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What exactly is Mill Scale?

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Q. My name is Frank Rea. I am a coatings consultant, predominately for steel structures. Arguments with contractors about mill scale are common. In order to discuss this issue knowledgeably I would like to know:
What is the chemical composition of mill scale?
Does it vary by process?
Are there primary constituents that must be present for a substance to be classified as mill scale.

thank you

Francis Rea
Consultant - Gainesville, Florida


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A. Mill scale consists primarily of magnetite, Fe3O4, of characteristic blue-gray "steely" color.
An extremely thin outer film of hematite, Fe2O3, is invisible to the naked eye.
The inner portion of the magnetite contains fine metal grains and sometimes, residual black FeO (see below), which contribute to the roughness of descaled metal. Mill scale is found on all hot-rolled steel products unless processed in a protective atmosphere or descaled (e.g., for galvanizing).

At hot rolling temperatures, an inner layer of wüstite, FeO, exists between the steel and magnetite.
"At elevated temperatures, FeO constitutes about 85% of the scale thickness, Fe3O4 about 10 to 15% and Fe2O3 about 0.5 to 2%. During slow cooling [below 1040 °F] of hot-rolled coils of hot-rolled strip [and heavy shapes], most of the FeO is transformed to Fe and Fe3O4, and the latter oxide is predominant after cooling."

--- The Making, Shaping and Treating of Steel, 10th Edn., p. 1083 (1985). ISBN 0930767004.

The alloying metals form cations within the mill scale at about the alloying proportions* due to the almost instantaneous oxidation of freshly exposed metal at high temperature. Fe3O4 contains both Fe+2 and Fe+3, and is sometimes written FeO·Fe2O3. Ni+2 substitutes for Fe+2, Al+3 and Cr+3 substitute for Fe+3. Thus, (Fe,Ni)O·(Fe,Al,Cr)2O3. Cations of other valences, e.g., Si+4 and Ti+4, are accompanied by cation vacancies to maintain overall electrical neutrality. With very slow cooling, small grains of Si- and Ti-containing oxides may precipitate within the scale.
*unlike general heating or heat treatment scale, where Al, Cr, etc. preferentially oxidize.

Steel mills descale sheet and plate by passage through scalebreaker rolls, which flexes the metal enough to fracture the scale. This allows pickling acid (HCl) to attack the more soluble (partially transformed) inner wüstite layer.

Ken Vlach
- Goleta, California  

Ken received a special
"Contributor of the Year" award
from finishing.com for his numerous
helpful and well researched responses


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Q. My name is Dr P K Maitra, (formerly G M ,Q/A & head R&D, BALCO), in past I have communicated & interacted through Finishing .com.
I have read the letter No 38657 of Mr KEN VLACH Dec 20-2005, & appreciated the efforts being done by Finishing.com & through this platform I want to ask & reply or propagate the information for future compilation for valuable readers.

Dr Pradeep Kumar Maitra
- Chhattisgarh, INDIA

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Ed. note: Thanks for the kind words, Dr. Maitra. You are welcome to attributed fair use, of course, and to mention my name ... but unless individual responders reply to your offer, we certainly can't speak for them regarding their permission to use their name in a different forum or media.



April 20, 2008

Q. I am particularly concerned about the effects of Mill Scale if left in place and painted over. Does it have any long term negative effects on the steel or subsequent paint or coating surfaces. Secondly if left in place and painted how can in be removed in the field.

Gary Kopp
- Barrie, Ontario, Canada


February 10, 2009

A. In response to the question on whether or not mill scale on hot rolled steel is detrimental, I would submit that is very much so as it is anodic to the steel. Meaning that once moisture enter the picture the steel corrode (rust) and not the mill scale. Which is why the most protective coating products designed for immersion and other tough environments require an SSPC SP-5 white metal degree of cleaning as this process removes all mill scale.

Burt Olhiser
- Middletown, California


February 16, 2009

A. When you are applying a coating to a steel surfaces in order to produce sufficient adhesion against corrosion it is necessary to remove all contaminants off the surface. Mill scale is porous and poorly adherent scale of magnetite, it will only give limited short term protection to steel against corrosion. If you are coating any steel surface against corrosion it is necessary to blast clean (with garnet or similar) to a finish of Sa2.5 blast standard before coating.

