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Testing,
Dip Galvanizing
Flux
and Control
of Hot
South Dakota
57747;
OF VARYING
THE GUADBAFLUX
FORMULATION
An effective flux solution must be periodically tested and adjusted to attain required galvanizing
results. Among the most important
measures of
results is the percent gross zinc usage (%GZU). It is
calculated:
%GZU = (zinc used/steel galvanized)
x 100%
OF VARYING
GUADBAFLUX
FORMULATION
Over the last 30 years the most effective flux solution for dry kettle galvanizing has been found to be
quadraflux with the composition shown in Table I.
For a 12.5 degree Baume flux solution 2 lb/US gal
(240 g/L) of quadraflux is required. Since quadraflux
is not normally available in the marketplace,
zinc
chloride, or double salt, or triple salt can be mixed
22
E-mail, ,galvecon@gwtc.net
CHLORIDE
NUMBER
The Ammonium
Chloride
Number
(ACN) was
coined by the author in 1980. It is a mathematical
relationship
that equals the ammonium
chloride
concentration
divided by the concentration
of all
other components in the flux solution. In this case
we calculate it:
ACN = %Ammonium
Chloride/%Zinc
Chloride
It should be noted that because ACN is a ratio having ammonium chloride in the numerator and zinc
chloride in the denominator, units cancel out making
ACN unitless, independent of concentration, and the
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REDUCING
DROSS
BY
CONTBOLLING
DISSOLVED
IRON
BLACK
SPOTS
BY CONTROLLING
SULFATES
pH
FOR
OPTIMIZED
FLUXING
The correct pH for fluxing steel prior to hot dip galvanizing is 4.2. My experience is that the traditional literature citing a pH of 5 is wrong. At a pH of 4.2,
the flux provides a final cleaning of the pickled steel,
giving a clean and bright surface ready to fuse
chemically with the molten zinc. Levels of pH below
about 3.5 attack the steel excessively causing soluble iron (Fe+2) to build internally
in the flux solution. It is true that the lower the pH of a flux, the
stronger it is. Values of pH higher than about 4.7 are
ineffective in cleaning the steel surface. Recalling
that the pH scale is logarithmic,
a pH of 4 has ten
times higher concentration
of hydrogen ions than a
pH of 5.
In my experience, pH meters do not work in flux
solution, tending
to give readings
substantially
lower than reality. Some, but not all, brands of pH
papers can be useful. Certain organic dye indicators
that have a distinct color change near pH 4.2 work
extremely well in maintaining
proper flux pH. In
testing and controlling pH, I prefer to use the following procedure: To a specific volume of settled or
filtered flux solution is added a suitable organic pH
indicating
dye. Using a plastic syringe filled with
either 1:lO hydrochloric
acid or 1:lO ammonium
hydroxide (as titrant), the flux solution is titrated to
a pH of 4.2. The calculated volume of either concentrated hydrochloric acid or concentrated ammonium
hydroxide is then added to the process flux tank. In
some plants, pH adjustment
of the flux solution is
required daily.
It is important
to keep in mind that the goal of
testing via a titration
is to determine
how much
hydrochloric
acid or ammonium
hydroxide to add
to maintain a pH of 4.2. Knowing the pH - but not
knowing what to add or how much to add - is not
useful. I am convinced that a pH meter should
never be used. I also contend that zinc slabs, zinc
ash, or dross added to the flux solution causes the
pH to slowly go too high and should also never be
used.
A fabricator and galvanizer having a flux solution
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FLUX
TEMPERATURE
2003
WETnNG
FOR
OPllMUM
ZINC
ADHESION
About 50 surfactants
(wetting
agents) have been
tested for effectiveness in flux solutions. There are
three main reasons or objectives for adding a surfactant to a flux solution. Most importantly,
a surfactant needs to help make the liquid flux drain
away from touching or closely spaced products such
as welds and threads. In basket work this can
reduce by three-quarters
the volume of liquid flux
that will be carried into the molten zinc, greatly
reducing zinc spatter and dry ash. To achieve this
objective, the surfactant
needs to be able to reduce
surface tension from 80 dynes/cm2 to 30 dynes/cm2
at a concentration
of 0.03% or less.
