in many strains of laboratory mice. We are selectively breeding two lines of mice to exhibit a large (FAST) response on this test, and two other lines to exhibit a small (SLOW) response (Crabbe et al. 1987). The lines initially diverged in response to EtOH, but despite continued selection pressure, the difference between each pair of FAST and SLOW lines has not increased over generations as much as expected. Our practice has been to test animals on the 1st day after saline injection, and repeat the test after EtOH injection 24 h later. Lister (1987) recently demonstrated that the order in which an animal was exposed to EtOH and saline influenced the magnitude of the response to EtOH, with animals tested initially after EtOH having greater stimulation. Middaugh et al. (1987) recently demonstrated that the magnitude of EtOH stimulation was greater under conditions of relatively bright light than under dim light. Using non-selected Swiss mice, the current experiments essentially confirmed Lister's findings. Using FAST and SLOW mice, the predictions of both groups were tested. Both hypotheses were confirmed. Additionally, these experiments demonstrated that the magnitude of the difference between FAST and SLOW mice was greater under bright light than under dim light. The line difference was also greater when tested in the EtOH-Saline order. In experiments with Swiss mice, the possible role of peritoneal irritation in the EtOH effect was eliminated, and the optimal dose and time for demonstrating the effect was determined. These experiments confirm the importance of lighting condition, order of testing, dose, and route of administration in eliciting EtOH-stimulated open field activity in mice. They demonstrate a genotype-environment interaction, since the magnitude of difference between genetically selected lines varied as a function of the testing parameters chosen. Finally, they indicate that the differences between FAST and SLOW lines in sensitivity to EtOH generalizes to several environmental conditions. We interpret this to mean that the various EtOH-induced activation traits represented by these different environmental and testing conditions are genetically correlated.
    Type of Medium: Electronic Resource
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  • 11
    Electronic Resource
    Electronic Resource
    Springer
    European archives of psychiatry and clinical neuroscience 237 (1988), S. 244-252 
    ISSN: 1433-8491
    Keywords: EEG ; Genetics ; MZ/DZ twins reared apart ; Within-pair similarity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary Within the broader context of our investigations into the heredity of the human EEG, we analysed the EEGs of 28 pairs of monozygotic and 21 pairs of dizygotic twins who were separated as infants and reared apart. The principal goal of this study was to determine the degree to which environmental factors possibly influence the development of a person's EEG. Monozygotic twins reared apart were, with respect to their EEGs, only slightly less similar to each other (if there is any difference at all) than the same person is to himself over time. For dizygotic twins reared apart, we verified the findings of our previous study, namely, that the average within-pair similarity of EEGs estimated from a sufficiently representative sample of fraternal twins was significantly higher than the average inter-individual similarity of EEGs obtained from unrelated persons. The results on both monozygotic and dizygotic twins, yielded conclusive proof that the individual EEG pattern is predominantly determined by hereditary factors.
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    Springer
    Journal of neurology 235 (1988), S. 422-424 
    ISSN: 1432-1459
    Keywords: Epidemiology ; Genetics ; Hereditary motor neuropathy ; Spinal muscular atrophy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Notes: Summary A 4-year-search for spinal muscular atrophies (hereditary motor neuropathies, HMN) in Benghazi, Libya, yielded a total of 24 patients, among whom 18 were index cases. This group comprised 6 acute infantile, 12 chronic childhood, and 3 each with adult-onset proximal, and distal forms of the disorder. Distal HMN constituted 12.5% of the total cases. The crude average annual incidence of acute infantile HMN was 0.3/100,000 total population and 1/12,500 births in Benghazi. The crude prevalence rates of chronic childhood, adult-onset proximal, and distal types of HMN were 2.3, 0.6, and 0.6/100,000 respectively. The segregation ratios, 0.26 for acute infantile HMN and 0.24 for chronic childhood HMN, suggested autosomal recessive inheritance. The consanguinity rates among parents of cases and the population did not differ significantly.
    Type of Medium: Electronic Resource
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  • 13
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and applied genetics 75 (1988), S. 889-901 
    ISSN: 1432-2242
    Keywords: Soybean ; Restriction fragment length polymorphism ; Genetics ; Allele ; Variation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Restriction Fragment Length Polymorphisms (RFLP) have been identified between widely distant cultivars (‘Minsoy’ and ‘Noir 1 ’) of soybean Glycine max (L.) Merrill. Using as probes randomly chosen clones of DNA, one in five probes revealed a polymorphism. More than half of these polymorphisms appear to result from rearrangements of the genomic DNA. Twenty seven markers were analyzed for linkage in F2 plants. Eleven of these markers were contained in four linkage groups. Five cultivars were compared in a search for new alleles. When RFLP markers corresponding to low copy DNA were used to analyze three other cultivars — ‘Sooty’, ‘Forrest’ and ‘Mandarin (Ottawa)’ — few new alleles were found. Using these probes, five different markers could be used to differentiate the five cultivars. Complex probes, which correspond to repeated DNA, revealed different polymorphisms in different cultivars and a single such probe could be used to distinguish the five cultivars from each other.
    Type of Medium: Electronic Resource
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  • 14
    ISSN: 1432-2242
    Keywords: Ornithine decarboxylase ; Chicken ; Muscle ; Genetics ; Growth differences
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Little is known about the biochemical correlates of selection for growth in farm or laboratory animals, or the identity of the gene products affected or produced by ‘trait-genes’. Modern broiler chickens have about 8-fold greater breast muscle mass than layer chickens at 7 weeks of age and over 2-fold greater breast muscle mass than their 1972 counterparts. This increase in muscle mass is associated with over 20-fold higher levels of ornithine decarboxylase (ODC) in broiler chickens at 1 week of age as compared with layer strain chickens; there is a comparable increase in a relaxed-selection strain of broilers. The increase in ODC levels is larger than the differences in muscle or body weight between broilers and layers at 7 weeks of age, occurs at an age when there is no difference in weights between the strains and precedes the major growth spurt. Increases in ODC levels and hence polyamine synthesis have been associated with, and usually precede, rapid growth and cell proliferation in a wide range of cell types and organisms in response to many different stimuli. Therefore, the correlation of ODC levels with genetic differences in muscle growth make it worth investigating the control of ODC gene expression in these strains.
