Passivation Film Simulator: Oxide Layer Growth & Stability

simulator advanced ~12 min
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d = 3.2 nm — stable passive film

An 18% Cr stainless steel in neutral pH at 0.3V develops a 3.2 nm passive film with excellent stability, providing corrosion protection at just microamps per cm² dissolution rate.

Formula

d = k × ln(1 + E/E₀) × (Cr%/12)  [High-field model]
E_breakdown = E₀ - 0.059 × log(Cl⁻)  [Breakdown potential]
i_passive = i₀ × exp(-αd/kT)  [Passive current density]

Nature's Invisible Shield

The remarkable corrosion resistance of stainless steel, aluminum, and titanium comes not from the bulk metal but from an invisible oxide film just 1-10 nanometers thick. This passivation layer forms spontaneously when the metal contacts air or water, creating a barrier that reduces dissolution rates by three to six orders of magnitude. The film is self-healing — scratch it, and it reforms within milliseconds in oxidizing environments.

Chromium: The Essential Ingredient

For stainless steels, chromium is the critical alloying element. Below approximately 10.5% Cr, the surface oxide is patchy and non-protective. Above this threshold, a continuous Cr₂O₃-rich film forms that is both dense and adherent. Each additional percent of chromium widens the passive potential range and increases the breakdown potential, which is why super-austenitic stainless steels contain up to 25% Cr for severe service.

Film Growth and the High-Field Model

Passive film growth follows the high-field model: the electric field across the thin film drives metal ions through the oxide lattice. Film thickness increases logarithmically with applied potential — a result of the exponential field-dependent ion migration rate. This self-limiting growth mechanism explains why passive films remain extremely thin even at high potentials: as the film thickens, the field drops and growth slows to a virtual stop.

Breakdown and Pitting

The Achilles heel of passivation is localized breakdown. Chloride ions preferentially attack the film at microstructural weak points — MnS inclusions, grain boundaries, or mechanical defects. Once a pit initiates, the local chemistry inside becomes acidic and chloride-enriched, preventing repassivation and driving rapid local attack. This simulation lets you explore how chromium content, pH, potential, and chloride concentration compete to determine whether the film survives.

FAQ

What is a passivation film?

A passivation film is an ultra-thin (1-10 nm) oxide layer that forms spontaneously on certain metals like stainless steel, aluminum, and titanium. This film is dense, adherent, and self-healing, reducing corrosion rates by factors of 1000 or more. Chromium oxide (Cr₂O₃) is the primary component of stainless steel passivity.

Why does stainless steel need at least 10.5% chromium?

Below ~10.5% Cr, there is insufficient chromium to form a continuous, self-healing Cr₂O₃ film across the entire surface. Above this threshold, the oxide film becomes complete and protective. Higher chromium content (18-25%) provides even more robust passivity in aggressive environments.

How do chlorides break down passivation?

Chloride ions penetrate the passive film at weak points (grain boundaries, inclusions), replacing oxygen in the oxide lattice. This locally dissolves the film, creating tiny active sites that become pitting nuclei. The breakdown potential decreases logarithmically with chloride concentration.

What is the transpassive region?

At very high anodic potentials (typically >1.2V vs SHE), chromium in the passive film oxidizes from Cr³⁺ to Cr⁶⁺ (chromate), which is soluble. This dissolves the protective film, causing renewed active corrosion — a phenomenon called transpassive dissolution.

Sources

Embed

<iframe src="https://homo-deus.com/lab/corrosion-science/passivation-film/embed" width="100%" height="400" frameborder="0"></iframe>
View source on GitHub