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Manganese phosphate coating on steel



A discussion started in 2005 and continuing through 2017 . . .

(2005)

Q. I would like to get a recipe for a manganese phosphate coating for steel. If someone perhaps can explain to me the actual chemical actions taking place on the surface too?

I've learned that there are many applications such as:
1 high wear resistance
2 better resistance against corrosion and a nice finish and 3 as a pre-treatment for painting etc.

Is there a big difference in the recipe and chemicals? The one I'm most interested in is protection against corrosion and finish.

Thanks

Jan Van Velde
hobbyist - Kesteren, Netherlands


Manganese Phosphate

(2005)

A. You can use next solution:
25 gm phosphoric acid
1,5 gm manganese dioxide
1 lit water
Boil your objects 2-4 hours.
you must oil,lacquer or wax it!
(according to Angier: "Firearm Blueing and Browning" [link is to info about book on Amazon])

Goran Budija
- Zagreb, Croatia


(2005)

A. Jan Van Velde

Manganese phosphating formulations contains basically a manganese salt, phosphoric acid and an accelerator. Deposition of manganese phosphate coating is normally performed at very high temperatures of the order of 95 °C for a period of 30-60 minutes.

It is a conversion coating process and involves the dissolution of the base metal which subsequently forms part of the coating. In manganese phosphate coating the species that deposits on steel is manganese iron phosphate and hence requires a large amount of metal dissolution so that the formation of manganese iron phosphate is possible. This is the reason for the requirement of high operating temperature and higher processing time.

Manganese phosphate coating offers good wear resistance. It can retain oil and lubricants and improves the scuffing resistance. Manganese phosphate coating with higher coating weight offers good corrosion resistance. Impregnation with oil further improves the corrosion resistance.

Zinc phosphate coating is mainly recommended as pretreatment coating for painting.

T.S.N. Sankara Narayanan
T.S.N. Sankara Narayanan
- Chennai, Tamilnadu, India



Heaters get sludged, then damaged

(2005)

My company conducts manganese phosphate coating on carbon steel pipe. We use heating elements to heat the bath where the pipe coating is carried out. The problem is after the coating maybe for a week the heating element is covered by sludge. The workers usually remove the sludge from the heating element by hammer (mechanical). It doesn't only remove sludge but also cause damage to the heating element (made from stainless steel). So: how to remove the sludge without causing damage to the heating element ?

Dodi Syafardi
- Cilegon, Banten, Indonesia



A. Hi Dodi. Two quick notes: heaters should be electropolished stainless steel because this surface has no "tooth" at all and will minimize build-up and make cleaning easier. Oversized (derated) heaters or coils should be used because the smaller the heater, the higher the required surface temperature, which accelerates the sludging.

Letters 11465 "Sludge buildup on heating coils in phosphating tank" and 5142 "Materials for zinc phosphating tank" address this issue in some depth. Patient use of our search engine will uncover still more tips on this subject. Good luck.

Regards,

pic of Ted Mooney
Teds signature
Ted Mooney, P.E. RET
finishing.com
Pine Beach, New Jersey
Striving to live "Aloha"


December 6, 2011

A. Dodi Syafardi
for exterior coating & if the ends of pipe are open then for interior coating, you may use glass heaters of required wattage and in required number.

Vijay Yadav
- Bhiwadi, Alwar, Rajasthan, India



How do I formulate a manganese phosphate bath?

October 1, 2010 -- this entry appended to this thread by editor in lieu of spawning a duplicative thread

Q. Hello,
I am looking after a Manganese Phosphating line in our company where cast iron components are coated. The phosphating bath concentrate is currently being outsourced and I am not aware of the contents of it.
I am trying to prepare a bath myself using MnO2 [1.5g/L] and H3PO4 [25g/L] and topping the rest with tap water. The problem is I'm not sure what other chemicals to be added (like accelerator, stabilizers etc) and also in what ratio. I also tried measuring the TA & FA values of the above mentioned bath and found them to be 35 & 17.4 respectively. Thus the TA/FA ration is close to 2. But I have read that it should be between 4 ~ 6. Kindly let me know how to improve the ratio.
Alternatively, It would be a great help if anyone can suggest me the method of preparing a Manganese Phosphating Bath and the chemicals required to prepare it in proper ratios.

