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Hot-dip galvanizing with zinc-bismuth alloys

Article  in  Metall · May 1999

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 After-Fabrication Hot-Dip Galvanizing with Zinc-Bismuth Alloys

Martin Gagné,
Noranda Technology Centre, 240 Hymus Blvd, Pointe-Claire, Quebec, Canada H9R 1G5

1 Introduction

Drainage of excess zinc after galvanizing is controlled by gravity, temperature, withdrawal

speed and the orientation of the workpiece. With poor drainage, zinc can accumulate in
corners and angles on the workpiece, and bridge over small holes and thin channels. The
drainage of zinc also contributes to icicle and drip formation. Depending on the severity of
these problems, and on the requirements of the customer, extra cleaning of the workpiece may
be required before it can be shipped.

Zinc-bismuth alloys with improved drainage have been developed for after-fabrication hot-dip
galvanizing. Laboratory and industrial plant testing revealed that bismuth additions to pure zinc
provide equal drainage when compared to a conventional lead-containing zinc. It was also
shown that combined bismuth and lead additions to pure zinc provide significant
improvements in drainage. Further testing revealed that bismuth does not have any detrimental
effects on rate of attack on the kettle wall, coating microstructure development, coating
formability, adhesion, corrosion resistance, chromating behaviour, paintability and resistance
to white rust formation when compared to conventional coatings.

The zinc-bismuth alloys can be used with either wet or dry galvanizing processes, and
industrial use of the alloys have also shown them to be compatible with existing galvanizing
technologies such as Technigalva and Polygalva. Additional benefits such as reduced dross
formation have also been reported. The alloys carry the trademark name ‘GalvaFlowTM ’ and
licenses are being sold to use the patented technology.

2 Alloy Development

The drainage of liquid zinc is influenced by the viscosity and surface tension [1,2]. Alloy
additions at the levels used in galvanizing have little or no effect on viscosity [1], but can have
a great effect on surface tension [2]. And it is the surface tension which most greatly influences
the drainage of excess zinc from the galvanized workpiece [1,2,3].

An extensive laboratory testing campaign of thirteen addition elements used in combination

with and without lead identified bismuth (Bi) as the most promising addition element for
improving the drainage of zinc [4]. The effect of Bi additions on drainage was investigated
using galvanizing tests of bolted assemblies. The tests were done over a range of Bi levels
up to 4.0 wt %, both with and without Pb. The bolt samples used for these tests had 2.5 mm

1
gaps between the washers. The thin gaps collected the most zinc and more easily showed the
differences in weight gain between alloys.
Figure 1 shows a summary of the laboratory tests using Bi additions. The graph shows the
weight gain measured on the bolted assemblies after galvanizing in four different alloys:
Special High Grade (SHG) zinc, Prime Western Grade (PWG) zinc, SHG zinc + Bi, and PWG
zinc + Bi. The SHG + Bi alloy performs much better than the SHG zinc, and slightly better than
the PWG zinc. When Bi is added to PWG zinc, the best drainage is obtained.

Surface tension measurements of these alloys were done using a sessile drop technique to
obtain comparative values. The results are shown in Figure 2. Note that there is good
correlation between the surface tension measurements shown in Figure 2 and the weight gain
measurements shown in Figure 1.

Weight Gain on Bolt Samples Surface Tension of Zinc Alloys

Summary of laboratory test results Sessile drop test
850
20
Surface Tension (Dynes/cm)
750
18
650
Weight Gain (%)

16
550

14 450

12 350

250
10 SHG PWG SHG + B i PWG + Bi
SHG PWG SHG + B i PWG + Bi
Alloy Composition
Bath composition

Figure 1 Figure 2

3 Alloy Performance Evaluation

The effect of Bi additions on other areas of interest to the galvanizer were also investigated
in detail [4]. A summary of the laboratory testing, including the rate of attack on the kettle wall,
coating microstructure formation, coating formability and adhesion, corrosion resistance,
chromating behaviour and resistance to white rust formation are presented here. Bi additions
have also been found to have no effect on paintability of the galvanized coating.

