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  • General Chemistry  (24,604)
  • Physics  (5,772)
  • Biochemistry and Biotechnology  (5,626)
  • Gas chromatography
  • Wiley-Blackwell  (36,316)
  • Springer  (276)
  • 2000-2004  (380)
  • 1995-1999  (11,029)
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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Entomologia experimentalis et applicata 34 (1983), S. 20-26 
    ISSN: 1570-7458
    Keywords: Dioryctria abietella ; Cone pyralid ; Lepidoptera ; Pyralidae ; Sex pheromone, (Z,E)-9,11-tetradecadienyl acetate ; Single sensillum recordings ; Electroantennography ; Gas chromatography ; Mass spectrometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Description / Table of Contents: Résumé L'analyse en chromatographie gazeuse associée à une détection électroantennographique a montré que l'acétate (Z,E)-9,11-tétradécadiényle (Z,E)-9,11–14:Ac est l'un des composants de la phéromone de Dioryctria abietella Schiff (Lepid.: Pyralidae). Couplage chromatographie en phase gazeuse spectrometrie de masse a montré la présence d'acétate tétradécadiényle avec un spectre de masse et un indice de rétention identiques au Z,E-9,11–14:Ac Un récepteur cellulaire sensible à la fois au Z,E-9,11–14:Ac et à un extrait de la femelle a été identifié sous l'antenne du mâle. Les analyses des antennogrammes et de la cellule isolée ont étayé la caractérisation du composant de la phéromone comme étant Z,E-9,11–14:Ac. Un récepteur cellulaire additionnel sensible à l'acétate (Z.)-9-tétradécadiényle et à l'acétate (Z.E.)-9,12-tétradécadiényle a été trouvé sur l'antenne du mâle, mais il n'était pas activé par l'extrait de la femelle. Sur le terrain Z,E-9,11–14:Ac, présenté seul, attirait des nombres importants de mâles de D. abietella. L'addition de l'acétate (Z)-9-tétradécényle a inhibé l'attraction des mâles par les pièges.
    Notes: Summary Gas chromatographic analyses coupled with electro-antennographic detection indicated that (Z,E)-9,11-tetradecadienyl acetate (Z,E-9, 11–14:Ac) is a pheromone component of the cone pyralid Dioryctria abietella. Gas chromatographic-mass spectrometric analyses confirmed the presence of a tetradecadienyl acetate with mass spectrum and retention index identical to Z,E-9,11–14:Ac. A receptor cell sensitive to both Z,E-9,11–14:Ac and the female extract was identified on the male antenna. An additional receptor cell sensitive to (Z)-9-tetradecenyl acetate and (Z,E)-9,12-tetradecadienyl acetate was found on the male antenna but was not activated by the female extract. In the field Z,E-9,11–14:Ac presented alone attracted significant numbers of male D. abietella. Addition of (Z)-9-tetradecenyl acetate inhibited the attraction of males to traps.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Journal of comparative physiology 179 (1996), S. 331-344 
    ISSN: 1432-1351
    Keywords: Hylobius abietis ; Olfaction ; Plant odours ; Receptor neuron responses ; Gas chromatography ; Electrophysiology
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract Receptor neuron responses to plant volatiles, trapped by head-space procedures, were examined in the pine weevil Hylobius abietis, using gas chromatography linked with electrophysiological recordings from single neurons. Seventy-two receptor neurons were tested 173 times for various plant volatile mixtures, either via a polar or a non-polar column. 1) All responses appeared as increased firing rates which followed the concentration profiles of the GC-eluted compounds. 2) The neurons were classified separately for the two column types in 17 and 19 groups respectively, according to the compounds they responded to. It suggests that the plant odour information is encoded by a large, but limited number of receptor neuron types. 3) Most neurons responded to a limited number of compounds (1–5) and showed a marked best response to one of them, whereas additional responses to several other components which seems to be structurally similar, was recorded for some neurons. It suggests that the plant odour receptor neurons are rather narrowly than broadly tuned, and that each neuron is specialized for receiving information about one or a few related compounds. 4) Most neurons responded to monoterpenes, whereas the other neurons responded to compounds of other categories. 5) Both major and minor plant volatile components activated specifically receptor neurons.
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  • 3
    Electronic Resource
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    Springer
    Journal of biomedical science 5 (1998), S. 415-420 
    ISSN: 1423-0127
    Keywords: Isoprostanes ; Oxidative stress ; Lipid peroxidation ; Gas chromatography ; Mass spectrometry ; Human disease
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract The development of a specific, reliable and noninvasive method for measuring oxidative stress in humans is essential for establishing the role of free radicals in human diseases. Currently, accurate techniques to assess oxidant injury in vivo are extremely limited although a number of approaches are being investigated. Of these, the measurement of specific products of nonenzymatic lipid peroxidation, the F2-isoprostanes (F2-IsoPs), appears to be a more accurate marker of oxidative stress in vivo in humans than other available methods. The purpose of this brief review is to acquaint the reader with the IsoPs from a biochemical perspective and to provide information regarding the utility of quantifying these compounds as indicators of oxidant stress.
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  • 4
    ISSN: 1432-072X
    Keywords: Key words Paracoccus denitrificans ; Paracoccus ; versutus ; CS2 oxidation ; CS2 oxygenase ; Autotrophy ; 16S rRNA phylogeny ; Plasmids ; Megaplasmids ; Murein ; Gas chromatography ; SDS-PAGE profiles
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Three distinct strains (KL1, KS1, and KS2) of facultatively chemolitho-autotrophic bacteria able to use carbon disulfide or carbonyl sulfide as sole energy substrates were identified as novel strains of Paracoccus denitrificans. Evidence for their identity as biovars of P. denitrificans and as close relatives of Paracoccus versutus is based on their DNA composition, total sequencing of the genes for their 16S rRNA, muropeptide profiles, amino acid composition of peptidoglycan, kinetics of murein degradation by lysozyme, possession of large plasmids (91–98 kb) and megaplasmids (〉 450 kb), and plasmid transfer between the strains and with P. denitrificans and P. versutus. No functions have been identified for the 91- to 98-kb plasmids of strains KL1 and KS2, but curing strain KL1 of its plasmid did not affect growth on carbon disulfide, thiosulfate or succinate. Emendation of the formal description of Paracoccus denitrificans is presented. Autotrophic growth on carbon disulfide and thiosulfate was confirmed by 14CO2 fixation. Evidence is presented for initiation of carbon disulfide oxidation by an NADH-dependent oxygenase. Cell-free extracts catalyzed (1) NADH-stimulated uptake of oxygen in the presence of carbon disulfide, and (2) carbon-disulfide-stimulated oxidation of NADH. The activity was not sedimented at 50,000 ×g. Intermediates in aerobic carbon disulfide metabolism were shown by GC and GC/MS to include carbonyl sulfide and hydrogen sulfide, but anaerobic production of COS and H2S from carbon disulfide did not occur. SDS-PAGE of cell-free extracts showed polypeptides that were unique to growth on carbon disulfide, common to carbon disulfide and carbonyl sulfide, or found after growth on carbon disulfide, carbonyl sulfide or thiosulfate. The possible identity of these as proteins involved in sulfur compound metabolism is discussed.
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  • 5
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    Springer
    Physics and chemistry of minerals 27 (2000), S. 665-678 
    ISSN: 1432-2021
    Keywords: Key words Amber ; Rumantite ; Succinite ; Pyrolysis ; Gas chromatography ; Mass spectrometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences , Physics
    Notes: Abstract  Romanian amber (rumanite) has been considered to be a separate species of fossil resin for more than a century. While earlier investigators held it to be very similar to succinite (Baltic amber), modern scholars have assigned it a distinctly different botanical origin. We have found that almost all of the constituents of the ether-soluble fractions of 13 specimens of authentic rumanite identified by gas chromatography–mass spectrometry have previously been reported in the soluble fraction of succinite, including succinic acid and its monoterpene esters. Additionally and significantly, the soluble fraction of rumanite contains a number defunctionalized compounds that do not preexist in succinite, but that are produced by pyrolysis of whole succinite or of its insoluble polymeric fraction. Simultaneous methylation pyrolysis–gas chromatography–mass spectrometry of the polymeric fraction of seven of the rumanite specimens yielded further copious amounts of dimethyl succinate, a number of diterpene resin acid methyl esters, and additional defunctionalized compounds known to be pyrolysis products of succinite. The evidence shows conclusively that the botanical origin of rumanite is not distinct from that of succinite. Rather, rumanite is a succinite that has suffered partial thermal degradation in the course of the folding of the Oligocene Kliwa sandstone formation in which it is most commonly found.
