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  • 1965-1969  (4,755)
  • 1890-1899  (1,243)
  • 1967  (4,755)
  • 1897  (1,243)
  • Chemistry  (5,998)
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  • 1965-1969  (4,755)
  • 1890-1899  (1,243)
Year
  • 101
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Samples of commercially prepared poly(methyl methacrylate) (Lucite) were irradiated with 13-M.e.v. electrons in the dose range 0-11 Mrad, and the induced changes in the index of refraction, density, and dielectric constant were observed. An attempt is made to interrelate the observed changes theoretically.
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  • 102
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    Journal of Applied Polymer Science 11 (1967), S. 1101-1116 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Radiation-induced solid-state polymerization in binary systems containing long-chain compounds has been investigated. Butyl stearate-methyl methacrylate and stearyl alcohol-methyl methacrylate systems have been studied in detail. In these systems insource polymerization does not occur but a remarkable post-polymerization takes place on warming after irradiation at low temperature. The limiting conversion characteristics of this post-polymerization depend greatly on the nature and the concentration of the long-chain compounds. The post-polymerization is observed to be more marked in the butyl stearate-methyl methacrylate system than in the stearyl alcohol-methyl methacrylate system, and it increases with increasing concentration of the long-chain component. An optimum warming rate and warming temperature exists for the maximum saturated conversion. Irradiation in air causes some decrease of conversion compared to irradiation in vacuo. The possible mechanism is that monomer diffuses into the crystals of the long-chain compound after melting at the eutectic temperature. The polymerization may be initiated by trapped radicals of the long-chain compound and carried out in the crystal of the long-chain compound with a smaller possibility of termination. In binary systems containing long-chain compounds, lowering of the melting point is slight, and the eutectic composition exists at the richer composition of monomer, so almost all the long-chain substance remains as excess crystals, which are suitable for holding trapped radicals. The crystal lattices of long-chain compounds may be softer than those of compounds of small molecular size. This fact is favorable for monomer diffusion. This explains why such a post-polymerization takes place only in systems containing long-chain molecules.
    Additional Material: 14 Ill.
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  • 103
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    Journal of Applied Polymer Science 11 (1967), S. 1173-1177 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Poly(vinyl isonicotinate) was prepared by esterification of poly(vinyl alcohol) with isonicotinoyl chloride in pyridine solution. Poly(vinyl nicotinate) was also prepared. Density, refractive index, and glass transition of the polymers were determined. The low temperature dynamic mechanical properties of poly(vinyl isonicotinate) are characterized by a relaxation effect which is associated with thermally excited motions of the pyridine rings (δ relaxation). The strong displacement of such a phenomenon toward higher temperatures, with respect to poly(vinyl benzoate), is interpreted as due to the elevated polarity of the pyridine ring.
    Additional Material: 2 Ill.
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  • 104
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    Journal of Applied Polymer Science 11 (1967), S. 1139-1153 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An ESR study of the free-radical mechanisms of the post-irradiation reactions of cotton cellulose with acrylonitrile is reported. The effects of atmosphere, moisture content, and solutions of acrylonitrile on the yield and stability of free-radical sites in irradiated cellulose were determined. On interaction of γ-radiation from a 60Co source with cotton cellulose, long-lived free-radical sites were found within the molecular lattice. Short-lived free-radical sites were apparently also formed on chain cleavage, gave strong singlet spectra, and were readily accessible to interaction with water. Other free-radical sites were formed within regions of the cellulosic fiber which were inaccessible to moisture or aqueous solutions even after contact times as long as three days. It was suggested that long-lived free-radical sites in cellulose I (containing regain moisture) resulted from dehydrogenation at C5, and in cellulose II (containing regain moisture) resulted from dehydrogenation at C5 and dehydrogenation of the OH group or dehydroxylation at C6. When irradiated cellulose was contacted with a solution of acrylonitrile (15%) in 75% aqueous zinc chloride, the initial rate of decrease in spin concentration was higher than the rate of decrease as the time of contact increased. The ESR spectrum of the reacted cellulose, observed at -100°C., as compared with the spectrum for the irradiated cellulose, had decreased in signal strength with increase in time of contact and changed from a three-line spectrum to an ill-defined spectrum. The free radical being observed was probably due to unreacted sites in the cellulose. The extent of the graft copolymerization reaction was directly related to the initial spin concentration in the irradiated cellulose.
    Additional Material: 8 Ill.
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  • 105
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    Journal of Applied Polymer Science 11 (1967), S. 1209-1215 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The electrolysis of solutions of p-methylbenzyltrimethylammonium nitrate or, better, p-xylylenebis(trimethylammonium nitrate) or p-xylylenebis(triphenylphosphonium chloride or bromide) in a polar organic solvent with an aluminum cathode and a platinum anode results in the formation of adherent coatings of poly-p-xylylene on the cathode. The mechanism of this reaction involves the electrochemical generation of p-xylylene and its subsequent polymerization on the aluminum cathode. Competing reactions are formation of p-xylene and reduction of the solvent.
    Additional Material: 3 Ill.
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  • 106
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    Journal of Applied Polymer Science 11 (1967), S. 1661-1665 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A simple theory is developed which correlates the Izod impact strength of polymers with (G′100-G′300)2/G′100, where G′100 and G′300 are dynamic shear moduli at 100°K. and 300°K., respectively. The theory assumes the Maxwell element for the material and the fracture time smaller than the relaxation time. The theory is verified by experimental data for numerous polymers. Another approach which correlates the impact strength with the integrated loss factor from 0 to 300°K. is also proved valid.
    Additional Material: 6 Ill.
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  • 107
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    Journal of Applied Polymer Science 11 (1967), S. 2021-2028 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The Hermans' average angle of orientation, the angle at 40% intensity, and the Hermans' orientation factor have been studied in raw and delignified jute and mesta fibers under different moisture conditions. It is observed that the average orientation of micelles in these fibers improves on moisture absorption and further improves when the moist fiber is subjected to tension, and that the action of water is more pronounced in delignified jute fibers. The derangement of a fraction of the regions, contributing to the x-ray pattern of these fibers, and the releasing of internal stresses have been cited here as possible caused of the phenomenon.
    Additional Material: 2 Ill.
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  • 108
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    Journal of Applied Polymer Science 11 (1967), S. 2467-2471 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: α-Cellulose dissolves in a mixture of SbCl3, KOH, and AsCl3. The resulting product as identified by PMR and infrared spectroscopy is α-D-glucose. This product is unexpected, and an explanation for its formation is suggested.
    Additional Material: 2 Ill.
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  • 109
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    Journal of Applied Polymer Science 11 (1967), S. 2507-2514 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Visible dichroism can be utilized as a measure of the degree of orientation of an amorphous region in a polymer. But the relations between dichroism and states of dyes in polymer must be elucidated before dichroism can be used more widely as a reliable means for study of amorphous orientation. To calculate the orientation factor for visible dichroism, it is necessary to decide the dichroism of an ideally oriented polymer chain. For this purpose, a single crystal of Congo Red was prepared and the dichroic spectrum of the crystal was measured. It was found that the dichroism of the Congo Red molecule itself is unity in a suitable wavelength region. As a result, a simple means for the treatment of dichroic spectra was given. The angle between the polymer chain axis and the principal axis of the absorbed dye molecule was discussed.
    Additional Material: 5 Ill.
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  • 110
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    Journal of Applied Polymer Science 11 (1967), S. 2525-2531 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polyacrylonitrile polymer powder was dissolved in 70% nitric acid and spun into isotropic filament through a glass nozzle of 0.5 mm. diameter in a coagulating bath of 30% nitric acid. Stretching was carried out in two stages: the first stretching was done in water at 20°C. followed by drying, and the second stretching was done in a boiling saturated solution of ammonium sulfate. The total stretching ratio was 23. These filaments were shrunk freely in water at 70-180°C. The change in orientation factors was traced by x-ray, infrared dichroism, visible dichroism, and sonic modulus methods. The relation between the reciprocal absolute temperature of thermal contraction and the logarithm of fiber length is a straight line which has two inflection points at 93 and 175°C. The orientation factors by x-ray and infrared dichroism remain unchanged up to 175°C. On the contrary, the orientation factors by visible dichroism and sonic modulus drop suddenly at about 90°C. This indicates the occurrence of relaxation of the amorphous chain at the glass transition temperature and shows the polymer is not perfect single-phase material. Orientation of crystalline and amorphous phases is stable from 100 to 170°C. in spite of considerable thermal contraction. The stability of orientation can be explained by the growth of a folded structure in the polymer.
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  • 111
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    Journal of Applied Polymer Science 11 (1967), S. 311-319 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A variety of polymers have been foamed with sulfur dioxide. Properties of the foams could be varied by choice of polymer to produce rigid, semirigid, flexible, rubbery, fibrous, self-extinguishing, and/or heat-resistant materials.
