Composition, Testing,
Dip Galvanizing Flux
by Dr. Thomas H. Cook
HC 52 Box 120-B, Hot Springs, South Dakota
I
t is well known that pretreatment is key to the
success of virtually every metal finishing opera-
tion. In hot dip galvanizing the fluxing operation
is a particularly critical step that directly affects the
quality and uniformity of the adhesion of the zinc to
the steel as well as the amount of zinc used. This
article summarizes a wide range of demonstrated
best practices and innovations in managing flux
chemistry and the fluxing process.
EFFECTS OF VARYING THE GUADBAFLUX
FORMULATION
An effective flux solution must be periodically test-
ed 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%
For steel averaging 3/16 in. thick to l/4 in. thick
(about 5 mm to 6 mm) a %GZU of about 5% can be
attained using an effective flux solution. For steel
which is on average thicker, an even lower %GZU
can be attained because of less surface area. For
%GZU no credits for ash or dross are allowed.
EFFECTS OF VARYING GUADBAFLUX FORMULATION
Over the last 30 years the most effective flux solu-
tion 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
and Control of Hot
57747; E-mail, ,galvecon@gwtc.net
with ammonium chloride. It is very important that
for each pound of zinc chloride there are 1.60 lb of
ammonium chloride. Because zinc chloride picks up
moisture, any partially used bags or barrels must be
properly resealed.
A Baume lower than about 11 causes “black spots”
(bare spots) on the steel. A Baume lower than about
12 causes the flux to release poorly from the zinc
surface resulting in excess zinc “clean-up.“A Baume
higher than about 14 gives excessive zinc spatter,
excessive ash, more smoke, and thicker zinc coatings
on the steel. A Baume of 21 is twice the concentra-
tion of a 12.5 degree Baume flux and gives terrible
zinc spatter at the kettle because there is a double
layer of flux on the steel. The outer layer is thin and
dry, whereas the inner thick layer is wet and mushy
This wet, mushy condition requires very slow entry
of the steel into the molten zinc. This produces a
very thick zinc coatings on the lower portion of the
steel products.
AMMONIUM 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 hav-
ing ammonium chloride in the numerator and zinc
chloride in the denominator, units cancel out making
ACN unitless, independent of concentration, and the
Metal Finishing
same number regardless of units. Thus it has the
same value whether one is working in English or
metric measures. The names, formulae, ACNs, and
common uses for galvanizing fluxes are shown in
Table II. Fluxes with ACNs lower than about 1 do not
dry well and collect moisture from the air. These wet
fluxes cause moisture explosions as the steel enters
the molten zinc. It is known that the lower the ACN,
the more thermally stable the flux. A flux used in a
high-temperature preheater or drying oven therefore
must have a low ACN. Fluxes with ACNs higher than
about 2 are thermally unstable and give loud, chemi-
cal explosions when immersed into the molten zinc. In
either case of an ACN lower than 1 or higher than 2,
the required slow entry into the molten zinc, causes
lower production and thicker zinc coatings on the
lower portions of the steel product.
The ACN of a flux solution usually does not remain
constant. It is common practice to reflux galvanized
rejects (with bare spots) rather than strip the zinc
(with acid). During the refluxing of galvanized rejects
some of the zinc dissolves in the flux solution forming
zinc chloride. This refluxing process lowers the ACN,
raises the pH, and raises the Baume. In some plants
zinc bars, dry ash, or even dross are added to the flux
solution to neutralize excess carried-over acid from
pickling. Also racking fixtures may be galvanized from
a previous cycle and enter the flux tank. Spin baskets
for centrifuge work may be “cleaned” (partially
stripped of zinc) in the flux solution. All of these latter
procedures also increase zinc chloride that lowers
ACN. In moderation, all of these practices are fine as
long as ACN and pH are readjusted as needed and the
Baume does not get too high. For some galvanizers
this system works so well that they have not added
commercial flux (containing zinc chloride) for several
years. They just add ammonium chloride as needed
and strip rejects, racks, or baskets in order to get the
required zinc chloride.
24
Thus a galvanizer initially using triple salt with
an ACN of 1.18 (Table I) who introduces zinc into his
flux will, in time, have a flux solution with a lower
and lower ACN. In 1975, a galvanizer using triple
salt had his flux tested and it was found to contain
0.55 lb/gal ammonium chloride and 0.72 lb/gal of
zinc chloride. Thus the ACN was 0.76 (0.55/0.72).