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  • 6
    ISSN: 1432-0878
    Keywords: Preputial glands ; Nude mice ; Ultrastructure ; Gas chromatography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The preputial glands of male nude (nu/nu) mice were analyzed by a combination of electron microscopy and gas chromatography to determine whether or not they are affected, like developing hairs and nails, by the nu/nu genotype. Results of the analyses revealed no differences between the glands of nude and normal male mice in either their ultrastructural characteristics or lipid secretory products.
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  • 7
    ISSN: 1432-0878
    Keywords: Adrenals ; Morphology ; Steroids ; Gas chromatography ; Mass spectrometry ; Clarias gariepinus (Teleostei)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract Interrenal-like tissue in male African catfish is localized in paired organs, situated retroperitoneally anterior of the kidney. Histological and enzyme-histochemical (3β-hydroxysteroid dehydrogenase) reactions were carried out on sections of these organs in order to localize steroid-producing cells. In vitro incubations were carried out to determine the steroidogenic capacity of the interrenal-like tissue. Twenty-one steroids could be identified and quantified in the incubation medium, by means of gas chromatography followed by mass spectrometry. Cortisol, 5α-and 5β-androstanedione and androstenedione together comprised about 80% of the total steroid content. In a previous study, twenty testicular steroids were detected in plasma after castration. In the present investigation we have shown that most of these steroids can be produced by the interrenal-like tissue, which thus can be considered as an extra-testicular source of gonadal steroids.
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  • 8
    ISSN: 1432-0878
    Keywords: Key words: Adrenals ; Morphology ; Steroids ; Gas chromatography ; Mass spectrometry ; Clarias gariepinus (Teleostei)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract. Interrenal-like tissue in male African catfish is localized in paired organs, situated retroperitoneally anterior of the kidney. Histological and enzyme-histochemical (3β-hydroxysteroid dehydrogenase) reactions were carried out on sections of these organs in order to localize steroid-producing cells. In vitro incubations were carried out to determine the steroidogenic capacity of the interrenal-like tissue. Twenty-one steroids could be identified and quantified in the incubation medium, by means of gas chromatography followed by mass spectrometry. Cortisol, 5α- and 5β-androstanedione and androstenedione together comprised about 80% of the total steroid content. In a previous study, twenty testicular steroids were detected in plasma after castration. In the present investigation we have shown that most of these steroids can be produced by the interrenal-like tissue, which thus can be considered as an extra-testicular source of gonadal steroids.
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  • 9
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    Springer
    Chromatographia 13 (1980), S. 203-206 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Carrier gas purity ; Sample stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The amount of oxygen which may be present in the gas volume corresponding to a peak is investigated and compared to the sample amounts. It is shown that even with high purity carrier gases one may have a significant excess of oxygen present at low sample amounts. Attention is drawn to the possibility of impurity build-up by diffusion e.g. through the septum.
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  • 10
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    Chromatographia 13 (1980), S. 263-270 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Metal complexes ; Enantiomers ; Isotopic composition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The high selectivity of complexation gas chromatography has been employed for enantiomer resolution and isotope separation. Thus, a chiral olefin, 3-methylcyclopentene, has been resolved analytically on optically active dicarbonyl-rhodium(I)-3-trifluoroacetyl-1R-camphorate in squalane. The deuterated ethylenes C2H4−nDn have been separated on the same rhodium(I)-containing stationary phase. The chiral aliphatic oxiranes epoxypropane andtrans-2,3-epoxybutane have been resolved on optically active nickel(II)-bis-3-trifluoroacetyl-1R-camphorate in squalane.
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  • 11
    ISSN: 1612-1112
    Keywords: Gas chromatography ; On-column abstraction ; Aliphatic aldehydes ; Amine antioxidants
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The selective on-column abstraction of aliphatic aldehydes by gas chromatographic stationary phases containing N-iso-propyl N′-phenyl-p-phenylenediamine is described.
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  • 12
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    Chromatographia 14 (1981), S. 19-22 
    ISSN: 1612-1112
    Keywords: Teflon columns ; Chemically modified teflon ; Gas chromatography ; Capillary columns
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Wall-coated open tubular columns prepared from chemically modified teflon tubing have been developed for gas chromatography. Chemical reaction of the inner walls of teflon tubing allows bonding of an adhesive layer on which a variety of stationary phaes can be coated. Test mixtures of alkanes and alcohols were used to investigate the chromatographic properties of these columns and the stability and mixing of the adhesive and stationary phae layers. the results in dicate that mixing of the layers is negligible and that the column is stable for a long period of time.
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  • 13
    ISSN: 1612-1112
    Keywords: Teflon capillary columns ; Chemically modified teflon ; Gas chromatography
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The preparation of teflon capillary columns employing direct coating of the stationary phase to the chemically modified teflon surface and the role of the chemically modified teflon in the separation mechanism are described. Two types of contributions from the modified teflon have been observed: nonspecific adsorption of the carbon surface and specific interactions of polar groups in the carbon skeleton. The use of polar liquid phases can eliminate adsorption due to the presence of polar groups in the modified teflon.
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  • 14
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    Chromatographia 14 (1981), S. 55-66 
    ISSN: 1612-1112
    Keywords: Capillary columns, glass ; Gas chromatography ; Column preparation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Kapillar-Gas-Chromatographie ist heute das sich am stärksten entwickelnde Gebiet der Gas-Chromatographie. Es gibt viele komplexe, neue Fragestellungen in der Analytik, welche den Einsatz spezieller Kapillarsäulen erfordem. Glücklicherweise gibt es aber auch eine große Zahl von Herstellungsverfahren für Kapillarsäulen, welche — noch mehr als bei der Herstellung von gepackten Säulen — eine Anpassung an die gestellten Aufgaben ermöglichen. In diesem Artikel werden die Herstellungsverfahren für Kapillarsäulen zusammengestellt und Anregungen gegeben, wie aufgaben-orientierte Säulen erreicht werden.
    Notes: Summary Glass capillary column chromatography is the most rapidly growing part of gas chromatography. There are many complex new analytical tasks and they require special capillary columns, Fortunately there is a wide range of column preparation methods available, and they make the preparation of glass capillary columns a more varied job than that of packed columns. In this paper these methods are reviewed and suggestions are given for making task-oriented columns.
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  • 15
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Urea herbicides ; Catalytic hydrolysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A method is described for the rapid catalytic hydrolysis of phenylurea herbicides on silica gel at elevated temperatures. After derivatisation of the anilines produced with heptafluorobutyric acid anhydride final analysis is done on a gas chromatograph equipped with an electroncapture detector. Detection limits are in the 1–5 picogram range. The method has successfully been applied to residue analysis of water samples at the 1 ppb level. The determination of free anilines present in water samples and the potential of various techniques to be used to discriminate between free anilines and parent herbicides are also discussed.
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  • 16
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Graphitised carbon black ; Phenols ; Water pllutants
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The fractionation of eleven phenols which may be contaminants in drinking water has been accomplished by using acid-washed graphitised carbon black modified with trimesic acid and PEG 20 M.
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  • 17
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    Chromatographia 14 (1981), S. 447-451 
    ISSN: 1612-1112
    Keywords: Headspace analysis ; Gas chromatography ; Residual analysis of polyethylene terephthalate ; Acetylene reduction assay ; Ethylene evolution in germinating seed ; Acetaldehyde generation in polyester resin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary New application areas for headspace gas chromatography in agricultural and polymer degradation research are described. Specific examples are drawn from the various forms of headspace analysis with emphasis on the automated static equilibrium method.
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  • 18
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    Chromatographia 13 (1980), S. 35-39 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Nitromethane ; Nitroalkanes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Impurities in commercially available nitromethane have been determined by gas-liquid chromatography using six different column packings. Besides nitromethane, 1-nitropropane, 2-nitropropane, acetonitrile, methanol, small amounts of ethanol and acetaldehyde have been detected. The presence of formaldehyde, ethyl acetate and acetone is probable. Mixtures containing comparable amounts of the four nitroalkanes could be separated on all columns, but plots of logarithms of the retention times vs. carbon number or boiling points of the nitroalkanes or column temperatures were linear only in case of columns packed with Porapak R and Q.