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  • 112
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    Journal of Applied Polymer Science 11 (1967), S. 251-287 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: In the part installment of the present paper, the authors formulated the dynamics of melt spinning by introducing a set of fundamental equations that consist of the equations of heat, force, and material balances. Some steady-state solutions were also given. Additional steady-state solutions corresponding to many different spinning conditions for polyester and polypropylene filament yarns consistently show good agreement with experimental results. These steady-state solutions that give filament cross-section A (x) and filament temperature t(x) as functions of position x are correlated with yarn qualities: yarn density and birefringence, crystallinity and molecular orientation, are correlated respectively with the speed of Polymer cooling at 100°C. and the maximum tensile stress (F/A)w acting on the filament. A transient solution of the fundamental equations computed on an IBM 1401 machine shows that the filament cross-section A at the take-up roll forms a large transient peak after a stepwise increase in the speed vy of cooling air. This agrees with experiments fairly well. The fundamental equations, therefore, clarify the dynamic relations between cooling air speed and yarn weight variations.
    Additional Material: 38 Ill.
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  • 113
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    Journal of Applied Polymer Science 11 (1967), S. 383-387 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Some crystalline organic compounds containing a β-naphthyl group stiffen rubbers considerably. This paper discusses the dynamic behavior of these systems when subjected to oscillatory strain of increasing amplitude. Modulus-strain amplitude plots similar to that in carbon black-natural rubber systems are obtained. The implication of these results to reinforcement theory is discussed.
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  • 114
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    Journal of Applied Polymer Science 11 (1967), S. 439-455 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The reversible gelation of acrylonitrile-vinyl acetate copolymers in concentrated solutions has been studied with the use of various solvents. These concentrated solutions gel or become rigid with time, but they become fluid again when heated above a certain temperature called the gel melting point. A technique involving the use of mercury drops was developed to measure this transition. This temperature was evaluated as a function of solids level, water content in the solvent, and the amount of vinyl acetate in the copolymer, dimethylacetamide being used as the solvent. Four other solvents were used to obtain limited data. Gel melting was studied further by differential thermal analysis and shear modulus measurements. The results are discussed in terms of network formation and solubility. The x-ray diffraction results imply that the tie points of the gel are crystalline.
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  • 115
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    Journal of Applied Polymer Science 11 (1967), S. 425-437 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Description / Table of Contents: Methyl methacrylate was grafted onto cellulose using Caro's acid-Fe3+ system as initiator. The effect of grafting time, ferric ion concentration, and cellulose/monomer ratio, on the per cent grafting, was investigated. From studies of the reaction mechanism with model compounds it was postulated that the grafting did not occur at the 1,2-glycol units or at the hemiacetal unit in the end of the cellulose molecule. Concurrent degradation of the cellulose during the graft copolymerization was examined. A linear relationship between the per cent grafting and the number of cellulosic broken chains by hydrolysis was found, from which it would seem that the structure of the graft copolymer was of block-type. The structure of the graft copolymers was also studied by determination of the molecular weights of the grafted PMMA branches, after hydrolysis of the cellulosic backbone. In all cases, independently of reaction conditions, the molecular weights of the grafted branches were very high and their number low. The number of graft branches per cellulose chain was calculated from the per cent grafting, the molecular weights of the PMMA branches and of the cellulosic backbone. This number was compared with the number of cellulosic bonds broken during grafting.
    Notes: Le méthacrylate de méthyle a été greffé a la cellulose en utilisant l'acide de Caro en présence de sel ferrique comme initiateur. L'effet de la durée du greffage, de la concentration en ions ferriques et du rapport cellulose-monomere sur le pourcentage du greffage a été étudié. Au départ d'études du mécanisme de réaction, a des composés modèles, on a admis que les greffages ne se passent pas via les unités glycols 1,2 ou à l'unité hémiacétalique ' la fin de la molécule cellulosique. Des dégradations concommittantes de la cellulose en cours de la copolymérisation greffée a été examinée. Une relation linéaire entre le pourcentage de greffage et le nombre de chaînes cellulosiques briées par hydrolyse a été trouvée, d'où il semble que la structure du copolymère greffé était plutôt du type séquencé. La structure du copolymere greffé a aussi été étudiée par détermination des poids moléculaires des branches de polyméthacrylate de méthyle greffées apres hydrolyse de la chaîne cellulosique. Dans tous les cas, indépendamment des conditions de réaction, les poids moléculaires des ramifications greffées étaient tres élevés et leur nombre faible. Le nombre de branches greffées par chaîne cellulosique a été calculé au départ du pourcentage de greffage, des poids moléculaires des branches de polyméthacrylate et des poids moléculaires de la chaîne cellulosique. Ce nombre a été comparé au nombre de liens cellulosiques brisés en cours de greffage.
    Additional Material: 8 Ill.
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  • 116
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    Journal of Applied Polymer Science 11 (1967), S. 553-566 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Two mercaptosilane monomers were prepared and polymerized by oxidation to yield mercaptan functional silane polysulfide polymers. The mercaptosilane monomers were of the general formula, [HS(CH2)x]2SiY2, where x = 3 and Y = Et or Me. These monomers were prepared by the addition of thiolacetic to diallyldialkylsilanes. The dithioldiacetate that resulted from the addition reaction was hydrolyzed in alcoholic NaOH yielding the dimercaptan. Polymerization of the dimercaptan was accomplished with peroxides, iodine, or sulfur, yielding polymers of a molecular weight of approximately 1200. These polymers were cured to solid elastomers with mild oxidizing agents. The mercaptan monomers were also redistributed with diethylformal polysulfide polymers, which were then cured to solid elastomers with mild oxidizing agents. The redistributed silane-diethylformal polymers were used to make composite solid propellants. A 50% increase in propellant burning rate and a 16°C. lowering of the glass transition temperature were found when the redistributed polymer was used in place of diethylformal polymers as a propellant binder. Experimental procedures are given.
    Additional Material: 3 Ill.
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  • 117
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    Journal of Applied Polymer Science 11 (1967), S. 575-585 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The change of the viscoelastic behavior of an unsaturated polyester resin during curing was followed by a vibrometric technique, while the portion converted to gel in applied films was also determined by means of extraction with a solvent. Some relationship between the viscoelastic properties and the amount gelling has been found to exist. The dependency of the curing rate of polyesters on the concentration of initiator as well as accelerator seemed not to be unity. A marked delay in cure has been observed in the region of low concentrations of initiator and accelerator.
    Additional Material: 9 Ill.
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  • 118
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    Journal of Applied Polymer Science 11 (1967), S. 639-657 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The purpose of this paper is to show how a theoretical molecular weight distribution can be found which would result in a given gel permeation chromatogram. Also, to show how the method can be applied to blending problems where one desires a given molecular weight distribution.
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  • 119
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    Journal of Applied Polymer Science 11 (1967), S. 727-734 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A two-step procedure for the preparation of methyl cellulose nitrate is described. The heterogeneity of the methylation step is reflected in the nonuniformity of the products obtained by nitration with either 98% nitric acid or a solution of 98% nitric acid in methylene chloride. On the basis of the experimental data it is calculated that methyl cellulose having a minimum degree of substitution of 1.8 is required for the preparation of a uniformly substituted methyl cellulose nitrate.
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  • 120
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    Journal of Applied Polymer Science 11 (1967), S. 753-771 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The polymerization of β-propiolactone (βPL) by sodium acetate catalyst has been investigated. The polymerization behavior with monomer purified with calcium chloride was found to be a little different from that previously reported for this monomer. That is, poly-β-propiolactone (PβPL) obtained from βPL dried with CaCl2 has a higher degree of polymerization than that obtained from conventionally treated βPL, and its infrared spectrum shows type II configuration, which differs from that reported in previous papers. Some chain transfer reaction is observed even for the polymerization of the CaCl2-dried βPL; however, this is less important in toluene. The electronegativity of the anion or cation in catalyst greatly influences the rate of polymerization.
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  • 121
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    Journal of Applied Polymer Science 11 (1967), S. 1009-1026 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: This paper describes an investigation into the degradation of a purified epoxide based on the diglycidyl ether of bisphenol A hardened with p,p′-diaminodiphenylmethane. The method used was that of hot-wire pyrolysis followed by gas chromatography. Special attention was given to the problem of solid residues formed on the pyrolyzer tube, and evidence was found that these probably contain oligomers. Resonance-stabilized free radicals also appear to be formed, and evidence is found to support the idea of dehydration during degradation, originally put forward by Lee. An attempt, based on first principles, is made to explain the degradation of epoxides, using evidence from previous work as well as that described in this paper.
