1.

PHOSPHATE CONVERSION COATINGS

Phosphating of metals is one of the most important of surface treatment methods and
a number of modern metal finishing procedures would not be possible without it. The
main areas of application of phosphating are;
• Corrosion protection in conjunction with organic coatings, e.g., paints and
polymer films,
• Facilitation of cold-forming processes, e.g., wire drawing and tube drawing, deep
drawing,
• Corrosion protection in conjunction with oils and waxes,
• Corrosion protection with no subsequent treatment.

Zinc phosphated metal pieces.

Phosphating can be executed using a variety of sequential processes. The list of these
and whether they are in fact called for or not, depends on many factors of which the most
important are;
• Nature of the metal to be coated,
• Shape and surface condition of the metal,
• Number of parts and uniformity of their surface state,
• Anticipated service duty of the phosphate coating,
• Organisational factors, e.g., limit on number of processing lines,

The phosphating sequence is normally broken down into the following stages;

1. Degreasing and cleaning,

2. Derusting and descalling,
3. Activation,
4. Phosphating,
5. Post-treatment.

There is normally a rinse between the individual processing steps in order to

remove the solution layer from the metal surface and to avoid carry-over of this as an
impurity to the subsequent stage. According to circumstances, the processing sequence
may be longer or shorter. Thus, for example, pickling can be omitted if no corrosion
products are present on the metal surface. Then, too, some of the individual stages can be
combined, for example, cleaning and phosphating.
 Of the many phosphating systems which have been proposed, the following are of
industrial importance: zinc phosphate, iron phosphate, manganese phosphate. Such
phosphating systems are predominantly applied to iron and steel, as well as zinc surfaces
whereas other metals which can be phosphated, e.g., aluminium, magnesium, are less
commonly processed by this method.

Phosphate coatings which adhere well to the basis metal and which, so far as
possible, cover it completely, can only be formed on clean surfaces which are free from
rust, scale, soot and other corrosion products. Oil and grease films likewise inhibit
phosphate coating formation, except when they are so thin that they are removed by
initial etching stage.

The nature of the pretreatment steps used before the phosphating itself, e.g., in the
cleaning, can considerably affect the growth rate of the phosphate coating, its thickness
and the crystal size. These effects can be chemical or mechanical and sometimes both
together.

The effect of metal pretreatment on coating weight depends on the phosphating

temperature. At high bath temperatures, the phosphate crystals form on the blasted steel
are largely of uniform size and very fine. On samples which have only been degreased, a
very large and very small crystal co-exists, whereas on blasted steel, there is much more
uniform coverage of very small crystals.

Chemical pretreatment of the metal, too, can significantly affect the formation of
the phosphate coating. These observations have industrial significance in terms of
alkaline degreasing and solvent degreasing as well as acid pickling. Phosphating
solutions based on zinc, iron and manganese produce rougher phosphate coatings with
higher weight per unit area, when strong alkaline cleaners are used, in contrast to solvent
degreasing. In addition, longer phosphating times are required for complete coverage of
the metal.

To suggest that a large range of steels are capable of being phosphated is not to
imply that, in all cases, these are suitable for industrial applications. Thus it has been
found that deep-drawn steel, as widely used in automobile industry, can be phosphated,
painted and subjected to accelerated corrosion testing.

All zinc-containing materials industrially used, including electro galvanized and

hot-dip galvanized steels, as well as zinc with small additions of copper or titanium, used,
for example, in diecastings, can be phosphated without problems. To improve corrosion
resistance and "white rust" formation, chromate passivation films must first be removed.

The colour of the phosphate coatings lies between light grey and pitch black. The
lightest are the zinc phosphate coatings on zinc which, when this is the only metal in the
bath, contain no other cationic species. When iron (II) also is present, and especially zinc
and nickel, darker, usually, mid-grey coatings are formed. Whit steel substrates zinc
phosphate coatings are darker than on zinc substrates, which is explained in terms of the
larger amount of iron in the coating. Zinc-calcium baths produce coatings of similar hues
to the zinc-only baths. Very dark, anthracite-black coatings result from the phosphating
of steel in manganese-based solutions.

