1.

PHOSPHATE CONVERSON COATNGS

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 theseand
whether they are in fact called for or not, depends on many factors of which the
mostimportant 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 line
The phosphating sequence is normally broken down into the following stages;
Degreasing and cleaning,
Derusting and descalling,
Activation,
Phosphating,
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
phosphatingtemperature. At high bath temperatures, the phosphate crystals form on the
blasted steelare largely of uniform size and very fine. On samples which have only been
degreased, avery large and very small crystal co-exists, whereas on blasted steel, there is
much moreuniform 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. n 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 () 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 huesto
the zinc-only baths. Very dark, anthracite-black coatings result from the phosphatingof
steel in manganese-based solutions.
ZNC PHOSPHATNG
n 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.
TECHNCAL APPLCATONS OF ZNC PHOSPHATNG;
Zinc Phosphating Prior to Powder Coating
Zinc Phosphating Prior to Wire Drawing
Zinc Phosphating Prior to Tube Drawing
MMERSON PROCESS
n 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): 55-95Time (min) : 5-10
2. Water rinse
Temperature (C): 15-30Time (min) : 0.5-1.5
3. Activation
Temperature (C): 20-40Time (min) : 0.5-1.5
4. Phosphating
Temperature (C): 40-60Time (min) : 3-10
5. Water rinse
Temperature (C): 15-30Time (min) : 0.5-1.5
6. Post-rinse
Temperature (C): 20-40Time (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
n 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. n 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): 40-60Pressure (bar): 1-2.5 Time (min): 2-2.5
2. Water rinse ; Temperature (C): 15-30Pressure (bar): 0.7-1.5Time (min): 0.5-0.7
3. Phosphating ; Temperature (C): 40-60Pressure (bar): 1-2 Time (min): 2-2.5
4. Water rinse; Temperature (C): 15-30Pressure (bar): 0.7-1.5Time (min): 0.5-0.7
5. Post-rinse; Temperature (C): 20-40 Pressure (bar): 0.7-1.5Time (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.
t 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.n 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.
RON PHOSPHATNG
ron 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. ron 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 ron Phosphating
Dip Application ron Phosphating
Spray Application ron Phosphating
ron 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 to6. 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. ron 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.
ron 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 PHOSPHATNG
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, dril
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 65-95C. Treatment times range from 5-15
minutes.
n recent years, a highly effective activating pre-rinse has been developed for
manganesephosphates which permits alkaline cleaning and pickling of the work, without
the penalty of coarse-crystalline phosphate formation. This is based on a finely-dispersed
manganesephosphate 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 95C and only in special cases can satisfactory coatings be formed
at temperatures around 80C.
The phosphated components, after drying, are immersed in the oil or lubricant baths
for0.5-2 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. n other industries, the process is used to treat components in refrigerator
compressors or oil pumps and their associated hydraulic rams for vehicle assembly
plants
- Operati ng parameters for some thi ck phosphati ng processes -
Phosphating System/Accelerator /Concentration(total
acidpoints)/Temperature(C)/TreatmentTime min.)/Coating Weight (g/m2)
Zinc
Phosphate
None
20-50
90-98
30-60
20-45
Zinc
Phosphate
Nitrate
50-80
70-98
5-15
10-35
Manganese
Phosphate
None
20-50
90-98
30-60
20-45
Manganese
Phosphate
Nitrate
30-60
90-98
5-15
8-30
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 work piece 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 work pieces are pre-rinsed in an activation rinse prior to
the phosphating.
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 .
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. t 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
anotherimproved 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 .
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 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]
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. t remains to be
seen if these, or other new electrochemical conversion coatings, will ultimately replace
traditional phosphating and Parkerizing.
Zinc and manganese phosphate coatings are the treatment of iron or steel by immersion in a
dilute solution of phosphoric acid and other additives. n the resulting chemical reactions, the
surface of the metal is chemically converted to an integral protective layer of insoluble zinc and
iron or manganese and iron phosphate crystals. Depending on the physical characteristics of the
substrate and the pretreatment methods used, the translucent crystals appear black to light grey
in color for zinc phosphate and black to dark grey in color for manganese phosphates.
For Lubrication During Cold Forming-
A phosphate-based lubricant soap system is superior to all other lubricants for severe extrusions
because of the ability of the coating to flow with the metal as it is deformed, reducing metal to
metal contact. This characteristic is the result of strong metal-to-phosphate bonds, which are
formed during coating and the excellent extreme-pressure properties of the soap used as a
supplementary treatment. Phosphate-soap coatings extend tool life, permit faster drawing
speeds, allow for maintenance of closer dimensional tolerances, and produce a smooth, glossy
surface on the finished parts. Low iron, light zinc phosphate coatings are typically used in this
application.
