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Replacement of Chromium(VI)
in Passivations on Zinc And Zinc Alloys
Patricia Preikschat, SurTec GmbH, D-64673 Zwingenberg

Topics:
● what are we searching for? – properties of hexavalent passivation films
● criteria for chromium(VI)-free alternatives
● examining the periodic table
● trivalent chromium passivation films
● application

SurTec GmbH June 2001/PP

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Properties of Hexavalent Passivations

hexavalent yellow chromate hexavalent black chromate

Zinc Zinc

Type of Passivation Chromium(VI) in Layer Thickness in Salt Spray to White

mg/m 2 nm Corrosion [hours]

Yellow Chromate 80-220 250-500 200-300

Olive Chromate 300-400 1000-1500 400-500
Black Chromate 80-400 250-1000 150-300
compare:
Trivalent
Blue Chromate 0 25-80 20-40

SurTec GmbH June 2001/PP

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Properties of Hexavalent Passivations

100 %

Zinc
80

60
Yellow Chromate
on Zinc
40

20
Chromium
Sputter Depth in µm
0
0.0 0.2 0.4 0.6 0.8 1.0

SurTec GmbH June 2001/PP

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Criteria for a Chromium(VI)-free Passivation

(how to get the same properties - or better - without hexavalent chromium)

Desirable Chemical Properties

▲ component with good water solubility in acidic media
(a conversion layer typically requires an initial attack on the metal)
▲ formation of oxides, which are utmost insoluble in water, in acids and in alkalies

General Requirements
▼ adequate availability to support large scale production
▼ recyclability (compatability with steel production)
▼ economics (consider demand for low raw material costs)
▼ known toxicity of all possible oxidation levels

SurTec GmbH June 2001/PP

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Periodic Table – Infinite Options?

➩ there are 93 natural elements

Gro
oup
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Period
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba * Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra ** Lr Rf Db Sg Bh Hs Mt

* Lanthhaniddes La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb
** Acctinid
des Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No

SurTec GmbH June 2001/PP

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Periodic Table – Infinite Options?

▼ all gases, radioactive elements as well as halogens drop out of the race

Gro
oup
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Period
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba * Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra ** Lr Rf Db Sg Bh Hs Mt

* Lanthhaniddes La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb
** Acctinid
des Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No

➩ 70 elements remain

SurTec GmbH June 2001/PP

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Periodic Table – Infinite Options?

▼ alkali and earth alkali elements, borium, phosphorus and selenium form only highly
soluble oxides; silicium has no well soluble compounds in acids

Gro
oup
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Period
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba * Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra ** Lr Rf Db Sg Bh Hs Mt

* Lanthhaniddes La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb
** Acctinid
des Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No

➩ 55 elements remain
SurTec GmbH June 2001/PP
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Periodic Table – Infinite Options?

▼ solubilities of oxides: light green (insoluble in water) - green (insoluble in acids or lyes) -
dark green (insoluble in acids and lyes)

Gro
oup
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
Period
1 H He
2 Li Be B C N O F Ne
3 Na Mg Al Si P S Cl Ar
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
6 Cs Ba * Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
7 Fr Ra ** Lr Rf Db Sg Bh Hs Mt

* Lanthhaniddes La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb
** Acctinid
des Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No

➩ 6 element oxides are possible, of those chromium(III) is the least soluble

SurTec GmbH June 2001/PP
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Layers With Trivalent Chromium

The formation of a conversion layer in solutions of trivalent chromium is described in two

reaction equations:
I elemental zinc is dissolved at the surface by the acidic attack:
Zn + 2 H
+
→
k1
Zn + H↑
2+

II and precipitates together with chromium(III) as zinc chromium oxide on the zinc surface:

→
→
k2
2+ +
Zn + x Cr(III) + y H2O ZnCrxOy + 2·y H
k3

A kinetic model was formed, comprising of differential equations for the concentration
development of Zn2+, H+, Cr(III) and for the thickness growth of the ZnCrO layer. The
mathematical expressions for the reaction speed take into consideration that reaction I is
increasingly slowed down by the growing passive layer.
The system of differential equations was numerically solved by a computer, resulting in the
development of layer thickness and concentration values as a function of time.