After adding 1,500 pounds of ammonium chloride to
this 5,000-gal flux tank (0.30 lb/gal) an ACN of 1.18
was re-established [(0.55+0.30)/0.721. After adding
the ammonium chloride, the rejects (steel going
through the zinc kettle twice) dropped from 3.1% to
0.2%. Even more importantly, the average zinc
thickness on the steel dropped from 5.7 mils (145
microns) to 2.4 mils (61 microns). Zinc icicles that
were like pencils hanging from the bottom end of the
product became small, thin, and flat like silver gum
wrappers. Zinc clean-up labor was reduced by half
The zinc coating was also remarkably brighter.
In 1977 in Pakistan (where zinc chloride is expen-
sive) ammonium chloride alone was used for a flux
solution. As a result of stripping zinc from rejected
parts, enough zinc chloride accumulated in the flux
to form a flux solution having a Baume of about 5
and an ACN of 5. The g-meter steel electricity tow-
ers took 4 minutes to become submerged into the
zinc due to intense chemical decomposition of the
thermally unstable flux on the product. Fortuitously,
adding 1 ton of zinc chloride gave a Baume of 12 and
an ACN of about 1.6. With this improved flux solu-
tion, the electricity towers could easily be lowered
into the molten zinc in 30 seconds. Production
increased, zinc usage was lowered by 20%, and the
product quality was greatly improved. Most North
American galvanizers achieving a %GZU of around
5% use an ACN between 1.4 and 1.6. Some auto-
matic pipe galvanizers use an ACN of about 1.9
because it causes much thinner zinc coatings, espe-
cially on the inside of the pipes.
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REDUCING DROSS BY CONTBOLLING DISSOLVED IRON
Dissolved iron (ferrous; Fe+2) iron is carried from the
pickling solution through the rinse into the flux solu-
tion. Iron (Fe+2) in the flux does not cause dross in a
“dry” kettle. In sharp contrast, iron (Fe+2) in the flux
solution does cause dross in a “wet” kettle. The essen-
tial first step to removing the unwanted dissolved
iron (Fe+2) is to determine accurately its concentra-
tion. The most accurate and reliable test is a volu-
metric titration using a standard potassium dichro-
mate solution. After accurately testing the pH of the
flux solution, it is adjusted up to pH 5 using 26 degree
Baume ammonium hydroxide solution. Next the cal-
culated volume of ammonium hydroxide is added [to
supply hydroxide ions (OH-l) for the insoluble
Fe(OH), that will be formed] and then the calculated
and diluted volume of 35% hydrogen peroxide is slow-
ly added. Mixing is done by air bubbling. The flux
solution is kept hot during additions. It normally
takes about 2 days for the insoluble iron III hydrox-
ide to properly settle and a suitable flocculent can be
added to speed up the settling process. The orange
sludge formed is normally put through a filter press
treated with diatomaceous earth to reduce the vol-
ume of sludge by about ten-fold. Additional peroxide
is required if the flux contains suspended oil, which
will be degraded to free carbon.
Air bubbling to oxidize soluble ferrous iron (Fe+2)
to insoluble ferric iron (Fe+3) is not possible at the
normal operating pH of the flux. Such bubbling
wastes heat energy and stirs up unwanted sludge
that gets on to the steel product. There is no reason
to test for “total” iron (Fe+2 and Fe+3) or insoluble
ferric (Fe+3) because the ferric will settle to the bot-
tom of the flux tank as insoluble Fe(OH),. Only iron
(Fe+2) is of interest and it is the iron that is reacted
with ammonium hydroxide and hydrogen peroxide
during purification [to form insoluble Fe(OH),l. In-
plant testing methods for iron (Fe+2> in the flux are
required so that a person will know when all the
soluble iron has been removed.
