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Influence of the interactions in aqueous mixtures of poly(vinyl methyl ether) on the crystallization behavior of water
Zhang, JM; Berge, B; Meeussen, F; Nies, E; Berghmans, H; Shen, DY
2003-12-02
Source PublicationMACROMOLECULES
ISSN0024-9297
Volume36Issue:24Pages:9145-9153
AbstractAqueous solutions of poly(vinyl methyl ether) are experimentally studied at temperatures below the equilibrium freezing temperature of water. Earlier investigations of the peculiar phase behavior of PVME/water gave evidence of the existence of a molecular solvent/polymer complex in which (at most) two water molecules per repeating unit are hydrogen bonded to the polymer chain. In favor of the complex formation hypothesis is the abrupt arresting of the crystallization and melting of water in mixture with omega(PVME) > 0.61. To relate this peculiar crystallization behavior and complex formation to the thermal and kinetic stability of the complex, the crystallization of water is explored in detail using thermal, volumetric, spectroscopic, X-ray scattering techniques, and morphological investigations. Our results clearly indicate the significant influence of the experimental conditions on the crystallization and subsequent melting of water. In agreement with previous results and for certain experimental conditions used in this study, the existence of a molecular complex is confirmed. However, additional experiments demonstrate that the complex is thermodynamically unstable and is only observed under certain kinetic conditions. For polymer concentrations omega(PVME) < 0.61 (almost) full crystallization of water can be realized by isothermal annealing in the temperature region -20 to -30 degreesC or slow cooling to low temperature. Furthermore, also in the concentration range omega(PVME) > 0.61 the crystallization of water can be realized provided the nucleation of water is facilitated. It is anticipated that the crystallization under previously employed crystallization conditions does not occur because the activation energy for nucleation is too large under the experimental conditions, and it is the nucleation that is arrested.
DOI10.1021/ma0303869
Indexed BySCI
Language英语
WOS IDWOS:000186857700031
PublisherAMER CHEMICAL SOC
Citation statistics
Cited Times:23[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/80756
Collection中国科学院化学研究所
Corresponding AuthorBerghmans, H
Affiliation1.Catholic Univ Louvain, Dept Chem, Polymer Res Div, B-3001 Heverlee, Belgium
2.Chinese Acad Sci, Inst Chem, Ctr Mol Sci, State Key Lab Polymer Phys & Chem,Grp 506, Beijing 100080, Peoples R China
3.Eindhoven Univ Technol, Lab Polymer Technol, NL-5600 MB Eindhoven, Netherlands
Recommended Citation
GB/T 7714
Zhang, JM,Berge, B,Meeussen, F,et al. Influence of the interactions in aqueous mixtures of poly(vinyl methyl ether) on the crystallization behavior of water[J]. MACROMOLECULES,2003,36(24):9145-9153.
APA Zhang, JM,Berge, B,Meeussen, F,Nies, E,Berghmans, H,&Shen, DY.(2003).Influence of the interactions in aqueous mixtures of poly(vinyl methyl ether) on the crystallization behavior of water.MACROMOLECULES,36(24),9145-9153.
MLA Zhang, JM,et al."Influence of the interactions in aqueous mixtures of poly(vinyl methyl ether) on the crystallization behavior of water".MACROMOLECULES 36.24(2003):9145-9153.
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