Savyasachi Hulikal
Plating shop - Shimoga, Karnataka, India


Manganese Phosphating Without Shot Blasting

Q. Hello,

Currently we are using Shot blasting as a surface preparation prior to Manganese Phosphating. Would the phosphating coating characteristics and adherence properties change if we change the preceding process to Vibratory finishing?

We have issues with dimensional distortion and surface roughness so we would like to ideally switch over to a milder form of deburring/pre treatment.

Any issues been foreseen with the change?

Abhishek Patel
- Ahmedabad, Gujarat, India


November 19, 2013

A. Hi Abhishek,

I must admit that I don't have experience with using vibratory methods of preparation before manganese phosphate, I have always used an abrasive blasting technique.

Before you go and start looking at new ways of finishing can you describe the exact blasting process you are using (blast media type, mesh size, blast pressure, stand off distance)? It may be with some modification of your technique blasting may still be a viable option for you.

For example I use 180-220 mesh alumina grit at a pressure of 40 psi nominal (some jobs have higher pressure needs, some lower) and a stand off distance of about 6-9". This works for about 80% of jobs I do and I suffer little to no distortion.

Brian Terry
aerospace - Yeovil, Somerset, United Kingdom


November 21, 2013

Q. Hi Brian

Being a mass production process, we are confined to use wheel blasting & not air....besides the issue is rather the geometry of the parts.

We use cut wire steel shots for blasting with tumblast wheel blasting machines.

Am of the understanding that phosphating happens at a molecular level so only surface cleanliness & uniformity along with proper surface conditioning should do the job.
Though, yes, higher roughness caused by blasting would give more surface area to the phosphate for better coating & adherence.

Just wanted to confirm from all the experts here.

Abhishek Patel [returning]
- Ahmedabad, Gujarat, India


November 29, 2013

A. Hi Abhishek,

Probably going to show a bit of my ignorance of wheel blasting machines now, can you not reduce the rate of feed of blasting media or change the speed of the wheel blasters so that you reduce impact speed? Alternatively can you change your media without modifications to your cabinet, you may be able to use a less aggressive cutting media?

You are perfectly correct that the reaction happens at the molecular level and that the increase in surface area by blasting increases the number of reaction sites.

If you wanted to go to a vibratory method then you need to talk to your local supplier to see what they have to offer in terms of media that will cut sufficiently to give your increase in reaction sites and still avoid distortion. I get a feeling you are going to have to try a bit of trial and error to see if the process is a viable method of manufacture.

Brian Terry
aerospace - Yeovil, Somerset, United Kingdom



January 23, 2014

Q. We have a situation where two pieces of gun steel were Ion Nitrided in a ammonia rich environment. Sample I was Nitrided at a High Temp (still 100 degrees lower than tempering temp) for a short time and Sample II was nitrided at a low temp for a long time. Both samples were subsequently sandblasted with 140 grit alumina then Mn Phosphated (using a conditioner and hex chrome rinse solutions). Sample I has very little Mn Phosphate, very gray in color, and looks terrible in general (in the nitrided and un nitrided sections of the sample) where Sample II looks very typical black coating in nitrided and un-nitrided sections of the sample.

I have been told that this will always happen but not given a good reason as to why (from my experience the only thing that would impact the ability to produce a good coating would be a layer of non-ferrous material/contaminant). Both samples were examined under a 1000X magnification (we hope to view it under SEM technology soon) and can not see any visible layers/differences/heat affected zones/etc. in the base metals. Does anyone out there have a "oh yeah knucklehead it's this" explanation?

John Cannon
Engineer - Watervliet, New York


January 24, 2014

A. The 2nd most frequent problem with Mn Phos is the absence of a "grain refiner" which I guess you covered with what you call a "conditioner". The first most frequent problem is the total/free ratio. You must adjust this ratio, preferably at the tank side, immediately before inserting the parts. If you check the T/F ratio on Monday and phosphate on Tuesday the ratio is too high,add manganous phosphate until you bring it into proper limits, then immediately phosphate.

Robert H Probert
Robert H Probert Technical Services

Garner, North Carolina

Editor's note: Mr. Probert is the author of Aluminum How-To / Aluminio El Como




January 27, 2014

Q. Hello sir, we are doing manganese phosphating on 4130, 4140, 4330 steel parts. It's a new plant we have installed, am not able to standardize the process; I face problems like uneven coating surface, carbon coming out of the surface after phosphating, uncoated areas.