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  • 19
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    Chromatographia 16 (1982), S. 60-62 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Amines ; Derivatization ; Chloroformate esters
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The gas chromatographic analysis of amines after conversion to electron capture sensitive carbamates in two-phase systems has been studied. Hydrophilic compounds, for instance methylamine, are reacted with 2,2,2-trichloro-tert. butyl chloroformate. Quantitation below 10−7 M can be made by thermionic or electron capture detection. A hydrophobic amine, namely N,N-dimethyl-n-octylamine, was derivatized with 2,4,6-tribromophenyl chloroformate with addition of iodide ion to the aqueous phase. The favorable effect of iodide ion as well as the choice of pH and chloroformate ester is discussed.
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  • 20
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    Chromatographia 16 (1982), S. 98-102 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Rectangular channel ; Efficiency ; Capacity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Gas chromatographic experiments have been performed in a truly rectangular channel with a 60∶1 cross-sectional aspect ratio, constructed according to the field-flow fractionation technology. It is shown that the peak broadening is controlled by the thickness of the channel while the maximum load is determined by the largest cross-sectional dimension. However, even with its elongated configuration, the side walls contribute significantly to the band broadening of solutes with a high diffusivity. Good agreement is found between the experimental plate height data and the recent theoretical calculations of Golay [13] taking into account the side-wall effect.
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  • 21
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    Chromatographia 17 (1983), S. 269-284 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Liquid chromatography ; Phenols
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Gas and high-performance liquid chromatographic methods in the analysis of phenols are reviewed. Among the great number of phenolic compounds analyzed, alkylphenols, chlorophenols, dihydroxy- and trihydroxybenzenes and biphenols are chiefly considered. The advantages and drawbacks of the methods are discussed, quoting the most important work. Relationships between the structural characteristics of phenols, the stationary phase structure, the mobile phase composition and the retention data are treated. Typical examples of the conditions for GC and HPLC analysis are summarized in tables. The literature comprises over 270 references, most of them recent.
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  • 22
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Average molecular polarizability ; Retention index ; Polycyclic aromatic hydrocarbons
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The Kováts retention indices of 10 polycyclic aromatic hydrocarbons were determined on SE-30, OV-101, SE-52, OV-7 and OV-17 stationary phases. A significant correlation has been found between the retention indices and the average molecular polarizabilities of the analyzed substances. Equations were derived for the direct determination of the average molecular polarizabilities from the retention index values. The influence of the temperature on this relationship is also indicated.
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  • 23
    ISSN: 1612-1112
    Keywords: Esterification in aqueous solution ; iso butyl esters of C1–C20 fatty acids ; Gas chromatography ; Fatty acid analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary C1–C20 carboxylic acids have been esterified in aqueous solutions with i-butanol. Gas chromatographic analyses have been performed from a single chromatogram. It has been established that esterification in the concentration range of [H2O]/[i-BuOH]=0.01–10.3 can be utilized for the quantitative determination of these carboxylic acids. The presence of water does not interfere in the range of [H2O]/[i-BuOH]=0.01–1.03. In the cases of [H2O]/[i-BuOH]〉1.03, anhydrous sodium sulfate has been used for binding the water, in an amount of [Na2SO4]anh./[H2O]≥0.2.
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  • 24
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Esterification in aqueous solution ; n-Butyl esters of C2−C16 dicarboxylic acids ; Dicarboxylic acid analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary C2−C16 dicarboxylic acids were esterified in aqueous solution in the presence of sulfuric acid. Esterification in water/n-butanol mixtures with mole ratios between 0.02 and 2.53 can be utilized for the quantitative determination of the dicarboxylic acids by gas chromatography. The presence of water does not interfere at water/n-butanol mole ratios below 0.27. For mole ratios above 0.27 anhydrous sodium sulfate has been used for binding the water. The mole ratio range was 0.25–0.75 for anhydrous sodium sulfate/water, and 0.32–1.3 for sulfuric acid/anhydrous sodium sulfate.
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  • 25
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    Chromatographia 18 (1984), S. 663-667 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Gas solubilities ; Enthalpies of solution ; Polar solutions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The gas-liquid chromatographic method has been used to determine the solubilities and partial molar enthalpies of solution of the gases H2S, CO2 and COS in four polar solvents. The results agree well with literature values obtained using conventional techniques, with the one exception of H2S in N-methyl-2-pyrrolidinone. In this case there is some evidence for the occurrence of adsorption at the gas-liquid interface.
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  • 26
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Esterification in aqueous solution ; n-Butyl esters of aromatic polycarboxylic acids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The direct esterification and gas chromatographic analysis of aromatic carboxylic acids as n-butyl esters is described. Derivatization is performed in aqueous solution with n-butanol in the presence of sulfuric acid. The butyl esters of benzoic, phthalic, hemimellitic, trimellitic, trimesic and pyromellitic acids permit their gas chromatographic separation from each other and from fatty acids and alipatic dicarboxylic acids. At mole ratios of [H2O]/ [n-BuOH]≤0.04 the water present does not interfere with the esterification reaction. At mole ratios above 0.04 anhydrous sodium sulfate is used for binding the water, at mole ratios of [Na2SO4 anh.]/[H2O]=0.25–0.75.
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  • 27
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    Chromatographia 18 (1984), S. 202-204 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Polysiloxane stationary phases ; Heat of adsorption ; Heat of solution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The changes in the heat of solution of polar compounds and xylene isomers in methylsilicone fluid OV-101 deposited on Chromosorb W AW DMCS were studied. It was shown that the heat of solution increases with an increase of the percentage loading of the OV-101 up to 10%. Solution and adsorption thermodynamic characteristics of the studied system are briefly discussed.
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  • 28
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Metal complexes ; Chemically bonded phase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Packings consisting of diphenylphosphine complexes with CoCl2 and CoBr2, chemically bonded to the silica surface, were synthesized and their retention parameters determined. The packings are capable of specifically interacting with electron-donating compounds by forming π-complexes. The interaction is considerably stronger in the case of CoBr2-containing packing than in the case of CoCl2-containing packing.
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  • 29
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    Chromatographia 18 (1984), S. 234-238 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Open-tubular columns ; On-column injection ; Stopped-flow operation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A simple, inexpensive, on-column injector of the septum moving-needle kind is described for quantitative analysis using open-tubular columsn. when operated in the stopped-flow mode an improvement incolumn efficiency is observed combined wit a diminished tendency to produce split-top peaks, particularly for late eluting peaks. Using electronic integration a relative error of about 2.7% was observed for peaks spanning a wide range of sample concentrations and volatilities.
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  • 30
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    Chromatographia 18 (1984), S. 243-248 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Carrier gas ; Viscosity ; Influence of temperature
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The vicosity-temperature relationship of the three gases (helium, nitrogen and hydrogen) most frequenly used as the carrier gas in gas chromatography is studied. Based on available data, equaitions are derived to describe this relationship. Using these equations viscosity data are tabulated for the chromatographically important temperature range.
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  • 31
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    Chromatographia 18 (1984), S. 260-264 
    ISSN: 1612-1112
    Keywords: Parabens and their dissolution ; Pharmaceutical dosage forms ; Derivatization ; Gas chromatography
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    Topics: Chemistry and Pharmacology
    Notes: Summary A specific, sensitive and general applicabla gas chromatographic method is described for the determination of parabens in various liquid pharmaceutical preparations: propylparaben and butylparaben in a liquid antacid dosage form (I); methylparaben, ethylparaben and propylparaben in a syrup (II); methylparaben and propylparaben in a solution for injection (III). Each time one of the parabens is used as internal standard. The parabens are extracted with diethylether and derivatized by silylation. Different columns are used for the analysis of the parabens: 3% SE-30 column, a 3% QF-1 column for different selectivity, a 2% OV-1 column for isothermal operation. Special attention is attributed to the standard: the parabens are dissolved in a minimal amount of 0.1 M sodium hydroxide and extracted in the same way as the pharmaceutical dosage form.
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  • 32
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Configuration ; Resolution ; Alcohols
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The study of the resolution of sixteen secondary aliphatic alcohols by gas chromatography on (+)-dodecyl (2R, 3R)-tartrate, trapping the ascending part of the peak from a conventional filled column, has allowed the determination in a single operation of the sign and order of emergence of enantiomers. A correlation between the configuration of these secondary alcohols and their order of emergence has been established.
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  • 33
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    Chromatographia 18 (1984), S. 309-312 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Carboxylic acids ; Acetonyl derivatives
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The preparation of the acetonyl esters of nine aliphatic carboxylic acids is described, the general formula of the derivatives being RCOOCH2COCH3 where R=alkyl or H. The derivatives show good chromatographic properties on both packed and capillary columns. The electron impact and chemical ionisation mass spectra of the derivatives are discussed.