ZINC PHOSPHATING

In most operations where the corrosion resistance of finished workpieces must be

especially high, conversion coatings are applied using zinc phosphate . This approach is
widely used in the automotive industry and in certain sectors of the appliance and
electronics industries. Similarly, zinc phosphating is often specified by the armed
services, especially for equipment that may be exposed to severe environments.
Moreover, many operations using electrocoating or powder coatings, particularly when a
one-coat finish will be exposed to the weather, pretreat workpieces with zinc phosphate.

TECHNICAL APPLICATIONS OF ZINC PHOSPHATING;

• Zinc Phosphating Prior to Powder Coating
• Zinc Phosphating Prior to Wire Drawing
• Zinc Phosphating Prior to Tube Drawing

IMMERSION PROCESS

In the immersion mode, zinc and alkali metal phosphating systems do not greatly differ
from one other. The individual steps, as normally carried out are ;

1. Cleaning stage ; Temperature (°C): 55-95 Time (min) : 5-10

2. Water rinse ; Temperature (°C): 15-30 Time (min) : 0.5-1.5

3. Activation ; Temperature (°C): 20-40 Time (min) : 0.5-1.5

4. Phosphating ; Temperature (°C): 40-60 Time (min) : 3-10

5. Water rinse ; Temperature (°C): 15-30 Time (min) : 0.5-1.5

6. Post-rinse ; Temperature (°C): 20-40 Time (min) : 0.5-1.5

Cleaning is usually based on alkaline or strongly alkaline solutions in the concentration

range 1-5%, and pH 10-13. Compared to the cleaners used in the spray mode, the
cleaners used for immersion contain larger amounts of silicate and sodium hydroxide.
The surfactants used often include the strongly-foaming anionic types, usually mixed
with non-ionic types.

Activation is mandatory for zinc phosphating and in its absence, because of the relatively
high pH values involved, a thick and coarse-crystalline coating is formed which is quite
unsuited of subsequent painting. Conditions for the rinse, post-rinse and drying stages
differ little from spray phosphating.

SPRAY PROCESS

In case of spray phosphating, major differences are found in the process sequences for
zinc phosphating and alkali metal phosphating systems.

Zinc phosphating lines are normally based on 5-stage to 6-stage plants. They differ little
in the pre-phosphating stages. The 5-stage type includes a rinse between cleaning and
phosphating steps. In the case of the 6-stage type, there are either two cleaning and one
rinse stages or one cleaning and two rinsing steps.

1. Cleaning ; Temperature (°C): 40-60 Pressure (bar): 1-2.5 Time (min): 2-2.5

2. Water rinse ; Temperature (°C): 15-30 Pressure (bar): 0.7-1.5 Time (min): 0.5-0.7

3. Phosphating ; Temperature (°C): 40-60 Pressure (bar): 1-2 Time (min): 2-2.5

4. Water rinse ; Temperature (°C): 15-30 Pressure (bar): 0.7-1.5 Time (min): 0.5-0.7

5. Post-rinse ; Temperature (°C): 20-40 Pressure (bar): 0.7-1.5 Time (min): 0.5-0.7

The cleaning stage is usually based on weakly alkaline products based on alkali
phosphates, alkali carbonates or borates, low-foaming surfactants and alkali silicates. To
these, further compounds such as titanium orthophosphates may be added to increase the
rate of the phosphating process and facilitate formation of uniform finely-crystalline
coatings.

It is normal to dry phosphated work before the application of conventional paints and in
the case of anodic electro coating paint, it is highly recommended. Circulating air ovens,
operating at 120-180 °C with a drying time of 5-15 minutes are typically used for such
drying.

In 4-stage plants the concentrations in the first bath run from 3-10 g/l, somewhat higher
(5-15 g/l) in the second bath. The rinse and post-rinse stages are operated on the same
basis as normal zinc phosphating systems.
IRON PHOSPHATING
Iron phosphating is the most preferred conversion coating method for indoor
equipments due to its advantage of low first investment cost and unit prices of the
chemicals. Iron phosphate coating chemicals are easy to use products that can be used by
wiping, spraying or dipping for the metal surfaces do not require high corrosion
resistance.
IRON PHOSPHATE CONVERSION COATING BY APPLICATIONS;
• Wipe Application Iron Phosphating
• Dip Application Iron Phosphating
• Spray Application Iron Phosphating
Iron phosphate coating ranges in color light yellow to blue-red. Coating weight is
generally between 0.2 - 1.0 gr/m2. Concentration of the coating solution varies in the
range of %1 – 10 and operating temperature is between room temperature – 65 °C.
Optimum pH value of phosphating solution is 4 to 6. Below pH 4 dusty coating may
occur and above pH 6 coating may be loose and unsatisfactory.