I have failed to do the pre cleaning properly; please suggest a best process for precleaning, and my chemical supplier only supplies the phosphating chemical; please suggest how to overcome these problems? My process is degreasing, water rinse, 5% H2SO4 rinse, water rinse, hot water rinse and phosphating; free acid 6, total acid 31, ferrous ion 1gm/ltr, temp. 90 to 95.,

Prakash Raj
oil and gas equipment manufacturers - Dubai, UAE


January 28, 2014

A. You must adjust the T/F immediately prior to putting the parts into the solution. For the 4000's series steels you must use a grain refiner. IF you supplier dos not have one, then change suppliers.


Robert H Probert
Robert H Probert Technical Services
Garner, North Carolina


January 30, 2014

A. Hi Prakash,

After degreasing, whether solvent based or aqueous based I would have an aqueous cleaning step (may sound odd, but the second stage cleaning really does help to get parts really clean). Do a water break check after rinsing to ensure you have an unbroken film of water on the parts, if not then repeat the cleaning process until you get a water break free surface.

Make sure you control the etch, don't over-etch, ensure you chemical analysis is OK and use as short a time as possible to obtain the etch required.

Grain refiners are a good idea to obtain even consistent phosphate crystal formation on your parts. As Robert says, your phosphate solution supplier should have a refiner available.

And I can't emphasise strongly enough that you need to keep the phosphate chemistry under control. Dependent on the level of use I would expect a minimum of twice a day analysis for free acid, total acid and iron, if this doesn't keep the solution under control then increase the frequency. If may be as Robert pointed out that you may need to do the analysis for each bath load, although that would indicate to me you have something else in your phosphate system upsetting the chemistry.

Brian Terry
Aerospace - Yeovil, Somerset, UK


February 1, 2014

thumbs up signThank you very much sir, I am getting good results, maintaining the free and total acid in correct ratio, and improved water rinses, and getting good results.

prakash rajagopal [returning]
- Dubai , uae



How to computer control Manganese Phosphate process

March 7, 2014

Q. Hello to all!

We are zinc and manganese phosphate plating company. Demand on Mn Phosphate coatings are rising, therefore also the demand for quality of our service. My question is: how should we make the process more computer controlled to eliminate the human error factor?

Currently we are controlling the temperature automatically with thermocouples, but pH, concentration and acid radio is measured by hand and with analysis.
What are the options for computer control of Mn Phosphate bath?

Second thing, how would you guys hang bush of dimensions 30 mm dia. x20mm for Mn Phosphating, to minimize contact marks? Both sides of bush are smooth finished.

Thanks in advance

Dobnik Doga
- Krsko, Slovenia



How to Manganese Phosphate the component without any dimensional reduction

Phosphating Metal Pretreatment
by Freeman



Phosphating of Metals
by Rausch

July 20, 2014

Q. How to Manganese Phosphate the component without any dimensional reduction to the base metal of grinding surface?

Required coating thickness is only 5 to 7 microns.

Ajay Pawar
- Pune, Maharashtra, INDIA


July 2014

A. Hi cousin Ajay. It is not possible to do phosphating without any dimensional reduction because, per John Donofrio in the Metal Finishing Guidebook, "The first reaction that occurs ... is the pickling reaction, which will dissolve some metal from the surface. On steel ... the pickling rate is in the range of 1-3 g/m2 of surface area treated ... This pickling reaction is essential for the coating formation ...". But if you run the numbers, this is very little metal -- well under a micron. Are you implying that your present manganese phosphating process is attacking the base metal? If so, there is surely something wrong.

Please do your best to describe your situation and your own findings from it so we can have an enthusiastic discussion of it here. Abstract questions can rarely garner anything but general guidelines; and there's little real value in our extracting these general guidelines from phosphating texts for you, when the first thing we're certainly going to say is that you should have the texts on hand yourself :-)

Luck and Regards,

pic of Ted Mooney
Ted Mooney, P.E. RET
finishing.com
Pine Beach, New Jersey
Striving to live "Aloha"



Manganese phosphate is not adhering to steel -- it rubs off

July 28, 2014

I was doing manganese phosphate on AISI4145 steel metal. After some pieces it is failing addition test (phosphate layer is removed). Can anyone tell why this happens?
The bath preparation is underground tank and heating coil is used to reach temperature required of 90 °C.

Suresh Thankappan
- Mussafah, Abudhabi, U A E



Must we check Ra BEFORE manganese-iron phosphating or AFTER?