    Type of Medium: Electronic Resource
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  • 15
    ISSN: 1432-2242
    Keywords: Taxonomy ; Germplasm identification ; Varietal identity ; Environmental interaction ; Genetics ; Multivariate analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Separations of kafirin and alcohol soluble glutelin proteins by reversed-phase high-performance liquid chromatography (RP-HPLC) from 7 inbreds and one hybrid of sorghum [Sorghum bicolor (L.) Moench] and one source of Johnsongrass [Sorghum halapense (L.) Pers.] were compared. Objectives were to assess the stability of protein profiles for seed sources produced at different locations and in different environments to examine the potential of RP-HPLC to provide genotypic profiles for sorghum. Analyses of variance data showed that levels of variation due to environments and locations were small; the majority of variation (93%) was among genotypes. Associations among inbreds revealed by multivariate and cluster analysis showed similarity with those that would be expected on the basis of pedigree. A chi-square analysis showed no deviation in the hybrid profile from the expected 2∶1 ratio of peaks from the female and male inbred parents, respectively. Improvements in the ability to correctly assign common peaks are necessary before associations among numerous sorghum genotypes can be reliably demonstrated by analysis of data from reversed-phase high-performance liquid chromatography (RP-HPLC).
    Type of Medium: Electronic Resource
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  • 16
    Electronic Resource
    Electronic Resource
    Springer
    Theoretical and applied genetics 76 (1988), S. 405-410 
    ISSN: 1432-2242
    Keywords: Zea mays ; Haploid induction ; Gynogenesis ; Genetics ; Inducer line
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The effect of genotype on maternal haploid plant production in maize was studied. The frequency of gynogenetic plants when “Stock 6” was used as pollinator varied according to the female parent genotype. No simple relation was observed between genotypic aptitudes for gynogenetic and androgenetic development, which occured after pollination of “W23” plant carrying the “indeterminate gametophyte” gene. Furthermore, the population NS, a favorably responsive genotype to anther culture, does not exhibit exceptional ability for in vivo gynogenesis. The effect of inbreeding and the influence of maternal haploid origin suggest that specific genes control maternal haploid initiation and development. However, gynogenetic development is not limited to a particular genotype. The frequency of maternal haploids may be increased by using specific pollen parents. Attempts were made to select for a high haploidyinducing trait and the present study reports the successful development of lines that can be utilized as pollen parents to induce haploids for experimental purposes and breeding programmes. When an inbred line “WS14”, derived from the cross W23 x Stock 6, was used as pollen parent, 2%–5% maternal haploids were obtained according to the female parent genotype. A high haploidy-inducing potential is a heritable trait and may be controlled by a limited number of genes. Genetic determination of the haploidy-inducing character was examined in relation to the efficiency of the selecting method and the mechanisms involved in the origin of maternal haploids.
    Type of Medium: Electronic Resource
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  • 17
    ISSN: 1617-4623
    Keywords: Nicotiana plumbaginifolia ; Nitrate reductase ; Genetics ; Molybdenum cofactor biosynthesis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary A total of 70 cnx mutants have been characterized from a collection of 211 nitrate reductase deficient (NR-) mutants isolated from mutagenized Nicotiana plumbaginifolia protoplast cultures after chlorate selection and regeneration into plants. They are presumed to be affected in the biosynthesis of the molybdenum cofactor since they are also deficient for xanthine dehydrogenase activity but contain NR apoenzyme. The remaining clones were classified as nia mutants. Sexual crosses performed between cnx mutants allowed them to be classified into six independent complementation groups. Mutants representative of these complementation groups were used for somatic hybridization experiments with the already characterized N. plumbaginifolia mutants NX1, NX24, NX23 and CNX103 belonging to the complementation groups cnxA, B, C and D respectively. On the basis of genetic analysis and somatic hybridization experiments, two new complementation groups, cnxE and F, not previously described in higher plants, were characterized. Unphysiologically high levels of molybdate can restore the NR activity of cnxA mutant seedlings in vivo, but cannot restore NR activity to any mutant from the other cnx complementation groups.
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  • 18
    ISSN: 0032-8332
    Keywords: Saimiri ; Human-type ABO blood groups ; Genetics ; Colony management
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The human-type ABO blood groups were determined for 94 families of the squirrel monkey which included 151 animals. Four phenotypes of ABO blood groups (A, B, AB, and O) were detected. Family analysis revealed that the human-type ABO blood groups in this species were governed by three alleles, codominantA andB and silentO. There were intraspecific differences in the distribution of phenotypes and gene frequency among three populations imported by different routes at different times. The usefulness of ABO blood groups for defining the genetic variability of a squirrel monkey breeding colony through successive generations is discussed on the basis of the difference in distribution of ABO blood groups between wild-originated parental and its first colony-born populations.
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  • 19
    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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  • 20
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    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    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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  • 21
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 605-609 
    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 static delamination behavior of graphite/epoxy composite specimens subjected to mode I tensile opening (using UDCBUniform double cantilever beam. specimens), and pure mode II shear loading (using ENFEnd-notched flexural. specimens) were studied. The graphite epoxy composites for the study were made from commercially treated fibers, with and without an electropolymerized interlayer. The mode I fracture energy (GIC) was found to be significantly higher (more than 50 percent) for the coated fibers. However, this improvement was accompanied by a high reduction (more than 3 times) in the mode II fracture energy (GIIC). This effect is apparently related to poor adhesion between the interlayer and the epoxy resin, which may be corrected by use of a “top layer” of appropriate composition to form chemical bonds between the phases. The fracture toughness (KIC) of composites made with commercially treated fibers was also evaluated, using double side-notched specimens.
    Additional Material: 6 Ill.
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  • 22
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 583-591 
    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 analytical methodology was developed capable of describing interrelations between thermal processing and polymer structure for thermoplastic based composite laminates. Specifically, this modeling methodology was used to describe experimental results generated with a specially designed match die quench mold by processing both neat PEEK polymer and carbon fiber reinforced laminate samples at different cooling rates. The developed model accurately predicted temperature profiles for PEEK laminates of different thicknesses, under normal as well as extreme quenching conditions of 114°C/s. surface cooling rates that are possible to generate with the quench mold. In general, the modeling methodology is capable of predicting a part's thermal profile during processing in terms of the composite's microscopic intrinsic properties (fiber and matrix), composition, and lamina orientation. Furthermore, by coupling to the thermal profile description, a previously developed crystallization kinetics model for PEEK polymer and its carbon reinforced composite, a quantitative description of structural development during processing was obtained. Thus, with this analytical methodology, a skin-core crystallinity profile, where the crystallinity varies with part-thickness as a result of uneven cooling experienced during processing, was predicted both for the neat PEEK polymer and its carbon reinforced laminate forms. Finally, the developed methodology clearly established the interplay of both microscopic heat transfer and kinetics of crystallization/solidification of the matrix that must be accounted for in predicting the final structure of a carbon fiber reinforced laminate that will, in turn, govern microscopic and macroscopic performance.
