The dynamical crossover in attractive colloidal systems

Journal Article · Sat Dec 07 04:00:00 EST 2013 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4833595· OSTI ID:22251293

Mallamace, Francesco ^[1]; Corsaro, Carmelo ^[1]; Stanley, H. Eugene ^[2]; Mallamace, Domenico ^[3]; Chen, Sow-Hsin ^[4]

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1. Dipartimento di Fisica e Scienze della Terra, Università di Messina and CNISM, I-98168 Messina (Italy)
2. Center for Polymer Studies and Department of Physics, Boston University, Boston, Massachusetts 02215 (United States)
3. Dipartimento di Scienze dell’Ambiente, della Sicurezza, del Territorio, degli Alimenti e della Salute, Università di Messina, I-98166 Messina (Italy)
4. Department of Nuclear Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States)

We study the dynamical arrest in an adhesive hard-sphere colloidal system. We examine a micellar suspension of the Pluronic-L64 surfactant in the temperature (T) and volume fraction (ϕ) phase diagram. According to mode-coupling theory (MCT), this system is characterized by a cusp-like singularity and two glassy phases: an attractive glass (AG) phase and a repulsive glass (RG) phase. The T − ϕ phase diagram of this system as confirmed by a previous series of scattering data also exhibits a Percolation Threshold (PT) line, a reentrant behavior (AG-liquid-RG), and a glass-to-glass transition. The AG phase can be generated out of the liquid phase by using T and ϕ as control parameters. We utilize viscosity and nuclear magnetic resonance (NMR) techniques. NMR data confirm all the characteristic properties of the colloidal system phase diagram and give evidence of the onset of a fractal-like percolating structure at a precise threshold. The MCT scaling laws used to study the shear viscosity as a function of ϕ and T show in both cases a fragile-to-strong liquid glass-forming dynamic crossover (FSC) located near the percolation threshold where the clustering process is fully developed. These results suggest a larger thermodynamic generality for this phenomenon, which is usually studied only as a function of the temperature. We also find that the critical values of the control parameters, coincident with the PT line, define the locus of the FSC. In the region between the FSC and the glass transition lines the system dynamics are dominated by clustering effects. We thus demonstrate that it is possible, using the conceptual framework provided by extended mode-coupling theory, to describe the way a system approaches dynamic arrest, taking into account both cage and hopping effects.

• OSTI ID: 22251293
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 21 Vol. 139; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
GLASS
LIQUIDS
NUCLEAR MAGNETIC RESONANCE
PHASE DIAGRAMS
SURFACTANTS
SUSPENSIONS
VISCOSITY