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  • 34
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Thermodynamic relationships ; Retention index ; Peak identification
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    Topics: Chemistry and Pharmacology
    Notes: Summary A thermodynamic criterion, ΔQ, is suggested which permits to estimate the difference in the functional group energy of interactions for two different stationary phases. The linear dependence of ΔQ on the homolog number m of any series Rm X can be used as the thermodynamic criterion for the identification of substances by GC analysis.
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  • 35
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    Chromatographia 18 (1984), S. 477-488 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Open tubular (capillary) columns ; Sample capacity ; Column comparison ; Film thickness ; Column diameter
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    Topics: Chemistry and Pharmacology
    Notes: Summary Wall-coated, open-tubular (capillary) columns prepared from different diameter tubing, with different liquid phase film thickness, are compared with each other and with packed and support-coated open-tubular columns. The comparison is based on the variation of the phase ratio and the capacity factor, and includes column efficiency (HETP, theoretical plate number), resolution, retention time, and sample capacity. Problems associated with the evaluation of the sample capacity are outlined. The influence of temperature on column performance is discussed in detail. Finally, the possibilities of short, wide-bore open-tubular columns prepared with a thick liquid-phase film are demonstrated.
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  • 36
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Retention-structure correlation ; Molecular descriptors ; Polycyclic aromatics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Statistical and factor analysis have been used to test the ability of several molecular descriptors to predict the retention indexes (I) of polycyclic aromatic hydrocarbons determined on SPB-5 and SPB-20 stationary phases. Regression analysis with both columns showed that linear regression with connectivity index and bending energy of the molecules as independent variables gave the best correlation coefficients. ΔI 20–5, considered to be a measure of the polar forces in retention, gave a good correlation with the van der Waals radii of the molecules, or strain, and bending energy.
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    Chromatographia 41 (1995), S. 15-22 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Average velocity of carrier gas ; Compressibility of carrier gas ; Pneumatic parameters of carrier gas
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary This report was conceived as a source for the relations between five pneumatic parameters of carrier gas-inlet and outlet pressure, inlet and outlet velocity, and average velocity. Any pair of these parameters can be independent while the remaining three can be expressed as functions of the independent pair. As the total number of the independent pairs is ten, thirty different functions describing relations between arbitrary independent pairs and dependent parameters can be identified. All thirty were derived below together with the complete set of bounds for variations of independent parameters. To derive some relations, a third order rational equation had to be solved. Some properties of that solution are discussed. A simple case of vacuum operations with zero outlet pressure has also been considered.
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    Chromatographia 41 (1995), S. 37-42 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Temperature programming ; Isothermal measurements ; Column efficiency ; Dead time
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    Topics: Chemistry and Pharmacology
    Notes: Summary If the dependence of HETP on temperature is specified under isothermal conditions, it is possible to predict the HETP for programmed temperature elution and subsequently peak width at half-height. This requires knowledge of isothermal retention time at retention temperature, which is computed by means of a model including the variation with temperature of dead time estimated from 3 homologs with carbon number: n, (n+j), (n+jk), where n, j and k are any integers. Predicted and measured peak widths corresponded within 4–9%.
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    Chromatographia 41 (1995), S. 678-684 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Solid phase micro extraction ; Graphitized carbon black ; Volatile organic compounds
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    Topics: Chemistry and Pharmacology
    Notes: Summary This paper presents the results obtained using fused-silica fibers coated with graphitized carbon black (Carbograph-Alltech) for solid-phase microextraction (SPME). The extraction and calibration curves relative to organic micro-pollutants present in gaseous and aqueous samples are reported. Examples of applications of this extraction procedure to GC and GC-MS analysis of organic micro-pollutants in actual samples are also reported.
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  • 40
    ISSN: 1612-1112
    Keywords: Gas chromatography ; New stationary phase ; Packed columns ; Specific retention volumes ; Activity coefficients
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    Topics: Chemistry and Pharmacology
    Notes: Summary The synthesis of 3-bromo-4-(4-methylbenzyloxy)azobenzene (BMBOA) and its use as a stationary phase in packed columns are described. Chromatographic characteristics such as column efficiency, polarity (McReynolds constants) and operating temperature range were studied. Retention factors, specific retention volumes and activity coefficients for alcohols, esters, ketones, aromatic hydrocarbons andn-alkanes were determined. Phenols and 2,3, and 4-chlorobenzyl chlorides were separated on the new phase. Based on experimental data some assumptions were made on the possible types of intermolecular forces between solute and solvent.
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  • 41
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Linear temperature programming ; Tekler-equation extension ; Retention index precalculation
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    Topics: Chemistry and Pharmacology
    Notes: Summary An extension of Rohrschneider's concept to the field of the linear temperature programmed gas liquid chromatography, is proposed, which is based on Antoine's equation for the temperature dependence of the reduction index of Takács et al. and Tekler. The new method presented in this paper, applied to retention data of two stationary phases of low polarity, PS-255 and OV-105, gives a new possibility of precalculating retention data.
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  • 42
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    Chromatographia 40 (1995), S. 550-556 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Open tubular columns ; Short chain fatty acids ; Intestinal fluids
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    Topics: Chemistry and Pharmacology
    Notes: Summary A capillary gas-liquid chromatography method for the analysis of free short chain fatty acids in intestinal samples was developed. Analytical results obtained with intestinal samples are influenced not only by high molecular mass matrix constituents but also by matrix components with a molecular weight smaller than 5000 daltons. To achieve a faithful transfer of SCFA into the chromatographic system it was important to avoid accumulation of involatile deposits on the surface of the inlet liner. Cleaning of the inlet linear lead to a significant weakening of matrix effects. The method described, using an Innowax column, is more effective, particularly with respect to precision and sensitivity, and is clearly superior to packed columns. The capillary is the column of choice for the separation of short fatty acids in samples from the small intestine and stomach.
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    Chromatographia 41 (1995), S. 726-727 
    ISSN: 1612-1112
    Keywords: Gas chromatography ; Retention indices ; Correlation equations ; n-Alkenes ; n-Alkynes
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    Topics: Chemistry and Pharmacology
    Notes: Summary The correlation equations between Kovats retention indices ofn-alkenes andn-alkynes, column temperature and number of carbon atoms in molecules of these compounds on OV-101, OV-225 and PEG 20M capillary columns have been calculated. The two variable equationI=A+B·n+C/T give a good fit and are the simplest for prctical use.
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  • 44
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    Plant systematics and evolution 194 (1995), S. 55-67 
    ISSN: 1615-6110
    Keywords: Onagraceae ; Clarkia ; Gas chromatography ; mass spectrometry ; monoterpenes ; benzyl esters ; floral fragrances ; intraspecific variation ; moth pollination
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Clarkia breweri (Onagraceae) is the only species known in its genus to produce strong floral fragrance and to be pollinated by moths. We used gas chromatography-mass spectrometry (GC-MS) to identify 12 abundant compounds in the floral headspace from two inbred lines ofC. breweri. These volatiles are derived from two biochemical pathways, one producing acyclic monoterpenes and their oxides, the other leading from phenylalanine to benzoate and its derivatives. Linalool and linalool oxide (pyran form) were the most abundant monoterpenoids, while linalool oxide (furan form) was present at lower concentrations. Of the aromatic compounds detected, benzyl acetate was most abundant, whereas benzyl benzoate, eugenol, methyl salicylate, and vanillin were present as minor constituents in all floral samples. The two inbredC. breweri lines differed for the presence of the additional benzenoid compounds isoeugenol, methyleugenol, methylisoeugenol, and veratraldehyde. We also analyzed floral headspace fromC. concinna, the likely progenitor ofC. breweri, whose flowers are odorless to the human nose. Ten volatiles (mostly terpenoids) were detected at low concentrations, but only when headspace was collected from 20 or more flowers at a time. Trans-β-ocimene was the most abundant floral compound identified from this species. Our data are consistent with the hypothesized recent evolution of floral scent production and moth pollination inC. breweri.