    Additional Material: 7 Ill.
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  • 23
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 634-639 
    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: Neat poly(ether-ether-ketone) (PEEK) and carbon fiber reinforced PEEK (APC-2) specimens were prepared using a variety of cooling rates to achieve a range of crystallinities. Amorphous specimens were exposed to a variety of fluids to determine the penetrant types which are able to strongly influence the material. This allowed the estimation of the solubility parameter and hydrogen bonding index for PEEK to be 9.5 and 3.1, respectively. Methylene chloride was used to investigate the kinetics of penetrant sorption. The data demonstrated Case II behavior, with the initial crystallinity having a pronounced effect on both the kinetic and equilibrium data. Accordingly, a model was proposed capable of describing the sorption level and penetration depth as a function of time given the sample crystallinity and sorption temperature. With Case II behavior there was no difference in the sorption kinetics of neat and fiber reinforced PEEK. Finally, the dynamic mechanical properties measured during sorption were found to be dependent on the sorption process.
    Additional Material: 8 Ill.
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  • 24
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    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 670-678 
    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 dynamic shear viscosity and the morphology of polypropylene homopolymer and copolymer blended with linear low density polyethylene are studied. A maximum in the dynamic shear viscosity vs. blend composition is reported for the polypropylene copolymer, linear low density polyethylene system. The increasing dynamic shear viscosity is in accordance with the occurrence of a morphology of polyethylene inclusions in rubber surrounded by a polypropylene matrix. Comparing calculations of the dynamic shear viscosities - based on a shell model with interlayer - and experimental results supports this view.
    Additional Material: 17 Ill.
    Type of Medium: Electronic Resource
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  • 25
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 684-687 
    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: Hydroxy-terminated copoly(fstyrene-b-1,2-butadiene) (HPSB) containing rubber-affinitive vinyl side chains and having a molecular weight of 2000 to 4000 were prepared, and block copolyurethanes were synthesized by using a low molecular weight hydroxy-terminated poly (ethyl en e terephthalate) as a PET-affinitive component and 4,4′-diphenylmethane diisocyanate as a chain extender. The relationships between the molecular weight of HPSB, copolymerization ratio of styrene to butadiene and the adhesive strength of PKT/rubber in high temperature atmospheres were examined. A peak of adhesive strength was observed at styrene copolymerization ratio of 20 wt percent and a HPSB molecular weight of 3000. The adhesion mechanism was estimated from the behavior of the characteristic infrared absorption of block Copolyurethane in heating.
    Additional Material: 2 Ill.
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  • 26
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 718-727 
    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 vibration welding of thermoplastics, frictional work done by vibrating two parts under pressure, along their common interface, is used to generate heat to effect a weld. The main process parameters in vibration welding are the weld frequency, the amplitude of the vibratory motion, the weld pressure, and the weld time. How these parameters affect weld quality, the conditions that result in the best welds, the weldability of dissimilar plastics, and the effect of fillers such as glass are of interest. To address these issues, a research vibration welding machine in which all the parameters can be independently and accurately controlled and monitored was designed and fabricated. The phenomenology of welding, as determined by experiments on the four thermoplastics polycarbonate, poly (butylene terephthalate), polyetherimide, and modified poly (phenylene oxide), is described.
    Additional Material: 19 Ill.
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  • 27
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 743-757 
    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 engineering analysis of the reactive extrusion process of a thermoplastic polyurethane was made through numerical simulation and actual experiment. The reactants used in this system were 4,4′diphenylmethane diisocyanate, polycaprolactone diol (M.W., 824), and 1,4-bu-tanediol with equivalent weight ratio of 2:1:1. As a catalyst, dibutyltin dilaurate was used. The reaction kinetics and the viscosity function were obtained through experiments, and the mathematical model which includes the conservation equations of mass, momentum, energy, and chemical species was solved numerically to obtain the velocity, concentration, temperature, viscosity, and pressure profiles. The actual experiments were performed in the laboratory scale extruder to compare the experimental results with those of the numerical simulation.
    Additional Material: 30 Ill.
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  • 28
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 775-784 
    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 polyurethane-urea/polyvinyl simultaneous interpenetrating polymer networks (SINs) were prepared starting from a mixture of isocyanate prepolymer blocked with N-(1-1′-dimethyl-3-cxobutyl) acrylamide oxime, chain extender, vinyl monomers, and catalysts. Their physical properties and morphology were investigated using differential scanning calorimetry, dynamic mechanical measurements, and small-angle X-ray scattering. The polyurethane-urea networks examined were two-phase in nature. The vinyl network was formed with diacetone acrylamide oxime, trimethylolpropane trimethacrylate, and N-vinyl-pyrrolidone. Calorimetric analyses revealed that the polyether soft segment phase separated within the SINs. At higher temperature, dynamic mechanical measurements demonstrated the presence of only one glass transition temperature (Tg) intermediate in temperature to the Tg of the vinyl network and the Tg of the urethane hard phase. This is indicative of chain entanglement (interpenetration) between the vinyl network and the polyurethane hard segments resulting in a two-phase morphology. Small-angle X-ray scattering analyses provided measurements of diffuse phase boundary thickness, phase mixing, and domain size distribution. Appreciable interfacial thickness was not observed and thus phase mixing occurred within the phases. Domain size distribution indicated that high network constraints hindered the development of domains and limited the phase segregation.
    Additional Material: 10 Ill.
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  • 29
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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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  • 30
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 1152-1155 
    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: Effects of absorbed moisture on degradation behavior of high nitrile barrier polymers were monitored using thermogravimetric analysis techniques. Non-modified and 10 percent rubber modified samples were heated isothermally at nitrile processing temperatures (200°C to 240°C) in air and nitrogen environments. Degradation was evaluated in terms of weight loss as a function of heating time and sample coloration. It was determined that complete removal of moisture, as well as high moisture concentration, contribute to increased degradation at the temperatures evaluated. Moisture levels in the range of 0.15 to 0.5 percent were found to minimize degradation. Heating environment, time, temperature, and rubber modification were also found to influence thermal stability.