Hence iron phosphate coating is not a thick coating relatively, passivation and drying
stages should be operated carefully. When outbreak of oxidation (rust) is observed after
the treatment, this indicates insufficient coating on the metal surface. Iron phosphate
coated but unpainted metal workpieces do not have improved corrosion protection, that’s
why it is an advantage to paint the phosphated surface immediately after phosphating.

Iron phosphating increases paint adherence and impact resistance along with improved
flexibility. Treated metal surface has the ability to stop progress of oxidation underneath
the paint when damaged by an external impact.

However iron phosphating suitable for ferrous metals, by the advantage of surfactant
content, it can also be employed in cleaning and etching of aluminium or galvanized
metals.

When iron phosphating applied by spraying, phosphating and degreasing can be operate
at the same stage with proper quantity of both chemicals.

MANGANESE PHOSPHATING

Manganese phosphate coating has the highest hardness and superior corrosion and
wear resistances of general phosphate coatings.

Manganese phosphating is extensively employed to improve the sliding properties

of engine, gear, and power transmission systems. The use of manganese phosphated
coatings for improved corrosion resistance can be found in virtually all branches of the
metal working-industry. Typical examples mentioned here include motor vehicle
components in brake and clutch assemblies, engine components, leaf or coil springs, drill
bits, screws, nuts and bolts, washers, anti-vibration washers, tools, magnet cores, casting
interiors and many other small items.

Manganese phosphate coatings for conferment of good corrosion resistance,

whether a post-treatment such as oil application is to be used or not, are invariably
applied by the immersion method. The processing sequence can be summarized as
follows:

• Degreasing and cleaning

• Water rinse
• Pickling in mineral acid (where necessary)
• Water rinse (only after pickling)
• Activation
• Manganese phosphating
• Water rinse
• Final oven drying (optional)
• Lubricating with special oils or emulsions.

The degreasing and cleaning are usually done with strongly alkaline cleaners at
concentrations of 1-5% and temperatures 65-95°C. Treatment times range from 5-15
minutes.

In recent years, a highly effective activating pre-rinse has been developed for manganese
phosphates which permits alkaline cleaning and pickling of the work, without the penalty
of coarse-crystalline phosphate formation. This is based on a finely-dispersed manganese
phosphate at concentrations 1-2 g/l.

Manganese phosphating is mainly by immersion. Treatment times range from 5-20

minutes, the optimum time depending on the surface condition. The bath operating
temperature is around 95°C and only in special cases can satisfactory coatings be formed
at temperatures around 80°C.

The phosphated components, after drying, are immersed in the oil or lubricant baths for
0.5-2 minutes, allowed to drain. The thickness of the resulting oil film depends on the oil
used and its concentration.

Manganese phosphating as a wear protection measure is widely used in the auto industry.
Gearwheels in the gearbox, crown and pinion gears in the differential, cam-shafts, valves
and valve-steams as well as pistons in larger diesel engines are frequently treated in this
way. In other industries, the process is used to treat components in refrigerator
compressors or oil pumps and their associated hydraulic rams for vehicle assembly
plants.

- Operating parameters for some thick phosphating processes -

Phosphating Accelerator Concentration Temperature Treatment Coating

System (total acid (°C) Time (min.) Weight
points) (g/m2)

Zinc None 20-50 90-98 30-60 20-45

Phosphate
Zinc Nitrate 50-80 70-98 5-15 10-35
Phosphate
Manganese None 20-50 90-98 30-60 20-45
Phosphate
Manganese Nitrate 30-60 90-98 5-15 8-30
Phosphate

The coating weight and crystal size of the manganese phosphate coatings are influenced
to an even greater extent than in zinc phosphating by the mechanical, thermal, and
chemical pretreatment of the workpiece surface prior to phosphating. For example,
cleaning in alkaline aqueous cleaning agents or pickling in acids produces coatings with a
much coarser texture. Even after such treatments, however, fine crystalline phosphate
coatings are still obtainable if the workpieces are prerinsed in an activation rinse prior to
the phosphating.
2. PARKERIZING

Parkerizing (also called phosphating and phosphatizing) is a method of protecting a steel

surface from corrosion and increasing its resistance to wear through the application of an
electrochemical phosphate conversion coating. Parkerizing is usually considered to be an
improved zinc or manganese phosphating process, and not to be an improved iron
phosphating process, although some use the term parkerizing as a generic term for
applying phosphating (or phosphatizing) coatings that does include the iron phosphating
process.