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  • 122
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    Journal of Applied Polymer Science 11 (1967), S. 1043-1053 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Time dependence in the melt indexing of polyolefins stabilized against thermally induced changes is well known, the prevalent effect being an increase in melt index toward a steady-state value. The melt index of polyethylenes compounded with carbon black has been found to decrease, in some cases radically, although oxygen uptake data show no evidence of thermal instability. The melt index-time plot can be restored to its normal shape by adding excess quantities of a standard thioether antioxidant. Data are rationalized by assuming that polyethylene adsorbs on the available pigment surface, forming a crosslink network. The thioether antioxidant, however, may adsorb preferentially, thereby restoring the normal response of the polymer to forces resulting in its capillary extrusion. The results emphasize the contribution of chain orientation effects to the time dependence of melt index.
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  • 123
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    Journal of Applied Polymer Science 11 (1967), S. 1079-1086 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A method is described for deriving by digital computer a temperature program which, when applied to batch polymerization, will keep the supply of new free radicals constant throughout the main part of the reaction.
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  • 124
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Reactions of various monoepoxides and diepoxides with diethylaminoethyl (DEAE) cellulose in the absence and presence of external catalysts have been studied. In the absence of additional catalysts, many epoxides which did not react with the unmodified cotton reacted with DEAE-cotton. Others, which reacted with unmodified cotton in the presence of external bases, imparted different properties when catalyzed by the builtin tertiary amino groups of DEAE-cotton. For example, epichlorohydrin reacted with DEAE-cotton to produce a fabric with excellent conditioned recovery, good wet recovery, and strong-base anion exchange properties. The same epoxide imparted only wet crease recovery to cotton when the reaction was catalyzed by external bases. Phenyl glycidyl ether and styrene oxide reacted with DEAE-cotton to produce a fabric with twentyfold improvement in resistance to flex abrasion. With 8% aqueous NaOH as an external catalyst, the DEAE-cotton displayed greater reactivity with all epoxides than did the unmodified fabric. DEAE-cotton-diepoxide reactions with added base catalyst generally resulted in a decrease in the conditioned recovery angle and an increase in the wet recovery angle. When Zn(BF4)2 was used as an additional catalyst, again the DEAE fabrics displayed the greater reactivity toward the monoepoxides; but the unmodified cotton was more reactive toward the diepoxides than was the DEAE-cotton. The Zn (BF4)2-monoepoxide-treated DEAE fabrics had higher wet recovery angles but lower dry recovery angles than the corresponding epoxide-finished control cottons. Butadiene diepoxide was the only diepoxide investigated which imparted higher dry recovery angles to the DEAE-cotton than to the unmodified cotton control in the presence of Zn(BF4)2. Tertiary amino groups in DEAE-cottons act as an internal catalyst for the opening of the oxirane rings, direct the site for reaction in the absence of additional catalysts, and react with some epoxides to form quaternary nitrogen groups.
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  • 125
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    Journal of Applied Polymer Science 11 (1967), S. 687-698 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The oscillating flow behavior of a variety of high-density polyethylene and copolymer samples was studied in a constant displacement rate rheometer. At any plunger velocity, the period of the oscillations decreases linearly with melt depth, suggesting a resonance phenomenon. As plunger velocity is increased, the load waveform changes in a regular manner that indicates a progressive increases in the proportion of each cycle spent on the right-hand branch of the flow curve. Little difference was found in the shear stress at which oscillating flow began for samples differing in molecular weight, molecular weight distribution, and manufacturing process. However, the shear rate at which oscillating flow begins depends, strongly on both molecular weight and distribution. Oscillating flow is shifted to higher shear rates by broadening distribution, reducing molecular weight, increasing temperature, or decreasing the L/D ratio of the capillary.
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  • 126
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    Journal of Applied Polymer Science 11 (1967), S. 859-870 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The kinetics of the radiation-induced grafting of styrene to cellulose in methanol have been studied in air at dose rates of 0.007, 0.014, and 0.078 Mrad/hr. in 60Co and spent fuel element facilities. The variables affecting rate of grafting include monomer concentration, radiation dose rate, and total dose. Grafting reaches a maximum at 60-70% by volume methanol in styrene. The results have been interpreted in terms of possible grafting mechanisms, including charge-transfer intermediates; however, a complete mathematical treatment of the data is not possible at present because of the absence of appropriate swelling data for cellulose in mixtures of styrene and methanol. Poor grafting observed in solutions of up to 10% monomer is attributed to radical scavenging (predominantly from the solvent) by the monomer leading to the formation of scavenged products including homopolymer. Rate of grafting falls off for solutions above 80-90% monomer concentration and radical scavenging by monomer radicals is again postulated to account for the observed behavior.
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  • 127
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    Journal of Applied Polymer Science 11 (1967), S. 909-919 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Ion-permselective membranes containing polyethylene in their base material have been examined by direct transmission electron micrography and x-ray diffraction. All of the electron micrographs showed white lines of about 100 A. thickness between somewhat thinner black lines composed of granules. These lines often occur as black-white-black triplets. We tentatively explain these structural elements by assuming that they are cross sections of the crystallite platelets, characteristic for polyethylene, reacted on both of their faces during sulfochlorination. It is known, that these platelets are about 100 A. thick, X-ray diffraction experiments also showed the characteristic lines of polyethylene crystallites, their intensity decreasing after sulfonation. The velocity of heterogeneous sulfochlorination of polyethylene sheets decreases abruptly when the film contains 6% S and 7% Cl (after hydrolysis). This m̰eans six substituted sites on a chain element across the platelet for a 100% crystalline film and accordingly less for a partially amorphous material. It is known that five CH2 groups of each chain element are exposed at the surface of the platelets, in good agreement with our findings.
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  • 128
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    Journal of Applied Polymer Science 11 (1967), S. 1539-1552 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A large-scale fractionation of poly(vinyl chloride) (3000 g.) has been carried out by a fractional precipitation method. The molecular weight distribution of some fractions has been controlled by refractionation. The fractions have been also characterized by viscometry, osmometry, light-scattering, and glass transition temperature measurements. The data available in literature concerning the molecular weight characterization of poly(vinyl chloride) fractions have been critically reviewed. It has been shown that most of the viscometric and osmometric data are in good agreement when the molecular weights are below 105. Above 105 the literature discrepancies can be attributed to aggregation.
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  • 129
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    Journal of Applied Polymer Science 11 (1967), S. 1571-1579 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The effect of preheat treatment at temperatures below the glass transition for various periods of time on selected properties of molded polycarbonate has been studied. Changes in tensile and flexural strength as functions of time and preheat temperature (80-140°C.) were determined and these are discussed in relation to changes in the nature of the β-transition region and the influence of the glass transition region. It is suggested that the preheat treatment produces a greater degree of order within the amorphous region of the polymer, resulting in an increase in strength at temperatures up to 132°C. The strength of the polycarbonate before and after heat treatment appears to be independent of the presence of the equilibrium water content.
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  • 130
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    Journal of Applied Polymer Science 11 (1967), S. 1593-1602 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Gel-point calculations based on the theory of polyesterification proposed by Flory do not agree with the experimental values even when Bobalek's concept of gel point as the first formation of infinite molecules (microgel) is used. Resins covering the range 30-60% oil length were prepared and examined by electron microscopy for the presence of microgel particles. The extent of reaction at which microgel forms is discussed in relation to the concept of equal reactivity. The conditions necessary for the formation of microgel particles and the significance of these observations to the basic assumptions used in developing the theory of polyesterification are discussed.
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  • 131
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    Journal of Applied Polymer Science 11 (1967), S. 1641-1647 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The thermal degradation in oxygen of fifteen polymers containing aromatic rings in the chain has been studied by a weight loss method. The relative thermal stabilities of the different polymers have been determined and, where possible, the overall activation energy for breakdown. The results have been compared with those for samples of the same polymers degraded in vacuum. The most thermally stable of the polymers examined under oxidizing conditions was poly(2,6-dichlorophenylene oxide), with a stability comparable with that of a copolymer of tetrafluoroethylene and hexafluoropropylene.