    Additional Material: 7 Ill.
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  • 31
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 1167-1172 
    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: High density polyethylene has been chlorinated by three different methods: in suspension and in solutions of two different solvents. Carbon-13 NMR and infrared analysis show that chlorination in chlorobenzene solution leads to statistically random distribution while chlorination in suspension gives highly blocky substitution. An intermediate distribution was obtained by chlorination in tetrachloroethane solution.
    Additional Material: 4 Ill.
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  • 32
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 1198-1202 
    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 energy stored in polystyrene after plastic deformation is measured by the differential scanning calorimetry (DSC) technique. Similar to metals, the stored energy increases with plastic straining, first rapidly, and then more slowly, and finally the stored energy seems to approach a saturation value (about 1 cal/gram). By comparing to the plastic work done, the fraction stored ranges from 30 percent after 10 percent compression to 10 percent after 60 percent compression. The fraction is about twice as large as that of copper. The release of stored energy has two distinct parts, one below Tg and the other above Tg. Most of the strain recovery seems to accompany the second part. By using the Kissinger plot, the second part has an activation energy, of 142 kcal/mole which is about 10 percent larger than that of compressive strain recovery.
    Additional Material: 6 Ill.
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  • 33
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 1219-1226 
    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 trial and error approach reflects the state of the art in reaction injection molding. Material and process parameters determine the “moldability” of a specific system in a particular application. The concept of “molding areas” on the critical parameters plane can be extended form thermoplastic injection molding (TIM) to reaction injection molding (RIM).In this work moldability diagrams for the filling and curing stages of a RIM process are obtained based on a simplified engineering approach. The key process parameters chosen for the filling stage are initial material temperature and filling time. In the curing stage, the critical parameters are considered to be mold wall temperature and demold time. Experimental results obtained on a laboratory-scale RIM machine on a Crosslinking polyurethane system are used to check the validity of the predicted molding areas. The agreement obtained is satisfactory considering the broad range of processing parameters used.
    Additional Material: 5 Ill.
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  • 34
    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 microstructure of injection molded bars (2.9 and 5.8 mm thick) of thermotropic liquid crystalline poly(p-hydroxy-benzoic acid-co-ethylene terephthalate) has been studied by SEM on samples etched with n-propylamine, SEM fractography, DSC, IR, ESCA, WAXS and polarized microscopy. The 2.9 mm bar consists of three different layers: a highly oriented surface skin, an oriented intermediate layer and a non-oriented core. The 5.8 mm bar has a more complex microstructure and is composed of five different layers: a highly oriented surface skin, an oriented layer just beneath, a non-oriented layer, another oriented layer and a non-oriented core. The thicknesses of the different layers vary, significantly, with distance from the mold gate. The thickness of the core increases, significantly, with increasing distance from the mold gate at the expense of the oriented layers. The structure within the different morphological layers is not perfectly uniform. Tensile testing demonstrated the mechanical anisotropy of the surface material (a ratio of almost 20 between the longitudinal and transverse moduli) and the isotropy of the central core material.
    Additional Material: 15 Ill.
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  • 35
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 1264-1269 
    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: Rolling-drawing is a simple, effective, solid state processing technique for manufacturing high strength and high modulus oriented polymer sheet products. The process is capable of increasing the tensile modulus and strength of polypropylene by more, than an order of magnitude with inexpensive equipment and straight forward controllable techniques. This paper gives an overview of the rolling-drawing of polypropylene. It is intended to answer the following questions. What is rolling-drawing? What changes in tensile properties can be expected as a result of this process? What deformation processes occur during rolling-drawing? What are the processing variables and how do these variables relate to the deformation ratio achieved by rolling-drawing? A tensile flow stress relationship was formulated from experimental data for oriented polypropylene. This constitutive equation, estimates the flow stress (or yield stress) of the polymer as a function of deformation ratio, strain rate and temperature. Since stretching was found to provide a significant portion of the deformation during the rolling-drawing process a Hoffman-Sachs computer analysis was written to predict plastic deformation and drawing forces in the stretch zone. The results of experimentation and the analysis are briefly compared in this paper.
    Additional Material: 8 Ill.
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  • 36
    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 extrusion-grade of high density polyethylene (HOPE) (3 ethyl groups per 1000 carbons) has been divided into 16 fractions by preparative GPC and selective p-xylene extraction. The fractions, with molecular weights ranging from 900 to 1,000,000, have been studied by IR spectros-copy, DSC, WAXS, polarized microscopy, and small-angle light scattering (SALS), The average degree of chain branching (percent C2H5) is 0.5 percent for the part of the sample having a molecular weight lower than 10,000 and it decreases monotonically with increasing molecular weight, finally approaching 0.1 percent C2H5. A crystallinity depression with respect to linear PE equivalent to 20 percent/(percent C2H5) is recorded for all samples except for the very low molecular weight samples for which the crystallinity depression is much larger (30 to 35 percent/ (percent C2H5)). The unit cell volume increases with increasing percent C2H5, presumably due to the inclusion of ethyl groups in the crystals as interstitlals at 2gl kinks. The concentration of ethyl groups in the crystals (∊c) unanimously follows the relationship: ∊c(percent) = 0.32 + 0.25 log(percent C2H5) except for the low molecular weight fractions which have significantly lower values for ∊c. Our admittedly speculative explanation for this major discrepancy between high and low molecular weight samples is based on the idea that segments with ethyl groups close to chain ends have a greater difficulty in crystallizing than segments containing ethyl groups located at positions far from the chain ends. The fractions obtained from the extrusion-grade HDPE show a solidification temperature depression with respect to linear PE which can only be explained by the presence of chain branches in these samples. The depression is particularly pronounced for the low molecular weight samples as is expected from the data on molecular structure. Well-developed non-banded spherulites are observed in rapidly cooled (crystallized at about 35 K supercooling), low molecular weight samples (6,000 〈 Mw 〈 8,000)from the extrusion-grade HDPE in contrast to the axialites observed in linear PE of the same molecular weight and thermal treatment. This discrepancy in morphology has been related to the presence of ethyl groups in the extrusion grade HDPE fractions. Higher molecular weight samples (20,000 〈 Mw 〈 1,000,000)from the extrusion-grade HDPE and linear PE both display well-developed banded spherulites of similar nature as is expected due to the similarity in molecular structure of the two sets of sample.