REDUCING BLACK SPOTS BY CONTROLLING SULFATES
Sulfate ion (SOam2)is carried into the flux solution in
the case of sulfuric acid pickling. In general, galva-
nizing a sulfate concentration over about 1% can
cause black spots. In galvanizing where steel
immersion times in the molten zinc are short, such
as sheet, wire, and pipes, a much lower sulfate con-
centration - 0.25% or even less - causes black
spots. A volumetric titration using barium chloride
gives the best sulfate test result. Because barium
chloride is extremely toxic, the crystal dihydrate
should be used for purification; and proper protec-
26
tive clothing and air filter masks are required. As
with iron removal, airlines are used to dissolve the
barium chloride and for reaction of barium ion with
sulfate ion. Anhydrous barium chloride (without
water) must be avoided because the dust can be
lethal if inhaled. If excess barium chloride is used,
then the flux solution will be extremely toxic. An in-
plant test for sulfate is required to know when the
sulfate has been removed and so that excess barium
chloride can be avoided in the flux solution.
CONTROLLING pH FOR OPTIMIZED FLUXING
The correct pH for fluxing steel prior to hot dip gal-
vanizing is 4.2. My experience is that the tradition-
al 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 solu-
ble iron (Fe+2) to build internally in the flux solu-
tion. 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 fol-
lowing 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 concen-
trated 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
Metal Finishing
with 1.7% sulfate and 0.1% iron (Fe+2) was having second half would be rejects. To compensate for
many black spots on the product. It was this galva- lower temperature, a higher Baume of about 20 to
nizer’s busiest season and the 3 to 4 days for purifi- 25 is normally used. Conversely, for spin galvaniz-
cation were just not available. Making matters even ing, a higher temperature and lower Baume allows
worse, neither flocculating agents nor a filter press the product to enter the kettle with less zinc spatter.
were available to speed up purification. Because the If the steel product is packed tightly together during
dissolved iron was only O.l%, it was suspected that the drying of the flux, the hotter the steel, the faster
the pH was too high. Usually the percent iron is it corrodes.
from one-third to one-half the percent sulfate. A pH
titration was completed and it was determined that CONTROLLING WETnNG FOR OPllMUM ZINC ADHESION
25 gallons of concentrated hydrochloric acid were About 50 surfactants (wetting agents) have been
needed to lower the pH to 4.2 for the 5,000-gal flux tested for effectiveness in flux solutions. There are
tank. After the hydrochloric acid was added all the three main reasons or objectives for adding a sur-
black spots immediately went away. Normal flux factant to a flux solution. Most importantly, a sur-
purification was done a few months later. factant needs to help make the liquid flux drain
away from touching or closely spaced products such
CONTROLLING FLUX TEMPERATURE as welds and threads. In basket work this can
The correct temperature of the quadraflux solution reduce by three-quarters the volume of liquid flux
with the composition shown in Table I is 160°F that will be carried into the molten zinc, greatly
(71°C). This flux solution does not function properly reducing zinc spatter and “dry” ash. To achieve this
at temperatures below 150°F. Below 150°F the flux objective, the surfactant needs to be able to reduce
solution is not aggressive enough to clean the steel surface tension from 80 dynes/cm2 to 30 dynes/cm2
and an insufficient amount of flux is deposited on at a concentration of 0.03% or less.
the steel surface. Temperatures above 170°F deposit Increased corrosion protection is a second reason
excess flux on the steel surface causing a double to use surfactants. Again, the target concentration of
layer of flux (outer dry layer and inner wet, mushy the wetting agent is 0.03% or less.
layer) giving excessive zinc spatter, thick zinc coat- The third reason to add a wetting agent is to pro-
ings, and excessive dry ash. Also, higher tempera- duce a one-inch layer of bubbles (foam) on the flux
tures cost more to maintain due to greater heat loss- solution surface in order to half heating costs. This
es. Typically, a temperature of 180°F requires twice foam is established and maintained with a small air
the energy as a temperature of 160°F. line near the tank heating coil. The surfactant con-
In addition to maintaining 160°F in the flux solu- centration needs to be about 0.06% to generate this
tion, the steel must be left in the flux solution at foaming effect.
least 3 to 5 minutes. This time allows final cleaning Many surfactant producers claim to have products
and enables the steel to fully attain the flux tem- that address all three of these objectives, but in my
perature of 160°F. Thus, when the steel is with- experience few actually deliver the promised per-
drawn from the flux solution the flux dries from the formance. In evaluating the effectiveness of wetting
inside out because of the hot steel. agents, it is easy to measure surface tension with a
During the energy crisis 25 years ago, a galvaniz- simple “drop size” test. A rounded glass eyedropper
ing workshop participant asked, “Why do we have so tip will produce about 20 drops/ml with distilled
many rejects on Monday mornings?” The answer water. With an effective surfactant at 0.03% or less
was simple. Heat to the flux tank was turned off on this same tip will produce about 40 drops/ml.
