SurTec

Technical Letter
_____________________________________________________________
4

Service Life Extension of Trivalent

Chromium Based Passivations for Zinc

Rolf Jansen March 1994

The service life of trivalent blue passivations for zinc is limited mainly by

the increase of dissolved iron during operation. The normally sky-blue

passive layers get an increasing yellowish colour with increasing

content of iron in the passivation bath. Depending on the desired

quality of the zinc-plated and passivated parts, the upper limit of

tolerable iron lies within 300 and 800 ppm.

Efficient control of the dissolution of iron and its effects will prolong

the service life of blue passivations by several times. This Technical

Letter presents actions which were proved in practice to extend the

durability of passivation baths.

 page 2

1 How does dissolved iron lead to yellowish passive films?

During zinc passivation in solutions of trivalent chromium, a very thin layer of blue

chromium(III)-zinc-oxide is deposited. In the presence of dissolved iron(III), the co-de-

position of brown-yellow iron(III)-zinc-oxide takes place which discolours the passive

layer to yellowish. Because this co-deposition is a competitive reaction, the intensity of

the yellowish colour is not only determined by the absolute value of the iron concen-

tration but also by its relation to the chromium concentration. Thus, a value of 400 ppm

iron in low concentrated passivation baths leads to yellowish parts, while higher con-

centrated baths with the same iron content are still able to yield acceptable results.

For maximum service life, the trivalent passivation baths should not be too thin.

2 Where is iron dissolved from?

In rack lines, the primary iron drag-in is produced by dissolution of parts fallen into the

bath. Secondly, iron dissolves from zinc free areas of tubes or other parts with deep

cavities, even during normal operation.

Barrel lines are not as sensitive as rack lines because barrels should (normally!) not loose

parts and most cavities should be covered with zinc properly during barrel plating. Also,

the drag-out is higher using barrels, thus the solution is "rejuvenated" regularily. But:

passing back of rinse water to the bath, drag-in of poor quality rinse water with a high

iron content and incompletely closing barrel doors, lead usually to a significant rise of

iron concentration.

3 Actions against the dissolution of iron

3.1 Maintenance of the Bath

The main iron drag-in can be avoided by a thorough bath control. Parts fallen into the

solution should be taken out immediately, at least once a shift. Good filtration of the

zinc baths and meticulous rinsing are important to reduce the drag-in of iron hydroxide.

3.2 Use of Iron Inhibitor SurTec 660 A

In trivalent blue chromate solutions of SurTec 660, 661, 662, 664 or 667, the corrosive

iron dissolution of parts or uncovered areas is hindered effectively by addition of 0.05 -

0.2 Vol% iron inhibitor SurTec 660 A to the bath.

 page 3

The diagram shows the rise of iron concentration in a rack bath with SurTec 660 before

and after addition of 0.05 Vol% iron inhibitor SurTec 660 A. The increase of iron after

addition was 3 times slower!

1. day 2. day 7. working-day

180
higher dosage
of iron-inhibito
160 (ca. 0.1 Vol%
SurTec 660 A
r
)
iron-concentration in ppm

140
A
60
120 T ec6
S ur
or
ibit
100 n-inh
ro
%i
vol
80 .05
h0
wit

60
tor
ibi
inh

40
n-
iro
ut

20
tho
wi

0
0 30 60 90 120
operation-time in hours
Diagram: Iron content of a rack bath with SurTec 660 (trivalent blue passivation of zinc); 5000 l bath

of an acid zinc line in a job shop.

Further increase of the inhibitor SurTec 660 A hindered the iron dissolution so effectively

that by build-in into the passive layer and drag-out at daytime, more iron was lost than

dissolved, thus leading to a decrease of the iron content. During the night it increased

again because parts fallen into the solution had not been taken out. This again

illustrates the importance of a good bath care.

