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  • 1
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have studied the effects of temperature, EDTA, and ionic strength on C-polysaccharides in solution by examining the details of the time-correlation function using a 96-channel single-clipped photon correlation spectrometer. Our linewidth results have shown that the C-polysaccharides in buffer solution form aggregates of very broad distributions. Thus, fractionation by gel-filtration chromatography is only mildly effective. Although the aggregate sizes seem to remain relatively constant from 4 to 25°C, a fraction of those aggregates break up to form smaller fragments or monomers at higher temperatures. However, the dissolution-association process is quite slow and takes days even at room temperatures before the equilibrium is reached. We have also shown that by adding an excess amoutn of EDTA, the aggregates can be broken up. Again the dramatic changes occur only at short delay times suggesting that a protion of the larger aggregates remains. Finally, the amount and size of aggregates depend upon the ionic strength which exhibit a maximum ΓT/sin2 (θ/2) around 0.1-0.2 M KCl.If the activities of polysaccharides in solution depend upon molecular size, the standard techniques such as gel-permeation chromatography and ultracentrifugation cannot properly characterize the detailed size distribution. Quasielastic laser light scattering can provide us with a qualitative model. The quantitative details must necessarily await more extensive investigations using a combination of the techniques and better fractionation procedures in an appropriate buffer solution.
    Additional Material: 10 Ill.
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  • 2
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Group-specific polysaccharides isolated by means of a cetavlon procedure are immunogenic in man and induce protective immunity against meningococcal meningitis. Minute quantities of the polymers in solution can act as vaccines. We now report the first characterization of a fractionated (C-1) group C polysaccharide in 0.4KM KCl and 0.05M sodium acetate by means of light-scattering spectroscopy. Independent measurements of refractive index increments, absolute scattered intensities, angular scattering intensities and line widths as a function of scattering angles and delay times at different concentrations using incident wavelengths of 632.8 nm from a He-Ne laser and of 488 nm from an argon-ion laser yield information on aggregation properties, molecular weight (Mr), radius of gyration 〈r0g〉1/2z, translational diffusion coefficient 〈D〉0z, and second virial coefficients A2 and B2 of C-1 polysaccharide.At relatively high ionic strength (0.04M KCl + 0.05M sodium acetate), we obtain for the C-1 polysaccharide in solution Mr = 5.15 × 105, 〈r2g〉1/2z = 345 Å, A2 = 1.25 × 10-4 ml/g, 〈D〉0z = 1.16 × 10-7 cm2/sec with a corresponding Stokes radius of 240 Å and B2 = 4.4 ml/g. A2 and B2 are the second virial coefficients from intensity- and diffusion-coefficient measurements. The C-1 polysaccharide aggregates in solution and behaves hydrodynamically like random coils. Viscosity and sedimentation studies further confirm our conclusions that the fractioned C-1 polysaccharide aggregates in solution and EDTA can partially break up those aggregates. However, the system remains polydisperse even after adding an excess amount of EDTA. The weight-average molecular weight of the C-1 polysaccharide in solution depends upon ionic strength and exhibits a minimum at ∼0.2M KCl. Finally, viscosity, light-scattering, and sedimentation results all show that the aggregated macromolecular system behaves like random-coiled polymers with no measurable shape factors.
    Additional Material: 5 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 27 (1981), S. 1024-1026 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Tab.
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  • 4
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 32 (1992), S. 944-955 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The ability to evaluate various mechanical test parameters of polymers using an instrumented impact tester is reviewed. The nature of the short chain branching (SCB) in a series of linear low density polyethylenes (LLDPE) was characterized and related to several impact test parameters for these materials. The impact strength, ductility, and impact fatigue life were observed to increase with increasing branch length. This was attributed, in fact, to an increase in the number of interlamellar tie molecules as the SCB length increased. With an increase in the SCB length the SCB distribution became broader; the number of chains rich in short chain branches increased. This component acts somewhat like the rubber particles in a rubber-toughened blend which gives rise to the concept of a “one copolymer blend”.
    Additional Material: 18 Ill.
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  • 5
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The angular distribution of scattered intensity and decay times of concentration fluctuations have been measured by means of digital photon counting and single-clipped photon correlation for solutions of Group C meningococcal polysaccharides at 31°C. The z-average diffusion coefficient 〈D〉z and its second moment 〈D2〉z have been determined from the time-dependent correlation function using the cumulant expansion technique. Very low observed values of 〈D〉z and the tremendous width of the polydispersity index, which is the z-average normalized variance, suggest a higher degree of aggregation than the monomer-dimer type self-association at finite concentrations.
    Additional Material: 6 Ill.
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  • 6
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report the first characterization of group B meningococcal polysaccharide at 28°C in 0.4M KCl and 0.05M sodium acetate at pH 5.61 and in pure water by means of light-scattering spectroscopy. In buffer solution, the weight-average molecular weight Mr = 1.46 × 105 g/mol, the Z-average radius of gyration 〈rg2〉z1/2 = 26.3 nm, the second virial coefficient A2 = (2.12 ± 0.17) × 10-4 cm3 mol/g2, and the second virial coefficient of the diffusion expansion kD ≈ 79 g/g. By using a histogram approximation on the correlation function profile analysis, we observed size fractions of two sizes with rhL/rhS = 298 Å/50 Å and AL/AS = 82/18, where rh and A are the respective effective hydrodynamic radius and the integrated intensity and the subscripts L and S denote the large and small size fractions. In pure water, rhL/rhS = 402 Å/29 Å with AL/AS = 84/16. The linewidth results are consistent with the measurements on the angular distribution of scattered intensity. Furthermore, if we take the large fraction to behave more like solid spheres, we are able to determine a molecular weight distribution of B-polysaccharide in buffer solution in a bimodal size distribution function.
