Gel-to-gel non-variant transition of an organogel caused by polymorphism from nanotubes to crystallites

• Published in: Soft matter Vol. 17; no. 16; pp. 4386 - 4394
• Main Authors: Schwaller, Duncan, Zapién-Castillo, Samuel, Carvalho, Alain, Combet, Jérôme, Collin, Dominique, Jacomine, Leandro, Kékicheff, Patrick, Heinrich, Benoît, Lamps, Jean-Philippe, Díaz-Zavala, Nancy P, Mésini, Philippe J
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 28.04.2021
• Subjects: Aging; Chemical Sciences; Condensed Matter; Cooling; Cooling rate; Crystal structure; Crystallinity; Crystallites; Crystals; Decalin; Fibers; Gels; Material chemistry; Nanotechnology; Nanotubes; NMR; Nuclear magnetic resonance; or physical chemistry; Phase diagrams; Physics; Polymorphism; Rheological properties; Rheology; Self-assembly; Soft Condensed Matter; Temperature; Theoretical and; Transformations (mathematics); Turbidimetry
• ISSN: 1744-683X; 1744-6848
• DOI: 10.1039/d1sm00195g

An amide based gelator forms gels in trans-decalin. Below concentrations of 1 wt% the gels melt at temperatures varying with concentration. Above a concentration of 1 wt%, upon heating, the gel transforms into an opaque gel at an invariant temperature, and melts at higher temperature. The gel-to-gel transition is evidenced by several techniques: DSC, rheology, NMR, OM and turbidimetry. The phase diagram with the domain of the existence of both morphs was mapped by these techniques. Optical and electronic microscopy studies show that the first gel corresponds to the self-assembled nanotubes while the second gel is formed by crystalline fibers. The fibers are crystalline, as shown by the presence of Bragg peaks in the scattering curves. Both morphs correspond to a different H-bonding pattern as shown by FTIR. The first gel forms at a higher cooling rate, is metastable and transforms slowly into the second one. The second gel is stable. It forms at a low cooling rate, or by thermal annealing or aging of the first gel. An organogel shows a gel-to-gel transition corresponding to the transformation of nanotubular aggregates into plain fibers, either by heating or aging. The domains of the existence of both gels are mapped in the c - T phase diagram.