Increased corrosion protection is a second reason
to use surfactants. Again, the target concentration
of
the wetting agent is 0.03% or less.
The third reason to add a wetting agent is to produce a one-inch layer of bubbles (foam) on the flux
solution surface in order to half heating costs. This
foam is established and maintained
with a small air
line near the tank heating coil. The surfactant concentration needs to be about 0.06% to generate this
foaming effect.
Many surfactant producers claim to have products
that address all three of these objectives, but in my
experience few actually deliver the promised performance. In evaluating the effectiveness of wetting
agents, it is easy to measure surface tension with a
simple drop size test. A rounded glass eyedropper
tip will produce about 20 drops/ml
with distilled
water. With an effective surfactant at 0.03% or less
this same tip will produce about 40 drops/ml.
OPTIMIZING
FLUX
COMPOSITION
Reducing
Rejects by Eliminating
NaCl
In the mid to late 1970s it was discovered that some
commercial
hot dip galvanizing
fluxes contained
anywhere from 1% to 20% of the nonvolatile
compound sodium chloride (NaCl dry ordinary
table
salt). A galvanizer using a flux with 4% sodium chloride was having 4% rejects. When he changed to a
flux free of sodium chloride his rejects went away. A
galvanizer had a flux with 14% sodium chloride and
27
Controlling
Smoke...at
a Price
Other
Flux
Components
Mostly
Unwanted
Other potential
components
in a flux solution
include barium chloride for sulfate control and zinc
oxide, zinc powder or zinc hydroxide for pH control.
These control additives cannot possibly exactly
match every galvanizers needs and need to be used
very rarely and with an awareness of their side
28
REAL-WORLD
SAVINGS
- A DETAILED
Quantifying
the Financial
Benefits
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Producing
a Better Product
In Table III the original average galvanizing price
was $0.20llb and the cost of galvanizing was considered to be $O.lO/lb. The 20% higher price gave a new
average price of $0.24/lb that was set and sustained
by true higher quality. Esthetically, the product was
brighter with near electroplate
quality. Even more
importantly,
the zinc coatings were much thinner
and more conforming
to the contours of the steel.
Thus mating surfaces fit and bolt holes accepted
bolts without reaming. In addition, most zinc coatings were under 6 mils (150 microns) so that the
zinc coating did not chip off during rough handling
and shipping. This galvanizer
successfully - and
profitably
- created a differentiated
product in a
traditionally
nondifferentiated
industry.
The 20% higher production
(first row, Table III)
was a surprise to everybody including the author.
With quadraflux,
the product entered the molten
zinc with almost no zinc spatter. Thus, the workers
no longer had to hide behind building supports. The
time the product entered the molten zinc and the
time the product was in the kettle were both cut in
half. Ultimately
the middle and lower resistance
electric heating elements for the zinc kettle furnace
had to be replaced by higher kilowatt units in order
to keep up with the increased production.
Increasing
Production
and Reducing
Zinc
Consumption
In the second row of Table III, the $O.l4/lb of total
profit reflects the 20% increased price and the
14,000,OOO lb reflects the 20% increased production,
both due to quadraflux.
It is interesting
that this
plant, as most galvanizing plants, regarded the kettle as the most critical step limiting
production.
However, it became increasingly
obvious that the
actual limitation
on increased production
throughput was not the kettle, but the old flux solution that
was the real bottleneck.
In the third row of Table III, the $0.85 was the
high price of zinc in 1982. The 0.0269 is the old
%GZU of 8.19% (using the old flux) minus the new
%GZU of 5.50% (using quadraflux)
all divided by
100 to get a fractional number. The reduction in zinc
30
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shipping. Changing
to quadraflux
cost only a few
thousand dollars and the investment has been paid
off many, many times over the last 20 years.
