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  • Polymer and Materials Science  (16)
  • Wiley-Blackwell  (16)
  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 10 (1970), S. 169-187 
    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: The possibilities for a systematic selection of the conditions for fractional precipitation in polymer/solvent/nonsolvent-systems based on data of the turbidimetric titrations have been tested experimentally. As criticism for the fractionation efficiency the molecular weight distribution of the fractions (determined by ultra-centrifuge) and the uniformity M̄w/M̄n (calculated therefrom) was taken. The successiv- and subfractionation, the dependence of the initial concentration and particularly the influence of the solvent/nonsolvent-system on the fractionation efficiency were investigated. Therefore a simple new method was developed, which allows to arrange systematically different solvent/nonsolvent-systems with few turbidimetric titrations as to be suitable for fractionation. For three selected solvent/non-solvent-systems the correctness of the selection method could be proved experimentally.
    Notes: Die Möglichkeiten zur gezielten Auswahl der Fraktionierbedingungen einer Fällfraktionierung in Systemen Polymeres/Lösungsmittel/Fällungsmittel auf der Grundlage von Fällungstitrationsdaten wurden einer experimentellen Prüfung unterzogen. Als Kriterium für die Güte der Trennwirkung diente die in der Ultrazentrifuge bestimmte Molekulargewichtsverteilung der gewonnenen Fraktionen und die daraus berechnete Einheitlichkeit (M̄w/M̄n/). Neben der Sukzessiv- und Unterfraktionierung wurde der Einfluß der Ausgangskonzentration und insbesondere des Lösungs-/Fällungsmittelsystems auf die Fraktionierwirkung untersucht. Dazu wurde eine einfache Methode entwickelt, welche verschiedene Lösungs-/Fällungsmittel-Systeme auf Grund weniger Trübungstitrationen bezüglich ihrer Eignung als Fraktioniersystem systematisch zu ordnen gestattet. Am Beispiel der Fraktionierung mit drei ausgewählten Lösungs-/Fällungsmittel-Systemen konnte die Richtigkeit der Auswahlmethode experimentell gesichert werden.
    Additional Material: 10 Ill.
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  • 2
    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: To prepare very narrow distributed polystyrene samples, a two step procedure of polymerization is proposed, which includes a change of solvent. The first solvent, used for the initiation step, has to be characterized by a high value of vst/vp, while the second one, used for the propagation step, should guarantee a good control of temperature during the polymerization reaction. In our case, tetrahydrofuran and benzene were chosen and n-Li-butyl has been used for the initiation.The polymerization products have been characterized by MW-averages and MW-distribution. Finally a preparative fractionation has been carried out to separate the low and high MW tail of the distribution thus leading to samples whose values for M̄w/M̄n can be shown to be about 1,01.
    Notes: Zur Herstellung hocheinheitlicher Polystyrole wird ein Verfahren angegeben, das auf einer zweistufigen Lösungspolymerisation mit Austausch des Lösungsmittel beruht. Die Lösungsmittel müssen so gewählt werden, daß bei der Vorpolymerisation die Startgeschwindigkeit wesentlich größer ist als die Wachstumsgeschwindigkeit, für die weitere Polymerisation jedoch die Reaktion thermisch gut kontrolliert werden kann; in dem beschriebenen Verfahren wurden Tetrahydrofuran und Benzol verwenigte Polymere entstehen sollten.Die Polymerisationsprodukte wurden durch ihr mittleres Molekulargewicht und ihre Molekulargewichts-Verteilungskurve charakterisiert. Nach einer Spitzenfraktionierung zur Abtrennung der hoch- und niedermolekularen Ausläufer liegt die erreichte Einheitlichkeit bei einem Wert M̄w/M̄n ≈ 1,01.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 69 (1978), S. 189-210 
    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: The solution instability (also called ageing or degradation) of high purity polyacrylamides(PAAm) was examined for a number of different molecular weights. This instability set in by a decrease of the solution viscosity and of [η] depending on time with simultaneous loss of flocculation activity.The instability appears only at molecular weights M̄ 〉 1,5 mill. in aqueous solutions; in formamide and ethyleneglycole PAAm-solutions however are stable. The viscosity loss was observed at a concentration range c = 0,001 to 5%. The standardization of several pH-values at a range from 1 to 12 by means of buffer substances as well as the addition of hydrochinone, chinone, NaNO2 and Na2SO3 do not lead to a stable solution. Only at pH = 5 a stable solution was obtained but by changing the buffer substance at the same pH the solution became instable again. Addition of isopropanol leads to stable aqueous PAAm-solutions from technical products as well as high purity polyacrylamides.The mechanism of the solution instability is not a decrease of the molecular weight due to chain scission but a change of conformation of the solution structure from single molecules based on hydrogen bonds.