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  • 37
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 1066-1070 
    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 this work, a concept of distributed damage, including its inception and propagation, was applied to creep induced buckling of specimens prepared from high density polyethylene (HDPE). Using a kinetic relationship for damage accumulation, an integral equation for the front of the damage zone was derived. A time parameter associated with the inception of the damage front was obtained. The motion of the front was approximated for small times. Long time estimation was obtained using an assumption for a shape of the damage distribution. These results enabled us to review reported experimental results on creep induced buckling using a new insight into the relationship between applied load and time to buckle.
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  • 38
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 1095-1106 
    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: We present a basic study of the thermal, dielectric, Theological, and mechanical properties of hydroxybenzoic acid-ethylene terephthalate copolymers (PHB-PET). It is argued that they have two-phase structures, one rich in ethylene terephthalate (PET) and one rich in hydroxybenzoic acid (PHB). Polystyrene (PS) is immiscible in 60% PHB-PET (60-PHB-PET) blends. Polycarbonate (PC) is partially miscible with the high PET phase of 60-PHB-PET. PET seems completely miscible with this high PET phase. Shear viscosity measurements on blends indicate that 60-PHB-PET gives rise to large reductions of viscosity. Extrudates and melt-spun fibers have been prepared. The phase morphologies of low PHB-PET blends as determined by scanning electron microscopy indicate ellipsoids or long fibrils of the, 60-PHB-PET in PS or PC matrices. High extrusion rates and melt spinning produce fibrillar structures. The mechanical properties of films, extrudates, and melt-spun fibers were studied. Blends with 10% 60-PHB-PET exhibited significant increases in Young's modulus and tensile strength.
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  • 39
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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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  • 40
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 1145-1151 
    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 the activated anionic polymerization of caprolactam to nylon-6 and its copolymers has been studied. Nylon-6 block copolymer and nylon-6 were prepared at various initial reaction temperatures (140°C to 165°C) by anionic polymerization in an adiabatic dewar flask. Different concentrations of poly(ethylene oxide) (PEO) in 4,4′-diphenyl methane diisocyanate (MDI)-capped PEO and 1 mole percent MDI, in a caprolactam solution, were used as the activators with the catalyst, the sodium salt of caprolactam. The kinetics of the reaction were analyzed from an adiabatic temperature rise. A new method was applied to determine the rate parameters. The activation energy, Ea, of nylon-6 and nylon-6 block copolymers were found to be 22 kcal/mole. The collision frequency factor, Ao, steadily decreased and the autocatalytic constant, Bo, decreased to a constant value of 16 with the introduction of PEO. However, it was found that the order of reaction, n, was almost a constant value at the second order for all experiments.
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  • 41
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 1173-1181 
    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: Chlorination of high density; polyethylene results in polymers which consist of unmodified methylene units and chlorinated methylene co-units. The effect of the concentration and distribution of chlorinated units on the solid state structure has been examined by thermal, wide angle X-ray diffraction and dynamic mechanical analysis. As the substitution becomes more random, the crystallinity, crystallite size, and crystalline perfection decrease for a given chlorine content. The chlorinated units are shown to be capable of co-crystallizing, and the concentration of chlorine in the crystalline phase increases as the distribution is made more random. Concurrently, the chlorine concentration of the amorphous phase decreases. Segregation of chlorine into the amorphous regions is most efficient when the substitution is blocky.
    Additional Material: 13 Ill.
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  • 42
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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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  • 43
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 1240-1247 
    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 reversible step growth polymerization in homogeneous continuous flow stirred tank reactors (HCSTRs), in which the condensation product (W) leaves the reactor through flashing, has been analyzed. The molecular weight distribution (MWD) of the polymer formed is governed by nonlinear coupled algebraic relations to be solved simultaneously. To find the MWD numerically a large number of these are normally solved simultaneously using a suitable iterative procedure. In this paper, these have been decoupled using the technique proposed in our earlier works (1, 2) and the MWD can now be obtained sequentially without any trial and error. This leads to considerable saving in computation time compared to methods currently used. To demonstrate the efficacy of the algorithm, the polycondensation step of the poly(ethylene terephthal-ate) (PET) formed in HCSTRs has been analyzed. The MWD, the average chain length and the polydispersity index of the polymer have been computed and it takes 0.1 CPU seconds on a DEC 1090 as opposed to the earlier method which would take seventy minutes for similar computations. The simple model of the HCSTR for the PET formation gives the effect of reactor temperature and pressure and the quantitative results have been presented in this paper.
    Additional Material: 6 Ill.
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  • 44
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 1270-1274 
    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 presented which describes the degree of cure in a thermosetting adhesive used to bond sheet molding compound (SMC) components. The model allows computer aided optimization of the thermosetting process for any type of electromagnetic heating of the various layers of the structure (e.g. dielectric, microwave or induction), arbitrary material properties and arbitrary layer thickness. Computer simulated results are given for the particular case when the cure of the thermosetting material is initiated by its exposure to a high-power radio-frequency electric field (dielectric heating). These results indicate a strong sensitivity of the process to the thickness of the adhesive layer and the degree of coupling with the electromagnetic field. The analysis demonstrates that substantial heat losses from the relatively thin adhesive layer to the structural members of the joint by diffusive heat flow can be counterbalanced by additional electric power dissipated either in the adhesive or the structural members of the joint. Although derived for dielectric heating, those results are general, being independent of the type of electromagnetic heating employed.
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  • 45
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 1275-1275 
    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: Linearly tapered coat hanger dies or T-dies are widely accepted. Nevertheless a newly proposed curvilinearly tapered coat hanger die has been shown to perform much better. It costs about the same as the other types of dies. This contribution is considered in terms of the recent literature.
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  • 46
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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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  • 47
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 1304-1312 
    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: We have determined the degree of stiffness of a poly(γ-benzyl α, L-glutamate) (PBLG) chain in benzyl alcohol by measuring the intrinsic viscosities of dilute Solutions with differing molecular weights. Viscoelastic properties in oscillatory shear flow have been studied and the dependence of the loss and storage moduli on temperature, composition, and frequency are reported. We have also studied the transient shear stress relaxation behavior of the PBLG gel at different temperatures and concentrations. A comparison has been made between these gels and a classical poly(dimethyl siloxane) (PDMS) network, as well as, typical glassy polymers. Shear creep and recovery measurements have been made for this system. Some extensional step strain experiments using lubricated squeezing have been investigated. Tensile experiments have been made to determine stress-strain relationship during elongation. Preliminary experiments using the impulse approach to viscoelasticity further indicate the high elastic contribution in the gel.