    Additional Material: 11 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 31 (1993), S. 1347-1362 
    ISSN: 0887-6266
    Keywords: polyethylene/polymethyl methacrylate blends ; reactive polymer blends ; ductile matrix/brittle dispersed phase blend ; instrumented impact testing ; toughening mechanism ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Blends of t-butylaminoethyl methacrylate grafted polyethylene (PE-g-tBAEMA) with methyl methacrylate-methacrylic acid copolymer (PMMA-MAA) and polymethyl methacrylate (PMMA) were prepared in a Banbury type batch mixer. The effects of component proportions and processing conditions on the melt flow index, morphology, impact, and tensile properties of the resulting polymer blends were investigated. The interfacial chemical reaction was studied using Fourier transform infrared (FTIR) technique. It was observed that the melt index of the blends was reduced with increasing melt processing temperature and mixing time, indicating the formation of PE-g-PMMA block copolymer. New IR bands at 1554, 1628, 1800, and 1019 cm-1 were observed only for PE-g-tBAEMA/PMMA-MAA, the reactive blends, but not for PE-g-tBAEMA/PMMA, the nonreactive blend. These IR bands were attributed to the amide, carboxylate anion and methacrylimide formation resulting from the chemical reaction between the secondary amine on the PE-g-tBAEMA/PMMA moiety and the carboxylic acid on PMMA-MAA segment. The morphology of the blends in various compositions was examined using scanning electron microscopy (SEM) and related to their mechanical properties. All of the blends have a domain structure whose morphology is strongly dependent on the concentration of the dispersed phase. Furthermore, the PE-g-tBAEMA/PMMA-MAA reactive blends were shown to have much finer morphology than the corresponding nonreactive blends. For the reactive polymer blends consisting of brittle particles dispersed in the ductile matrices, the PE-g-tBAEMA/PMMA-MAA, impact and tensile result higher than predicted by the additivity rule were observed. The toughening of polyethylene by PMMA was explained by a “cold-drawing” mechanism. The Young's modulus of the blends and the extent of interfacial adhesion were analyzed with Takayanagi and Sato-Furukawa's theories. © 1993 John Wiley & Sons, Inc.
    Additional Material: 16 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 62 (1996), S. 1807-1818 
    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: Very few polymeric systems are suitable for preparing engineering parts using reaction injection molding (RIM) processing. A new two-component metallocene catalyst, which is able to polymerize bulk styrene at high rates to the syndiotactic form, was studied. The catalyst used in this work was based on monocyclopentadienyl analogs of titanium (Cp*TiMe3), which was used in conjunction with a boron cocatalyst [B(C6F5)3]. When separate streams of the catalyst and cocatalyst, dissolved in either styrone or styrene/toluene solutions, met in a mixhead, the styrene polymerized rapidly to form crystalline, syndiotactic polystyrene (s-PS). Using a bench scale RIM device, the monomer conversion during polymerization was monitored through the quasi-adiabatic temperature rise, recorded by a rapid data acquisition system. The rate equation was found to be second order with respect to the monomer concentration and first order with respect to the catalyst concentration, given some assumptions. The s-PS was brittle and attempts were made to incorporate elastomer toughening into the reacting system. Several potential problems associated with using this system for RIM process discussed. © 1996 John Wiley & Sons, Inc.
    Additional Material: 10 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 753-763 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Instrumented impact testing of linear low density polyethylene (LLDPE I) (ethylene and 1-octene copolymer) was carried out using a Rheometrics Drop-Weight Tester (RDT-5000). A method of partial penetration at controlled impact energy was used and developed. The set impact speed was raised step by step in small intervals of 0.25 m/s over a range of 0.76 m/s to 9.14 m/s. The impact deformation profiles of LLDPE I were obtained for a series of specimens impacted at different speeds. The stress states of the LLDPE I during the corresponding impact events were obtained with the instrumented impact tup. By comparing the observed impact profile with the force-displacement trace, the yield point and the initial failure point of LLDPE I were assessed. The point of 100 percent of the maximum load on the force-displacement trace of a total penetration impact was shown to be the yield point. On the basis of the determination of the yield point, a parameter, ductile ratio (D.R.), was redefined to characterize the ductility of polymers. The initial break point of LLDPE I was determined. The effect of specimen thickness and test temperature on the impact properties was investigated.
    Additional Material: 15 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 56 (1995), S. 345-354 
    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: Instrumented impact testing has been used to study castor-oil-based polyurethanes. The energy-absorbed capacity of these materials in impact is dependent on several factors, such as the type of isocyanate, NCO/OH ratio, and testing temperature. An approximate but simple method for the low-temperature impact testing was proposed. A change from ductile response to brittle fracture was observed as the temperature of the specimen was reduced. This characteristic ductile-brittle transition temperature is to be found highly sensitive to crosslinking degree. © 1995 John Wiley & Sons, Inc.
    Additional Material: 11 Ill.
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