For Corrosion Resistance-
Alone or in combination with rust-inhibiting oils, waxed, or other organic coatings, zinc and
manganese phosphates are a low-cost alternative to electroplating. Depending on the
supplemental coating, it can withstand from 48-480 hours of neutral salt spray exposure per
ASTM method B-117. Although heavy zinc phosphates are normally considered superior for this
application, both types of phosphates extend the shelf life of aftermarket replacement parts in
corrosive environments.
To Reduce Break-n Wear On Adjacent Moving Surfaces-
Nonmetallic, oil absorptive zinc and manganese phosphate coatings on bearing surfaces permit
rapid break-in of moving parts without scuffing or welding by preventing metal to metal contact, as
the friable coating is easily crushed when a load is applied. Additionally, the oil held by the
crystals improves the lubrication of the treated surface and imparts corrosion resistance. After
break-in, and even and fine distribution of oil "reservoirs" remains, assuring continued lubrication.
Manganese phosphate is generally preferred for this application because of its higher wear
resistance.
For Torque-Tension Requirements-
Zinc and manganese phosphated fasteners sealed with a lubricating oil guarantee repeatable
torque-tension relationships in applications where automated assembly equipment cannot be
conintually adjusted to compensate for varying surface conditions. The excellent uniform
lubrication provided by our special "TORQ-TECH", zinc, and manganese phosphate coatings
eliminate stick-slip conditions and galling during assembly. Additionally, the parts are protected
from oxidation during storage.
For Bonding Organic Coatings to Metals-
Reducing the electrochemical activity of the ferrous surface and forming strong physical and
chemical bonds with organic coatings, zinc and manganese phosphates are widely used as a
bare under adhesives (in rubber to metal bonding), paints, and other organic coatings. The highly
absorbent phosphate crystals allow paint to penetrate into tiny fissures and also increase the total
surface area available for bonding. Acting as a dielectric film that insulates the active anode and
cathode centers which exist over the surface of the base metal, phosphate coatings retard
corrosion "creep", extending the life of the finished product. Light zinc phosphate coatings with
small, uniform crystal sizes produce the best bond.
Hydraulic system manufacturers Military armament suppliers Rod-by-coil manufacturers
Nuclear component fabricators Cold-Forming industries Sports equipment manufacturers
Automotive fastener companies Aerospace industries Motorcycle specialty groups
Marine equipment vendors Various stamping applications Diesel engine manufacturers
Electrical connector
manufacturers
Heavy equipment
manufacturers
Gear & bearing manufacturers
Material to be coated is cleaned by immersion in a hot alkaline solution that removes most oils
and loose soil. f surface oxides are present, the parts are then stripped in an acid-cleaning step
that undercuts the rust or scale, exposing the bare metal beneath. The work is then rinsed
thoroughly and coated in a chemically balanced hot phosphoric acid solution via an autocatalytic
reaction. The temperature, time and chemical composition of this bath must be carefully
controlled to produce consistent results. After coating is completed, excess acid is neutralized
and a supplementary treatment is applied if required. Material to be zinc or manganese
phosphated may either be racked or bulk-processed in barrels, depending on the specifications of
the end user. Normally threaded parts, soft alloys, or parts which weigh in excess of 6 ounces are
racked to avoid nicks, distortion, and coating damage which result from bulk handling practices.
Depending on the intended purpose of the finish, the crystal size, shape, coating weight, and
color can be modified to meet many industrial military specifications. Because the hardness,
composition, and surface condition of the raw material greatly influence the results of a given
processing cycle, it is often necessary to use different cleaning cycles, refiners, and phosphate
bath formulations to effect identical results on dissimilar substrates. We are currently using more
than 70 different zinc and manganese phosphate cycles to accommodate our customers' needs.
These processing programs must be selected with great care to match specification requirements
with results.
The primary indicators of zinc and manganese phosphate quality are coating weight
measurement and neutral salt spray resistance. Crystal size and form are important for some
applications, but due to the expense of the electron microscopy necessary to make an accurate
determination, this characteristic is not commonly checked on a production basis and is normally
limited to first article (layout) inspection. Some specifications also include thickness requirements,
but much controversy exists regarding the accuracy and methods of testing because the
phosphate crystals are extremely friable and crush under even the slightest pressure. Diagnostic
tests for coating integrity, torque-tension relationships and for the presence of zinc and
manganese are also available. All tests performed on zinc and manganese phosphated material
are destructive.