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  • 48
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 1342-1342 
    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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  • 49
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 1347-1354 
    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: It is well known that equilibrium, thermodynamic properties are governed by different functional derivatives of the thermodynamic functions of state. For example, the phase behavior of mixtures of low and/or high molar mass components is determined by the compositional derivatives of the free energy. In this contribution, the merits of the Simha-Somcynsky theory in describing and predicting the phase behavior of mixtures are considered. The influence of temperature and composition on the miscibility behavior for practically binary polymer solutions are studied. Furthermore, the important aspect of polydispersity, inherent to synthetic polymer systems will be addressed.
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  • 50
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 1572-1577 
    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 effect of titanate, zirconate, and zircoaluminate coupling agents on the viscosity of zirconia-polypropylene injection molding blends was investigated. The zircoaluminate did not influence viscosity while the two former additives effected a considerable reduction. The titanate coupling agent also reduced the viscosity of the polymer in the absence of ceramic powder, and was more efficient in this respect, as a flow modifier than dioctyl phthalate. A comparable effect on the ceramic suspension was obtained by adding a species similar in molecular structure to the titanate coupling agent but without coupling ability.
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  • 51
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    Polymer Engineering and Science 28 (1988), S. 1581-1585 
    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 dielectric properties of thermoplastic and cross-linked polyethylene compounds with a low structure medium thermal carbon black are described in the frequency range between 30 and 8000 kHz as a function of frequency, temperature, and carbon black loading. Very high values of the dielectric constant were obtained for the conductive samples. The systems investigated are shown to follow percolative type models with experimental critical exponents in good agreement with the predicted values. The dielectric constant increases slowly with the carbon black concentration up to roughly the percolation concentration, then increases rapidly, and subsequently decreases at the higher black loadings. The dissipation factor-concentration curves show maximum values in the vicinity of the percolation concentration. The dielectric properties of these systems are discussed in terms of interfacial Maxwell-Wagner polarization effects.
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  • 52
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    Polymer Engineering and Science 28 (1988), S. 372-376 
    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 a method for analyzing the cure of multilayer circuit boards containing chemically reactive adhesive interlayers. The cure kinetics of the adhesive are first quantified by differential scanning calorimetry, using the method of Freeman and Carroll to obtain the numerical kinetic parameters. These parameters are then used in a finite-element model of the circuit board which solves the heat and species transfer equations simultaneously. It is then possible to predict the temperature and extent of reaction at any time and position within the laminate, enabling the curing program to be optimized.
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  • 53
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    Polymer Engineering and Science 28 (1988), S. 403-403 
    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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  • 54
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    Polymer Engineering and Science 28 (1988), S. 429-433 
    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 for estimating the polymer melt extrudate temperature fluctuation in the single screw extrusion process is proposed. Predictions of the melt temperature fluctuation is feasible if the extrusion process parameters are known. The method is superior to these in the literature because it incorporates effects of the melting process on the temperature fluctuation. The method has been verified experimentally.
    Additional Material: 5 Ill.
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  • 55
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    Polymer Engineering and Science 28 (1988), S. 453-459 
    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 investigation was undertaken to study the extrusion behavior of composite systems. A compound made up of approximately 50 percent ceramic particulates by volume dispersed in a high molecular weight thermoplastic polymer was characterized by measuring the shear viscosity on an Instron capillary viscometer. The experimental data indicated that the ceramic composite exhibited an apparent yield stress. As a result, an expression that was previously shown to provide flexibility for describing a yield stress at low rates of deformation could explain the viscosity of the ceramic composite. The expression was then applied to the flow analysis of both a “rod” and a “slit” die in an extrusion process, and the derived equations adequately correlated experimental volumetric flow rate us. Pressure drop data obtained on a laboratory extruder.
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  • 56
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    Polymer Engineering and Science 28 (1988), S. 485-490 
    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 model for the molding by reactive injection of reinforced plastics for systems in which fiber glass reinforcements are placed into the molds, is proposed. It allows for the determination of processing parameters and their influence on dependent variables: conversion, temperature, and pressure. Moldability areas, where premature gelling is avoided, are defined. Operating conditions are selected to reduce cycle time, produce small load losses, and provide a fairly uniform curing stage throughout the product.
    Additional Material: 9 Ill.
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  • 57
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    Polymer Engineering and Science 28 (1988), S. 510-516 
    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: For linear copolymer molecules, the refractive index increment depends on the chemical composition of the molecules. However, the polydispersity in chemical composition of the sample introduces a great complexity in the data analysis in order to obtain a true molecular weight distribution. Even when the mean chemical composition does not depend on the molecular weight, a correction has to be applied when the output of an instrument depends quadratically on the refractive index Increment of the sample, such as in a light-scattering measurement. For that purpose, the light-scattering expressions are written in terms of polydispersity in chemical composition, which in turn is modeled using linear copolymerization equations. The microstructure effects, which are related to the order in which two different kinds of monomers appear along the chain, are not as yet taken into account in this approach.
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  • 58
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    Polymer Engineering and Science 28 (1988), S. 506-509 
    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 this work, creep induced buckling was studied for a number of thermoplastic materials. The effect was observed by monitoring top displacements of thermoplastic bars as a function of time under static loading conditions. The recorded times to failure were averaged and correlated with the applied loads. The experiments, conducted for different materials, established an exponential dependence between the critical time and the load. The evolution of the buckling eigenvalues was modeled numerically. The simulations of eccentric columns behavior under compressive loads were coupled with the eigenvalue analyses. The correlation of the time-load predictions obtained from the numerical simulations followed the experimental results within acceptable limits. The observed phenomenon of creep induced buckling was explained by damage accumulation leading to an effective reduction of the load carrying capability.
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  • 59
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    Polymer Engineering and Science 28 (1988), S. 1042-1045 
    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: Over the last four decades, numerous reports have appeared on the physico-chemical kinetics, especially crystallization kinetics, based on the Avrami equation, φ = exp [-Ktn] where φ is the fraction of material unchanged at time t, K is an overall rate constant and “n” is the Avrami exponent indicative of process mechanism. The usage of the Avrami equation has been limited to the determination of “n” and its temperature dependence. It is shown that the evaluation of K and the activation energy (E) using this equation is erroneous since K and E are both influenced by “n” although such would be unexpected from the Avrami equation. On the other hand, if one uses a modified expression, φ = exp[-Kt]n, then in addition to the value of “n”, correct values of K and E are obtained. This retains the original correspondence of the Avrami equation to nuclea-tion and crystal growth processes but extends its applicability to (i) correctly evaluate K and E parameters, and (ii) correctly compare transformation rates when the systems differ in their n values. Experimental data are presented to support these conclusions.
