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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 14 (1970), S. 789-797 
    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: Ethyl acrylate was graft-copolymerized from acetone-water systems with γ-irradiated, purified cotton cellulose. The scavenging of the free radicals in the irradiated cellulose by water, acetone, and water-acetone systems was determined by electron spin resonance spectroscopy. The ESR spectra of free radicals, scavenged by water and acetone, were recorded by the use of a time-averaging computer attached to the ESR spectrometer, in which the ESR spectrum of the irradiated cellulose, which had been immersed in water and/or acetone, was electronically subtracted from the ESR spectrum of the irradiated cellulose control. For both water and acetone, the ESR spectra of the scavenged free radicals were singlets. This indicated that free radical sites formed on carbon C1 or C4 on radiation-initiated depolymerization, which would generate singlet ESR spectra, were readily accessible to these solvents. The maximum scavenging of the radicals was observed when irradiated cellulose was immersed in acetone-water solution which had a composition of 25/75 vol-%. The scavenging of the free radicals in irradiated cellulose when immersed in acetone-water solutions was less than when immersed in methanol-water solutions. Also, the extent of graft copolymerization of ethyl acrylate from acetone solutions with irradiated cellulose was less than that of ethyl acrylate from methanol solutions. These differences were probably due to differences in the diffusion rates of acetone and methanol into the cellulosie structure. The Trommsdorff-type effect in the acetone solutions would be less than in the methanol solutions, since acetone is a better solvent for poly(ethyl acrylate) than methanol.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 17 (1973), S. 3439-3456 
    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: Flow properties of aqueous solution of methylcellulose, especially nonlinear viscoelasticity, were investigated. The peculiar flow properties of the aqueous solution of methylcellulose were compared with the existing theories of non-Newtonian viscosity of concentrated polymer solutions and the experimental results obtained for the aqueous solution of sodium alginate which behaves as polyelectrolyte in solution. The characteristic time for the formation of entanglement couplings between molecular chains was mainly examined. To investigate the elastic behavior under steady-shear flow, normal stress difference was measured with a coaxial cylinder apparatus, and extinction angles were determined with a flow birefringence apparatus. The values of normal stress difference obtained by the mechanical and the optical methods coincided with each other. For the aqueous solution of methylcellulose as reported for solutions of nonpolar polymers, the relation between normal stress difference and shear stress was represented by a single curve irrespective of temperature and concentration. Non-Hooken behavior was observed for the relation between recoverable shear and shear stress and attributed to the strong intermolecular interactions and the stretching-out effect of structural networks.
    Additional Material: 19 Ill.
    Type of Medium: Electronic Resource
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  • 3
