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One method is to give every particle a sufficiently large surface charge density of the same sign. For example, attach ionizable sulfonate groups covalently to the surface. Dissociation leaves negatively charged surface groups and releases mobile positive counterions into the water. A surfactant with a strongly bound head group can provide another charging route, provided it does not desorb during the experiment.

Each charged particle is surrounded by an electric double layer. As two such particles approach, overlap of these ionic clouds raises the electrostatic and ionic free energy, producing repulsion. In a dilute electrolyte, the range is set by the Debye–Hückel screening length,For identical weakly charged spheres a representative screened Coulomb pair potential isIts sum with the Van der Waals force attraction is the DLVO theory pair potential. Choose the charging level so that the repulsive barrier is many $k_{B}T$ high; particles then rarely reach the primary attractive well during the observation time. This is kinetic stabilization rather than removal of all attraction.

Deionized water is useful because low added ionic strength gives a long-ranged repulsion. It does not mean that the charged dispersion contains no ions: the surface's own counterions are unavoidable and contribute to screening. Surface dissociation, contamination and particle concentration therefore matter even without added salt. An alternative valid route is a dense, firmly attached layer of water-soluble polyethylene glycol, producing steric stabilization without relying on a large electrostatic barrier.

Without stabilization, the potential energy is predominantly attractive outside the molecular core and drops into a deep primary minimum. With the charging treatment, the DLVO theory sum develops a positive barrier between distant particles and that primary minimum. The barrier must be large compared with $k_{B}T$ to inhibit aggregation on the experimental timescale. A shallow secondary minimum can remain at larger separation, depending on parameters.

The horizontal axis is the surface gap, so the molecular exclusion boundary is at its origin. Both interactions tend to zero at large separation. Raising salt concentration shortens the Debye–Hückel screening length and can reduce the barrier, allowing particles to stick again.

Write the particle volume fraction as $\eta =(4\pi a^3/3)n_p$. In a stable, repulsion-dominated colloid, low $\eta$ gives a disordered fluid. Increasing $\eta$ makes the interaction between neighboring particles important and can produce an ordered crystal, separated from the fluid by a phase coexistence curve. Increasing the Debye–Hückel screening length at fixed charge strengthens the repulsion at a given separation and allows freezing at smaller geometrical volume fraction.

The geometric intuition is that particles behave as though they occupy more than their bare diameter: roughly, an effective exclusion diameter $d_{\mathrm{eff}}$ extends out to the separation where $U_{\mathrm{el}}$ is of order $k_{B}T$. A hard sphere comparison then uses ${\eta }_{\mathrm{eff}}\sim \eta [d_{\mathrm{eff}}/(2a){]}^3$. This explains the trend; it is not an exact freezing criterion.

At short Debye–Hückel screening length and negligible attraction, the diagram approaches hard sphere fluid–crystal coexistence. For longer-ranged soft repulsion, body-centered cubic lattice and face-centered cubic lattice crystals can both be stable, with the former often appearing towards the softer, lower-density freezing boundary. Screened-Coulomb simulations exhibit both these crystal structures.^[ref]

No universal quantitative diagram follows from $(\eta ,{\lambda }_D)$ alone: the charge, Hamaker constant and surface conditions must also be fixed. If salt suppresses the stabilizing barrier enough for Van der Waals force attraction to dominate, a colloid-poor/colloid-rich separation or aggregation can replace part of this repulsive reference diagram. Dense colloidal glasses or colloidal gels may also be observed after kinetic arrest; they should not be mistaken for additional thermodynamic equilibrium thermodynamic phases.

First hold the surface electric charge fixed and increase the bulk salt concentration. Since ${\kappa }^2\propto c$, the Debye–Hückel screening length decreases as $c^{-1/2}$. For surface gap $h=R-2a\ge 0$,Thus both the range and the strength of repulsion decrease. In the repulsive phase diagram, the sample moves downwards at fixed volume fraction and can melt from a crystal into a fluid. Because screening length is already a diagram axis, changing salt moves the state through that diagram rather than independently changing its fixed-charge coexistence curves. If Van der Waals forces become dominant, however, adding salt may instead destabilize the dispersion and cause aggregation. These are distinct physical regimes.

Second increase $\sigma$ at fixed salt concentration and particle size. The electric charge is $Q=4\pi a^2\sigma$, so the pair repulsion increases approximately as ${\sigma }^2$ within the Debye–Hückel approximation, while the reservoir screening length remains unchanged. Freezing then becomes possible at lower volume fraction or shorter screening length. At fixed ${\lambda }_D$, the coexistence curves shift towards lower $\eta$; a previously fluid sample may crystallize.

These statements assume fixed, uniform charge and a salt reservoir dominating the screening. Strong charging requires nonlinear screening and possibly charge regulation. At very low added salt or appreciable particle concentration, particle-released counterions also contribute to ionic strength, so the screening length is no longer independently fixed by the added salt alone.

A screened Coulomb pair potential models the effective electrostatic interaction of particles in an electrolyte. For identical weakly charged spheres of radius $a$, charge $Q$, and Debye–Hückel screening length ${\kappa }^{-1}$, a common pairwise approximation is $U(R)=Q^2{e}^{-\kappa (R-2a)}/[4\pi \epsilon (1+\kappa a{)}^{2}R]$ for $R\ge 2a$. The near-contact interaction can require more detailed boundary conditions or nonlinear screening. Charge, screening length and temperature all matter to a resulting phase diagram.