    Notes: Die Lösungsinstabilität(auch Alterung oder Viskositätsabbau genannt) von hochreinen Polyacrylamiden (PAAm) verschiedener Molekulargewichte wurde untersucht. Diese Instabilität äßert sich durch eine Abnahme der Lösungsviskosität und des [η] in Abhängigkeit von der Zeit bei gleichzeitigem Flockungsverlust.Die Lösungsinstabilität tritt nur bei Molekulargewichten M̄ 〉 1,5 Mill. in wäßriger Lösung auf. PAAm.-Lösungen in Formamid und äthylenglykol sind stabil. Die Viskositätsabnahme erfolgt in einem Konzentrationsbereich von c = 0,001 bis 5%. Die Einstellung verschiedener pH-Werte im Bereich von pH = 1 bis 12 mittels Puffersubstanzen sowie die Zusätze von Hydrochinon, Chinon, NaNO2 und Na2SO3 führen nicht zu einer Lösungsstabilität. Nur pH = 5 zeigte sich eine Stabilisierung der Lösung, die jedoch beim Wechsel der Puffersubstanz bei gleichem pH wiederum in eine Instabilität überging. Zusätze von Isopropanol führen sowohl bei technischen Handelsprodukten als auch bei hochreinen Laborprodukten zu einer Stabilisierung wäßriger PAAm-Lösungen.Der Mechanismus der Lösungsinstabilität besteht nicht in einem Molekulargewichtsabbau durch Kettenbruch, sondern offenbar in einer änderung der Lösungsstruktur der Einzelmoleküle unter Beteiligung von Wasserstoff-Brücken.
    Additional Material: 14 Ill.
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  • 4
    ISSN: 0887-6266
    Keywords: tensile drawing ; morphology ; polybutylene ; terephthalate ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The concept of the drawing of a molecular network has been employed to derive a total network draw ratio from the combination of the two deformations occurring in the production of poly(butylene terephthalate), PBT, fibers by the consecutive processes of melt spinning and cold drawing. The mechanical properties of PBT can then be more readily explained in terms of increases in this total network draw ratio. However, the preorientation and crystallization that occurs in the melt-spinning process can occur at different strain rates and temperatures, depending on the wind up speed employed, on the extensional viscosity of the polymer, and on the variation of the extensional viscosity with temperature. Therefore, for polymers such as poly(butylene terephthalate), which can exist in two crystalline forms, the morphology of the final drawn fiber might be expected to depend on the first melt-spinning stage of the process as well as on the total network draw ratio. In this work, density, birefringence, mechanical measurements, and WAXD measurements, which have been made on the melt-spun fibers and on the drawn fibers, are described. Small differences in some of the drawn yarn mechanical properties at the same overall network draw ratio are related to the crystallinity and in particular to differences in the proportion of the α and β phases present in the drawn yarn. These in turn are related to differences in the temperature and stress during melt spinning and drawing. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2465-2481, 1997
    Additional Material: 18 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 14 (1970), S. 1927-1938 
    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: All current fractionation techniques - based on sol-gel equilibria - are characterized by a variation of the solvent power after each fractionation step in a discontinuous as well as in a continuous way. Overlapping of consecutive fractions is the consequence of this procedure. It can be shown that this overlapping can be diminished essentially by a multistage technique based on complete extraction at a given solvent power which then will be changed in discontinuous steps. As a further consequence, it is possible to obtain very homogeneous fractions of M̄w/M̄n 〈 1.03. A theoretical analysis of this technique on the basis of phase equilibrium data will be given, the results of which can be confirmed experimentally.
