Melting and Freezing Lines for a Mixture of Charged Colloidal Spheres with Spindle-Type Phase Diagram

TL;DR

This study investigates the phase behavior of a charged colloidal mixture, revealing a spindle-shaped coexistence region and aligning experimental melting points with theoretical Yukawa system predictions.

Contribution

It provides the first detailed experimental phase diagram for a binary charged colloidal mixture with a spindle-shaped coexistence region and compares it with Yukawa system models.

Findings

Solid solutions form for all compositions.

Opposite behavior of freezing and melting lines creates a spindle-shaped coexistence region.

Experimental melting points agree with Yukawa system predictions.

Abstract

We have measured the phase behavior of a binary mixture of like-charged colloidal spheres with a size ratio of 0.9 and a charge ratio of 0.96 as a function of particle number density n and composition p. Under exhaustively deionized conditions the aqueous suspension forms solid solutions of body centered cubic structure for all compositions. The freezing and melting lines as a function of composition show opposite behavior and open a wide, spindle shaped coexistence region. Lacking more sophisticated treatments, we model the interaction in our mixtures as an effective one-component pair energy accounting for number weighted effective charge and screening constant. Using this description, we find that within experimental error the location of the experimental melting points meets the range of melting points predicted for monodisperse, one component Yukawa systems made in several theoretical approaches. We further discuss that a detailed understanding of the exact phase diagram shape including the composition dependent width of the coexistence region will need an extended theoretical treatment.