Friday nights and not turned back on until Monday
mornings. The cold (140°F) flux solution did not OPTIMIZING FLUX COMPOSITION
function properly. Thus, the galvanizer’s savings of
$50 on energy was actually spoiling $30,000 of gal- Reducing Rejects by Eliminating NaCl
vanized product. In the mid to late 1970s it was discovered that some
All flux solutions should not be at 160°F. For commercial hot dip galvanizing fluxes contained
example, an automatic pipe galvanizer doing X-in. anywhere from 1% to 20% of the nonvolatile com-
diameter pipes must use about 122°F (50°C) pound sodium chloride (NaCl dry ordinary table
because each bundle contains a few hundred pipes salt). A galvanizer using a flux with 4% sodium chlo-
and there would be corrosion touch lines within the ride was having 4% rejects. When he changed to a
bundle on the outside of the pipes. Thus, the first flux free of sodium chloride his rejects went away. A
half of the bundle would galvanize fine, but all the galvanizer had a flux with 14% sodium chloride and

July/August 2003 27
had 14% rejects, but when he switched to sodium effects. Fluxes containing barium chloride are made
chloride free flux his rejects went away A pipe gal- suddenly highly toxic, whereas without barium chlo-
vanizer had a flux with 20% sodium chloride and ride, they are merely hazardous. Excess barium
had 20% rejects. He even had a special crane system chloride in a flux solution can quickly kill many
to return rejects to the kettle. With sodium chloride workers. If a new flux solution were made up with
free flux the rejects disappeared and the special “sulfate control” additives, the excess barium chlo-
crane system was taken down. ride would be there on day one. All too frequently,
A U.S. galvanizer had the caustic rinse and acid “pH control” flux gives a flux with excessively high
rinse interconnected for water treatment reasons. pH. Based on my experience, I cannot recommend
After about 8 months, the sodium ion from the caus- these controller additives.
tic soda in the caustic tank built up so much in the In addition to these deliberate additives of question-
acid rinse and also in the flux solution that this gal- able value, contaminants as well as calcium carbonate
vanizer got thicker and thicker zinc coatings on the and magnesium carbonate may be unavoidably pres-
steel. These increasingly thicker zinc coatings were ent due to using ‘hard” water. All are unwanted.
a result of longer and longer “cook-off” times in the
kettle due to the nonvolatile sodium chloride. DRAMATIC REAL-WORLD SAVINGS - A DETAILED
Another galvanizer has only one rinse tank used EXAMPLE
both to rinse after caustic as well as after acid. In a In 1982 a South African galvanizer started using
few months this galvanizer had permanently “poi- quadraflux and had excellent results. This company
soned” his flux solution with sodium chloride. His was galvanizing 70,000,OOO pounds of steel annual-
only choice was to change out the flux solution ly. Their old flux solution was: 32 deg. Baume; ACN
because there is no purification method to remove 0.62; iron (Fe+2) 0.8%; pH 5.5; temperature 70°F
sodium chloride. (unheated); and no surfactant. To make quadraflux,
about 3/4 of their old flux solution was pumped out
Controlling Smoke...at a Price to a storage tank, several tons of ammonium chlo-
Both sodium chloride and potassium chloride do ride were added to the remaining flux solution in
have a potential beneficial use in flux solutions - their flux tank and dissolved with an air line. About
namely to reduce smoke. In ancient time, during the 45 gallons of concentrated hydrochloric acid were
building of the great pyramids, sodium chloride was added to lower the pH to 4.2. A few gallons of effec-
added to oil lamps to reduce smoke inside the pyra- tive surfactant were dissolved in hot water and then
mids. In Germany, smoke reduction in the galvaniz- added to the flux tank. Stainless steel pipe
ing industry has been studied scientifically and (although titanium is the material of choice for use
NaCl or KC1 is sometimes deliberately recommend- with flux solutions) was screwed together to make a
ed. It is effective. However, for most galvanizers it steam coil to heat the flux tank to 160°F. Finally,
carries the unfortunate economic price of higher water was added to bring the flux solution up to the
zinc usage. In any case, the NaCl and KC1 concen- normal working depth. In short the final solution
trations are lower than in the cited cases. This matched that of Table I
smoke reduction will be addressed later in connec-
tion with another technology. Quantifying the Financial Benefits
Some flux producers offer products with a few per- For this galvanizer the change to quadraflux had
cent KC1 for use as a top flux on a “wet” kettle. I am several major benefits. A dramatic improvement
unaware of any scientific or practical plant data to in quality allowed a 20% price increase while
show any advantage. Considering the very similar simultaneously decreasing labor costs by 20%.