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  • 132
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    Journal of Applied Polymer Science 11 (1967), S. 1667-1682 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Oil-bearing formations often consist of loose sandy material. In the production of oil from these formations sand tends to be carried to the well bore along with the oil. The flow of sand can be prevented by consolidating or cementing together the sand particles of the formation around the well bore. The cementing has to be accomplished in such a manner that fluid flow channels between particles remain open. This paper describes a new three-step process that was developed to consolidate oil well sand. The steps in the process involve injection of: (1) resin, (2) inert fluid, and (3) inert fluid containing a catalyst. In the first step of the process, resin in injected into the formation where it fully saturates the interstices between sand grains. Permeability is established in the second step by displacement of the excess resin from the interstices, thereby leaving a thin film of resin on the sand grains. In the third step, polymerization is activated by migration of catalyst from the inert fluid into the thin resin film on the sand. The process has the advantage that resin is placed and permeability is established before the resin is catalyzed. This avoids premature polymerization of the resin which might cause plugging of the formation or the tubing string used to inject resin. Desirable characteristics of a resin for the three-step process are: (1) viscosity of 25-200 cp. at well bore temperature; (2) stability for several days at well bore temperature; (3) high adhesion to sand in the presence of an inert flushing fluid; (4) polymerization by less than 10% catalyst; (5) the polymerized resin binds sand together with a strong bond that is not affected by well fluids. Five different resin types have been tested for use in the three-step sand consolidation process. These are: (1) epoxy-anhydride cured with a tertiary amine; (2) epoxy-epoxy diluent cured with a primary-tertiary amine mixture; (3) furan; (4) unsaturated polyester-vinylpyrrolidone; (5) unsaturated polyester-styrene. The two epoxy resins give strong, permeable consolidated sand which is resistant to well fluids such as brine and crude oil. The furan resin gives a weak consolidation. The unsaturated polyester-vinylpyrrolidone gives good strength and oil resistance but is sensitive to brine. The unsaturated polyester-styrene is difficult to apply. Many oil wells have been successfully treated in the Gulf Coast area and in California with the two epoxy resins. Almost all of these wells are producing free of sand, and, to date, more than five million barrels of oil have been produced from these wells.
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  • 133
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    Journal of Applied Polymer Science 11 (1967), S. 417-424 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Bueche's theory is modified to account for the effect of polydispersity on viscosity of polymeric fluids. Results indicate that the ratio of weight-average to number-average molecular weight, 〈Mw/Mn〉, though a common measure of polydispersity, is insufficient to account completely for the effect of polydispersity on viscosity.
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  • 134
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    Journal of Applied Polymer Science 11 (1967), S. 1315-1323 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The fracture edge of a strip of regenerated cellulose film broken under tension can usually be divided into three regions: (A) the site of the initial failure, (B) the slow-tear region, and (C) the fast-tear region. Photomicrographs showing these regions are presented and discussed. Three different types of initial failure are described and some data presented relating the breaking strain to the type of initial failure.
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  • 135
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A study of the effect of catalyst (base) concentration and N-acylcaprolactam cocatalyst size and substitution on the fast anionic polymerization of caprolactam indicated that a steric effect due to cocatalyst size exists, and perhaps an electronic effect due to cocatalyst substitution was noted. The rate of polymerization, degree of polymerization, and yield of polymer are related to these effects. It was also noted that at high base concentrations, the rate and degree of polymerization along with the product yields all decrease. These latter observations suggest that reinterpretation of some of the reaction mechanism data may be important if polymer degradation is not an appreciable factor during the reaction.
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  • 136
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    Journal of Applied Polymer Science 11 (1967), S. 1361-1369 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Introduction of primary covalent crosslinks into linear, segmented elastomers was followed by observing their modulus-temperature behavior. The behavior of the linear segmented polymers is explained by association of glassy segments into regions which act as filler and quasi-crosslink. In several cases crosslinkage disrupts these regions and thereby lowers the “plateau” modulus.
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  • 137
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    Journal of Applied Polymer Science 11 (1967), S. 1431-1438 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Several phosphorus derivatives of methyl 2-(chloromethyl)acrylate, including three phosphonium salts and one phosphonate ester have been prepared. A brief study was made of their polymerization characteristics under free-radical conditions. Several factors were noted which prevented the synthesis of methyl 2-[(diethoxyphosphinyl)-methyl]acrylate in high yields in initial experiments. Homopolymerization of these phosphorus derivatives does not take place readily in the presence of free-radical initiators.
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  • 138
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    Journal of Applied Polymer Science 11 (1967), S. 1449-1460 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Differential thermal analyses of many 66 nylon samples have shown two endotherms in the melting range. This effect occurs with drawn nylon yarn, as previously observed by White, and also with annealed and precipitated nylon samples. Methods for the preparation of these samples are reported. At 242°C. the development from the melt of crystalline material which gives two melting peaks is associated with annealing rather than with the primary crystallization process. Previous observations of multiple melting peaks with other polymers are discussed.
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  • 139
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    Journal of Applied Polymer Science 11 (1967), S. 1475-1481 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Dynamic mechanical measurements were made with a torsional pendulum of a TiO2- filled epoxy polymer (crosslinked with hexamethylene diamine) over a temperature range from 20-90°C., at filler concentrations of 0-40 wt.-%. The second-order transition temperature (Tg) was raised as the filler content increased. The behavior of TiO2 filler results in a long-range immobilization of the highly crosslinked system with resultant increases in shear modulus (higher G′) as well as decreased capacity for energy dissipation (lower damping factor). The out-of-phase modulus (G″) increased with filler content as well. The magnitudes of the slope parameters Hr (representing G′ data above Tg) and Hg (representing G′ data below Tg) decreased with greater filler content. The possibility is set forth that the TiO2 filler causes a different distribution of mobility around the nitrogen junction as well as a change in the effective number of CH2 units between crosslinks.
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  • 140
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    Journal of Applied Polymer Science 11 (1967), S. 1603-1611 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Graft copolymerization of natural rubber and MMA was carried out in the presence of Bz2O2 or AIBN as thermal initiator and hydrogen peroxide or benzophenone as photosensitizer. From the overall copolymerization product, the rubber-PMMA graft copolymer fraction was isolated from unreacted rubber and free PMMA fractions and composition characterization of the separated fractions was done by determination of rubber unsaturation. The efficiency of grafting under different conditions has been calculated and compared.
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  • 141
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    Journal of Applied Polymer Science 11 (1967), S. 817-828 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The present paper describes the results of a preliminary study of certain physical and thermal properties of benzhydrylated cotton yarns. The 200-yd. lengths of 7/2 yarn consisting of purified mercerized cellulose were reacted in a special reactor to various degrees of substitution from DS 0.31 to DS 1.22 with benzhydryl bromide in a mixture of equal volumes of 2,6-lutidine and dimethylformamide. The products were examined for tensile strength at break, which decreased only slightly with substitution; ultimate elongation, which was relatively uniform at 60-70% of the control yarn; and tenacity, which decreased with substitution largely due to added weight. The energy of rupture remained relatively constant at about 50% above the control. Tensile stiffness decreased progressively with substitution to about 25% of the control. Density decreased 10-11% with substitution. Crystallinity of the cellulose largely disappeared with substitutions above DS 1, and the lattice of benzhydryl cellulose began to appear. Stiffness, elastic recovery and work recovery were measured on 5-in. specimens of the yarn in an oven while they were subjected to repeated extension to about 1-2% and relaxed as the temperature was raised twice to 200°C. and lowered. During the heating phase of the first cycle the yarn underwent considerable heat adaptation. However, during the cooling phase and during both heating and cooling phases of the second cycle, the yarns showed generally favorable behavior. Attempts are made to interpret the results in terms of molecular modifications.
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  • 142
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    Journal of Applied Polymer Science 11 (1967), S. 901-907 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Infrared spectral analysis has been applied for the study of cotton-polyacrylonitrile copolymers prepared by using the preirradiation method. The degree of grafting was determined from the absorption at 2249 cm.-1, which is characteristic of the polyacrylonitrile spectrum, with an accuracy of ± 1.5%.
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  • 143
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    Journal of Applied Polymer Science 11 (1967), S. 953-961 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: By means of x-ray diffraction, the lattice spacing of the (100) plane for molded polytetrafluoroethylene was measured at different temperatures from 25 to 190°C. In the crystalline region, the linear expansion coefficient, in the direction perpendicular to the molecular chain axis, was obtained as 1.1 × 10-4°C.-1 below 60°C., as 1.2 × 10-4°C.-1 above 90°C., and as a minimum value of some 0.2 × 10-4°C.-1 at about 80°C. As the linear expansion coefficient of the crystalline region in bulk was observed as some 0.6 × 10-4°C.-1, the expansion coefficient in the direction of molecular chain axis must be negative except in the transition region near 80°C. The variation of molecular chain axis separation with temperature showed an irregularity at about 80°C. but none near 130°C. in the crystalline region. Infrared absorbance of film samples of PTFE was measured at different temperatures of 25 to 150°C. range for 518, 627, and 639 cm.-1 bands. On absorbance-temperature curves for those b̰ands, irregularities were observed near 30, 50, 90, and 130°C. Particularly with 518 cm.-1 band, a more crystalline sample gave more distinct irregularities near 50 and 90°C. than a less crystalline sample. The change at about 90°C. in infrared spectra may correspond to that obtained by x-ray measurements near 80°C., which was thought to occur in the crystalline region. The results obtained by x-ray and infrared measurements support the previous results by thermal, rheological, and dielectric methods: there exist first-order transitions in the crystalline region at about 90°C. and second-order transitions in the amorphous region at about 130°C.
