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Journal of Chinese Society for Corrosion and protection  2021, Vol. 41 Issue (5): 571-578    DOI: 10.11902/1005.4537.2020.240
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Research Status and Progress on Growth Kinetics of Trivalent Chromium-based Conversion Film
WANG Laibin, LIU Xiahe(), WANG Mei, GAO Junjie
Department of Resource and Environment, Institute of Metallurgical Resources and Environmental Engineering, School of Metallurgy, Northeastern University, Shenyang 110819, China
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Abstract  

The trivalent Cr-based conversion (TCC) film on metal and alloy has low toxicity, but unexpectedly poor stability and easy to crack. How to form a high-quality TCC film becomes the key issue for acquiring such films with comprehensive performance both in good corrosion resistance and stability. By investigating the relevant worldwide research of TCC film growth, the corresponding properties, like electrochemical performance, microstructure, phase constituents etc. of the film are reviewed. Taking the thermodynamic theory of oxides system and the kinetic model of film growth into consideration, the stability and growth mechanism of TCC film are analyzed, the existing problems and future developments for the growth of TCC film are proposed.
Key words:  trivalent chromium      oxide film      kinetics      electrochemistry      microstructure     
Received:  18 November 2020     
ZTFLH:  TG172  
Fund: National Natural Science Foundation of China(51701038);Fundamental Research Funds for the Central Universities(N162503002)
Corresponding Authors:  LIU Xiahe     E-mail:  liuxiahe@smm.neu.edu.cn
About author:  LIU Xiahe, E-mail: liuxiahe@smm.neu.edu.cn
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Laibin WANG
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WANG Laibin, LIU Xiahe, WANG Mei, GAO Junjie. Research Status and Progress on Growth Kinetics of Trivalent Chromium-based Conversion Film. Journal of Chinese Society for Corrosion and protection, 2021, 41(5): 571-578.

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https://www.jcscp.org/EN/10.11902/1005.4537.2020.240     OR     https://www.jcscp.org/EN/Y2021/V41/I5/571

StageEnvironmentOxide layers on baseRegularity of corrosion potentialReferences
Two stagespH1.2~4 SurTec 650 solution, ＜600 sCr(III)-based film on Al or Al alloyPotential decreases first and then tend to stabilize[15,16]
Three stagespH 2.0-4.0 Socosurf TCS solution, ＜1200 sCr(III)-based film on Al or ZnThe potential first decreases, then increases, and finally stabilizes[17-22]
Four stagespH2.0 Cr(NO3)3 base solution, ＜1200 sCr(III)-based film on ZnThe potential first decreases, increases, then decreases and finally stabilizes[23,24]
Table 1  Evolution rule of OCP vs time during the growth of TCC coating[15-24]
Model

CMM[55-57]

(air phase formation)

FMM[58,59]

(air phase formation)

PDM[60-62]

(electrochemical formation)

Oxide growth mechanismMigration of interstitial cationsMigration of interstitial anionsMigration of anion vacancies
Growth law

Weak Electric Field: L2=εLt

Strong electric field:

1/L=A-Blnt1/L

Activation energy function of thickness L=Cln(1+Dt)Transport controlled:L=(1/2K)[ln2Ka(b-1)+lnt] Interface controlled:L=Lt=0+(1/b)ln[1+abtexp(-bLt=0)]
Electric FieldεL=V/LIndependent of LIndependent of L
Limiting Growth Step

Weak electric field:

Transport of cations through the film Strong electric field:

Cation injection at m/f interface

Anion transport through the film

Transport controlled:

Oxygen vacancies through film

Interface controlled:

Anion vacancy injection at m/f interface

Dissolutionn/an/aDissolution of metal dissolution of oxide
Interfacial potential dropn/an/aFunction of pH and Vext
Table 2  Summary of the main characteristics of the growth models for passive film[55-62]
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资助项目 国家自然科学基金 (51701038) 和中央高校基本科研业务费专项 (N162503002)
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