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  • 45
    ISSN: 0009-2940
    Keywords: Cross-coupling ; Grignard reactions ; Pyrrolidinephosphanes ; Asymmetric amplification ; Gas chromatography ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An investigation of the asymmetric synthesis of 3-phenyl-1-butene by the Grignard cross-coupling reaction is presented. The reaction is catalysed by nickel complexes of bisphosphane and 3-diphenylphosphanylpyrrolidine-type ligands. A comparison of the results obtained with our P,N monophosphane ligands with those obtained with the most effective known amino acid derived P,N ligands shows a similar enantioselectivity but an inverse sense of optical induction. An X-ray structural analysis of the 1-phenylethyl Grignard compound is reported. Quantitative analysis and the determination of enantiomeric composition of the catalytic samples is accomplished using a novel enantioselective GLC separation. Compared to the popular model reaction that uses a chloride-containing Grignard compound and vinyl bromide as starting compounds, we obtain improved enantioselectivities of P,N monophosphane catalysts by substituting vinyl bromide with vinyl chloride. With two of the new P,N ligands we find a nonlinear dependence of enantioselectivity on the enantiomeric purity of the ligands (asymmetric amplification). Catalytic results subject to such nonlinear effects show a dependence on the ligand to nickel ratio.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 19-34 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is demonstrated that dicarboxylic acids of uniform lengths, obtained by degrading chain-folded polyethylene single crystals, can be converted to paraffins via the intermediate diiodide by means of the procedure of Barton et al. Thus we are now in the position of obtaining uniform paraffins of chain lengths longer than hitherto available for the study of the crystallization of oligomeric chains. Measurements of melting points and heats of fusion revealed major differences between the paraffins and the corresponding parent dicarboxylic acids. It follows that such measurements on the unmodified products of the nitric acid degradation cannot be used directly for the assessment of the chain traverse length and the degree of crystallinity. It was found further, that the intermediate diiodide is a sufficiently close approximation to the paraffin for the purposes just quoted.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 89-103 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The theoretical justification for using M[η], or a similar quantity, as a universal calibration parameter in GPC is reviewed. The equation based on this parameter is applied to transform the primary calibration curve, obtained by means of polystyrene samples, into calibration curves for poly-α-methylstyrene, polypropylene, and linear polyethylene. The Mark-Houwink equations for these polymers, as they are used in the transformation, are discussed. The resulting GPC calibration curves are compared with molecular weights and peak elution volumes of fractionated poly-α-methylstyrene and polypropylene. The same comparison is made with samples of polypropylene and polyethylene having very broad molecular weight distributions. The agreement lies within experimental error.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 148-152 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 482-482 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 207-224 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: A discussion is given of the behavior of a mathematical model chosen to approximate conditions during precipitation chromatographic fractionation of polymer (Baker Williams fractionation). With only one molecular weight species of polymer a complete solution of the mathematical model was obtained. With more than one species it was necessary to use a computer solution. Curves showing the movement of polymer containing one and two species of polymer are given for a variety of conditions of operation. It was found that the degree of fractionation of polymer approaches a limiting value with increasing length of column. Under some conditions the degree of fractionation may go through a maximum with length of column. The equilibrating distance (distance of travel of the liquid phase required to establish equilibrium of polymer between the liquid and the bed) was found to be very important in determining the fractionation.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 277-287 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Studies have been made on the dynamic and steady-shear melt rheology of an ethylene-methacrylic acid copolymer and two of its salts obtained by partial neutralization with sodium and with calcium bases. Measurements were made with a Weissenberg rheogoniometer over a broad range of shear rates and frequency in the temperature interval mainly from 100 to 160°C. The temperature coefficients of dynamic and steady shear viscosity are evaluated at both constant shear rate and constant stress. Likewise, complex dynamic viscosities and apparent high steady-flow viscosities and intercompared at equivalent frequencies and shear rates. The un-ionized acid copolymer shows good correlation between the frequency dependence of the complex viscosity and the shear rate dependence of the apparent viscosity. This is not true for either the sodium salt or the calcium salt. These results are consistent with the two-phase structural model for these materials, i.e., a matrix of hydrocarbon in which are embedded ionic domains.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 305-310 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The enchanced low-shear melt viscosity of branched polybutadienes is shown to be sensitive to dilution with low molecular compounds. The viscosity of branched polymers falls more rapidly with dilution than that of linear polymers, i.e., branched polymers show increased response to plasticization. At least one instance is demonstrated in which the viscosity ratio ηbr/ηlin reverses from a value greater than unity to less than one in passing from dry polymer to rubber extended with relatively large quantities of oil.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 371-381 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Normal stress and shear stress of concentrated polystyrene solutions in a chlorinated diphenyl were measured under steady flow and oscillatory shear flow in a Weissenberg rheogoniometer. The normal stress difference was observed to oscillate at double the frequency of the applied shear strain with amplitude proportional to the square of the applied amplitude, while the shear stress was found to oscillate at the same frequency with amplitude proportional to the applied amplitude. A theoretical relation between the displacement of the oscillatory normal stress difference from zero level and the dynamic modulus derived by Lodge and other investigators was confirmed experimentally, and the theoretical predictions of Coleman and Markovitz concerning the relation among steady-flow normal stress difference and dynamic modulus were also confirmed. However, the theoretical predictions of Lodge, of Spriggs, Huppler and Bird, and of Williams on the relation between the amplitude and phase of oscillatory normal stress and those of oscillatory shear stress did not agree with experimental results.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 47-59 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple method of preparing thin uniform films of high polymers has been examined for growing single crystals from solution. Single crystals of polyethylene, polypropylene, polybutene-1, polyacrylonitrile, and cellulose triacetate have been obtained by this method. Different stages of growth reveal different growth features that are also obtained from solutions of these polymers by changing temperature and concentration.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 81-87 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The high degree of flexibility of blends containing minor amounts of partly crystalline copolymers of ethylene and vinyl acetate in paraffin wax seems to be a manifestation of some type of interaction. Low-angle x-ray diffraction of such blends showed a new long spacing intermediate in length between the polymer long spacing and the c axis length of the wax unit cell. This new long spacing appears to be a consequence of isomorphism involving cocrystallization of polymeric ethylene sequences and wax molecules. A lesser type of isomorphic interaction, epitaxy, occurs in polyethylene-wax blends: wax overgrows crystals of already crystallized polyethylene in the same orientation without a change in its c axial dimension.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 143-147 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 893-901 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: We have derived from the Eyring theory of non-Newtonian flow a yield condition which is valid for an arbitrary state of stress. Experimental data obtained in simple axial compression tests show the influence of the hydrostatic stress on the yielding of poly(vinyl chloride). This fact confirms the proposed condition and disproves the von Mises criterion. Tension-torsion tests performed on thin tubes lead to results which fit our condition fairly well. The pattern of Lüders' lines appearing on the surface of thin tubes subjected to simple tension, simple shear, and tension-torsion are parallel to the direction where the value of the normal stress is equal to the hydrostatic stress.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 957-967 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: The melting temperatures of homopolymers of poly(ethylene sebacate) possessing a most probable molecular weight distribution and ordered copolymers of ethylene sebacate/propylene adipate were studied by slow heating processes and by the analysis of the dependence of the melting temperature on the crystallization temperature utilizing rapid heating rates. For the ordered copolyesters, where the composition of the crystallizing co-units ranged from 0.8 to 0.2 mole fraction the latter method gave results which were similar to those that have been obtained for the other polymer systems that have been studied. Extrapolated equilibrium melting temperatures could be obtained in a straightforward manner and were found to be independent of the copolymer composition in accord with theoretical expectations. On the other hand, a unique set of results were obtained for the homopolymers. A plot of the relationship between the melting temperature and the crystallization temperature for all the molecular weights studied gave a slope close to unity. This made it operationally impossible to extrapolate to the equilibrium melting temperature for this system.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 999-1010 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An investigation of the internal motion in organosilicon polymers by wideline nuclear magnetic resonance has been extended to a pair of dimethylpolysilazanes crosslinked through trifunctional silicon. The data suggest that there is considerable internal motion in all silazanes at 77°K. Evidence is presented for the presence of C3 rotation of the methyl groups, as well as rotation or torsional oscillation of the Si(CH3)2 groups about the polymer backbone. Upon warming the NMR line is seen to narrow, and this is associated with the onset of additional motion, including chain translation and chain flexing or bending. Crosslinking through silicon increases the barrier to chain translation while decreasing the barrier to chain flexing or bending.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1027-1037 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly-2,5-distyrylpyrazine (poly-DSP) was investigated by differential thermal analysis (DTA), thermogravimetric analysis (TGA), and measurements of dynamic viscoelastic and electrical properties. From DTA and TGA studies it was confirmed that poly-DSP melts at 321°C and depolymerizes rapidly to the monomer at temperatures between 335°C and 345°C in helium. The polymer is affected by oxygen above 200°C. The E′ value from dynamic viscoelasticity measurements on amorphous film is 2 × 1011 dyne/cm2 at room temperature. It decrease abruptly in the temperature range 140-150°C; but the net decrease of E′ within this temperature range is relatively small. The electrical properties of amorphous poly-DSP are characterized by a small temperature dependence of the dielectric constant between room temperature and 100°C. The dielectric loss tangent was observed to be small, and the dc conductivity was extremely small. It is concluded that rotation of the phenyl branches in the polymer occurs above -30°C and the glass transition occurs at about 150°C. These properties are discussed in some detail in relation to the polymer structure.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1111-1126 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Comonomer and stereosequence distributions in linear high polymers are considered from the point of view of the general theory of stationary random sequences. Although the discussion is centered about binary polymerizations which may be regarded as stationary Markov processes of low order, attention is paid to distinguish results valid for any stationary random process including stationary non-Markov processes from those special to a particular Markov process. Alternative derivations of copolymer composition equations are given along with a corrected version of a previously suggested scheme of relating conditional probabilities of different orders. The nature and relative merits of the several measures proposed in the literature to characterize comonomer and stereosequence distributions are also discussed in some detail.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1177-1186 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dielectric behavior of poly(vinylidene fluoride) is affected by orientation and crystal modification. The loss peak caused by molecular motion of the molecules in crystalline regions appears at about 70°C (110 Hz) (α1 absorption) for the α form, and at about 110°C (110 Hz) (α2 absorption) for the β form. Orientation significantly affects the magnitude of the β absorption which appears at about -40°C. The very high value of the dielectric constant for stretched film is believed to be due to the orientation effect. The γ absorption, which is assumed to be local-mode absorption, is not so much affected by orientation. An additional loss peak has been found at around 0°C in dynamic mechanical measurements, but the molecular mechanism is unknown.