SurTec GmbH June 2001/PP

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Simulated Development of Layer Thickness

Thickness
Dicke der of the
Chromate Layer
Chromatschicht
k2 = 10
0,1

k1 = 10

k2 = 1

k2 = 0,1
k2 = 10
k1 = 1
k2 = 1

k2 = 0,1

k1 = 0,1 k2 = 10
k2 = 1
k2 = 0,1
Treatment
Behand-
0 5 10 15 20 25 Time
lungsdauer

SurTec GmbH June 2001/PP

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SurTec GmbH June 2001/PP

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Layers With Trivalent Chromium

▲ the layer thickness is growing with growing immersion time

Chromium Content in mg/qm
300

250
Chromiting
200

150

100
Blue Chromate
50

0
0 50 100 150 200 250 300
Immersion Time in s

SurTec GmbH June 2001/PP

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Layers With Trivalent Chromium

100 %

Zinc T [°C] pH t [s] SEM GDOS Ellipso- Ø

80 metry
60 2.5 60 195 195
60
60 2.5 90 295 295
Chromiting 60 2.0 60 300 312 353 322
60 2.5 120 300 435 353 363
40
60 2.0 120 400 440 420
100 2.0 60 360 580 470
20
Chromium
Sputter depth in µm
0
0.0 0.2 0.4 0.6 0.8 1.0

SurTec GmbH June 2001/PP

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Layers With Trivalent Chromium

▲ layer thickness and relative chromium content are rising with rising temperature

200 800

Corrosion Protection in h salt spray DIN 50021 SS

A B C D
1 Temperature 700
Chrome Temperature Corrosion Protecti
2 25 50,8 25 180
3
Chromium Content in mg/sqm

150 30 63 600 35 240

4 35 59,3 45 270
5 40 60,7 55 310
6 500
45 63,2 65 320
7 50 67,1 75 330
100 8 55 71,1 400 80 400
9 60 80,3 90 500
10 65 83,8 100 700
11 300
70 87,8
12 75 92,8
50 13 80 96,3 200
14 90 123,7
15 100 181,3
16 100

17
0 0
20 30 40 50 60 70 80 90 100 20 30 40 50 60 70 80 90 100
Treatment Temperature in °C Treatment Temperature in °C

SurTec GmbH June 2001/PP

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Application Conditions
trivalent Chromiting hexavalent yellow chromate

make-up: 12.5 Vol% 1 Vol%

= 10 g/l Cr(III) = 2 g/l Cr(VI)

pH-value: 1.7-2.0 1.6-1.8

temperature: ≥ 60 °C room temperature

contact time: 60 s 20 s

heating: necessary in the winter

ventilation: necessary recommended

rinsing: 3 steps 2 steps

activation: recommended

agitation: rack agitation/barrel rotation and/or air agitation

tank material: (insulated) plastic or steel with plastic inliner

SurTec GmbH June 2001/PP

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Qualitätsförderkreis Chromitierung
(German Chromiting quality promotion circle)

▲ a qualified group of job platers in and in the vicinity of Germany (currently 7 members)
▲ the group applies Chromiting and/or Black Chromiting as well as future developments
▲ it exchanges field experience (trouble shooting)
▲ commitment to maintain coating parameters at optimum values within a narrow range
▲ development of common standards
(measuring and testing procedures, with guaranteed processability and reproducibility)

➩ objective:
to provide ample plant processing capacity with predictable high quality to
meet the (German) car industry‘s requirements

SurTec GmbH June 2001/PP

pdf-files to read, print and download

http://www.SurTec.com
↓
"English Version"
↓
Publications
↓
Presentations
↓
"Replacement of Hexavalent Chromium"
and
"Chromiting"
SurTec GmbH June 2001/PP