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  • 144
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    Journal of Applied Polymer Science 11 (1967), S. 991-999 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Fractions of dimethylsiloxane polymer with viscosity-average molecular weights from 2.4 × 105 to 1.3 × 106 were dissolved in toluene in concentrations from 0.01 to 1.0 g./dl. These solutions were subjected to ultrasonic degradation at 20,000 cps for periods extending to as much as 960 min. in a water-cooled reaction vessel. Gel permeation chromatography shows that samples with different initial distributions approach the same distribution after 120 min. of degradation. Dilution of the polymer from 1.0 to 0.01 g./dl. more than triples the degradation per gram of polymer but requires 10 times as much energy per gram of polymer to degrade from a number-average molecular weight of 106 to 105. Increasing the power input from 36 to 72 w. almost doubles the degradation rate per gram of polymer.
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  • 145
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    Journal of Applied Polymer Science 11 (1967), S. 1903-1914 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The regulating efficiency of four aliphatic mercaptans was studied in emulsion copolymerization of butadiene with styrene, at +5°C. with the use of the redox system, diisopropylbenzene hydroperoxide-complexed ferrous iron-sodium formaldehyde sulfoxylate as an initiator and the sodium soap of disproportionated rosin as an emulsifier. The apparent transfer constants C of tertiary mercaptans decreased logarithmically with increasing length of molecule. This tendency is connected with the analogous dependency of solubilities of these compounds in water. The mercaptans did not affect the rate of polymerization. The value of C is independent of the amount of regulator used. With the value of C, the amount of regulator, and the conversion known, it is possible to predict the molecular weight of the polymers, except for the region of poor regulation, where the deteriorative influence of termination and crosslinking reactions takes place. The apparent transfer constant of tertiary dodecyl mercaptan decreased with increasing rate of polymerization. After elimination of diffuse processes, the value of the actual relative transfer constant was calculated. The tertiary dodecyl mercaptan has been selected as the most convenient molecular weight regulator for emulsion copolymerization of butadiene with styrene of all compounds studied for the system mentioned.
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  • 146
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The manner in which a series of silcarboranylene-siloxane polymers behave in air at elevated temperatures was investigated by thermogravimetric, isothermogravimetric, and differential thermal analyses techniques. Results indicate that methyl pendant groups on the polymers undergo thermal and oxidative degradations at temperatures under 600°C. Final weight losses of the polymers, however, are significantly lower than that shown by dimethylsiloxanes. The reduced volatility is attributed to the inhibition of thermooxidation by the m-carboranylene group in the polymer molecules. This protective influence decreases apparently as the distance between the carborane nucleus and the methyl groups increases.
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  • 147
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Four α,ω-diisocyanates (tetramethylene, hexamethylene, decamethylene, and eicosane) and six α,ω-diacid chlorides (succinyl, adipyl, pimeloyl, sebacyl, dodecane, and docosane) were allowed to react with two types of nylon 66 yarn made from polymers of 14,800 and 21,000 number-average molecular weights. The higher molecular weight yarn had a more ordered structure initially, as indicated by density measurements. Both diisocyanates and diacid chlorides crosslinked the yarn as shown by insolubility in 90% formic acid. Isocyanates were more efficient crosslinking reagents than diacid chlorides. Diacid chlorides caused simultaneous degradation of the yarn. The overall rate of reaction of the reagents with the yarn responded to temperature, reagent concentration, and time as expected for low molecular weight materials bearing the same functional groups. Catalysts had only a small effect on the rate of reaction. The reaction occurred in the less ordered regions of the yarn, as indicated by (1) a faster rate of reaction with the less ordered yarn, (2) the accelerating effect of swelling solvents on the rate, and (3) the reduction in extent of reaction with increase in molecular size of the reagent even though the reaction was not limited by diffusion. Both diisocyanates and diacid chlorides reduced the dyeability of yarn with acid dyes. Diacid chlorides increased the dyeability of yarn with basic dyes and diisocyanates decreased this dyeability.
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  • 148
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    Journal of Applied Polymer Science 11 (1967), S. 2077-2078 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 149
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    Journal of Applied Polymer Science 11 (1967), S. 2097-2108 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: We measured the rate of thermal decomposition of azobisisobutyronitrile (AIBN) from the rate of loss of 2,2-diphenylpicrylhydrazyl (DPPH) on reaction of the free radicals formed by thermal decomposition of azobisisobutyronitrile (AIBN) in organic solvents with DPPH. There has been some doubt about the quantitative relation between AIBN and DPPH required to get the rate constant of thermal decomposition of AIBN. In the past, AIBN has been used in excess, and the rate constants measured by using DPPH are smaller than they ought to be. In our experiments we used as little of AIBN relative to DPPH as possible and obtained a value of 3.8 × 10-4 min.-1 at 50°C. as the rate constant of the first-order reaction, which was shown satisfactorily by the linearity of the graph. We also obtained 32 kcal./mole as activation energy. We were also able to make clear the meaning of the result when a large quantity of AIBN was used.
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  • 150
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    Journal of Applied Polymer Science 11 (1967), S. 2593-2594 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 151
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    Journal of Applied Polymer Science 11 (1967), S. 2331-2341 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The separation of poly(acrylic acid) from its mixtures with polystyrene emulsion by gel filtration, without destroying the state of dispersion, was undertaken. It was found that the poly(acrylic acid) not absorbed on the polymer surface is almost completely seperated by gel filtration, if the ionic strength, in this emulsion is not so high. Furthermore, the gel filtration study revealed that poly(acrylic acid) molecules are not adsorbed on the polymer surface saturated with surfactant molecules, whereas poly(acrylic acid) molecules, when already adsorbed on the polymer surface, are not easily desorbed by adding another surfactant.
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  • 152
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    Journal of Applied Polymer Science 11 (1967), S. 2343-2348 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The process of solid-phase crystallization in poly(ethylene terephthalate) has been followed by means of differential enthalpic analysis. Kinetic data for the process has been obtained for isothermal annealing from 100 to 115°C., showing induction times and first-order rate dependence. For the material studied, undrawn polyester filaments, an activation energy of 44 kcal./mole was determined. The technique used provides more direct monitoring of the crystallization phenomenon than that achieved with other methods.
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  • 153
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    Journal of Applied Polymer Science 11 (1967), S. 2361-2372 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: An electron-microscope technique is presented to permit detailed examination of the fine structure of the rubber particles in reinforced polystyrenes. Several rubber-modified polystyrenes, prepared by different methods, have been examined by this technique, and the resulting photomicrographs compared with those of the previously used phase contrast method. Polymers produced by the agitated-solution process are examined in more detail. It is shown that the rubber particle fine structure is basically unaltered as the amount or type of rubber is changed or if the polymer is diluted by mechanically blending with polystyrene. It is characterized by the presence of numberous polystyrene occlusions within the particle.
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  • 154
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    Journal of Applied Polymer Science 11 (1967), S. 2373-2379 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Poly(methyl methacrylate) has been photolyzed with 2537 A. radiation in dioxane and in methylene chloride at about 25°C. in the presence and absence of air. In degassed solutions, quantum yields for random scission are only slightly affected by either intensity or polymer concentration. Oxygen is an apparent inhibitor for photodegradation. The inhibiting and sensitizing effects of a variety of added solutes, including aromatic hydrocarbons, aliphatic dienes, and ketones were investigated; the behavior is similar whether or not oxygen is present. The results are best explained on the basis of an electronic energy transfer mechanism involving the lowest excited triplet levels of the polymer and the added solutes.
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  • 155
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    Journal of Applied Polymer Science 11 (1967), S. 2397-2398 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
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  • 156
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    Journal of Applied Polymer Science 11 (1967), S. 2485-2497 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The physical properties of nylon 66 yarn treated with α,ω-diisocyanates (tetramethylene, hexamethylene, decamethylene, and eicosane) and diacid chlorides (succinyl, adipyl, pimeloyl, sebacyl, dodecane, and docosane) were compared to the properties of a control exposed to the same reaction conditions but without the reagent being present. Two types of yarn were used: (1) a highly ordered yarn, as judged by density and x-ray, from polymer of number-average molecular weight 21,000; and (2) a less-ordered yarn from polymer of molecular weight 14,800. Treatment was carried out with yarn in both constant-length and relaxed conditions. The properties were changed most by constant-length treatment and by the use of less-ordered yarn. Treatment with diisocyanates resulted in an increase in the tenacity and modulus simultaneously. The strength properties often went through a maximum as a function of the degree of reaction. Treatment with diacid chlorides degraded the physical properties as a result of polymer chain scission and weakening of the interchain forces. Treatment with either type of reagent lowered the zero strength temperature, but had little effect on the moisture regain or ability of the yarn to dissipate static electricity.