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  • 63
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 467-479 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A dynamic method for investigating the mechanism of permeation and diffusion through polymers has been explored. The permeation cell consists of two compartments separated by the membrane. The permeant (gas, vapor, or liquid) is introduced into one compartment; a carrier gas (helium) flows at constant rate through the other and sweeps the permeant which diffuses through the membrane to the thermal conductivity detector. Both compartments are at atmospheric pressure; thus no or little membrane support is required, and leakage problems are minimal. Moreover, the same membrane can be used over a wide temperature range and for diverse permeants. The detector signal is at any instant proportional to the permeation rate. A simple mathematical formalism for deriving the diffusion coefficient from the transient permeation rates has been developed. The measured diffusion and permeability coefficients of CO2, O2, and N2 through low-density polyethylene closely agree with literature values. Permeation of hexane and benzene through polyethylene follows a complex diffusion law, and the rate depends on the thermal history of the system. The dynamic method is particularly suited to the study of transitions in polymers. Changes in permeation rates, usually occurring at transition points, can easily be discovered by slow temperature scanning of the system.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 487-487 
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    Keywords: Physics ; Polymer and Materials Science
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 519-528 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three transitions are detected dilatometrically when partially isotactic poly(propylene oxide) melts. One transition, the temperature of which is independent of the crystallization temperature over a wide range below 60°C, is ascribed to the melting of lamellar crystallites which are limited in thickness by the average isotactic sequence length alone. The other two transitions, the temperatures of which vary with the crystallization temperature, are ascribed to the melting of lamellar crystallites with thickness determined predominantly by three- and two-dimensional primary nucleation acts. The theory of Flory is adapted and applied quantitatively to the melting points of three crystalline fractions of poly(propylene oxide), obtained from a polymer produced via the zinc diethyl and water catalyst system. This method leads to a thermodynamic melting point of isotactic poly(propylene oxide) near 82°C.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 583-594 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Characteristic markings of concentric bands are formed on the fracture surface of tensile specimens under certain loading conditions. The marking form in the fast crack growth region of the mirror area of fracture. Optical and electron optical microscope techniques have been used to study the morphology of the markings. It is shown that in this region the crack propagates along the interface between the craze, in which the crack nucleated, and the bulk material. The mackerel pattern is caused by the crack jumping from one craze-matrix interface to the other.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 605-624 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Incorporation of plasticizers or other inert, liquid diluents causes a profound weakening of rubbers. The modulus of elasticity and tensile strength decrease approximately with the square of the gel fraction v0 of rubber which was present at the time of formation of the three-dimensional network. Equlibrium swelling of plasticized rubbers is well represented by v2m = kv0, where v2m is the volume fraction of rubber network in the swollen state, at equlibrium, and k a constant equal to v2m for the unplasticized rubber. This swelling law is independent of the way in which v0 is obtained; inert liquid diluents, comprising molecularly dispersed compounds, as well as suspensions of insoluble liquids, gases, and chemically inert, solid fillers yield the same relation. Further, it is independent of the chemical nature of solvent and rubber. It appears that also the mechanical properties of foams, liquid-filled foams, and plasticized elastomers containing the same volume fraction of network rubber are very similar.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 649-652 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 657-678 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: On axial extension of polymer melts at constant deformation rates, the development of high-elastic deformation is of predominant importance during the initial period. High-elastic deformation is accompanied by a rise in viscosity and in the modulus of high-elasticity and by retardation of the relaxation processes in the region of large relaxation times. At relatively low deformation rates, the rise in viscosity and high-elasticity modulus and the retardation of relaxation processes may give way to a decrease in viscosity and high-elasticity modulus and acceleration of relaxation processes, so that stationary flow regimes are attained. The transition from strain regimes with increasing viscosity and modulus of high elasticity to those with a decrease of these quantities corresponds to an increase in the rate of accumulation of irreversible deformation. Accordingly, a competing influence due to the orientation effect and to destruction of the network of intermolecular bonds becomes evident while stationary flow is being attained. The orientation effect must be responsible for the retardation of the relaxation processes, whereas rupture of the intermolecular network bonds results in structural relaxation accelerating relaxation processes. In contrast to shearing, during extension the orientation effect is of predominant importance. Hence in stationary flow regimes the viscosity may not only remain independent of the rate of strain, but even increase with it. In this case the contribution of the large relaxation times to the relaxation spectrum increases with increasing stress in stationary flow regimes. The fact that the longitudinal viscosity and the modulus of high elasticity are independent of the stress in stationary flow regimes does not guarantee linearity of the mechanical properties of the polymer in the prestationary stage of deformation when complex changes occur in its relaxation characteristics. At high deformation rates the viscosity and the modulus of high elasticity keep rising with increasing deformation until rupture occurs. Determination of the strength of polystyrene samples vitrified after extension showed that it is due not to the entire degree of extension, but only to the value of accumulated high-elastic deformation. The strength of the vitrified samples is to a first approximation independent of the rate at which the melt was extended.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 727-738 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dielectric relaxation data have been obtained for two ethylene-methacrylic acid copolymers (containing about 4 mole-% methacrylic acid units and about 8 mole-% methacrylic acid units, respectively) and the lithium, sodium, and calcium salts prepared by partial neutralization of the polyacids. The frequency range employed was from 50 Hz to 10 kHz and the temperature range was from -130°C to 100°C. Attention is focused on three dielectric loss regions labeled β, β and α in order of increasing temperature. The β′ process (-10°C at 100 Hz in the salts only) correlates with a mechanical loss process previously reported and is attributed to microbrownian motion taking place in an amorphous hydrocarbon phase. The β′ process (20°C at 100 Hz) has also been observed mechanically and is attributed to the same mechanism as the β process. The higher temperature of this relaxation compared to the β relaxation is attributed to the presence of acid groups which form crosslinks composed of interchain hydrogen bonds. The α process (〉50°C at 100 Hz in the salts only) correlates with dielectric and NMR data previously reported for a sodium salt and is assigned to motions within ionic domains formed by the clustering of salt groups.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 807-811 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 815-816 
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    Keywords: Physics ; Polymer and Materials Science
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    Notes: Sedimentation equilibrium in the ultracentrifuge means that there is such a distribution of molecular species throughout the cell, that the centrifugal forces are balanced by differences in the activities. This provides a method for determination of the activities and the chemical potentials in polymer solutions which, in principle, is very simple and reliable. A complication is caused by polydispersity of the dissolved polymer. If one assumes that the interaction parameter depends on concentration and temperature, but not on molecular weight, it is possible to determine the chemical potential of polymer and solvent from the ultracentrifugal data. Experiments have been carried out on the systems polystyrene-toluene and polystyrene-cyclohexane at different temperatures and in the concentration range 0-80 wt-%. The results are expressed in the data for the chemical potential of the solvent, the number average chemical potential of the polymer and the interaction parameter χ.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 921-935 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Several partially interpenetrating polymeric networks (IPN) were made by combining chemically different linear elastomers. The polymer combinations were deposited as films from aqueous emulsions made by mixing the individual emulsions in equal proportions. The films were crosslinked to form two superimposed networks. In two cases, the networks were cleanly separated by hydrolysis of one of the component networks to demonstrate that there was no chemical interaction between the polymers. Measurement of crosslink density showed that, in most cases, partial interpenetration does occur as evidenced by an effective crosslink density of the IPN's greater than the arithmetic mean of the crosslink densities of the component networks. The swelling ratios, densities, and stress-strain properties were determined. For one of the network combinations, a poly(urethane-urea) and a poly(butadiene-acrylonitrile), a series of IPN's varying in polymer composition was made. The swelling ratios and densities are close to the arithmetic means; however, both the tensile strength and crosslink density exhibit a maximum at about 70% poly(butadiene-acrylonitrile). The maximum tensile strength is actually significantly higher than that of either of the component polymers. The elongations all approach that of the poly(urethane-urea), the more extensible material, except for compositions approaching 100% poly(butadiene-acrylonitrile), which exhibit a very low extensibility.