The inhibitor covers bare iron areas hindering the acidic attack. So it is dragged out of

the solution and has to be maintained. Best and easiest way of dosage will be together

with the chromium(III) concentrate, in the same relation as for bath make-up. If for

example a bath was made-up with 7 Vol% SurTec 660 chromium(III) concentrate and

0.07 Vol% SurTec 660 A iron inhibitor, with 1 litre concentrate 10 ml iron inhibitor has

to be added.
 page 4

For easier handling SurTec 661 is available, which is the chromium(III) concentrate plus

1 % iron inhibitor. At a bath make-up with 5-10 Vol%, an inhibitor concentration of

0.05-0.1 Vol% is reached which should be sufficient for most purposes. If the solution

was made-up thinner, or severe iron drag-in was expected, additional inhibitor SurTec

660 A is necessary and should be added before treating the critical parts.

3.3 Masking of the Iron Content by Citric Acid

Citric acid can be used to mask already dissolved iron in the passivation bath. Citric acid

is a weak complexing agent hindering the co-deposition of iron in the passive layer

(which would create the yellowish colour). In baths with SurTec 660, more than

800 ppm iron can be masked with citric acid without appearance of yellowish parts.

800 ppm iron without citric acid normally lead to intense yellowish passive layers.

As an overdosage of citric acid could accelerate the iron dissolution, ca. 100 ppm of un-

masked iron has to be kept in the bath. For masking 100 ppm iron, 375 g citric acid is

required per 1000 l bath (e.g. 1 l SurTec 660 C, an aqueous solution of 375 g/l citric

acid). If citric acid was already added to the bath solution, this amount has to be

subtracted.

At an iron concentration of x ppm, (x-100)·0.01 l citric acid solution SurTec 660 C is

required per (x-100) ppm for 1000 l bath volume.

Example 1: The iron content is 150 ppm, no citric acid was used up to now. So per

each 1000 l bath volume, (150 - 100)·0.01 l = 0.5 l SurTec 660 C should

be added. By this way, 100 ppm iron remain unmasked, 50 ppm iron is

masked by the addition of 0.5 l SurTec 660 C per 1000 l bath volume.

Example 2: 1.5 l SurTec 660 C per 1000 l bath has already been added, and the iron

content is analysed as 350 ppm. For this amount of iron:

(350 - 100) · 0.01 l = 2.5 l SurTec 660 C would be required. 1.5 l per

each 1000 l are already in the solution, so only 2.5 l - 1.5 l = 1 l SurTec

660 C per 1000 l have to be added.

Please be advised that the addition of citric acid results in strange appearance with some

trivalent blue passivations. Therefore, SurTec can recommend the use of citric acid or

SurTec 660 C only for its own trivalent blue passivations SurTec 660, 661 and 662. In

the blue passivations SurTec 664 and 667, citric acid must not be applied.
 page 5

4 Conclusion

By good bath control together with the use of the iron inhibitor SurTec 660 A, the

service life of trivalent blue passivations can be extended significantly. With citric acid, it

is possible in some baths to mask already dissolved iron substantially, leading to further

service life prolongation. A guide to longer durability involve:

1. measuring the iron content with AAS or just semiquantitative with test

stripes, e.g. Merckoquant Iron Test.

2. adapting the dosage of the iron inhibitor SurTec 660 A by tracing the iron

concentration. If the rise is too fast a higher dosage must be applied.

3. masking already dissolved iron with citric acid. Keep 100 ppm unmasked!!

4. of course, removing parts fallen into the bath as soon as possible.

Following these guidelines, the service life of SurTec 660 can be extended by 3 times

minimum. "Champion" up to now is a 5000 l SurTec 660 rack bath, 2 shifts/day, per-

manent operation, 50-60 % tubes and pipes, reaching a service life of more than 25

weeks.
SurTec 66x
Control of Trivalent Blue Chromates

Make-Up
Concentration*: (summer): vol% at °C

(winter): vol% at °C

pH-Value: 1.8 (adjust with nitric acid, see back side)

Immersion time: s

Transfer time: s

* During operation the nominal value decreases by 0.5-1 vol% on 5 g/l increasing zinc. It decreases
on 5 °C increasing temperature or increases on 5 °C decreasing temperature by 0.5-1 vol%.

