Chen, Siming

Duan, Dongping

Li, Ting

Zhou, E

English

Engineering Conferences International

Engineering Conferences InternationalECI Digital Archives5th International Congress on Green ProcessEngineering (GPE 2016) Proceedings6-21-2016Development and industrial application of novelnon-cr passivity for electrolytic manganeseSiming ChenKey Laboratory of Green Process and Engineering, Institute of Process Engineering, CAS, China, smchen@ipe.ac.cnDongping DuanQinghai Institute of Salt Lakes, Chinese Academy of Sciences, Qinghai, ChinaE ZhouKey Laboratory of Green Process and Engineering, Institute of Process Engineering, CAS, ChinaTing LiKey Laboratory of Green Process and Engineering, Institute of Process Engineering, CAS, ChinaFollow this and additional works at: http://dc.engconfintl.org/gpe2016Part of the Chemical Engineering CommonsThis Abstract and Presentation is brought to you for free and open access by the Proceedings at ECI Digital Archives. It has been accepted for inclusionin 5th International Congress on Green Process Engineering (GPE 2016) by an authorized administrator of ECI Digital Archives. For moreinformation, please contact franco@bepress.com.Recommended CitationSiming Chen, Dongping Duan, E Zhou, and Ting Li, "Development and industrial application of novel non-cr passivity for electrolyticmanganese" in "5th International Congress on Green Process Engineering (GPE 2016)", Franco Berruti, Western University, CanadaCedric Briens, Western University, Canada Eds, ECI Symposium Series, (2016). http://dc.engconfintl.org/gpe2016/30Research on mechanism of one-step preparation of intelligent self-healing protective coating on Mn surfaceSiming Chenmail: Smchen@ipe.ac.cn5th Internatioal Congress on Green Process Engineering2016.6.21ContentsI.  Introduction Ⅱ. Membrane preparationⅢ. Corrosion behavior of Phosphate membraneⅣ. Novel passivity in industrial applicationⅤ.  Conclusions ContentsI.  Introduction Ⅱ. Membrane preparationⅢ. Corrosion behavior of Phosphate membraneⅣ. Novel passivity in industrial applicationⅤ.  Conclusions 1. IntroductionMn, as an important raw material, is readily oxidized in air  Phosphate membrane:Passivation method:chromate treatmentGood passivation behaviorsPollutionDeveloping direction:chromate free passivity P-based passivity of MnCurrent situation:Bad passivationsimple & anti-corrosionContentsI.  Introduction Ⅱ. Membrane preparationⅢ. Corrosion behavior of Phosphate membraneⅣ. Novel passivity in industrial applicationⅤ.  Conclusions 2. Membrane preparation2.1 Passivation method (H3PO4 as passivity):Schema of treatment processAppearances of Mn treated by chromate(Cr-Mn) (left) and H3PO4 (P-Mn) (right)  Requirement of manganese productBright appearance Acceptable Impurity content Element Mn P OContent（%） 23.02 16.22 60.762.2 Analysis of P-based membrane:2. Membrane preparationChemical content of coatingMn3(PO4)2SEM image of  P-MnSEM cross-section image of  P-Mn2. Membrane preparationParameter of  Tafel curve in 3.5% NaCl solution 2.3 Corrsion resistance :Sample Ecorr (V) Icorr (µA/cm2)High current density implys high corrosion rateTafel curve of Mn treated by different methods in 3.5% NaCl solution   Corrosion resistance:P-Mn>Cr-Mn>EMEM -1.41 321Cr-Mn -1.29 12.9P-Mn -1.25 5.3ContentsI.  Introduction Ⅱ. Membrane preparationⅢ. Corrosion behavior of Phosphate membraneⅣ. Novel passivity in industrial applicationⅤ.  Conclusions 3. Corrosion of P-based membrane3.1 Corrosion process:SEM image of Mn (left), Cr-Mn (centre) and P-Mn (right) before immersion in 3.5% NaCl solution24h corrosion SEM image of Mn (left), Cr-Mn (centre) and P-Mn (right) after immersion for 24 h3. Corrosion of P-based membraneMn TO* Cr P RO** O：Mn***MnBefore 84.93 0 - - 0 0After 23.29 54.22 - - 54.22 2.38Before 94.48 0 0.12 - 0 0Compositional variation of membraneMnO2Cr-MnAfter 60.72 19.10 0.10 - ~19.10 ~0.31P-MnBefore 23.02 60.76 - 16.22 ~0 ~0After 53.30 31.49 - 9.40 ~0 ~0*: TO: total O**: RO: remaining O, RO= TO- (P×4)***: O:Mn=RO÷MnCorrsoion inhibition3. Corrosion of P-based membraneSample Ecorr (V) Icorr (µA/cm2)EM -1.29 3130Cr-Mn -1.29 284Parameter of  Tafel curve in 3.5% NaCl solution after 24h immersion P-Mn -1.25 140Tafel curve of Mn treated by different methods in 3.5% NaCl solution after 24h immersionRetention of  Corrosion resistance:P-Mn>Cr-Mn>EM3. Corrosion of P-based membrane3.2 : self-healing capability