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  • 157
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    Journal of Applied Polymer Science 11 (1967), S. 2515-2523 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The orientation factor by infrared dichroism of polypropylene film was compared with the other orientation factors. After the correction of imperfect polarization and the suitable choice of the base line, it was found that infrared dichroism is a reliable indicator of the orientation factor. Orientation factors obtained from the 998 and 842 cm.-1 bands agreed with the x-ray orientation factor, and that from the 975 cm.-1 band agreed with the optical orientation factor.
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  • 158
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    Biotechnology and Bioengineering 9 (1967), S. 33-44 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The bacterial degradation of catechol, 3-methylcatechol, 2,3-dihydroxy-β-phenylpropionic acid, and protocatechuic acid has been studied in detail. From the results obtained a general sequence has been proposed for the microbial oxidation of dihydroxy aromatic compounds.
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  • 159
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    Biotechnology and Bioengineering 9 (1967), S. 91-105 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 160
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    Biotechnology and Bioengineering 9 (1967), S. 585-602 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A continuous culture apparatus of 5-liter capacity is described which is capable of control of dissolved oxygen. Combined turbidostat and constant feed operation permit control of cell population density and one or more nutrients. A system for the measurement of oxygen uptake and CO2 output is described. Sufficient detail is supplied to enable construction and operation of the apparatus.
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  • 161
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    Biotechnology and Bioengineering 9 (1967), S. 617-622 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The yeast S. cerevisiae was grown on dilute, chemically defined media in continuous culture with either glucose or ammonium sulfate as the growth-limiting ingredient. Changes in dilution rate or glucose concentration induced decaying oscillations in the numbers of yeast growing on ammonium sulfate-limited media. Spot checks indicated that Cell dry weight and Kjeldahl nitrogen followed the cell numbers during these oscillations. With glucose-limited media, there was no response to step changes in ammonium sulfate concentration, and dilution rate step changes gave non-oscillatory transient responses.
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  • 162
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    Biotechnology and Bioengineering 9 (1967), S. 545-558 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Interfacial phenomena are directly involved in the adhesion of a strain of Chlorella, a unicellular alga, to glass surfaces in simple ionic solutions. The principal mechanisms governing the adhesion appear to be electrostatic interaction between electrical double layers and various specific surface interactions resulting from surface heterogeneity and ion adsorption. Under most conditions the algal cells and glass surfaces have negative zeta potentials, and adhesion to glass will not occur; but if, for example, FeCl3 is added to an algal-glass system immersed in 0.05M NaCl, the algal and glass surfaces will possess very different zeta potentials, and adhesion will be strongest under those conditions which produce the greatest, difference in zeta poentials. Prior pretreatment and usage of glass apparatus greatly affect the glass zeta potentials and the adhesion of algal cells to glass. An apparatus for measuring a relative set of numbers representing the force of adhesion of algal cells is described.
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  • 163
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    Biotechnology and Bioengineering 9 (1967), S. 623-625 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Ill.
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  • 164
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    Biotechnology and Bioengineering 9 (1967), S. 635-639 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Steam-sterilizable membrane probes that are virtually maintenance-free and capable of operation for over 1 year are described. The probes can withstand repeated steam sterilizations. They have a silver cathode, a lead anode, an acetate buffer, and a Teflon membrane. The probes have a linear response from below 0.00002 to over 0.2 atm. of oxygen.
    Additional Material: 5 Ill.
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  • 165
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    Biotechnology and Bioengineering 9 (1967), S. 515-531 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A method for the control of dissolved oxygen tension in growing microbial cultures is described. The apparatus consists of a motor-driven air sparge pipe which may be lowered or raised to give a variable point of entry of the air stream into the culture liquid and hence a variable gas dispersion and gas-liquid contact time. Control of the sparge pipe position is by means of a feedback control loop consisting of a dissolved oxygen probe, an on/off controller, and a reversing electric motor which drives the sparge pipe. The difficulty presented by the relatively slow response of the oxygen probe has been overcome by incorporating an adjustable rate of control action.
    Additional Material: 10 Ill.
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  • 166
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    Biotechnology and Bioengineering 9 (1967), S. 559-574 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An electronic apparatus is described that permits rapid determination of the concentration and size distribution of bacteria in electrolyte suspensions by a resistance method. The resulting size-concentration distribution may be displayed on an oscilloscope and recorded with an X-Y plotter and an electric typewriter-tape punch unit. The paper tape is analyzed with a computer program. Comparisons are made between electronic measurements of bacterial cell concentration and size distribution and values obtained by other methods. Effects of heat-killing and disruption of the cell membrane on the electrical counting characteristics of the organisms are discussed.
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  • 167
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Conditions for the preparation of an aminoacylase column using DEAE-Sephadex as a carrier were investigated. The aminoacylase column having the highest activity was obtained when 7500 μmoles/hr. of partially purified aminoacylase was charged into a column packed with 9 ml. of DEAE-Sephadex A-25 (bead type, hydroxy form). By employing a DEAE-Sephadex-aminoacylase column, conditions for continuous optical resolution of acyl-DL-amino acids were investigated. When a solution of 0.2M acetyl-DL-methionine (pH 7.0, containing 5 × 10-4M Co2+) or 0.2M acetyl-DL-phenylalanine (pH 6.0, containing 5 × 10-4M Co2+) was passed through the aminoacylase column at the flow rate of SV = 2.5 or 2.0, respectively, at 50°C., the highest rate of hydrolysis of both substrates was attained. From the column effluents, enzymatically hydrolyzed L-methionine and L-phenylalanine were isolated in a good yield.
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  • 168
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    Biotechnology and Bioengineering 9 (1967), S. 630-634 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A device is described for aseptically metering liquids at rates as low as 10 ml./hr. The metering rate is constant, but can be readily changed. The device delivers a measured increment of liquid every 10 sec. The volume added is controlled by electrical contants in an electrolyte tube. The medium does not enter this tube.
    Additional Material: 2 Ill.
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  • 169
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    Biotechnology and Bioengineering 9 (1967), S. 429-437 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An aflatoxin-producing isolate of Aspergillus flavus was found to be a consistent producer of aflatoxin on all substrates which supported the growth of the mold. In competition with six other selected molds, this isolate was dominant except with one species of Penicillium. Aflatoxin production was parallel to the extent of A. flavus growth whether effected by substrate or competition.
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  • 170
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    Biotechnology and Bioengineering 9 (1967) 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 171
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    Biotechnology and Bioengineering 9 (1967) 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 172
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    Biotechnology and Bioengineering 9 (1967), S. 187-194 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An experimental investigation is presented of the foam separation of six species of bacteria: Escherichia coli, Serratia marcescens, Proteus vulgaris, Pseudomonas fluorescens, Bacillus cereus, and Bacillus subtilis var niger. A cationic surfactant, ethylhexadeeyldimethylammonium bromide is used and results are evaluated in terms of total cell count, using a membrane filtration technique. From similar neutral distilled water suspensions of the pure cultures (approximately 107 cells/ml.) and using the same operating conditions, ratios of cell concentrations in the residual suspensions to those in the initial suspensions range from 0.0013 for Bacillus subtilis var niger to 0.25 for Serratia marcescens. The presence of bacteria, compared to pure surfactant solutions, produces lower collapsed foam volumes; the foam volumes have a strong influence on the separations achieved with the various species, with enrichment ratios ranging from 27 to 3088 and residual ratios ranging from 0.001 to 0.247.
    Additional Material: 2 Ill.
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  • 173
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    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Studies are made of the behavior of liquid contents in a closed cylindrical vessel vibrated vertically along its axis. The situation is one which had been investigated by Rodgers and Hughes (1960) because of applications in microbiology and biochemistry. By use of motion pictures it was found that surface waves develop, sonic fog is produced, and air bubbles are formed at the onset of the motion. Bubbles then move downward until, under conditions of practical interest, air is divided equally between top and bottom of the vessel. Steady-state vertical oscillation of the central liquid body then ensues, superposed on turbulent action of air-water mixtures at the top and bottom of the vessel. Reference is made to available theory for surface wave excitation, and bubble migration. A nonlinear differential equation is considered for the steady-state oscillation.
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  • 174
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    Biotechnology and Bioengineering 9 (1967), S. 273-273 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 175
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    Biotechnology and Bioengineering 9 (1967), S. 343-356 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Some of the problems involved in the scale-up of enzyme isolation procedures have been examined. In particular the isolation of prolyl-tRNA synthetase has been investigated. Using a modified procedure (500 × laboratory scale) the enzyme has been separated from 25 kg. of Phaseolus aureus (mung bean) and Partially purified by acid precipitation followed by fractional precipitation with ammonium sulfate. The yield of enzyme was 42 g. (10.5% recovery).