3.1 Rate of Attack on the Kettle Wall

Long term immersion tests were performed to investigate the effect of Bi additions on the rate
of attack on the kettle wall. Samples of firebox steel were suspended on quartz rods for up to
28 days in a bath containing SHG + Bi. At predetermined intervals, a sample was removed
and examined metallographically. The metallographic examination revealed no intergranular
or localized attack on the steel. A dense protective intermetallic layer had formed on the steel.

2
3.3 Coating Microstructure Formation

The coating structure obtained with SHG + Bi on rimmed and reactive steels was examined
metallographically. It was revealed that Bi additions do not effect the coating structure
development.

3.4 Coating Formability and Adhesion

Steel sheet and plate samples were galvanized in both SHG + Bi and PWG zinc in order to
investigate the effect of Bi on coating formability and adhesion. The sheet samples were bent
over various diameters to evaluate the coating formability while the plate samples were
subjected to scribe and impact tests to measure the coating adhesion. The results showed no
difference between the performance of the two alloys.

3.5 Corrosion Resistance

The atmospheric corrosion resistance of the alloys is being measured by weight loss
measurements on test coupons exposed at the Noranda Technology Centre (NTC) outdoor
exposure site. Coupons galvanized in PWG, SHG + Bi, and PWG + Bi have been exposed
at NTC's exposure site for five years. Visual examination of the coupons shows no difference
in the development of a natural patina on the samples. The results of the weight loss
measurements show a corrosion rate of about 6 g/m2/year for each of the samples. This
corrosion rate is low compared to typical rates for urban areas [5,6]. The exposure tests are
continuing.

3.6 Chromating Behaviour and Resistance to White Rust Formation.

Stack tests were used to evaluate the effect of Bi additions on the development of white rust.
The performance of SHG + Bi in a stack test was compared to the performance of
conventional PWG zinc in both the chromated and untreated conditions. The chromated panels
behave in a similar manner and each have less than 5 % white rust after 33 days of testing.
The untreated panels show a slower progression of white rust on the SHG zinc + Bi panels
compared to the PWG panels. The results of the stack tests show that Bi does not increase
the sensitivity to white rust formation or react adversely with chromate treatments.

3.7 Paintability

Both a high build two component epoxy paint system and a polyester powder paint were
tested. The results of paint adhesion testing (ASTM D3359-95) and cyclic corrosion testing
of painted coupons (ASTM D5894) show no difference between the painted SHG + Bi, PWG
+ Bi and PWG coatings.

3
4 Industrial Testing

Extensive industrial testing of the alloys was performed before making them commercially
available. Up to two years of industrial experience was obtained with the new alloys for
comparison with historical records [7,8]. A summary of the results is presented. Table 1 lists
the details of the plant trials.

After operating for 18 months with SHG + Bi at Plant #1, the zinc on work had decreased by
12% and the dross production had decreased by 11 %. However, ash increased by 5 % and
flux residues increased by 7 %. Total zinc consumption was down by 9% compared to
previous data using PWG. No problems in drossing the Pb-free kettle, or with the fluidity of the
top flux blanket were reported.

Results from the two dry kettles in Plant #2 using PWG + Bi showed decreases in zinc on
work, dross and ash formation. Total zinc consumption on each kettle had decreased by 13
% and 14 % respectively.

Plant #3 tested PWG + Bi with a dry kettle for 10 months. The zinc on work decreased by 10
% and dross production decreased by 25 %. However, at this plant the ash production rose
dramatically by 40 %. The reason for the increased ash production is still unknown.

Other qualitative benefits observed in the plants are a better appearance of work, especially
complex parts, no bridging of drilled holes in work by zinc, and less labour for clean-up of
drips, etc. from the work before shipping.