August 7, 2014 -- this entry appended to this thread by editor in lieu of spawning a duplicative thread

Q. WE ARE IN THE LINE OF MANUFACTURING CAST IRON PISTONS. OUR COMPONENTS HAVE MIP COATING OPERATION AFTER FINISH. WE OBSERVE VARIATION IS SURFACE FINISH VALUES (Ra) AFTER MIP COATING GETS CHANGED TO HIGHER SIDE, AND NO CONSISTENCY IN READING. OUR QUESTION IS WHETHER THESE VALUES MUST BE CHECKED BEFORE MIP COATING.

ANIL KHOT
Engg. Works - karad, maharastra, India


August 2014

A. Hi Anil. Based on the context, I assume MIP means manganese-iron phosphating, so we assigned a title and appended your inquiry to this related thread. Phosphatization is a soft coating (compared to iron), and manganese phosphate is often used as a "break-in" coating ... so I would assume that the surface finish before phosphatizing is far more important than the finish after it.

Regards,

pic of Ted Mooney
Ted Mooney, P.E. RET
finishing.com
Pine Beach, New Jersey
Striving to live "Aloha"



Manganese phosphate & oil safe for kitchen knives?

April 28, 2015-- apologies; finishing.com misfiled this question, and didn't post it until June 20

Q. Dear Sir, I am a custom cutlery manufacturer and have been using Manganese Phosphate impregnated with oil as a corrosion inhibitor on knife blades for some time with good success. I would like to treat kitchen knives the same way, but have concerns about food safety. Is there any reason to suspect that manganese phosphate treatment of carbon steel might be non food safe?

Adam DesRosiers
- Juneau Alaska USA


June 2015

A. Hi Adam. First, I don't want to toss around the term "food safe" without agreeing what it means :-(

wikipedia
Food contact materials

Many materials that are not "poison" or "toxic materials" are not "food safe" either. For example, zinc is an essential micro-nutrient rather than a poison, but it can dissolve in acids or alkalis, possibly even resulting in an overdose, and it's not food safe by anyone's measure, even if you find no regulation forbidding it. Some of the laws & guidelines set limits on "dissolution" and manganese phosphate is probably not food safe simply by this definition.

Further, if you want to sell such a product there probably are FDA regulations that you can only use GRAS ("generally recognized as safe") materials; there might be NSF or some other applicable guidelines on appropriate materials as well. There are a boatload of regulations in the world today, and they are expanding rapidly; I would not be willing to say that anyone can offer anything for sale without a careful study of the laws regulating that trade.

Then too, what kind of "oil" are you speaking of? A few, like olive oil and mineral oil, are non-poisonous, but petroleum oils are poison.

Interesting question. I hope someone with specific tableware or kitchenware experience will respond.

Regards,

pic of Ted Mooney
Ted Mooney, P.E. RET
finishing.com
Pine Beach, New Jersey
Striving to live "Aloha"



June 20, 2015

Q. Hi,
Good times.
I am Hamidreza from Iran. Sorry that my English is not good.
I have read your article about manganese phosphate and the questions you had.
I do not know during tests of the mixing materials.
Also, after removing the piece of soluble phosphate, phosphate coating on the surface is easily separated.
My solution is mixed as follows:
Manganese carbonate 15 grams per liter
25 ml phosphoric acid per liter
2 grams per liter of nickel nitrate
3 grams per liter of iron sulfate
Sodium fluoride 0.7 grams per liter
Rochelle Salt 2 grams per liter
5 ml of nitric acid per liter
pH = 1.5
Temperature 95 °C
Time: 30 minutes

If possible, please help.
Grateful,

ali ahmad
- iran, tehran



Manganese Phosphating: Lost power for 5 minutes

October 30, 2015

Q. Hello Sir,
During manganese phosphating process if the power goes for 5 minutes and no DG, what are the quality issues can be raised.

S Raghavi
- bangalore,India



Different colour tones on finished Manganese phosphating product

November 12, 2015

Q. Dear Sirs, I am involved on the inspections of the manganese phosphating process. I would like to know if the difference in colour tones of the final coated surface be cause for rejection. Other parameters were within acceptable limits. In the project specs, it is stated that uniformity in appearance as acceptance criteria. Does it include colour tone for uniformity? What is the cause of this defect? And how to rectify?

