Time-resolving Analysis of Cryotropic Gelation of Water/Poly(Vinyl Alcohol) Solutions via Small Angle Neutron Scattering
The structural transformations occurring in initially homogeneous aqueous solutions of poly(vinyl alcohol) (PVA) through application of freezing (-13 degrees C) and thawing (20 degrees C) cycles is investigated by time resolving small-angle neutron scattering (SANS). These measurements indicate that formation of gels of complex hierarchical structure arises from occurrence of different elementary processes, involving different length and time scales. The fastest process that could be detected by our measurements during the first cryotropic treatment consists of the crystallization of the solvent. However, solvent crystallization is incomplete, and an unfrozen liquid microphase more concentr…
Structural Organization of Poly(vinyl alcohol) Hydrogels Obtained by Freezing and Thawing Techniques: A SANS Study
The structural organization of matter in poly(vinyl alcohol) (PVA) hydrogels obtained by repeatedly freezing and thawing dilute solutions of PVA in D2O is investigated by use of small-angle neutron scattering measurements (SANS). This study is the first systematic and quantitative investigation in the medium range of length scales on PVA hydrogels obtained by freezing and thawing techniques. The studied gels have a complex hierarchical structure, extending over a wide range of length scales. The structural organization on the micron length scale originates from the presence of two separated phases constituted by polymer-rich and polymer-poor regions. The network structure may be interpreted…
Molecular Features Behind Formation of α or β Co-Crystalline and Nanoporous-Crystalline Phases of PPO
Guest molecular features determining the formation of α and β phases of poly(2-6-dimethyl-1,4-phenylene) oxide (PPO) are explored by collecting literature data and adding many new film preparations, both by solution casting and by guest sorption in amorphous films. Independently of the considered preparation method, the α-form is favored by the hydrophobic and bulky guest molecules, while the hydrophilic and small guest molecules favor the β-form. Furthermore, molecular modeling studies indicate that the β-form inducer guests establish stronger dispersive interactions with the PPO units than the α-form inducer guests. Thus, the achievement of co-crystalline (and derived nanoporous crystalli…
Slow Crystallization Kinetics of Poly(vinyl alcohol) in Confined Environment during Cryotropic Gelation of Aqueous Solutions
The gelation kinetics of aqueous solutions of poly(vinyl alcohol) (PVA) during freezing at −13 °C has been investigated with time-resolved small angle neutron scattering. Crystallization of PVA takes place inside an unfrozen liquid microphase that forms in the matrix of ice crystals and follows a first-order kinetics during the early stages and becomes very slow in the later stages with an apparent Avrami exponent lower than 1. Crystallization of PVA at low temperatures is responsible of formation of strong physical gels upon defrosting, provided that the concentration of PVA is higher than a critical value.
Mesoscopic and Microscopic Investigation on Poly(vinyl alcohol) Hydrogels in the Presence of Sodium Decylsulfate
The structure of poly(vinyl alcohol) (PVA) hydrogels formed as a result of freeze/thaw treatments of aqueous solutions of the polymer (11 wt % PVA) in the freshly prepared state is analyzed through the combined use of small (SANS) and ultrasmall (USANS) angle neutron scattering techniques. The structure of these hydrogels may be described in terms of polymer rich regions, with dimensions of the order of 1-2 microm, dispersed in a water rich phase, forming two bicontinuous phases. The PVA chains in the polymer rich phase form a network where the cross-linking points are mainly crystalline aggregates of PVA having average dimensions of approximately 45 A. The structural organization of freeze…