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 969-977 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Characteristic wide-line proton magnetic resonance absorption spectra of a number of representative cellulose preparations have been obtained in the dry state and after addition of about 7% water. Line widths, second moments, spin-spin and spin-lattice relaxation times have been determined. The second moment of the absorption curve of dry cellulose was found to correlate well with the crystalline fraction for most specimens. A technique is described for determining the number of water-cellulose protons exchanging relative to the number of cellulose protons not exchanging. The reduction in absorption line width observed when water is added to cellulose is shown to be quantitatively consistent with such a proton exchange phenomenon.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1755-1772 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphology of selenium has been studied in light of present concepts of crystallinity in crystalline organic polymers. Spherulitic crystallization and resultant morphology were examined as a function of temperature by transmission and replication electron microscopy, electron diffraction, and optical microscopy. Evidence is given for polymer chain folding during crystallization of trigonal selenium. Theoretical thermodynamic calculations presented yield several thermodynamic values including an equilibrium melting point of 219.2°C, a fold surface energy of 337 ergs/cm2 and a lateral surface energy of 9.8 ergs/cm2.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1803-1821 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Various procedures for universal calibration in gel-permeation chromatography with polystyrene gels are examined for polystyrene and polydimethylsiloxane fractions. For o-dichlorobenzene at 138°C, experimental intrinsic viscosity-molecular weight data show that the Mark-Houwink exponents are 0.70 and 0.57 for polystyrene and polydimethylsiloxane, respectively. In principle, this difference permits a distinction between the various polymer size parameters proposed for universal calibration. An interpretation of the experimental polydimethylsiloxane calibration for o-dichlorobenzene at 138°C requires a consideration of errors in average molecular weights and errors arising from the use of average molecular weight instead of peak molecular weight. When calibration procedures utilizing hydrodynamic volume and unperturbed dimensions are examined, the difference between them is comparable with experimental error. If the Flory-Fox viscosity expression is employed, the perturbed end-to-end distance (or radius of gyration) and the hydrodynamic volume give equivalent universal calibrations. The experimental data are sufficiently accurate to show that the perturbed dimension determined with the Ptitsyn-Eizner relation does not give an adequate universal calibration.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1545-1564 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystallization of compression-molded isotactic polypropylene and polyethylene is invariably spherulitic; generally, nucleation occurs randomly throughout the sample. In a special case where nucleation predominates at the surface, spherulitic growth centers become crowded and are forced to propagate unidirectionally into the bulk (transcrystallinity). Conditions for the formation of transcrystallinity have been investigated by optical and scanning electron microscopy. The occurrence of transcrystallinity is attributed to heterogeneous nucleation induced at the mold surface. To be effective, the mold surface must have a nucleating efficiency equal to or greater than that of adventitious nuclei present in the polymer. As the crystallization temperature approaches the melting point, the activity of mold surfaces is found to increase leading invariably to transcrystalline formation. The degree of activity of various mold surfaces correlates with the known activity of specific dispersed nucleating agents having similar chemical structures. Contrary to claims in the literature, the surface energy of the mold surface and temperature gradients across the melt surface do not play a primary role in transcrystalline formation of polypropylene.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1909-1916 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The flow behavior of α,ω-dihydroxypolydimethylsiloxanes, having a weight-average number-average molecular weight ratio of 1.1-1.2, was studied with a Cannon-Manning viscometer and an Instron rheometer. Comparison of the flow behavior of samples with narrow and broad molecular weight distributions indicated that the onset of non-Newtonian behavior occurred at a much higher shear rate for narrow-distribution polydimethylsiloxanes than for polydisperse polydimethylsiloxanes. A plot of reduced viscosity versus \documentclass{article}\pagestyle{empty}\begin{document}$ \dot \gamma \eta _0 {M \mathord{\left/ {\vphantom {M T}} \right. \kern-\nulldelimiterspace} T} $\end{document} gave two experimental master curves, one for polymer of narrow distribution and the other for polydisperse polymer. The experimental master curve obtained from the narrow-distribution polymer was found to fit the theoretical master curve derived from Graessley's entanglement theory. The viscosity-molecular weight relationship for the higher molecular weight polydimethylsiloxanes was found to be the same for both hydroxydimethylsilyl- and trimethylsilyl-endblocked polymers. However, at low molecular weight, the viscosity-molecular weight curve deviated from linearity because of the association of polydimethylsiloxanols, which apparently is not significant at higher molecular weights. The critical molecular weight of entanglement, Mc, was found to be about 30,000.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1937-1953 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It has been considered for some time that the presence of birefringence in an oriented polymer must affect the light-scattering behavior. Previous analyses of this phenomenon are restricted to single-particle scattering. A more complete theory of the effect of birefringence on the scattering of light from correlated systems is presented. The measured scattering intensity is shown to be dependent upon the optical properties of the sample as well as the experimental technique and conditions.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2029-2032 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2039-2050 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Fujita equation relating molecular weight distribution to concentration of solution subjected to centrifugal forces in equilibrium proved to be an improperly posed problem in the Hadamard sense. Application of Tikhonov's regularizing functions leads to a good approximate solution of Fujita's equation. Such functions have been applied to a monomodal and a bimodal molecular weight distribution, and approximate results have been computed.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2095-2103 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Electron-microscopic texture and physical properties of a styrene-butadiene-styrene (SBS) block copolymer obtained by casting from toluene, carbon tetrachloride, ethyl acetate, and methyl ethyl ketone are discussed. Two peaks are observed in the mechanical loss (tan delta;) curve at -70 and 100°C which are attributed to segmental motion of polybutadiene and polystyrene, respectively. The polybutadiene peak heights are in the order of solubility in the solvent used; the polystyrene peak heights are in converse order. In addition to these peaks, a third peak is observed at 10°C for specimens cast from ethyl acetate or methyl ethyl ketone. A transition corresponding to this peak is also noticed in thermal analysis. It is proposed that aggregation of styrene blocks is relatively incomplete in specimens cast from solution in poor solvents.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 2141-2151 
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    Keywords: Physics ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology , Physics
    Notes: Low molecular weight poly(ethylene terephthalate) samples were crystallized isothermally at 120-245°C from both the amorphous state and the melt. Isothermal annealing of these polymers at 215°C provided polymers which exhibited multiple melting peaks in thermal analysis, referred to as form I and form II, as assigned by Bell and Dumbleton. In these samples the peak temperature of the form II melting endotherm and the average crystallite size are dependent on the temperature of initial crystallization. This result requires a mechanism for retaining some structural feature during the conversion from morphological form I to form II. DSC thermograms obtained at varying heating rates on samples showing only form II endotherms support the assignment of superheating as the cause of the shift to higher peak temperatures with increasing heating rate.
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1411-1412 
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    Keywords: Physics ; Polymer and Materials Science
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 1457-1465 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect upon seeding behavior of adding well characterized fractions has been studied, so as to assess the technique as a measure of small amounts of high molecular weight. The material available to us restricted the study to fractions with comparatively low average molecular weights. Self-seeding is shown to be an extremely sensitive measure of high molecular weight tails. Knowledge of the molecular weights concerned enabled estimates to be made of the weight of molecules involved in seeding. Instability of seeds has been observed, and is explained in terms of a particular amorphous crystalline “equilibrium” within the seeds.