chemical and physical properties of NaCl and KCl, Much of the labor savings came from eliminating
the use of KC1 in a flux solution is probably not the need for 40 laborers assigned to clean up
desirable. work. Another major savings came from a dra-
matic drop in the reject rate from 4.4% to 0.3%.
Other Flux Components - Mostly Unwanted All of these benefits from changing to quadraflux
Other potential components in a flux solution are quantitatively presented in Table III. The
include barium chloride for sulfate control and zinc total economic benefit for this operation was
oxide, zinc powder or zinc hydroxide for pH control. $8,210,000 annually based on a 250-day work
These “control” additives cannot possibly exactly year and an improvement of $32,840 per work
match every galvanizer’s needs and need to be used day. All of these benefits occurred instantly upon
very rarely and with an awareness of their side conversion to quadraflux.

28 Metal Finishing
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Producing a Better Product consumption was the result of thinner zinc coatings
In Table III the original average galvanizing price on the steel, less dry ash (a drop from four to only
was $0.20llb and the cost of galvanizing was consid- one barrel per day), and fewer rejects that needed to
ered to be $O.lO/lb. The 20% higher price gave a new be stripped and redone.
average price of $0.24/lb that was set and sustained
by true higher quality. Esthetically, the product was Slashing Reject Costs
brighter with near electroplate quality. Even more In the forth row of Table III, the $0.30/lb is the total
importantly, the zinc coatings were much thinner galvanizing cost to process rejects, calculated at
and more conforming to the contours of the steel. $O.lO/lb the first time through the kettle and
Thus mating surfaces fit and bolt holes accepted $0.20/lb the second time. Considering the zinc strip-
bolts without reaming. In addition, most zinc coat- ping cost and time, the tripling of galvanizing cost is
ings were under 6 mils (150 microns) so that the reasonable. The 0.041 is the old reject rate (4.4%
zinc coating did not chip off during rough handling using old flux) minus the new reject rate (0.3%
and shipping. This galvanizer successfully - and using quadraflux) all divided by 100 to get a frac-
profitably - created a differentiated product in a tional number. It was amazing how many of the old
traditionally nondifferentiated industry. reject types were eliminated using quadraflux.
The 20% higher production (first row, Table III) Welding slag rejects were virtually all eliminated.
was a surprise to everybody including the author. Somehow quadraflux got under the welding slag
With quadraflux, the product entered the molten and fully galvanized the product. Black spots virtu-
zinc with almost no zinc spatter. Thus, the workers ally disappeared.
no longer had to hide behind building supports. The Basically the only remaining rejects (0.3%) were
time the product entered the molten zinc and the due to paint identification markings on the steel.
time the product was in the kettle were both cut in This galvanizer tested various paint pigment mark-
half. Ultimately the middle and lower resistance ing pens and found a Japanese aluminum paint pig-
electric heating elements for the zinc kettle furnace ment pen that was removed both by caustic and by
had to be replaced by higher kilowatt units in order acid due to the amphoteric nature of aluminum.
to keep up with the increased production. This galvanizer purchased a case of the pens
imprinted with the galvanizer’s advertisement on
Increasing Production and Reducing Zinc them and gave them away to their customers to
Consumption mark their steel.