TESTING
FLUX
CHEMISTRY
July/August
2003
g/mL). The solution has an ammonium chloride concentration of 7.26%, a zinc chloride concentration
of
7.26%, an ACN of 1.00, an iron (Fe+2) of 0.70%, and
a sulfate (S0,-2) of 1.21% as shown on the first row
of Table IV marked STD.
Lab Results
The second, third, and fourth rows of Table IV are
test results for Bob, Tom (the author),
and
Erik (see acknowledgements.).
For the second,
third, and fourth rows, the zinc chloride concentration was determined
mathematically
by accurately knowing the density, the iron (Fe+2), and the
sulfate (SObm2). This methodology
works very well
as shown in Table IV because the worst zinc chloride concentration
of 7.35% is only 1.2% higher
than the true value of 7.26%. For rows two, three,
and four the, ACN is directly measured
by two
methods within a single test procedure. The first
way was based on heat of solution knowing that
ammonium
chloride gets cold when dissolved in
water and zinc chloride gets hot when dissolved in
water. The second way was by density knowing
that ammonium
chloride forms low density solutions and zinc chloride forms high-density
solu-
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of low results for iron, insufficient volumes of ammonium hydroxide and hydrogen peroxide would be used
during purification
and all the iron would not be
removed. In the case of reporting high results for iron
the result would be that too much ammonium hydroxide and hydrogen peroxide would be added. This
would have resulted in too high pH and an excess
hydrogen peroxide which would bubble for days, not
allowing insoluble iron III hydroxide to settle.
From Table IV only labs B, G, K, and L got
within 5% of the true value for sulfate. In the case of
low results being reported for sulfate, an insufficient
amount
of barium
chloride would be added for
purification.
This would result in leaving unwanted
sulfate in the flux solution. In the case of reporting
too high results for sulfate, an excess of barium chloride would be added giving a very highly toxic flux
solution.
As Table IV clearly shows, no single lab is capable
of usable results for ACN, ammonium
chloride, zinc
chloride, iron (Fe+2), and sulfate. In addition, if the
pH of the flux is high, and there is an air bubble in
the sample bottle, the iron (Fe+2) will oxidize during
transit to the lab. If cold shipping conditions exist,
ferrous sulfate can crystallize from solution when
the sulfate is about 2% or higher.
Testing Summary
Turn-around
times for labs A through IVY were 2
to 6 weeks, which is far too long to keep up with
needed flux adjustments.
None of the labs indicated
having any problem in their testing. In view of the
results from labs A through M, it is the authors
opinion that it is pointless for a galvanizer to send a
flux solution sample to any of these labs.
KEEPING
THE
FLUX
SOLUTION
OPTlNllZED
STAKTED
Finishing
nizing results. However, it does hope to have summarized a vast amount of real-world experience and
identified those variables that have a direct effect on
performance,
cost, and quality results. Controlling
flux composition,
temperature,
and use requires
knowledge,
understanding,
and experience.
The
impact on the bottom line, however, justifies all the
time and all the effort.
It goes without saying that the starting materials,
such as ammonium
chloride, zinc chloride, and commercial flux, must be of adequate purity. Beyond
that starting point, one has to ask where can these
materials be tested? Will the test results be correct?
What are my surfactant
requirements
and what
surfactant
should be used? How will pH be adjusted? What adjustment
may be necessary each day?
How will ACN testing be done? How much ammonium chloride should be added and how often? When
and how should the flux be purified? Will there be
more or less smoke from quadraflux?
There are a lot of questions
that need to be
answered
in the context of ones own operation.
There is no substitute
for hands-on testing under
your actual working conditions. For small scale testing of quadraflux,
I recommend making up 4 gallons
ELIMINATE
THESE PROBLEMS
AND WORRIES
IN 128 SECONDS!
Lcfie%?
4 fEEr+
METRE-GENERAL,
INC.
2003
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