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 85-114 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of the small-angle scattering power and the degree of crystallinity in melt-crystallized high-density polyethylene have been used to evaluate the “amorphous” density in situ by the relation, \documentclass{article}\pagestyle{empty}\begin{document}$ (2\pi/V)\int_0^\infty {S\tilde g} (S)dS = (\rho_{\rm c} - \rho_{\rm a})^2 \upsilon_{{\rm er}} (1 - \upsilon_{{\rm er}}) $\end{document} where V is the irradiated volume and ḡ(S) is the “slit-smeared” absolute intensity. The amorphous density is a function of sample history and is always higher than the extrapolated melt density. After slit-height correction, and within the experimental error, the ratio of the two observed long periods is 2:1 at all temperatures (25--126°C). The lamellar thickness and the average interlamellar spacing are obtained from the degree of crystallinity and the first corrected long period. At increasing temperatures between 25°C and 110°C, the lamellae become thinner while the interlamellar zone expands by almost half. Over this range the changes are reversible with temperature. Above 110°C, both the lamellae and the interlamellar region expand with temperature. The thickening is partially reversible upon recooling. Other results obtained include measurements of stacking disorder and of microstructural changes with crystallization temperature and with time at ambient temperature.
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 143-160 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Work on two sheet organosilicon polymers, one derived from the mineral chrysotile and the other from the mineral apophyllite, is described. This work provides direct evidence that both these polymers are composed of sheets. In addition, it shows that in the chrysotile-derived polymer the sheets curl into scrolls, and that in the apophyllite-derived polymer the sheets are essentially flat.
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 209-243 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The shear creep and creep recovery behavior of narrow molecular weight distribution polystyrene samples of low molecular weight, 1.1 × 103, 3.4 × 103, and 1.57 × 104 are reported as a function of temperature, near and above the glass temperature. Time-temperature equivalence for the total creep compliance is found to be nonapplicable, and in fact the steady-state recoverable compliance, Je, is a strong function of temperature. The time-scale shift factors for the recoverable compliance are analyzed in the light of free volume theory. Viscosity data are presented for samples with molecular weights between 1.1 × 103 and 6.0 × 105. The temperature dependence of the characteristic time constant ηJe can be explained in terms of free volume concepts whereas that of viscosity η cannot. Effects of residual molecular weight heterogeneity are demonstrated.
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  • 90
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 295-311 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theoretical calculation of the Hv light-scattering patterns for deformed three-dimensional spherulites is presented. Affine deformation is assumed. The optic axis of the scattering element is allowed to lie at an arbitrary angle ß to the radius which is permitted to change in the course of the deformation in a manner that may depend upon the angular location in the spherulite. The consequences of twisting of the optic axis about the spherulite radius are also explored.
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  • 91
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 331-343 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The adsorption of polydimethylsiloxane polymers from solution on glass has been studied. The amount of polymer adsorbed depends markedly on the solvent because of specific solvent - surface interactions. The presence of silanol groups in the polymer, particularly as endgroups, markedly increases the amount of polymer adsorbed. Large differences are shown between the adsorption of the commercially available, and fully trimethylsilylated polydimethylsiloxanes of narrow molecular weight distribut on. Possible adsorption mechanisms are discussed.
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  • 92
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 383-384 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 93
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 421-430 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method is given for the analysis of long-chain branching in polymers by using combined GPC and intrinsic viscosity measurements. A computer program was written to evaluate branching indices by a tabular, iterative method. The method was applied to the evaluation of long-chain branching in low-density polyethylene.
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  • 94
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    Journal of Polymer Science Part A-2: Polymer Physics 9 (1971), S. 431-435 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of stereoregularity on the low-temperature relaxation processes were studied by dynamic mechanical measurements on isotactic and syndiotactic polyisobutyl methacrylates (iso-PiBMA and syn-PiBMA). The α, β, and γ relaxation processes were observed in both stereoregular forms. Both the α, and β loss peaks were at lower temperatures for iso-PiBMA than for syn-PiBMA. The γ loss peak was observed at about -155°C at 30 Hz for both forms, and the apparent activation energy of this process was same for both samples within experimental error (6.7 ± 0.5 kcal/mole). It was reduced from these results that the α and β processes are both considerably influenced by the isotactic configuration but the γ process is not.
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  • 95
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 541-554 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dilute solution parameters were determined for polymethylphenylsiloxamer fractions (5 × 104 〈 M 〈 1.5 × 106) in toluene, cyclohexane, and diisobutylamine (θ ≈ 30.4°C). The data are interpreted by the procedure suggested by Flory and Fox. Minor deviations from theory are noted. Polymers from both cis- and trans-cyclotrisiloxanes were investigated. The major portion of the work, however, was concentrated on fractions derived from the trans form. From the data obtained, a characteristic ratio of dimensions (r02/rof2)½ of 1.56 was determined. The hydrodynamic parameter Φ was determined to be (2.0 ± 0.3) × 1021. The appropriate model for the polymer is indicated to be the impermeable random coil with slight hindrance to rotation about backbone skeletal bonds.
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  • 96
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 595-603 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The adsorption of tritium-labeled sodium stearate and 35S-labeled sodium dodecylsulfate from aqueous solution on bent and on stretched polyethylene strips was directly measured. The amount of adsorption increased from 2.5 to 4.5 times on surfaces of various polyethylene samples stretched from 5.2 to 5.3 times the original length. For one sample, adsorption increased 8 and 2.5 times, respectively, on the convex and concave surfaces of a bent strip. Autoradiographs of the strips taken after adsorption revealed the appearance of both homogeneous and heterogeneous adsorption on the stretched surface of the polyethylene. The electron micrographs of the strips showed that many small fissures, about 1-5μ in length, formed on their surfaces after the strips were bent or stretched. Enhanced adsorption of the surface-active substance along these fissures was suggested. On the basis of these observations, it is proposed that in stretching or bending, fissures increase adsorption of the detergent, and the adsorption in turn promotes further development of fissures. Thus, bending and adsorption mutually promote the growth of fissures which finally result in failure of the polyethylene.
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  • 97
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 655-656 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 98
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 689-703 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The reduced specific viscosity of poly(methacrylic acid) has been studied in ethanol-0.002N HCI solvent mixtures as a function of polymer concentration, alcohol concentration, and temperature. In addition, experiments were performed at different HCI concentrations and with KCI instead of HCI. Both intrinsic viscosity and Huggins coefficient were shown to undergo unusually strong variations. Two minima and two maxima could be demonstrated in intrinsic viscosity. The Huggins coefficient seems to show corresponding variations. The first minimum in intrinsic viscosity indicates that the coil volume has collapsed almost to an Einstein sphere. In this region the Huggins coefficient is extremely large (of order 102) and is controlled by coil association. It was shown that several forms of intramolecular interaction must be assumed to be competing to account for this behavior. The presence of HCI, particularly in the preponderantly aqueous phase, is required to suppress the polyelectrolyte effect. It is found, however, that the behavior of the solutions at relatively high ethanol concentrations is more sensitive to HCI content than is that of highly aqueous solutions. KCI can be used to replace HCI over most of the range. Increase in temperature shifts the turning points of the curves to lower alcohol concentrations. Some evidence has been found that the association constant giving rise to dimers increase with rate of shear. The importance of poly(methacrylic acid) as a chemically simple model substance for various biopolymer effects is stressed.
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  • 99
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 747-752 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Growth rates of G of low-melting spherulites in fractions of trans-1,4-polyisoprene have been measured. The data were analyzed by use of an equation, ln G = ln G0 - ΔF*/RTc, valid at temperatures close to the equilibrium melting point. Plots of ln G against a function of the critical free energy of nucleation ΔF* result in a family of straight lines having a common intercept, ln G0, which is independent of molecular weight. The slope of these lines is a measure of the interfacial free energy of the crystallites and increases with the molecular weight, reflecting increasing irregularity in the structure of the semicrystalline mass. Comparison of growth rates of low-melting and high-melting trans-1,4-polyisoprene indicates that G0 does not, to a first approximation, depend on the nature of the crystals growing from the melt. The temperature at which spherulites of the two crystalline forms grow at equal rates has been calculated.
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  • 100
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    Journal of Polymer Science Part A-2: Polymer Physics 8 (1970), S. 489-497 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A quantitative theoretical calculation is made of the effect of birefringence of the surrounding medium on the light-scattering pattern from a two-dimensional anisotropic spherulite. The calculated modification of the light-scattering pattern is in accord with the prediction previously made on the basis of qualitative considerations and model experiments.
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