test Photos of Cr-Mn and P-Mn with damaged membrance after immersion in 3.5% NaCl solution for 24 h 3. Corrosion of P-based membranea bAABBSEM image: before immersion: Cr-Mn(a) and P-Mn(b) with damaged membrane;after immerison in 3.5% NaCl solution: Cr-Mn(c) and P-Mn(d) with damaged membranedcAABBImmersion time (h)Membrane statueMn TO* Cr P RO** O：Mn***Cr-MnBeforeZone A 89.4 0.7 0.36 - 0.7 0.007Zone B 100 - - - 0 0Compositional variation of membrane3. Corrosion of P-based membraneMost of Mn are oxidized. AfterZone A 55.3 18.0 0.2 - 18.0 0.325Zone B 33.2 64.4 - - 64.4 1.94P-MnBeforeZone A 27.5 57.6 - 14.9 ~0 ~0Zone B 86.4 11.6 - 2.0 3.6 0.042afterZone A 58.3 36.1 - 5.6 13.7 0.234Zone B 39.7 38.4 - 1.28 33.28 0.838*: TO: total O**: RO: remaining O, RO= TO- (P×4)***: O:Mn=RO÷MnSelf-healing capability: P-Mn>Cr-MnPart with intact membranePart with damaged membraneDegree of oxidation is much lower3. Corrosion of P-based membraneParameter of Tafel curve in 3.5% NaCl solution Tafel curve of samples with damaged membrane  in 3.5% NaCl solution for 24 h  P-Mn has better retention of corrosion inhibition capability when its membrane damaged.    3.3  mechanism:3. Corrosion of P-based membraneMnH3PO4MnMn(H2PO4)2DryingMn3(PO4)2 H3PO4MnSchema of P-based membrane formation Mn Mn MnSchema of anti-corrsion processMnH3PO4 Mn3(PO4)2CorrsionmigrateMn+H3PO4 →Mn(H2PO4)2+H2↑3Mn(H2PO4)2 →Mn3(PO4)2↓+4H3PO4ContentsI.  Introduction Ⅱ. Membrane preparationⅢ. Corrosion behavior of Phosphate membraneⅣ. Novel passivity in industrial applicationⅤ.  Conclusions 4. Novel passivity in industrial applicationP-based coating on Mn surface has good anti-corrosionand self-healing capability. However, it’s harmful for quality ofMn with high P content. A novel passivity with lower P contenthave been invited, and used in Mn industrial production.4. Novel passivity in industrial application4.1 Industrial application of novel passivity Impurity contentOur product StandardsC 0.0064% ≤0.02%P 0.0032% ≤0.005%Photos of Mn treated by novel P-based passivity in industrial production in XES. LTD. Accord with production standardsYB/T051-93, which used current.S 0.020% ≤0.03%Cr-Mn NP-Mn MnE V -1.29 -1.414. Novel passivity in industrial application-4-3-2-1Log (Current / A )Parameter of Tafel curve in 3.5% NaCl solution 4.2 Anti-corrosion capability:corr（ ） 1.34icorr（μA/cm2） 12.9 40.7 3130-1.0 -1.1 -1.2 -1.3 -1.4 -1.5 -1.6-7-6-5NP-MnCr-MnLog (Current / A )Potential / V vs. SCEMnTafel curve of Mn treated by different methods in 3.5% NaCl solution  Even though corrosion current density ofNP-Mn is higher than Cr-Mn in corrosionmedia , it just covers ca. 1/75 of Mn. Itimplies novel passivity we developed has agood passivation capability for manganese.4. Novel passivity in industrial application24h4.3 analysis of corrosion product:TO P Mn RO O:Mnbefore 7.26 0.57 73.47 4.78 0.065after 26.42 0.77 47.08 23.34 0.50immersionSEM image of NP-Mn SEM image of NP-Mn after immersionin 3.5% NaCl solution for 24 h Compositional variation of membraneGood anti-corrosion behavior than pure Mn in corrosion media Cr-Mn:O:Mn=0.3254. Novel passivity in industrial application4.4 Product of Mn in industrial productionPhotos of Mn treated by chromate (left) and novel P-based passivity (right) in industrial production(preserve at arbitrary temperature for Ca. 3 months)ContentsI.  Introduction Ⅱ. Membrane preparationⅢ. Corrosion behavior of Phosphate membraneⅣ. Novel passivity in industrial applicationⅤ.  Conclusions 4. Conlusions1. According to deficiency of current chromate and non-Cr passivity,H3PO4 is used as a main passivity in our research. It’s found thatphosphate membrane formed on Mn surface had a great anti-corrosion capability. Results from EDS showed that its maincomponent is Mn3(PO4)2.2. Experiment results show that phosphate membrane have betterself-healing capabilities.3. Results of industrial application of novel P-base passivity showedthat Mn which treaded by novel P-based passivity had a brightappearance and good anti-corrsion capability. Its impurity contentaccorded with production standards YB/T051-93.

Development and industrial application of novel non-cr passivity for  electrolytic manganese

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Development and industrial application of novel non-cr passivity for electrolytic manganese

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