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Chromiting
The Thick Layer Passivation for Zinc and Zinc Alloys Free of Hexavalent Chromium
SurTec GmbH, SurTec-Strae 2, D-64673 Zwingenberg
SurTec

SurTec GmbH

April 2001

Topics

w w w w w

Corrosion and Corrosion Protection Cathodic Corrosion Protection of Steel Properties of Conventional Chromates Application, Properties and Corrosion Protection of Chromiting Outlook

SurTec GmbH

April 2001

Corrosion and Corrosion Protection of Steel w steel is dissolved in salt and air containing water while oxygen is reduced and hydrogen is evolved, and forms iron oxide/hydroxide which precipitates as a voluminous corrosion product on the surface = Red Rust w iron oxide layers are not protecting against further corrosion, in contrary to chromium oxide on metallic chromium or aluminium oxide on aluminium
water

Fe2+ Fe(III) hydroxide and oxide iron

q corrosion protection is provided: barrier layers oil, conversion layers, lacquer, combination, metallic layers redox buffer less noble layers, conversions layers with different oxidation levels, organic corrosion protectors duplex layers combination of both
SurTec GmbH April 2001

Cathodic Corrosion Protection of Steel w this is the typical method to protect steel and other iron material, because in the electrochemical series of elements, iron is more positive than zinc, and this means w zinc is less noble than iron and represents the anode in the galvanic element - iron is the cathode w thus, iron will be - as the more noble metal - protected cathodically, until the zinc is corroded completely q mechanism: water
Fe2+ Zn2+

chromating zinc iron

Zn / Zn2+ : Fe / Fe2+ :

Zn Fe2+ + 2 e-

Zn2+ Fe

2 e-

SurTec GmbH

April 2001

Cathodic Corrosion Protection of Steel w basic task is the protection of the base metal against rust and consequently also against hydrogen induced embrittlement w side purposes are a decorative function (brightness, colour) as well as tribological properties w higher layer thickness and more even metal distribution are extending the cathodic corrosion protection

w zinc alloys (Co, Fe, Ni, Sn) are more noble than pure zinc and extend also its cathodic corrosion protection w in addition to the cathodic protection, the zinc layer is passivated by a chromate layer, which is improving strongly the corrosion protection (by its barrier effect) w the colour is defined by the chromating: possible tints are transparent-blue and transparent-green (trivalent) as well as yellow, black and olive green (hexavalent)
SurTec GmbH April 2001

Cathodic Corrosion Protection of Steel metal distribution

15,1

conventional cyanide-free alkaline zinc process

15,5 17,5 12,3 11,8 17,0 20,9 m

9,9

13,8

14,2

14,2

15,6

15,1

14,1 m

new cyanide-free alkaline zinc process

conventional cyanide-free alkaline zinc process

11,9 7,0 8,6 7,1 6,6 9,6 11,1 m

9,9

9,5

9,6

9,3

9,3

9,6

9,6 m

new cyanide-free alkaline zinc process

SurTec GmbH

April 2001

Corrosion and Corrosion Protection of Steel

zinc mechanism: parameters: cathodic protection thickness, metal distribution, trace metals (e.g. alloys)

passivation mechanism: parameters:

type

barrier effect, specific effect of chromium(VI) ?

chromium(VI) in the chromate layer in mg/m 2 0 80-220 300-400 80-400 layer thickness in nm corrosion protection in hours salt spray test until first white corrosion 20-40 200-300 400-500 150-300

blue (trivalent) yellow olive-green black

25-80 250-500 1000-1500 250-1000

SurTec GmbH

April 2001

Properties of Conventional Chromates

edge of a broken steel sheet, bright zinc plated and trivalent blue passivated, at a magnification of 40,000x

edge of a broken steel sheet, bright zinc plated and hexavalent yellow passivated, at a magnification of 40,000x

if chromium(VI) had a specific corrosion protecting effect, we shall always expect a disadvantage with trivalent chromates with regard to its anticorrosive properties

SurTec GmbH

April 2001

Properties of Chromiting q if the corrosion protection of a chromate layer was based on it barrier effect only, then trivalent passivations with the same layer thickness should provide the same corrosion protection as hexavalent passivations

Stunden im Salzsprhschrank (DIN 50021) hours in salt spray (DIN 50021 SS)

450 400 350 300 250 200 150 100 50 0

Trommel barrel Gestell rack Trommel barrel Gestell rack Trommel barrel Gestell rack

bis 10 % WR to 10 % WC bis % WR to 55% WC to first attack bis Erstangriff

Blauchromatierung Blue Chromate dreiwertig

trivalent

Gelbchromatierung Yellow Chromate sechswertig

hexavalent

Chromitierung Chromiting dreiwertig

trivalent

edge of a broken steel sheet, bright zinc plated and trivalent chromited, at a magnification of 40,000x

Corrosion Protection Comparison in Comparison Corrosion Protection in Comparison

SurTec GmbH

April 2001

Application: Chromiting in Comparison to Yellow Chromate

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trivalent Chromiting make-up: pH-value: temperature: contact time: heating: exhaust: rinsing: activation: agitation: tank material: 12.5 Vol%
= 10 g/l Cr(III)

hexavalent yellow chromate 1 Vol%

= 2 g/l Cr(VI)

1.8-2.2 60 C 60 s necessary necessary 3 steps recommended

1.6-1.8 room temperature 20 s in winter season recommended 2 steps

rack agitation/barrel rotation and/or air agitation (insulated) plastic tanks or steel tanks with plastic inliner

