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Effect of solvent on single crystal formation from dilute polyethylene solution

I. Surface free energy of single crystals estimated from kinetic theory

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Summary

With fractionated linear polyethylene, single crystals were prepared isothermally from dilute solutions in various solvents asn-octane,n-hexadecane, decaline, tetralin, toluene,p-xylene and diphenyl ether, which differed in the size and the thermodynamic properties. The fold length of lamellae was plotted against the crystallization temperature. For tetralin,p-xylene and toluene systems, their observed points lay nearly on the same curve, but for other solvent systems, the relation was obviously not independent of the kind of solvent from which the single crystals were formed. To discuss the effect of solvent on single crystal formation from dilute solution, the end surface free energy of single crystal was estimated from the equation based on the kinetic theory. It was pointed out that more regularly folded single crystals may be formed with solvent having larger thermodynamic interaction parameter and larger molar volume.

Zusammenfassung

Die Arbeit gilt der Frage, wie weit die Morphologie von Polyäthylen-Einkristallen vom Lösungsmittel beeinflußt wird. Hierzu werden solche Einkristalle unter isothermen Bedingungen aus Lösungen von fraktioniertem Linearpolyäthylen inn-Oktan,n-Hexadecan, Dekalin, Tetralin, Toluol,p-Xylol und Diphenyläther dargestellt. Zwischen den aus der röntgenographischen Kleinwinkelstreuung ermittelten Faltungslängen der Lamellen und den Kristallisationstemperaturen besteht bei Tetralin,p-Xylol und Toluol ein einfacher Zusammenhang. Die anderen untersuchten Lösungsmittel zeigten dagegen einen spezifischen Einfluß.

Zur Diskussion wurde die freie Oberflächenenthalpie der Einkristalle abgeschätzt. Es wurde gezeigt, daß um so regelmäßiger gefaltete Einkristalle entstehen können, je größer der thermodynamische Wechselwirkungsparameter und das Molvolumen der verwendeten Lösungsmittel sind.

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Author notes

  1. Akio Nakajima, Fumiyuki Hamada, Seiichi Hayashi & Takuji Sumida

    Present address: Department of Polymer Chemistry, Kyoto University, Kyoto, Japan

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    1. Akio Nakajima
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    2. Fumiyuki Hamada
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    3. Seiichi Hayashi
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    4. Takuji Sumida
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    Additional information

    The authors gratefully acknowledge ProfessorB. Wunderlich's kind supply of his high pressure crystallized polyethylene specimen. Thanks are also due to ProfessorI. Sakurada for the facilities in the low-angle X-ray measurement, and to ProfessorN. Utsumi for his help in the electron microscopy.

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    Nakajima, A., Hamada, F., Hayashi, S. et al. Effect of solvent on single crystal formation from dilute polyethylene solution. Kolloid-Z.u.Z.Polymere 222, 10–16 (1968). https://doi.org/10.1007/BF01507361

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    • DOI: https://doi.org/10.1007/BF01507361

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