    Additional Material: 9 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is proposed that the mobility of sufficiently long molecules undergoing translational diffusion through solid polyethylene is significantly reduced by tie molecules and fixed entanglements within the interlamellar regions of the matrix. The effect on the diffusion coefficient both of diffusant molecular length and of the host matrix morphology is considered, and a semiquantitative relation between them obtained. This indicates that the mobility of long diffusants is higher in polyethylene which has been cooled slowly from the melt than it is in quenched polyethylene, in marked contrast to the behavior of gaseous and other small diffusants.
    Additional Material: 4 Ill.
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  • 7
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The diffusion coefficient for two diffusants of the type n-(CH2)NX is measured, where N ≃ 25, 45 and X is a suitable label; the matrix is linear polyethylene cooled at two widely differing rates from the melt. The measuring technique used is a recently developed one based on infrared microdensitometry. The results indicate that these diffusants diffuse faster in the slowly cooled matrix, in marked contrast to the behavior of gaseous diffusants. They are in agreement with the predictions of the model developed in a previous paper (part I), in which the constraints imposed by interlamellar tie molecules on long diffusants were shown to be important.
    Additional Material: 3 Ill.
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  • 8
    ISSN: 0323-7648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Direct depth profiling techniques to date have largely lacked the necessary depth resolution to investigate interfacial phenomena of the order of the bulk correlation length (5 - 10 nm for a wide range of systems). Here we investigate the optimal spatial resolution and depth of probe that may be attained for composition  -  depth profiling of polymeric samples via nuclear reaction analysis (NRA) using the 2H(3He, 1H)4He reaction. We find that the spatial resolution can be greatly improved by using a grazing incidence geometry of the incident 3He beam on the sample, and analyzing the emitted protons in a backwards direction. This results in spatial resolutions down to about 3 nm at the sample surface, compared to a value of some 7 nm or more previously reported in earlier studies when emitted α-particles were detected in the forward direction. At the same time the depth to which samples can be profiled via the backwards emitted protons may be considerably extended relative to the α-particle detection mode, when the 3He beam impinges on the sample surface at normal incidence (up to about 4 μm into the sample for incident energies of 1.2 MeV in the proton-detection mode compared to only 1 μm for the equivalent α-particle detection mode).
    Additional Material: 5 Ill.
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  • 9
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The composition of sol- and gel-phases as formed during precipitation fractionation in various systems polymer-solvent-nonsolvent is examined analytically.It is shown that the polymer concentration in the gel-phase is independent of the initial concentration of polymer in the solution. The polymer concentration of the gel-phase increases with increasing molecular weight, if the nonsolvent-solvent-ratio is kept constant.The nonsolvent-solvent-ratio in the gel-phase is always smaller than in the corresponding sol-phase, it is constant during the early steps of fractionation and decreases slightly at the end of fractionation.
    Notes: Die Zusammensetzung der Sol- und Gelphasen, wie sie bei der Fällfraktionierung in verschiedenen Systemen Polymer-Lösungsmittel-Fällungsmittel gebildet werden, wird analytisch untersucht.Dabei zeigt sich, daß die Konzentration des Polymeren in der Gelphase unabhängig von der Ausgangskonzentration des Polymeren ist. Bei konstantem Fällungsmittelgehalt der Solphase nimmt die Polymerkonzentration in der Gelphase mit steigendem Molekulargewicht zu.Das Fällungsmittel-Lösungsmittel-Verhältnis in der Gelphase ist stets geringer als in der korrespondierenden Solphase. Es ist im Laufe einer Fraktionierung zunächst konstant und nimmt gegen Ende der Fraktionierung langsam ab.
    Additional Material: 11 Ill.
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  • 10
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: By partial sulfonation, desulfonation and ion exchange polytsyrene sulfonic acid resins were synthesized having the same capacity (1.3 milliequivalents/g). By the variation of the preparation methods, however, the distribution of the acid groups within the resins could be changed in a defined way so that different concentration profiles were obtained. It is shown that the properties and reaction behavior of the polymeric resins are determined to a large extent by the local concentration of the functional groups.
    Additional Material: 13 Ill.
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