Parkerizing is commonly used on firearms as a more effective alternative to bluing,

which is another electrochemical conversion coating that was developed earlier.

The Parkerizing process cannot be used on non-ferrous metals such as aluminum, brass,
or copper. It similarly cannot be applied to steels containing a large amount of nickel, or
on stainless steel. Passivation can be used for protecting other metals

Application

The process involves submerging the metal part into a phosphoric acid solution whose
key ingredient is often zinc or manganese, with varying additional amounts of nitrates
and chlorates and copper. In one of the many processes that have been developed, the
solution is heated to a temperature of 190–210 °F (88–99 °C) for a period ranging
between 5 and 45 minutes. A stream of small bubbles is emitted from the metal part as
the process takes place; when the bubbling stops, the process is complete. In addition to
this particular processing temperature, there have also been various similar Parkerizing
processes developed and patented that permit using either lower temperatures (for energy
efficiency) or higher temperatures (for faster processing).

Appearance and use

Zinc phosphating results in a non-reflective, light- to medium-gray finish. Manganese

phosphating produces a medium- to dark-gray or black finish. Iron phosphating produces
a black or dark gray finish similar to manganese phosphating. The grain size of the zinc
phosphating is usually the smallest among the three processes, providing a more
appealing cosmetic appearance in many applications. Many firearms that are Parkerized
turn to a light greenish-gray color within a few years, as the coating ages, with the
protective coating remaining intact. Cosmoline, especially, interacting with Parkerizing,
can cause the highly-desired and attractive greenish-gray patina to develop on firearms
that are stored in armories.

Manganese and iron phosphating coatings are usually the thickest electrochemical
conversion coatings, being thicker than electrochemical conversion coatings such as zinc
phosphating and bluing.

None of the electrochemical conversion coating finishes are painted coatings, but
chemically become part and parcel of the metal surface to which they are applied.

As for all electrochemical conversion coatings, the Parkerized surface must be

completely covered with a light coating of oil to maximize corrosion and wear resistance,
primarily through reducing wetting action and galvanic action. A heavy oil coating is
unnecessary and undesirable for achieving a positive grip on Parkerized metal parts.

Alternatively, the Parkerized surface may be painted over with an epoxy or molybdenum
finish for added wear resistance and self-lubricating properties.

Early history

Development of the process was started in England and continued by the Parker family in
the United States. The terms Parkerizing, Parkerize, and Parkerized are all technically
registered U.S. trademarks of Henkel Adhesives Technologies, although the terminology
has largely passed into generic usage for many years. The process was first used on a
large scale in the manufacture of firearms for the United States military during World
War II.

The earliest work on phosphating processes was developed by British inventors William
Alexander Ross, British patent 3119, in 1869, and by Thomas Watts Coslett, British
patent 8667, in 1906. Coslett, of Birmingham, England, subsequently filed a patent based
on this same process in America in 1907, which was granted U.S. Patent 870,937 in
1907. It essentially provided an iron phosphating process, using phosphoric acid.

An improved patent application for manganese phosphating based in large part on this
early British iron phosphating process was filed in the US in 1912, and issued in 1913 to
Frank Rupert Granville Richards as U.S. Patent 1,069,903.

Clark W. Parker acquired the rights to Coslett's and Richards' U.S. patents, and
experimented in the family kitchen with these and other rust-resisting formulations. The
ultimate result was that Clark W. Parker, along with his son Wyman C. Parker, working
together, set up the Parker Rust-Proof Phosphating Company of America in 1915.
Colquhoun of the Parker Rust-Proof Phosphating Company of America then filed another
improved phosphating patent application in 1919. This patent was issued in 1919 as U.S.
Patent 1,311,319, for an improved manganese phosphating (Parkerizing) technique.