In the second row of Table III, the $O.l4/lb of total The fifth row of Table III calculates the yearly
profit reflects the 20% increased price and the wage (with 25% allowance for fringe benefits) of
14,000,OOO lb reflects the 20% increased production, forty zinc clean-up laborers who were laid-off within
both due to quadraflux. It is interesting that this a few days after changing to quadraflux. With
plant, as most galvanizing plants, regarded the ket- quadraflux the hanging zinc icicles that originally
tle as the most critical step limiting production. looked like the point of a pencil became small, very
However, it became increasingly obvious that the thin, flat foil, like a silver gum wrapper that practi-
actual limitation on increased production through- cally blew away with the wind. Zinc clean-up
put was not the kettle, but the old flux solution that changed from intense, high-speed side grinding to
was the real bottleneck. very light, to no hand filing.
In the third row of Table III, the $0.85 was the Obviously the South African galvanizer was very
high price of zinc in 1982. The 0.0269 is the old pleased with the $8,210,000 annual benefits. When
%GZU of 8.19% (using the old flux) minus the new he ran out of surfactant, he had it air shipped from
%GZU of 5.50% (using quadraflux) all divided by the U.S. to South Africa at a cost of $6,000 per bar-
100 to get a fractional number. The reduction in zinc rel - $1,000 for the surfactant and $5,000 for air

30 Metal Finishing
shipping. Changing to quadraflux cost only a few g/mL). The solution has an ammonium chloride con-
thousand dollars and the investment has been paid centration of 7.26%, a zinc chloride concentration of
off many, many times over the last 20 years. 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
TESTING FLUX CHEMISTRY of Table IV marked “STD.”
A galvanizer should now be able to initially make up
a quadraflux solution as shown in Table I. As the Lab Results
flux is used, the composition of this solution will The second, third, and fourth rows of Table IV are
change. The Baume, ACN, iron (Fe+2), sulfate (SO,-2) test results for “Bob, ” “Tom” (the author), and
(sulfuric acid pickle), pH, and surfactants will all “Erik” (see acknowledgements.). For the second,
change. Accurate testing to control the flux is third, and fourth rows, the zinc chloride concen-
required. A galvanizer needs fast, accurate, and low tration was determined mathematically by accu-
cost test results. rately knowing the density, the iron (Fe+2), and the
sulfate (SObm2). This methodology works very well
Methodology as shown in Table IV because the worst zinc chlo-
The author wanted to evaluate the performance, ride concentration of 7.35% is only 1.2% higher
cost, speed, and accuracy of a wide range of labora- than the true value of 7.26%. For rows two, three,
tories performing this critical analysis. To create a and four the, ACN is directly measured by two
standardized test, the author made up 8 liters of a methods within a single test procedure. The first
standard flux. This standard solution was made up way was based on heat of solution knowing that
by dissolving 10 mL of concentrated (37%) ammonium chloride gets cold when dissolved in
hydrochloric acid, 21.05 grams of anhydrous ferrous water and zinc chloride gets hot when dissolved in
sulfate, 80 grams of ammonium chloride, 80 grams water. The second way was by density knowing
of zinc chloride all dissolved in each liter of solution. that ammonium chloride forms low density solu-
The resulting density is 13.4 degrees Baume (1.102 tions and zinc chloride forms high-density solu-

July/August 2003 31
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 tions. The ACN is found directly on the tables by
comparison of other standard solutions.
These ACN tests developed by the author have
been very successful for about 20 years. For rows
two, three, and four the ammonium chloride concen-
tration is calculated by knowing the zinc chloride
concentration and the ACN. The worst result of
6.91% for ammonium chloride is 4.8% lower than
the true value of 7.26%. In rows two, three, and four
the iron (Fe+2) and sulfate (SO,-2) were determined
by modified dropper bottle test kits developed by the
author 30 years ago. The modifications are putting
the titrants into l-cc plastic syringes and using a
specific volume of flux such that 1 cc of titrant
equals 1% of impurity As shown in Table IV (rows
two, three, and four) the worst result is 0.72% for
iron (Fe+2), which is 2.9% higher than the true value
of 0.70%. The worst value for sulfate, 1.19% is only
0.017% lower than the true value of 1.21%.
In Table IV, rows five through seventeen give test
results from thirteen labs, some of which have test-
ed galvanizing fluxes for many years. Prices charged
for testing this standard flux solution ranged
between $0 and $100. Row eighteen gives the num-
ber of results from a possible of thirteen that are
within 5% of the true value.
As Table IV shows only labs “F” and “G” got within
5% of the true value of ACN (which was 1.00).
