Trivalent chromium plating, anode and cathode

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1 Presentation title, change View >> Header & Footer Tata Steel Slide Arnoud de Vooys Trivalent chromium plating, anode and cathode Making packaging steel in the 21st century

2 Tata Steel Slide 2 ECCS packaging steels ECCS = Electrolytically Chromium Coated Steel ECCS excels in adhesion to organic coatings (lacquers, polymer coatings) ECCS is used in the production of DRD (Drawn & Redrawn) two-piece cans and components that do not have to be welded, such as ends, lids, crown corks, twist-off caps and aerosol bottoms and tops

3 Tata Steel Slide 3 ECCS electroplating process Tata makes ca ktonnes/year Say m2 Typical coil dimensions: Length: m Width: 1.2 m Thickness: 0.2 mm Coating weight: mg m -2 Cr 7 35 mg m -2 CrOx Line speed: Up to 10 m s -1 Total rectifier current: A Deposition time: A few seconds

4 Tata Steel Slide 4 Cr6+ replacement ECCS requires hexavalent chromium electrolytes, a.k.a Cr6+ Hexavalent chromium is considered a hazardous substance In response to REACH legislation, Tata Steel R&D has developed an electrolyte based on Cr3+ and formic acid Registration, Evaluation, Authorization & Restriction of CHemicals 2017 Cr e - Cr 3+

5 ECCS replacement How hard can it be? Tata Steel Slide Pretty hard actually: ECCS works very well Search for alternatives (brittle, electrochem. active, soluble, poisonous, etc.) In the end, we went back to Chrome with different application

6 Tata Steel Slide Characterising Cr layer, FIB-TEM cross section Smooth part, homogeneous Cr layer Cr layer, Lower density than Fe

7 Tata Steel Slide Characterising Cr layer, FIB-TEM cross section Rough part Chrome follows surface roughness Steel shows surface crack

8 Tata Steel Slide Characterising Cr layer, FIB-TEM cross section Rough part Steel had small surface crack Chrome is deposited in the crack Good throwing power

9 Tata Steel Slide Does it work? the proof of the pudding is in the eating Cr layer was coated with PET laminate and compared to PET laminated ECCS Material was shaped into cans, filled with de-aerated brine, sterilised, stored for two weeks and evaluated visually Laminated ECCS reference Laminated Cr layer

10 Tata Steel Slide One danger: the anode In theory it is possible to oxidise Cr3+ to Cr6+ at the anode (steel coil is the cathode) Need to check to avoid danger

11 Tata Steel Slide 11 Results of long-term galvanostatic experiments anode Cr(VI) mg l -1 current efficiency % Pt ca MMO IrO 2 + Ta 2 O applied current density = 92 ma (ca A m -2 ) for 3600 s Cr6+ is not just a theory, but can happen with the wrong anode

12 Tata Steel Slide 12 Core of electrolyte is Cr3+ and formic acid stable complex 3 6 Cr(H 2 O) formate + destabilised complex 2 2 5(HCOO ) Cr(H O) Source: Zhixiang Zeng, Yaling Sun and Junyan Zhang, Electrochem. Commun., 11 (2009)

13 Tata Steel Slide 13 Formic acid on Pt i / ma cm Reaction 1: formic acid to CO2 Reaction 2: formic acid to CO, which sticks to the electrode CO is a poison to the reaction (not just for humans) Hence the drop in current = drop in reaction rate E vs. SCE / V

14 Tata Steel Slide 14 Cr3+ and formic acid on Pt i / ma cm No CO 2 formation: Cr(III) complex blocks formic acid So it adsorbs, sticks Pt does something to Cr3+ question: is sticking the only thing that happens? E vs. SCE / V

15 I / ma ion current CO 2 (m/z = 44) / a.u. I / ma ion current O 2 (m/z ION Meeting Cr3+ and formic acid on Pt 3.0E-09 Tata Steel Slide 15 arb. unit E E Mass -0.2spectrometer measures no CO2 E nor vs. SCE / V CO 2 2.0E-08 Formic acid has 150 nothing to do with it Must be Cr3+ CO 2 1.5E Cr3+ oxidation 1.0E uh oh 5.0E-09 O E E vs. SCE / V

16 i / ma cm -2 ION Meeting 2016 Tata Steel Slide 16 MMO: sodium sulphate + sodium formate + chromium(iii) sulphate 30 No sticking of Cr3+ no oxidation of Cr3+ no Cr E vs. SCE / V

17 Tata Steel Slide 17 Conclusions Cr(III)-formate adsorbs strongly on platinum Cr(III)-formate is oxidised at platinum Platinum is therefore catalytically active for Cr(VI) formation Cr(III) adsorption and Cr(VI) formation also occurs in the absence of formate (not shown here) Adsorption of Cr(III)-formate is absent on MMO and consequently no Cr(VI) is formed at MMO

18 Tata Steel Slide 21st century ECCS 21st century ECCS formally presented at Tinplate Conference in London (international fair for steel packaging producers and users) Launch: soon

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