Similarly, Baker and Dingman of the Parker Rust-Proof Company filed an improved
manganese phosphating (Parkerizing) process patent in 1928 that reduced the processing
time to 1/3 of the original time that had been required through heating the solution to a
temperature in the precisely-controlled range of 500 to 550 °F (260 to 288 °C). This
patent was issued as U.S. Patent 1,761,186 in 1930.

Manganese phosphating (Parkerizing), even with these process improvements, still

required the use of expensive and difficult-to-obtain manganese compounds.
Subsequently, an alternative technique was developed by the Parker Company to utilize
easier-to-obtain compounds at less-expense through using zinc phosphating (Parkerizing)
in place of manganese phosphating (Parkerizing). The patent for this zinc phosphating
(Parkerizing) process (utilizing strategic compounds that would remain available in
America during a war) was granted to inventor Romig of the American Chemical Paint
Company in 1938 as U.S. Patent 2,132,883, just prior to the loss of easy access to
manganese compounds that occurred during World War II.

Somewhat analogous to the improved manganese phosphating process improvements

discovered by Baker and Dingman, a similarly-improved method was found for an
improved zinc phosphating process as well. This improvement was discovered by Darsey
of the Parker Rust Proof Company, who filed a patent in February 1941, which was
granted in August 1942, U.S. Patent 2,293,716, that improved upon the zinc
phosphatizing (Parkerizing) process further. He discovered that adding copper reduced
the alkalinity requirement over what had been required, and that also adding a chlorate to
the nitrates that were already used would additionally permit running the process at a
much lower temperature in the range of 115 to 130 °F (46 to 54 °C), reducing the cost of
running the process further. With these process improvements, the end result was that a
low-temperature (energy-efficient) zinc phosphating (Parkerizing) process, using
strategic materials which the United States had ready access to, became the most
common phosphating process used during World War II to protect American war
materials such as firearms and planes from rust and corrosion.

As a tragic aside, during the Great Depression, Parker Company co-founders Clark W.
Parker and his son Wyman were found guilty of investor fraud. The details of the story
were contained in a 20 July 1931 Time Magazine article: "Clark W. Parker and his son
Wyman stood before Federal Judge John Munro Woolsey in Manhattan last week, were
fined $11,000 each and sentenced to five years in Atlanta Penitentiary for conspiracy and
using the mails to defraud. Worthless was not only $1,250,000 worth of stock in
Automotive Royalties Corp. but also that of two previous companies Mr. Parker had
formed. Many a mulcted clergyman sadly agreed when Judge Woolsey called him "an
enemy to society." Swindler Parker shrugged." "[1]
Future

Glock Ges.m.b.H., an Austrian firearms manufacturer, uses a black Parkerizing process

as a topcoat to a Tenifer process to protect the slides of the pistols they manufacture.
After applying the Tenifer process, a black Parkerized finish is applied and the slide is
protected even if the Parkerized finish were to wear off. Used this way, Parkerizing is
thus becoming a protective and decorative finishing technique that is used over other
underlying improved techniques of metal protection.

Traditional iron phosphate, zinc phosphate, and manganese phosphate electrochemical

conversion coatings, including Parkerizing variations, have all been criticized in recent
years for introducing phosphates into surface water systems, encouraging the rapid
growth of algae (eutrophication). As a result, in recent years, new, emerging technology
alternatives to traditional phosphate coatings have started to see limited use, for replacing
all phosphating coatings, including Parkerizing. The majority of these newer conversion
coatings are fluorozirconium-based. The most popular of these fluorozirconium-based
conversion coatings, introduced in 2005, incorporates the transition metal vanadium. This
new, more environmentally-friendly coating is referred to as a vanadate conversion
coating. Besides vanadate coatings, arsenate coatings may theoretically provide similar
protection, at the risk of being a health hazard to humans and animals. It remains to be
seen if these, or other new electrochemical conversion coatings, will ultimately replace
traditional phosphating and Parkerizing.

Various if similar recipes for stovetop kitchen Parkerizing circulate in gun publications at
times, and Parkerizing kits are sold by major gun-parts distributors such as Brownell's.