Unfortunately for lab “G” the very high zinc chloride
result of 15.45% makes the calculations “blow up” pre-
scribing that 830 pounds of ammonium chloride/l,000
gal of flux should be added to raise the ACN from 1.00
to 1.60. This would actually produce an ACN of 2.24,
which is not at all desirable. This ammonium chloride
addition is more than twice the real value of 400 lb of
ammonium chloride/l,000 gal of flux.
Lab “F” got a usable value for ACN, zinc chloride,
and ammonium chloride to properly adjust the ACN
to a target value of 1.60. The results from lab “F” for
iron of 0.57% (true value 0.70%) and for sulfate of
1.36% (true value 1.21%) does not justify a high level
of confidence in their work. The values reported by lab
“F” are 18.6% lower and 12.4% higher for iron and sul-
fate respectively. This standard flux solution was the
first galvanizing flux sample that lab “F” ever tested.
A different standard flux solution has been sent to lab
“F” to see if they can get additional good results for
ACN, zinc chloride, and ammonium chloride. A second
sample (also with an ACN of 1.00) was sent to lab “H”
and they returned a result of 1.20, which is worse than
their original 1.12 ACN for the standard flux sample
dealt with in this article.
As Table IV shows only labs “B” and “H” got iron
(Fe+2) correct within the 5% error margin. In the case
34
of low results for iron, insufficient volumes of ammo-
nium 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 hydrox-
ide 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 chlo-
ride 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 author’s
opinion that it is pointless for a galvanizer to send a
flux solution sample to any of these labs.
KEEPING THE FLUX SOLUTION OPTlNllZED
Getting accurate analysis of the flux is only a first
step. The real challenge is to use the analysis to cal-
culate the correct amounts of chemicals to add to the
flux solution. Returning to the South African exam-
ple, a few months after the successful conversion to
quadraflux, zinc consumption (%GZU) began to rise.
The reason was easily found in the daily log book
and it was a straightforward task to write a com-
puter program, which freed individuals from having
to make detailed calculations manually, The %GZU
went back down and stayed down. Currently, this is
being converted by the author to a more accurate
“fluxcalc” EXCEL computer program.
GElTlNG STAKTED
This article is not a universal blue print to make up
a universal quadraflux formula to improve galva-
Metal Finishing
nizing results. However, it does hope to have sum- (15 liters) in a &gal ceramic or porcelain coated
marized a vast amount of real-world experience and steel container (a “canning pot”). This allows you to
identified those variables that have a direct effect on make side-by-side comparisons with the old flux
performance, cost, and quality results. Controlling solution. Remember that 160°F (71°C) is required
flux composition, temperature, and use requires for quadraflux and the steel must remain in the
knowledge, understanding, and experience. The quadraflux 3 to 5 minutes. Compare zinc spatter as
impact on the bottom line, however, justifies all the the fluxed steel enters the molten zinc, compare
time and all the effort. “cook off” times (when bubbling stops), compare dry
It goes without saying that the starting materials, ash formed, and evaluate galvanizing quality. Use
such as ammonium chloride, zinc chloride, and com- shorter and shorter kettle times until quadraflux
mercial flux, must be of adequate purity. Beyond gives too thin zinc coatings or the old flux produces
that starting point, one has to ask where can these black spots. Take the time to get some experience
materials be tested? Will the test results be correct? with a flux that can generate more profit. If you are
What are my surfactant requirements and what like the South African galvanizer, a delay in making
surfactant should be used? How will pH be adjust- this decision costs $32,840 a day.
ed? What adjustment may be necessary each day?
How will ACN testing be done? How much ammoni- ACKNOWLEDGEMENTS
um chloride should be added and how often? When The author thanks Bob Olsen of T and L Irrigation
and how should the flux be purified? Will there be in Hastings, Nebraska, and Erik Jacobs of Ace
more or less smoke from quadraflux? Galvanizing in Seattle, Washington, for testing the
There are a lot of questions that need to be standard flux solution in Table IV. The author also
answered in the context of one’s own operation. thanks long-time Metal Finishing editor, Michael
There is no substitute for hands-on testing under Murphy, for encouragement in writing galvanizing
your actual working conditions. For small scale test- articles for this magazine.
ing of quadraflux, I recommend making up 4 gallons

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July/August 2003 35