SurTec GmbH

April 2001

The Green Alternative

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SurTec GmbH

April 2001

Sputter Profiles in Comparison

100 % zinc 80

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60 Chromiting 40

100 % zinc 80

20 chromium 0 0,0 0,2 0,4 0,6 sputter depth in m 0,8 1,0

60 Yellow Chromate 40

20 chromium sputter depth in m 0 0,0 SurTec GmbH 0,2 0,4 0,6 0,8 1,0 April 2001

Chromiting Layer Thickness Measured with Different Methods

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Layer Thickness in nm ellipsometry, glow discharge spectroscopy (GDOES) and scanning electron microscopy

Chromiting

immersion temperature time in s in C 60 60 120 60 60 60 90 60 120 60 60 100

pH-value 2.0 2.0 2.5 2.5 2.5 2.0

scanning electron microscopy 300

glow discharge spectroscopy 312 400 195 295 435 360 60 440

ellipsometry 353 440 230 300 400 580 100 395

in comparison: Blue Chromate Yellow Chromate

60 300

SurTec GmbH

April 2001

Chromium Content in the Chromiting Layer depending on the immersion time

300

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250

Chromium Content in mg/sqm

om C hr
200

iting

C h r 150 o m 100

50

Blue Passivation
0 0 50 100 150 200 250 300 350 Chromitierung Immersion Time in s

SurTec GmbH

April 2001

Chromium Content and Corrosion Protection depending on the treatment temperature

200 800

15

150

100

50

A B C D 700 1 Temperature Chrome Temperature Corrosion Protecti 2 25 50,8 25 180 3 30 63 35 240 600 4 35 59,3 45 270 5 40 60,7 55 310 500 6 45 63,2 65 320 7 50 67,1 75 330 8 55 71,1 80 400 400 9 60 80,3 90 500 10 65 83,8 100 700 300 11 70 87,8 12 75 92,8 13 80 96,3 200 14 90 123,7 15 100 181,3 100 16 17
0 20 30 40 50 60 70 80 90 100 20 30 40 50 60 70 80 90 100

Treatment Temperature in C

Corrosion Protection in h salt spray DIN 50021 SS

Chromium Content in mg/sqm

Treatment Temperature in C

SurTec GmbH

April 2001

German "Qualittsfrderkreis Chromitierung" (just founded)

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w old members Collini, Holder, Vollmerhaus new: Holzapfel, Huster, Kronenberger, Zeschky w application of Chromiting, Black Chromiting and possible further developments w exchange of experience (trouble shooting) w commitment to keep narrow parameter ranges for the coating w development and guarantee of common standards (measuring procedures, setting and guaranteeing process safety, reproducibility) q task: to provide capacity in a sufficient volume and in constantly high quality

SurTec GmbH

April 2001

Colour Effects
1. Chromiting on Zinc

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The natural colour is transparent and significantly green iridescent. This colour is no body colour caused by pigments, but a layer thickness related interference colour. A significantly green layer has a thickness of 100-700 nm. This colour will disappear completely after an organic sealing with SurTec 552 or 555 (different refraction index than the passivation itself). 2. Chromiting on Zinc/Iron or Zinc/Nickel The colour of Chromiting on zinc/iron is stronger iridescent and slightly darker. Also here it is disappearing to a great extent by an organic sealer, resulting in a colour similar to that of titanium. On zinc/nickel, a thinner Chromiting layer appears dark blue - iridescent; thicker layers are looking yellowish-green. After sealing, a uniform grey shade is formed. 2. Chromiting on Other Surfaces On zinc/cobalt, the colour is similar to zinc/iron, but the layer composition of zinc/cobalt is less uniform and so is its colour. On hot dip zinc, it is opaque greyish green, on zinc dye cast often spotted (copper!).

SurTec GmbH

April 2001

Outlook: Other Colours

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What About Black Chromitings? x black layers on zinc/iron are possible with a variation of Chromiting; its further optimisation is a current project x black layers on zinc/cobalt are possible with the same solution (but less uniform) x for zinc/nickel there is no Black Chromiting up to now

Dyeability x high-coloured dyes can be used to tint the layer; blue, yellow, "brass" and pinkish-red are already tested x black dyes (as for aluminium) are to weak in colour to result in an opaque black colour

SurTec GmbH

April 2001

Outlook: Completely Chromium-Free Layers? w minimal traces (between 1-3 mg/m2) of chromium(VI) are always present in high amounts of chromium(III), due to the chemical equilibrium w the analysis of chromium(VI) traces in chromium(III) bulk is not trivial q a theoretical replacement for chromium(VI) in passivations must fulfil a series of criteria: Chemical Properties good water solubility in acidic pH (a conversion layer always requires a prior etching) the formation of oxides, insoluble in water, acids and lyes General availability (mass production) recyclability low raw material costs known toxicology of all possible oxidation levels

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SurTec GmbH

April 2001

Outlook: Completely Chromium-Free Layers?

the solubility of element oxides is coded in greys. light grey = insoluble in water; grey = insoluble in acids or lyes; dark grey = insoluble both in acids and lyes

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Group Period

* Lanthanides ** Actinides

SurTec GmbH

April 2001

Outlook

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Conclusion
q Chromium(III) is the best alternative to Chromium(VI), other - more appropriate elements are not in sight q with trivalent thick layer passivations (Chromiting), the requirements of the EU End of Life Vehicles Directive are easily met (2 g chromium(VI) per car are allowing 600 to 2000 m2 passivated surface) q in collaboration with the VDA, chemical suppliers are developing an analytical method for the detection of chromium(VI) in passivations

SurTec GmbH

April 2001