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  • 176
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    Biotechnology and Bioengineering 9 (1967), S. 357-364 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The design and operational characteristics of a sell-priming aerator are described. The aerator works without a compressor. H sucks the desired air quantity into the tank and distributes it, uniformly and in very fine bubbles over a certain cross-section. The design and operational characteristics of a mechanical defoamer are described. The defoamer is mounted to the top of the fermentation tank and separates foam by centrifugal force into air and liquid. It is capable of handling foams of different composition and quality without, the addition of anti foam agents. Using submerged vinegar fermentation, production of baker's yeast., and industrial waste, water treatment as examples, the performance of aerators and defoamers of different, sizes is discussed.
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  • 177
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    Biotechnology and Bioengineering 9 (1967), S. 413-427 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The alcoholic fermentation of grape juice by a wine yeast was studied batchwise at pH 3.6 and 4.05 to develop kinetic equations relating cell concentration, N, to product concentration, P. In the exponential growth phase \documentclass{article}\pagestyle{empty}\begin{document}$$ dP/dt + BP = A{\rm ln}N/\mu - C $$\end{document} where A, B, and C are constants, and μ is the specific growth rate. In the stationary phase, where the cell population is constant, \documentclass{article}\pagestyle{empty}\begin{document}$$ dP/dt = B(P_m - P) $$\end{document} was found to apply. This equation, which incorporates a stoichiometric constant, Pm, predicted correctly the operation of a continuous fermentor at pH 3.6 and at 4.05. To study more fully the effect of alcohol concentration on yeast growth, a continuous fermentor was used in which the grape juice feed was supplemented with pure alcohol. At pH 3.6 the specific growth rate varied as, \documentclass{article}\pagestyle{empty}\begin{document}$$ ({\rm 1}/N)(dN/dt) = \mu _{{\rm max}} [{\rm 1} - 0.235(P - 2.6)] $$\end{document} There was no growth inhibition below an alcohol concentration of 2.6 g./100 cc., but inhibition was complete above 6.85 g./100 cc. This is a modified form of the relation suggested by Hinshelwood.1 The data suggest that growth in batch culture was limited not only by alcohol but also by some other factor, probably a nutritional deficiency.
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  • 178
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    Biotechnology and Bioengineering 9 (1967), S. 443-447 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A description is given of a large glass vessel suitable for growing algae and other microorganisms in shaken culture. The main feature of the flask is the coneshaped base around which water circultes when the flask is shaken on a reciprocal mechanism.
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  • 179
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    Biotechnology and Bioengineering 9 (1967), S. 471-485 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In bacterial extraction of copper from low-grade copper sulfide ores, at least three contributions are made by Thiobacillus ferrooxidans. They are: (1) enzymatic oxidation and consequent solubilization of insoluble sulfides; (2) regeneration of ferric lixiviant for chemical oxidation and solubilization of insoluble sulfides; and (3) partial fixation of externally introduced iron in the ore. Although it is not possible at the present time to measure each of these contributions separately, it is possible to measure the combined contributions. Such measurements reveal a strong dependence of extraction efficiency on various physical, chemical, and biological factors. The following physical factors may affect the rate of bacterial copper extraction: particle-size of ore, oxygen and carbondioxide supply, oxidation-reduction potential, pH, temperature, adsorption and ion exchange capacity of ore, and surface tension effects. The following chemical factors may influence the rate of copper extraction: the mineralogy of the ore, the nature of the gangue, the distribution of the sulfide minerals in the host rock, the external supply of ferrous or ferric iron, and the availability of inorganic and organic nutrients. Finally, the following biological agents in addition to T. ferrooxidans may influence the rate of copper extraction: fungi, protozoa, Thiobacillus thiooxidans, and heterotrophic bacteria. Proper control of these various factors is essential for efficient bacterial extraction of copper from low-grade ore. It is recognized that the foregoing environmental factors also influence chemical copper extraction.
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  • 180
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    Biotechnology and Bioengineering 9 (1967), S. 321-327 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Geosmin, an earthy smelling substance, has been obtained from several actinomycetes in addition to those previously reported. On the basis of the NMR and mass spectra of geosmin and its acid transformation product, argosmin, tentative partial structures have been proposed for both.
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  • 181
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    Biotechnology and Bioengineering 9 (1967), S. 533-544 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A rapid and internally consistent technique has been developed to measure the volumetric oxygen transfer coefficient, kLa, in fermentation systems. The method consists of tracing the dissolved O2 concentration of the fermentation broth during a short interruption of the aeration. The O2 concentration trace thus obtained can be analyzed to determine the values of kLa. Additional experiments on prolonged O2 starvation, carried out to find the limitation of the technique, suggest that O2 uptake rate will vary if a prolonged (2-10 min.) O2 starvation occurs.
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  • 182
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    Biotechnology and Bioengineering 9 (1967), S. 45-54 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The production of L-glutamic acid from hydrocarbons by a newly isolated bacterium, which was identified as Corynebacterium, was investigated. The outstanding characteristic of this bacterium was found to be an accessory requirement of thiamine for growth. The optimum concentration of thiamine for growth was 50 μg./liter, while that for L-glutamic acid production was 3-5 μg./liter. n-Paraffins ranging from dodecane to heptadecane were best for L-glutamic acid production, and about 5 g. of L-glutamic acid were obtained from 30 g. of these individual n-paraffins. On the other hand, a tracer experiment using oxygen-18 revealed that molecular oxygen was incorporated into L-glutamic acid produced from dodecane. Based on the incorporation value of molecular oxygen in L-glutamic acid, a hypothetical pathway for the biosynthesis of L-glutamic acid from dodecane was discussed.
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  • 183
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    Biotechnology and Bioengineering 9 (1967), S. 77-89 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Although air-lift fermentors have been employed industrially and in the laboratory, little information has been published on the effects of design on performance. With respect to both liquid circulation and mass transfer, not only the actual rates but the efficiency in relation to power consumption is strongly influenced by lift height and diameter, submergence ratio, and air-flow rate. Relatively wide tubes, operating at high submergence ratios and rather low air-flow rates favor high efficiency. Since these conditions lead to rather low absolute values of circulation and mass-transfer rates, the microbial population which can be supported will also be rather small. Mass transfer can be increased by the insertion of an orifice some distance; above the air-inlet point and by suitable arrangement of the discharge from the air lift into the headspace of the fermentor.
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  • 184
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    Biotechnology and Bioengineering 9 (1967), S. 171-186 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Submerged acetification experiments were performed to determine conditions necessary for the production of a satisfactory vinegar from waste pineapple juice using a pure culture inoculum. Vinegars containing up to 7%, by weight of acetic acid could be produced in less than 24 hr. with a conversion efficiency greater than 90% in both laboratory and pilot plant equipment. None of the bacterial nutrients added to the juice improved either the rate of production or the yield of acetic acid. Oxygen transfer during the process is discussed.
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  • 185
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    Biotechnology and Bioengineering 9 (1967), S. 223-233 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: (1) Samples of yeast which varied over an arbitrary 0-100% scale with respect, to cytochrome concentration were prepared. (2) The reflectance spectrum of each sample was scanned. (3) These reflectance spectra were analyzed numerically on a digital computer to determine the bandwidths and intensities as a function of cytochrome concentration. Band shapes using the profiles of Cauchy, Gauss, and Giovanlelli were used. The correlations may be used to estimate cytochrome concentrations with a standard deviation of about 3%.
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  • 186
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    Biotechnology and Bioengineering 9 (1967), S. 271-272 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 1 Ill.
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  • 187
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    Biotechnology and Bioengineering 9 (1967), S. 289-304 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 7 Tab.
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  • 188
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    Biotechnology and Bioengineering 9 (1967), S. 329-342 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A process for manufacturing disodium 5′-guanylate was devised. 5′-Amino 4-imidazole carboxamide riboside (AICA-R) was accumulated with an amount over 100 times those reported in the literature by fermentation of D-glucose with a non-exacting purineless mutant derived from Bacillus megaterium JAM 1245) by x-ray irradiation. The influence of RNA, amino acids, and salts on AICA-R accumulation was clarified. Appropriate aeration and agitation was found necessary. The (60-hr, cultivation of the medium containing 8% of D-glucose gave AICA-R in the concentration above, 11 g/l. AICA-R thus accumulated was separated from the fermentation broth by ion-exchange technique and subjected to synthetic processes to yield disodium 5′-guanylatc with the yield over 40%, based on AICA-R.
