Overcooked agar solutions: impact on the structural and mechanical   properties of agar gels
  Thermoreversible hydrogels are commonly prepared by cooling down to ambient temperature, aqueous polymer solutions first brought to a boil. The incubation time of the polymer solution at such a high temperature is traditionally kept to a minimum to minimize its impact on the subsequent gelation. Here we study the effect of a prolonged heating of a 1.5\% w/w agar solution at $T=80^{\circ}$C, well above the gelling temperature. The incubation time $\mathcal{T}$ of the polysaccharide solution is varied from a few hours up to five days. We show that the agar solution ages as the result of both the hydrolysis and the intramolecular oxidation of the polysaccharides. As a consequence, both the viscosity and the pH of the solution decrease continuously during the incubation period. Furthermore, samples withdrew at different incubation times are cooled down to form gels which structure and mechanical properties are systematically determined. Cryo-microscopy and X-ray diffraction experiments reveal that agar gels formed from solutions of increasing incubation times, display a coarser microstructure composed of micron-sized foils which result from the condensation of the polysaccharides and contrast with the fibrous-like microstructure of gels prepared from a fresh agar solution. Along with structural changes, a prolonged incubation time of the polymer solution at $T=80^{\circ}$C leads to weaker agar gels of significantly lower shear elastic modulus. Moreover, extensive macro-indentation experiments coupled to direct visualization show that increasing the incubation time of the agar solution up to a few days decreases the yield strain of the gel, while the rupture scenario turns continuously from brittle to ductile-like. Our study suggests that the incubation time of agar solutions at high temperature could be used to tune the mechanical properties of agar-based gels. 
Bosi Mao, Ahmed Bentaleb, Fr\'ed\'eric Louerat, Thibaut Divoux,   Patrick Snabre
cond-mat.mtrl-sci cond-mat.soft