Ng twuan Huat
Quality Inspections - Singapore


November 13, 2015

A. Good day Ng Tuan Huat.

Surely you are working toward a specification.
I work with a minimum/maximum coating weight requirement.
I would think the variations in colour tones is a process control issue.
You state all other parameters are within acceptable limits.
What are your parameters? Do you have a water-break free surface on the substrate before phosphating? Are you using an acid dip before phosphate? I have found dilute HCl to produce denser crystals.
Are you using a dilute chrome solution after phosphate, and if so, what is the concentration?
What is your free/total acid ratio? What is your iron concentration? What is the temperature?
All of these parameters affect the crystal structure of the deposit.
What is the substrate, and does it contain chromium, and if so,how much?" Max 2% will prove difficult.
Do you examine the deposit under a microscope to determine the density of the crystals? If so, can you see the substrate in between the crystals?
Are you conducting salt spray testing, and if so, what is the outcome?
There were only three questions in your posting, and I have posted you a total of eleven.
There are many variables involved to produce a uniform/acceptable deposit.
Hope this helps.

Regards,

Eric Bogner, Lab Tech.
Aerotek Mfg. Ltd. - Whitby, Ont., Canada



November 30, 2015

Q. I am facing a problem in distinguishing two washers having almost the same dimension and both are Manganese Phosphate coated. How can I ask the two source to make some visual difference? Please answer, it's urgent.

ARIJIT DAS
- JAMSHEDPUR, JHARKHAND, INDIA



Manganese Phosphate color variation within the same lot of parts

March 22, 2016

Q. I would like to know if anyone has experience with some steel parts that are manganese phosphate all together as part of a big lot show some brown/pinkish appearance

Rodrigo Ramos
- Salisbury, Maryland, USA
  ^- Privately contact this inquirer -^


March 23, 2016

A. Good day Rodrigo.

Good Info @ letter #26694. This web site has a plethora of info!

Regards,

Eric Bogner, Lab. Tech
Aerotek Mfg. Ltd. - Whitby, Ontario, Canada


March 2016

thumbs up signYes indeed, we have a plethora.

Regards,

pic of Ted Mooney
Ted Mooney, P.E. RET
finishing.com
Pine Beach, New Jersey
Striving to live "Aloha"



March 9, 2017

Q. Respected Sir,

We have a new coating plant and are going to perform Manganese Phosphate coating. Customer specifications are written as: Zn Manganese / Nickel Manganese / Manganese Coating for different parts. What is the difference in all above three or are all above same?

Are there different types of Manganese Phosphating?

Nitin Gunjal
- Pune, India


March 2017

A. Hi Nitin. Unfortunately you can't ask a third party to put a fine point on someone else's slang and casual phrasing. There is no way for me to know whether "Zn Manganese" is intended to mean "Zinc Phosphating with additional dicationic ions of manganese" vs. "Manganese Phosphating", or what exactly "Nickel Manganese" was intended to mean, or whether "Manganese Coating" was intended to mean "Manganese Phosphating". Guessing is not the way to proceed; you must get clarification and hopefully mutually agree to a more carefully worded specification.

Normally there will be additional criteria like salt spray hours for testing, coating weight, compliance with a specific standard number from a generally recognized organization like ASTM or ISO, etc. Good luck.

Regards,

pic of Ted Mooney
Ted Mooney, P.E. RET
finishing.com
Pine Beach, New Jersey
Striving to live "Aloha"



June 26, 2017

Q. Dear readers,

I have set up zinc phosphate and manganese phosphate coating plant in our company.

I wanted to know if we can distinguish parts which are zinc phosphate coated from those coated with manganese phosphate.

Karthik Padmashali
- Pune, Maharashtra, INDIA


June 2017

A. Hi Kathik. Tracking the parts seems a lot more practical than mixing them and then chemically testing every individual piece to re-separate them.

Although I personally have very low confidence in visual identification of finishes, I think only you can answer whether your people can reliably visually sort your specific zinc phosphate from your specific manganese phosphate. Sorry to be of no help :-(

Regards,

pic of Ted Mooney
Ted Mooney, P.E. RET
finishing.com
Pine Beach, New Jersey
Striving to live "Aloha"


July 20, 2017

A. Regarding visual identification of phosphate coatings:
Zinc phosphate coatings will typically exhibit a dark gray color. Manganese phosphate coatings will typically exhibit a dark black color.

Daniel Englebert
Imagineering Finishing Technologies - South Bend Indiana

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