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  • 60
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    Polymer Engineering and Science 28 (1988), S. 1071-1075 
    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: Thermosetting resin/glass cloth composites find extensive use in the packaging of electrical circuits into multi-layered circuit boards. To determine optimum processing conditions, it is necessary to understand the rheology of the resin as it cures. In this study, a squeezing flow geometry was used to determine the shear viscosity of a high performance epoxy resin during cure; Viscosity profiles were obtained during rising temperature cure. The results were compared with the complex viscosities obtained using the dynamic oscillatory parallel plate geometry. A numerical optimization algorithm was used to obtain the dual Arrhenius viscosity model parameters from the experimental viscosity data. The sensitivities of the model parameters and their effects on the predicted viscosity profiles were also determined.
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  • 61
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    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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  • 62
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    Polymer Engineering and Science 28 (1988), S. 1107-1114 
    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: Rheological and spiral mold flow measurements were made on blends of a chlorinated poly (vinyl chloride) (CPVC) compound and a thermotropic liquid crystalline copolyester of p-hydroxybenzoic acid/poly (ethylene terephthalate) (60/40), hereafter referred to as LCC, at 210°C. Several interesting flow phenomena have been observed. While the shape of the flow curve (i.e., G′ vs. ω; G″ vs. ω) of LCC is solidlike, those of the blends are pseudoplastic. The dynamic viscosity of the blends increases as the concentration of LCC increases. However, the shear viscosity of the blends is reduced with LCC and may be described using the relationship of additivity of fluidity. Although the melt elasticity of the blends is increased with the concentration of LCC, the extrudate swell of the blends after extrusion from a capillary is decreased. This phenomenon, however, is complicated. A Theological analysis based on an idealized runner system is used to describe the spiral flow length as a function of the Theological properties of the molten polymers and also the operating conditions. The relative improvement of the spiral flow length of the CPVC compound due to blending with LCC could be correlated with the power-law fluid model at high shear rates.
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  • 63
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    Polymer Engineering and Science 28 (1988), S. 1355-1361 
    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: Several authors have suggested a monotonic variation of the glass transition temperature (Tg) of miscible polymer blends as a function of composition. They usually express the results in terms of equations proposed by Couchman-Karasz, Gordon-Taylor, Fox, and several others. However, we have noticed that numerous systems exhibit a cusp when Tg is plotted as a function of composition (after correction for the presence of crystallinity when semi-crystalline polymers are involved). This cusp cannot appear when the Tg's of the two homopolymers involved are separated by less than about 52 degrees., It will be shown that this observation is quite general since it has been observed with several polyester/chlorinated polymer blends, polycaprolactone/nitrocellulose blends, and polystyrene/poly(vinylmethylether) blends; It will also be shown that this behavior is predicted in the framework of the free volume theory, with equations derived by Kovacs. According to this theory, above a critical concentration φc (relative to the plasticizer) and below a critical temperature Tc, the high-Tc, polymer no longer contributes to the free volume of the mixture whereas it does above Tc. This difference leads to a Tg-composition variation which has to be expressed by two different equations, one below Tc and the other above Tc, the cusp defining the limit of applicability of each equation.
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  • 64
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    Polymer Engineering and Science 28 (1988), S. 1401-1404 
    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: There is a reciprocal relation between flow and structure in multiphase systems such as polymer blends or composites. For this reason characterization of these materials must be carried out under conditions which guarantee minimum modification of structure. Capillary rheometry is particularly ill suited as a test tool, but the small strain dynamic oscillatory method may provide the true material responses, Most frequently these are expressed as frequency, ω, dependent storage and loss shear moduli, G′ and G″, or real and imaginary viscosities, η′ = G″/ω and η″ = G′/ω. However, two other methods of data presentation seem to be more sensitive to melt structure. They are the Cole-Cole plot of η″ vs. η′ and the relaxation spectrum. Frequently, both of them indicate a binomial response. Various mechanisms leading to such behavior will be discussed.
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  • 65
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    Polymer Engineering and Science 28 (1988), S. 1416-1426 
    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 morphology of compatibilized polyolef in/polyamide blends was found to be significantly dependent on the concentration of an ionomer compatibilizer (polyethylene-methacrylic acid-isobutyl acrylate terpolymer) in the blend. For a dispersed phase content of 10% by weight, a maximum reduction in phase size was observed when only 0.5% by weight of ionomer was added to the blend, A more significant reduction of the dispersed phase size was observed when the minor phase was nylon, due to interactions which exist between the ionomer and the polyamide. These interactions have been confirmed by Fourier transform infrared spectroscopy. At high concentrations of the ionomer, flocculation of the nylon dispersed phase was observed. In comparison to one-step mixing, blends prepared by two-step or batch mixing were characterized by a smaller dispersed phase when nylon was the matrix, and a larger particle size when nylon was the minor phase. The results observed are explained in terms of a speculative model of the interactions occurring across the nylon-polvolefin interface.
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  • 66
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    Polymer Engineering and Science 28 (1988), S. 1445-1449 
    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: It is shown that polyethylene and crossllnked polyethylene resins used for cable applications contain an antioxidant synergist in addition to an antioxidant. Their nature and content have been determined by a combination of ultraviolet and Fourier transform infrared spectroscopy and neutron activation analysis measurements. The results thus obtained suggest that part of the antioxidant compound is grafted to polymer chains during crosslinking.
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  • 67
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    Polymer Engineering and Science 28 (1988), S. 1455-1461 
    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 effect of Cryogenically Ground Rubber (CGR) from old tires on some mechanical properties of an unsaturated polyester resin is presented. A delay in the free radical cure reaction of the unsaturated polyester resin was observed upon the addition of ground rubber. This delay in the cure reaction could be overcome with the further addition of the free radical initiator. The particle size, surface chemistry, and the chemical composition of the rubber had an effect on the cure and on the final properties of the rubber-filled composites. It was also found that the rubber particles decreased the tensile, flexural, and storage shear modulus of the unsaturated polyester. Composites made from silane-treated ground rubber showed better mechanical properties than composites made from untreated CGR. Finally, the particle size of the ground rubber was apparently too large to produce a toughening effect on the filled materials.
