Excluded volume interactions and phase stability in mixtures of hard spheres and hard rods

Opdam, Joeri; Gandhi, Poshika; Kuhnhold, Anja; Schilling, Tanja; Tuinier, Remco

doi:10.1039/d2cp00477a

Cited by 4 publications

(4 citation statements)

References 36 publications

(69 reference statements)

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“…First we evaluated the accuracy of our method for hard spherocylinders for various values of γ. In a previous study, 54 we already confirmed the accuracy of eq 5a for a specific aspect ratio of γ = 6. In Figure 3a, the data points are Monte Carlo computer simulation results for the free volume fraction, and the curves are predictions of eq 5b.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Equation of State of Charged Rod Dispersions

Tuinier,

Kuhnhold

2023

J. Phys. Chem. B

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We study the accuracy of the theory of Stroobants, Lekkerkerker, and Odijk [Macromolecules 1986, 19, 2232−2238, called SLO theory, to describe the thermodynamic properties of an isotropic fluid of charged rods. By incorporation of the effective diameter of the rods according to SLO theory into scaled particle theory (SPT), we obtain an expression for the rod concentrationdependent free volume fraction and the osmotic pressure of a collection of charged hard spherocylinders. The results are compared to Monte Carlo simulations. We find close agreement between the simulation results and the SLO-SPT predictions for not too large values of the Debye length and for high rod charge densities. The deviations increase with rod density, particularly at concentrations above which isotropic−nematic phase transitions are expected.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Equation of State of Charged Rod Dispersions

Tuinier,

Kuhnhold

2023

J. Phys. Chem. B

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“…In section 3 of the Supporting Information, it is shown that eq is the canonical equivalent to the expression used for the semi-grand canonical potential of a colloidal mixture in FVT. ,, This method has recently been used to study phase boundaries in binary mixtures of hard spheres and hard rod/sphere mixtures. , In these works, ordered phases of only one component were accounted for whereas the depletants are treated as a fluid with a constant chemical potential that is fixed by an external reservoir. Because we are interested in mapping the phase behavior of colloidal mixtures in which both particles can form ordered phases, a canonical ensemble, without the need to use an external reservoir, is used here.…”

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confidence: 99%

“…Here, we present a simple and general framework that enables one to compute the phase behavior of colloidal mixtures, including anisotropic particles, and we apply this to the case of rods (spherocylinders) mixed with spheres and also show results for binary mixtures of platelets (disks) and rods. The phase behavior of binary mixtures of colloidal particles has been investigated previously with a variety of theoretical methods such as density functional theory (DFT), , Parsons–Lee theory (PL), , and free volume theory (FVT). ,, However, these studies include positionally ordered phases of only one component. This imposes a limitation on the range of applicability with regard to size ratios and concentrations and does not allow computation of the coexistence between a phase in which one component exhibits positional order and a phase in which the other component exhibits positional order.…”

mentioning

confidence: 99%

“…The phase behavior of binary mixtures of colloidal particles has been investigated previously with a variety of theoretical methods such as density functional theory (DFT), 43 , 44 Parsons–Lee theory (PL), 4 , 12 and free volume theory (FVT). 14 , 45 , 46 However, these studies include positionally ordered phases of only one component. This imposes a limitation on the range of applicability with regard to size ratios and concentrations and does not allow computation of the coexistence between a phase in which one component exhibits positional order and a phase in which the other component exhibits positional order.…”

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Multiphase Coexistence in Binary Hard Colloidal Mixtures: Predictions from a Simple Algebraic Theory

Opdam

Peters

Wensink

et al. 2022

J. Phys. Chem. Lett.

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A general theoretical framework is proposed to quantify the thermodynamic properties of multicomponent hard colloidal mixtures. This framework is used to predict the phase behavior of mixtures of rods with spheres and rods with plates taking into account (liquid) crystal phases of both components. We demonstrate a rich and complex range of phase behaviors featuring a large variety of different multiphase coexistence regions, including two five-phase coexistence regions for hard rod/sphere mixtures, and even a six-phase equilibrium for hard rod/plate dispersions. The various multiphase coexistences featured in a particular mixture are in line with a recently proposed generalized phase rule and can be tuned through subtle variations of the particle shape and size ratio. Our approach qualitatively accounts for certain multiphase equilibria observed in rod/plate mixtures of clay colloids and will be a useful guide in tuning the phase behavior of shape-disperse mixtures in general.

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