    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: Improvements in physical properties of polyvinyl alcohol fibers were attempted by means of both crosslinking and graft copolymerization. By using the ceric iron redox system on synthetic fibers spun from polymer blends containing polyvinyl alcohol (PVA) and its partially (about 15 mole-%) N-methylolcarbamoylethylated products (PVM) in which the blend ratios were 0/100, 10/90, 15/85, and 20/80 by weight, methyl methacrylate (MMA) was grafted at 30°C. in the aldehyde-free acetone-water system after crosslinking by heat treatment or successive acid treatment. Grafting increases with increasing PVM component. This may be ascribed to the coarsening of the fiber texture caused by polymer blending and the increasing of methylol groups as a reducing agent. Moisture regains decrease with increasing graft fraction, but these appear to be greater than the additive values of backbone and graft polymer. Less shrinkage in boiling water is obtained with the increase of PVM component and grafting; the decreased shrinkage is significant in the acid-treated PVM-PVA fibers, and it reaches a nearly sufficient value at about 50% graft-on. The PVA fibers do not give sufficient shrink-proofing. The inherent tenacity and elongation of the grafted fibers increase slightly with increasing graft-on or denier except at the high grafting above about 100, 150, and 300 in the PVA, acid-treated, and acid-untreated PVM/PVA fibers, respectively; whereas the tensile strength in grams/denier decreases with grafting. Although at high grafting, a destruction in the fiber texture will perhaps occur, the coarser the texture of backbone fiber, the harder the change by grafting. The knot/normal ratios in tensile strength or elongation of the grafted fibers have been retained at above 90%. The elastic recovery of the grafted fibers is considerably improved as compared to the conventional Vinylon fibers. The improvements in the acid-treated and grafted PVM/PVA (20/80) fibers are significantly greater above and below 50% graft-on, especially in the range of lower extension. As expected, the thermosetting property is also appreciably imparted with grafting. In the conventional Vinylon fibers, the formalization for shrink-proofing is usually at a sacrifice of elastic recovery. But MMA grafting in the PVM/PVA fibers gives a fairly good elastic recovery and less shrinkage in addition to thermosetting property, making the most of the characteristics in the longer intermolecular crosslinkages formed between methylol groups or PVA-OH groups and methylol groups.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 149 (1971), S. 291-294 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 24 (1972), S. 89-99 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß des Lösungsmittels und der Art des Polyvinylalkohols (PVA) auf die durch heterogene Formalisierung entstehende Vernetzung des PVA wurde untersucht. Die Vernetzungsreaktion wird zurückgehalten, wenn man PVA-Film in methanol-, äthanol- oder propanolhaltigen Lösungen formalisiert, während es in acetonhaltiger Lösung zur Vernetzung kommt. Die Vernetzungsreaktion erfolgt leichter in stärker syndiotaktischem PVA als in ataktischem PVA (handelsüblichem PVA).
    Notes: The effect of the solvents of poly(vinyl alcohol) (PVA) species on the crosslinking reaction accompanying in the heterogeneous formalization of PVA was studied. The crosslinking reaction was prevented when PVA film was allowed to react with formaldehyde in the solution containing methanol, ethanol or propanol, whereas it occurred in the solution containing acetone. The crosslinking reaction occurred more easily in syndiotacticity-rich PVA than in atactic PVA (commercial PVA).
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 27 (1972), S. 189-200 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Kationische Copolymerisationen von Cyclopentadien und 2-Chloräthylvinyläther wurden bei -78°C mit Borfluoridätherat als Initiator durchgeführt. Toluol, Methylenchlorid und Nitroäthan wurden als Lösungsmittel verwandt. Die Copolymerisationsparameter wurden für jedes Lösungsmittel bestimmt, und dabei wurde ein Einfluß des Lösungsmittels auf die Copolymerisation beobachtet, d. h. Cyclopentadien war in den polareren Lösungsmitteln reaktiver. Dieser Lösungsmitteleinfluß konnte mit den Unterschieden in der Nucleophilität und der Stabilität der Carboniumionen interpretiert werden.Die Copolymeren konnten mit Schwefel vernetzt werden; einige physikalische Eigenschaften der Polymeren und der Vulkanisate wurden untersucht.