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  • 68
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    Polymer Engineering and Science 28 (1988), S. 1517-1526 
    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: We describe the computer-aided engineering analysis of a linearly tapered coat-hanger die in this paper. The general governing equation for flow distribution inside the die was derived first. On the basis of this equation, we have developed the design formula for a die to deliver uniform flow. In addition, we have also examined the variations of lateral flow uniformities and residence time distributions of polymeric liquids under several different design and operating conditions: (1) using manifolds with non-circular cross-sections, (2) adjusting production widths, (3) delivering fluids with different viscosities, and (4) enlarging manifolds for practical production considerations.
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  • 69
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    Polymer Engineering and Science 28 (1988), S. 1559-1564 
    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 pressure drop/flow rate equation for non-Newtonian fluid flow in channels of irregular cross-section is determined theoretically by two numerical methods. Two representative non-Newtonian fluid models, the Ellis and the Herschel-Bulkley models, have been studied for several commonly encountered non-circular channels. The empirical methods proposed by Kozicki, et al, and Miller have been analyzed. The validity of their methods is discussed.
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  • 70
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    Polymer Engineering and Science 28 (1988), S. 1600-1606 
    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 observation of a novel phenomenon is reported whereby the processing history of a nylon 6 leads to a memory effect which in turn affects its crystallization rate from the molten state. Differential scanning calorimetry (DSC) and optical microscopy are the primary techniques used to demonstrate that the melt-crystallization behavior of nylon 6 can be controlled by processing variables. Characterization data is presented to show that obvious parameters such as molecular weight, impurities, monomer and oligomers, etc. are not responsible for the observed changes in crystallization behavior upon processing. It is shown that the mechanical properties and/or morphology of a nylon 6 article can depend upon the processing technique (e.g., compression or injection molding) as well as the processing history of the nylon 6 resin itself.
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  • 71
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    Polymer Engineering and Science 28 (1988), S. 1616-1627 
    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: Bubble nucleation in a mixture of volatile liquid and polymer melt under shear flow conditions was investigated, using a light scattering technique. In the study, a mixture of polystyrene and trichlorofluoromethane was extruded through a slit die having glass windows and bubble nucleation in the flow channel was observed optically. A He-Ne laser was used to illuminate the nucleating and growing bubbles. The light flux scattered by the growing bubbles at a fixed angle was detected by a photomultiplier with the aid of a high-voltage power supply. The bubble nucleating site in the flow channel was located using a computer controlled tracking system, which was designed to move the entire optical system automatically in the three dimensional space, and also had the ability to follow the software control command and cooperate with the data acquisition system. When the site of bubble nucleation was located, the coordinates of this site in the flow channel and the experimental conditions were automatically recorded on a floppy diskette by entering a software command. The pressure profile along the flow channel was measured by pressure transducers, with the aid of a microprocessor-based pressure reading system. It has been found that the site of bubble nucleation varies with the position in the direction perpendicular to the flow direction, which is attributed to the nonuniform velocity and stress distributions in the slit flow channel. The present investigation suggests that bubble nucleation can be induced either by flow and/or shear stress; specifically, flow-induced bubble nucleation is the dominant mechanism at positions near the center of the die opening, and shear-induced bubble nucleation is the dominant mechanism at positions near the die wall. It should be mentioned that the bubble near the die wall may also be generated by cavitation brought about by the surface roughness of the wall and also by thermal fluctuations due to the heat transfer between the metal (die wall) and the mixture of polymer and volatile component. The present study indicates that bubble nucleation in a shear flow field can occur at an unsaturated condition. This is in contrast to bubble nucleation under static conditions, where supersaturation is necessary.
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  • 72
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    Polymer Engineering and Science 28 (1988), S. 578-582 
    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 describes the utility of Torsion Impregnated Cloth Analysis, a very versatile technique to characterize resin behavior during cure or after repeated thermal and environmental treatment. Multi-frequency scan data have been shown to help tremendously in interpreting the behavior during experimentation. The technique is also very useful in defining the cure conditions for new resin chemistry/systems.
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  • 73
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    Polymer Engineering and Science 28 (1988), S. 568-577 
    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: Oxidized carbon fibers were coated using an on-line filament winding process with an elastomeric adduct crosslinkable and compatible with an epoxy matrix. The coating and modifications of the epoxy network were studied by dynamic mechanical measurements. Assuming that apparent activation energies of the secondary relaxation βe of the epoxy network and main relaxation αa of adduct are very different, it is possible at low frequencies to separate the two peaks. The composite material can be described as a three phase system: an epoxy network as matrix, carbon fibers, and a soft interlayer. The mechanical behavior of unidirectional composite materials studied by impact and bending tests is strongly dependent on the presence and the thickness of the coating at the carbon fiber surface.
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  • 74
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    Polymer Engineering and Science 28 (1988), S. 610-625 
    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 influence of the hard or soft inclusions and the mesophase layers in either a soft-hard-soft or hard-soft-hard combination of biphase plates submitted to dynamic tensile loads on the fracture mode and bifurcation process in both phases was investigated in this paper. It was assumed that the soft or hard matrix is infolding the hard or soft inclusion of the plate, so that the plate constitutes a meridional section of the representative volume element of a unidirectional fiber composite, or a principal section of a particulate. The influence of the mechanical properties of either phase on the crack propagation velocity and the initiation of crack bifurcation was studied by using high-speed photography and dynamic caustics. The results showed that the propagating crack tended to bifurcate either in the brittle or in the mesophase layer under certain conditions of propagation velocity. It was shown that bifurcation of a propagating crack depends on the elastic moduli and Poisson's ratios of the phases, as well as on the extent of the mesophase layer, which depended on the adhesion quality of phases.
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  • 75
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    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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  • 76
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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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  • 77
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    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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  • 78
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    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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  • 79
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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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  • 80
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    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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  • 81
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    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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  • 82
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    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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  • 83
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    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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  • 84
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    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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  • 85
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    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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  • 86
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    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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  • 87
    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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  • 88
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    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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  • 89
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    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.
    Additional Material: 1 Tab.
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  • 90
    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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  • 91
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    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.
    Additional Material: 1 Ill.
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  • 92
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    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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  • 93
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    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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  • 94
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    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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  • 95
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    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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  • 96
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    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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  • 97
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    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.
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  • 98
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    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.
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  • 99
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    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.
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  • 100
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    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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