Dosage by sight control of the parts

The iridescent colour of the chromate layer is an indication of its thickness and therefore is
an excellent hint for adjusting the optimal operating conditions.

Place a part inclined on a white

sheet of paper and look from an
angled point of view down at the
part.

Adjust the chromating bath in

dependence on the colour effect
according to the table.

Iridescent colour Cause Actions

golden chromate layer much too thin increase concentration and

immersion time
reddish-golden chromate layer too thin increase concentration
reddish-blue chromate layer little too thin small increase of concentration or
immersion time
blue chromating optimal no actions
greenish-blue chromate layer little too thick small decrease of immersion time
greenish little overchromating decrease of immersion time;
1. aid: pH-value may be tempo-
rarily decreased (but not beyond
1.65) while decreasing the con-
centration by working-out.
dilute the bath, when not satisfied
greenish-yellow heavy overchromating dilute the bath

IMPORTANT: It is necessary to distinguish between the golden and the yellowish colour,
therefore observe the parts very carefully in either case.
SurTec 66x
pH-Adjustment of
Trivalent Blue Chromates

desired pH 1,6 1,7 1,8 1,9 2 2,1 2,2

meas. pH amount of NaHCO3 in kg per 1000 l bath

1 6,29 6,72 7,07 7,34 7,56 7,73 7,87

1,1 4,56 5,00 5,34 5,62 5,83 6,01 6,14
1,2 3,19 3,62 3,97 4,24 4,46 4,63 4,77
1,3 2,10 2,53 2,88 3,15 3,37 3,54 3,68
1,4 1,23 1,67 2,01 2,29 2,50 2,68 2,81
1,5 0,55 0,98 1,33 1,60 1,82 1,99 2,13
1,6 0,43 0,78 1,05 1,27 1,44 1,58
1,7 0,46 0,34 0,62 0,84 1,01 1,15
1,8 0,83 0,37 0,27 0,49 0,66 0,80
1,9 1,12 0,66 0,29 0,22 0,39 0,53
2 1,35 0,89 0,52 0,23 0,17 0,31
2,1 1,54 1,08 0,71 0,42 0,18 0,14
2,2 1,68 1,22 0,85 0,56 0,33 0,15
amount of 53 % HNO3 in kg per 1000 l bath

2,3 1,80 1,34 0,97 0,68 0,45 0,26 0,12

2,4 1,89 1,43 1,06 0,77 0,54 0,35 0,21
2,5 1,97 1,50 1,14 0,84 0,61 0,43 0,28
2,6 2,02 1,56 1,19 0,90 0,67 0,49 0,34
2,7 2,07 1,61 1,24 0,95 0,72 0,53 0,39
2,8 2,11 1,64 1,28 0,99 0,75 0,57 0,42
2,9 2,14 1,67 1,31 1,01 0,78 0,60 0,45
3 2,16 1,70 1,33 1,04 0,81 0,62 0,48
3,1 2,18 1,72 1,35 1,06 0,82 0,64 0,49
3,2 2,19 1,73 1,36 1,07 0,84 0,65 0,51
3,3 2,20 1,74 1,37 1,08 0,85 0,67 0,52
3,4 2,21 1,75 1,38 1,09 0,86 0,68 0,53
3,5 2,22 1,76 1,39 1,10 0,87 0,68 0,54
3,6 2,23 1,76 1,40 1,10 0,87 0,69 0,54
3,7 2,23 1,77 1,40 1,11 0,88 0,69 0,55
3,8 2,23 1,77 1,40 1,11 0,88 0,70 0,55
3,9 2,24 1,78 1,41 1,12 0,88 0,70 0,55
4 2,24 1,78 1,41 1,12 0,89 0,70 0,56

Because of the buffering property of dissolved zinc, the actual amounts

may be higher to a small extent than given in the table above.