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  • 189
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    Biotechnology and Bioengineering 9 (1967), S. 25-32 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Microorganisms have been found which concomitantly convert hydrocarbons, selected naphthenic acids, and atmospheric nitrogen into cellular substance. Bacteria are included in the genera Pseudomonas, Mycobacterium, and Azotobacter. Carbon sources utilized include the hydrocarbons methane, n-butane, n-tetradecane, toluene, and a naphthenic acid, cyclohexane-carboxylate. Uptake of isotopic nitrogen was employed as a criterion of nitrogen fixation. The results indicate a rather wide prevalence in nature of hydrocarbon-oxidizing bacteria capable of fixing atmospheric nitrogen. Their occurrence helps explain the high concentration of organic nitrogen commonly found in soils exposed to gas leakage from pipelines or natural-gas seeps, and suggests further consideration of the possibility of applying selected petroleum residua to soils in order to increase the agricultural potential by nitrogen-fixing processes.
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  • 190
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    Biotechnology and Bioengineering 9 (1967) 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 191
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    Biotechnology and Bioengineering 9 (1967), S. 57-76 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: From soil and from the plant Elodea, we have isolated an organism which has not, yet been identified; it is a comparatively large Bacillus, which thriven in a medium of mineral salts saturated with a gaseous mixture of 40%, methane (or natural gas), 40% oxygen, 15% nitrogen, and 5% carbon dioxide. The isolated cells have amino acid and vitamin contents comparable to, or, in some cases greater than, those found in such nutrients as yeast, fish meal, or milk solids.
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  • 192
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    Biotechnology and Bioengineering 9 (1967), S. 109-109 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 193
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    Biotechnology and Bioengineering 9 (1967), S. 129-170 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Mathematical models for microbial growth in batch and continuous cultures are formulated. The models have been referred to as distributed models since the microbial population in a culture is looked upon as protoplasmic mass distributed uniformly throughout the culture. Growth is regarded as the increase in this mass by conversion of medium components into biological mass and metabolic products. Two sets of models have been presented. The first arise from introducing additional considerations into the model proposed by Monod to account for the stationary phase and the phase of decline in a batch culture. These have been referred to as unstructured, distributed models since they do not recognize any form of structure in the protoplasmic mass. The models in the second set are referred to as structured, distributed models. Structure is introduced by considering the protoplasmic mass to be composed of two groups of substances which interact with each other and with substances in the environment to produce growth. The structured models account for the dependence of growth on the past, history of the cells; thus they predict all growth phases observed in batch cultures, whereas the unstructured models do not predict a lag phase. The full implications of the models for continuous propagation, as determined by the method of stability analysis and transient calculations, are discussed. The models prediet a number of new results and should be confronted with experiments.
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  • 194
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    Biotechnology and Bioengineering 9 (1967), S. 205-221 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Batch growth characteristics of various organisms were determined on a number of pairs of sugars to find a stable system showing clear-cut classical diauxie. The system selected for further study was a strain of Klebsiella (Acrobacter) aerogenes, NCIB 8021 growing on a mixture of glucose and maltose in minimal salts medium at 30°C. This showed a specific growth rate (μ) of 1.19 ± 0.03 hr.-1 on 0.01% (w/v) glucose, followed by a diauxie lag of 0.73 ± 0.04 hr and then further growth on 0.01% (w/v) maltose at μ = 0.60 ± 0.03 hr-1. This system was applied to a two-stage continuous, stirred, aerated fermentor system, with working volumes of 1.85 and 2.77 liters, respectively, and growth was followed (mainly by optical density, referred to dry weights and viable counts) and also the concentrations of the sugars were measured. Except at the very highest flow rates, glucose was immediately and virtually completely consumed, but the utilization of maltose showed interesting variations: (a) At low feed rates between 0.09 and 0.4 vol./hr. exactly the same response was found with mixed sugars as with double concentration glucose, showing that the organism was able to metabolize maltose as well and as quickly as glucose. (b) At medium feed rates of 0.46 to 1.03 vol./hr. two deviations were observed, both of which increased as the dilution rate increased: the system showed a time lag on maltose before the cell population began to rise and the volume of medium used before the steady state was established was greater than predicted, (c) At fast feed rates, approaching “washout” condition of 1.055 to 1.135 vol./hr. the first culture vessel showed no reaction to a step change which included maltose, although, of course, with doubled glucose it responded immediately. The second vessel, however, quickly metabolized the overflow maltose, and showed a steady increase of cell population to the theoretical steady state. These results may have significance for industrial systems using complex commercial substrates.
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  • 195
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    Biotechnology and Bioengineering 9 (1967), S. 257-265 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The growth of Semliki Forest Virus in stirred culture vessels at volumes of 4 and 301. is described. Virus can be produced on a large scale in deep culture using industrial type vessels. Control of pH within close limits is important for maximum production of infective virus. With the parent, strain of SFV, virus yields were found to be influenced by an interference phenomenon which was apparently not due to interferon. Growth of a cloned strain of SFV obtained by serial selection of large plaques was not affected by this phenomenon. The cloned strain, when inoculated at a cell/virus input ratio of 1:1, gave maximum virus titers of 1010 p.f.u./ml., indicating an average yield of 10,000 p.f.u/BHK cell.
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  • 196
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    Biotechnology and Bioengineering 9 (1967), S. 487-497 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The results of our survey of several mining operations have shown in every instance typical T. ferrooxidans bacteria to be present in the leaching solutions. The numbers of bacteria found are in general what, one would expect considering the chemical reactions occurring in these processes. A major difficulty is encountered when one considers the complex and unknown series of events which occur, as the bacteria-bearing, acidic, ferric-ion solution penetrates the massive ore dumps. Laboratory studies show microbial activity to be the major cause of rapid solubilization of copper sulfide ores. Field studies suggest that microbial activity cannot explain all observations in a typical leaching operation.
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  • 197
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    Biotechnology and Bioengineering 9 (1967), S. 3-24 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 14 Ill.
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  • 198
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    Biotechnology and Bioengineering 9 (1967), S. 375-386 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This paper deals with a theoretical study on the dynamic, character of the chemostat system. It. is primarily based on the Monod model for growth limitation, although certain more complex models are considered. Since the Monod model is described in terms of two variables, an analysis by use of a phase plane plot will show the various possible types of behavior theoretically expected for transient conditions of the system. In this paper it will be shown that the chemostat system might show an overshoot (or an underswing) with respect to changes in cell and substrate concentrations, depending on the extent to which the system might be disturbed from steady-slate conditions. Other types of transient behavior ran also be expected when one of the system parameters such as dilution rate or input substrate concentration is disturbed in a stepwise manner. The simple Monod chemostat model was found never to oscillate in either a damped or a sustained manner as has been experimentally reported. Discussion is included about the transient behavior of other chemostat models such as that involving a variable yield coefficient, i.e., including the effect of cell maintenance requirements.
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  • 199
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    Biotechnology and Bioengineering 9 (1967), S. 387-411 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The kinetic behavior of heterogeneous microbial populations was studied in a continuous flow completely mixed reactor operated at various dilution rates. Glucose was used as the growth-limiting nutrient. The physiological growth parameters for cells harvested from continuous flow reactors were determined using batch experiments. It, was found that the growth parameters, maximum growth rate (μm), saturation constant (ks), and cell yield (Y) vary for each dilution rate, and cannot be considered as precise constants in depicting the kinetic behavior of heterogeneous populations. In addition, it was found that the yield coefficients obtained from batch experiments were always lower than those obtained from continuous flow experiments. Levels of substrate and biological solids calculated for different dilution rates using growth constants from batch experiments did not agree with the experimental values observed in steady-state experiments. However, when the yield values from, the continuous flow experiments were used in conjunction with batch values for μm and ks the theoretical and experimental dilute-out curves agreed fairly closely (within the range needed for engineering prediction) until the culture began to wash out of the unit. In general, the data substantiated the use of the single phase relationship between growth rate and substrate concentration described by the Monod equation, μ = μmS/(ks + s).
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  • 200
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Differences in the concentration and retention of 137Cs by unicellular diatoms, filamentous green algae, and filamentous blue-green algae were demonstrated under both batch and continuous-flow culture conditions. 137Cs concentration factors were generally higher by a factor of 2 in batch tests than in continuous flow tests. In retention studies, 137Cs was desorbed more rapidly from algae under continuous-flow conditions. Studies with blue-green algae indicate that 137Cs concentrations in the various species were more closely related to the surface-to-volume ratios of algal cells than to the systematic relationships of the three species. Continuous-flow studies indicated no differences among three species of filamentous green algae in the concentration of 137Cs, 65Zn, and 85Sr. However, the average concentration factors of the radionuclides were considerably different: 3800 for 65Zn, 460 for 137Cs, and 230 for 85Sr. These radionuclides were rapidly desorbed following the transfer of algae to nonradioactive media. The desorption rate was inversely related to the concentration rate.
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