    Notes: Cationic copolymerizations of cyclopentadiene with 2-chloroethyl vinyl ether were carried out at -78°C using boron trifluoride etherate as a catalyst. Toluene, methylene chloride, and nitroethane were used as polymerization solvents. In each solvent the monomer reactiviety ratios were determined and a solvent effect on the copolymerization was observed, i. e., cyclopentadiene was more reactive in the polar solvents, but less in toluene. This solvent effect could be interpreted based on the differences of monomer nucleophilicities and of stabilities of the two carbonium ions.The copolymers were able to be cured with sulfur and some physical properties of polymers and of their vulcanizates were investigated.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 18 (1974), S. 615-623 
    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: Crystallization during melt spinning is studied as an example of the nonisothermal crystallization of polymers. The following equation is derived, taking the temperature distribution within a filament into consideration: \documentclass{article}\pagestyle{empty}\begin{document}$$ \kappa \nabla ^2 T = {\rm V} \cdot {\rm grad } \ T - \frac{{\Delta H}}{{C_p }}{\rm V} \cdot {\rm grad } \ X $$\end{document} where T = temperature, X = crystallinity, κ = thermal diffusivity, V = velocity, ΔH = heat of crystallization, and Cp = specific heat at constant pressure. The assumptions and the procedure for a numerical calculation of crystallinity and temperature within a running filament are described, and some results of calculation are illustrated. The results are compared with those obtained by a simpler calculation in which the radial temperature distribution is neglected. The simpler method proved useful in connection with x-ray measurements.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 8
    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 types of free radicals produced in the water-accessible regions of cellulose I and cellulose II fibers by γ-irradiation in nitrogen atmosphere at room temperature were studied by ESR spectroscopy. The ESR spectra of the irradiated cellulose I and II change by contacting the fibers with water, and after immersion in water the spectral shape depends on the orientation of the fiber axes to the magnetic field. These spectra are probably related to the free radicals generated in the highly ordered regions inaccessible to water in irradiated cellulosic fibers. The ESR spectrum of free radicals generated in decrystallized cellulose after irradiation consists of a singlet and a doublet. When the ESR spectra of free radicals formed in the highly ordered regions of cellulose I and II and the singlet and the doublet are combined in adequate ratio, the constructed spectra are similar to those of the radicals scavenged by water in the irradiated cellulose I and II fibers. From these facts, the spectra due to the free radicals in the water-accessible regions in irradiated cellulose I and II are considered to consist of the singlet and the doublet formed by free radicals in the typical amorphous regions and the spectra of other types of radicals generated in the semicrystalline regions.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 9
    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: Elastomers, based on cellulose fibers, were synthesized by grafting ethyl acrylate onto fibers preirradiated by a high-energy electron beam. The rheological properties and fine structure of the elastomers were investigated in order to determine factors in development of rubber-like elastomeric behavior. Mechanical properties of the elastomers depended on (1) degree of polymerization of irradiated cellulose molecules, (2) extent of grafting, and (3) experimental methods of evaluation, particularly in varying environmental conditions, for example, in making measurements in air, water, or ethyl acetate. Glass transition temperatures of the elastomers were dependent on the environmental conditions of evaluation; stiffnesses of the elastomers levelled off at about 0°C; and in all environments, a rubber-like plateau was observed. Poly(ethyl acrylate) separated from the elastomers was not soluble in acetone. The mean molecular weight of the separated poly(ethyl acrylate) of the elastomer was determined in ethyl acetate by the equilibrium swelling method. It was concluded that crosslinks existed in the elastomers. Electron microphotographs of cross sections of the elastomers, which exhibited rubber-like behavior, indicated that the fibrillar structure of the irradiated cellulose fibers formed a uniform network and that poly(ethyl acrylate) was uniformly distributed among the fibrils.
    Additional Material: 19 Ill.
    Type of Medium: Electronic Resource
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  • 10
    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 effects of oxygen on graft copolymerization of ethyl acrylate from methanol-water systems with γ-irradiated fibrous cotton cellulose were investigated by electron spin resonance spectroscopy and by the formation of cellulose-poly(ethyl acrylate) copolymer. The concentrations of free radicals in cellulose irradiated dry in an atmosphere of nitrogen at 25°C decreased during postirradiation storage in nitrogen or oxygen. The concentration of free radicals in the irradiated cellulose, moisture regain of the irradiated cellulose, and formation of cellulose-poly(ethyl acrylate) copolymer decreased with increase in temperature and time of postirradiation storage and to a greater extent when stored in oxygen rather than in nitrogen. From the decrease in moisture regain of irradiated cellulose during postirradiation storage, it was concluded that increased intermolecular bonding occurred in irradiated cellulose during storage in both nitrogen and oxygen atmospheres. When irradiated celluloses which had been stored in either oxygen or nitrogen were copolymerized with ethyl acrylate at 60°C, less formation of copolymer was observed than when the copolymerization reactions were conducted at 25°C. It was concluded that there was no evidence for the formation or decomposition of cellulose peroxides during these reactions and that formation of graft copolymer depended primarily on the concentration of free radicals in the irradiated cellulose at the time of copolymerization.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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