Table 1
Plant Trials

Company Process Kettle Length Alloy Start Date

Plant #1 Wet 3.7 m (SHG + Bi) October, 1995

Plant #2 Dry 7.7 m (PWG + Bi) April, 1995
Dry 4.0 m (PWG + Bi) July, 1995
Plant #3 Dry 10.8 m (PWG + Bi) June, 1996

Examination of the analytical results of the by-products produced during the plant trials reveals
that the Bi level of the dross is generally between 1/2 to 1 times the level in the bath. However,
concentrations as high as 5 to 10 times the bath level have been observed, possibly due to
the sampling. The analytical results show that the ash tends to have the same Bi level as the
bath. The flux residues from the wet kettle have only about 1/5 to 1/10 the Bi when compared

4
to the bath level.

5. Distribution of Bi in PWG zinc

Mass balances in the plants using PWG + Bi failed to account for significant amounts of Bi
added to the kettle. In fact, Bi was accumulating preferentially in a Pb layer or heel at the
bottom of the kettle. That is, when the Bi is added to the kettle some dissolves in the Zn and
some dissolves in the Pb. Theoretical calculations show that the amount of Bi dissolved in
each liquid metal layer is inversely proportional to the ratio of the activity coefficients (?) for Bi
in each liquid metal. That is:

Amount of Bi in Pb = ? Bi in Zn
Amount of Bi In Zn ? Bi in Pb

Unfortunately, the activity coefficient for Bi in Zn is almost 70 times the activity coefficient for
Bi in Pb [9]. Therefore:

Amount of Bi in Pb = 70
Amount of Bi in Zn 1

A balance is reached when the amount of Bi in Pb is 70 times the amount of Bi in Zn. The
results of chemical analyses of laboratory and plant samples confirms the calculations.

The results show that the recovery of Bi in a PWG kettle is variable and depends on the
amount of Pb laying at the bottom of the kettle. The Bi is 'stored' in the Pb and is released as
the Pb layer is consumed. This can be done for example, by adding SHG zinc to a PWG kettle.

6 Conclusions

The results of the laboratory and plant trials show that Bi additions improve the drainage of
zinc from the galvanized workpiece. Other benefits include reductions in dross formation and
labour required for clean-up of work. The plant data shows that Bi recovery in PWG zinc is
variable.

The three plants involved in the industrial testing have continued to use Bi with success, and
Plant #1 has expanded the use of Bi to three kettles. The zinc-bismuth alloys were made
commercially available in May, 1997 under the trademark name ‘GalvaFlowTM ’. There are now
21 registered users of GalvaFlowTM in North America and Europe covering a wide range of
operating practices and products.

5
 References

[1] H.R. Thresh et al, Properties of Molten Zn and Zn Alloys - Viscosity

Canada Department of Mines and Surveys, Report PM-R-64-27

[2] H.R. Thresh et al, Properties of Molten Zn and Zn Alloys - Surface Tension
Canada Department of Mines and Surveys, Report PM-R-64-28

[3] The Influence of Pb in After-Fabrication Hot Dip Galvanizing, Zinc Corporation Of

America publication.

[4] M. Gagné, Zinc-Bismuth Alloys for After-Fabrication Hot-Dip Galvanizing, American

Galvanizers Association TechForum ‘96

[5] C.J. Slunder and W.K. Boyd, Zinc:Its corrosion resistance, ZDA, 1971

[6] F.C. Porter, Corrosion resistance of zinc and zinc alloys, Marcel Dekker Inc, 1994

[7] M. Gagné, Industrial Testing of Zinc-Bismuth Alloys for After-Fabrication Hot-Dip

Galvanizing, Intergalva ‘97

[8] M. Gagné, Update: Zinc-Bismuth Alloys for After-Fabrication Hot-Dip Galvanizing,

American Galvanizers Association TechForum ‘97

[9] R.R. Hultgren et al., Selected Values of the Thermodynamic Properties of Binary Alloys,
ASM Metals Park, Ohio, 1973.

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