Regards

Vijay

Vijay Vijayaraghavan
- Adelaide, South Australia, Australia



July 14, 2008

Q. As per some friends, the mill scale can be used in production of steel production, put in the trench when steel liquid get out, thus it will automatically smelt in the liquid, and no wastage, steel still proper, want to know if it is the best way to use mill scale?

Howard Li
mineral resources development - Tianjin, P.R China


October 25, 2008

Q. Is there any free iron available in typical Mill scales.

Dr. Zubair Alam
Chemist - Al Khobar, Eastern Province, Saudi Arabia



May 14, 2010

Q. If you are installing heavy, rotating equipment what are the policies for the base plates, regarding mill scale. I have been taught that it is poor engineering practice to install equipment on a mill scale surface. Can anyone corroborate my thinking.

Les Pulman
Engineering - U.K.


May 17, 2010

Hi, Les. It may depend on what type of equipment, but to the limits of my experience base plates are always painted, and to properly paint them requires removal of mill scale.

Regards,

pic of Ted Mooney Teds signature
Ted Mooney, P.E. RET
finishing.com
Pine Beach, New Jersey

May 18, 2010

Ted,
The base plates support a Gas Turbine weighing 370 tonnes. If the Mill Scale is on the plates, under vibration, the scale breaks down to dust and effectively leaves a void. The underside of the plate is coated with scale also and sits on a cementitious grout. The grout is water based which could result in the Mill Scale separating from the plate.

Les Pulman
Engineering - Wales U.K.


May 18, 2010

Hi, Les. I never designed in that field and can't comment on codes or standard practices for heavy gas turbines, but I do agree with you in general that steel structures require removal of mill scales, and that same opinion has already been offered here by Burt Olhiser and Vijay Vijayaraghavan. Good luck.

Regards,

pic of Ted Mooney Teds signature
Ted Mooney, P.E. RET
finishing.com
Pine Beach, New Jersey

May 18, 2010

It is easy to understand why the oxides form in a specific sequence in a mill scale. The highest oxide (the one with maximum proportion of oxygen) forms on the surface as it is directly exposed to air (the source of oxygen) and the lowest oxide forms next to the base metal (the source of Fe). However, the lowest oxide, FeO, is said to form only above 570 °C. Therefore, its presence could be indicative of the scale being mill scale, which might be easy to confirm if FeO is retained at room temperature, without further oxidation to a higher oxide, for sufficiently long time.

If only mill scale was dense, adherent and continuous it could have provided necessary protection against corrosion but unfortunately it is not. Moreover, it is cathodic (and not anodic like zinc) to iron and hence will corrode much faster at locations of discontinuity due to unfavorably large area ratio of cathode to anode. In such a case, a bare metal surface might be better than a discontinuous mill scale (or any other cathodic coating) as the former will corrode more uniformly as against the possible severe localised corrosion of the latter.

Dr. Azharul HAQ
- Sydney, NSW, Australia


August 17, 2010

I have a question about what happens to make scale? What is the chemical reaction that happens?

Gus Wimmer-Brown
- St. Louis, Missouri, U.S.A.


June 11, 2011

Comments on applying finishes over mill scale gave me a sculptor's idea. I don't fight Mother Nature, I leave my outdoor steel sculptures to develop a handsome rust finish. So, if I was to remove some of the mill scale selectively, in a decorative pattern, the finished piece might develop a pattern as parts rust differently. However, would the mill scale and non-mill scale rust soon catch up with each other and soon look the same?
I posted an earlier question with no response - whether applying a rust converter in a selected pattern on a rusted surface would also allow you to add visual interests or does the rust margin creep under and push off the converted rust?

Ed Russell
- Plymouth Massachusetts US


May 18, 2012

Q. I want to remove the oil from the mill scale; does anybody have an approved process which can cost less than 10 dollars/ton?

Vk Murarka
Engineering Company - Marion, Ohio, USA


July 10, 2012

A. Hi Vk. Murarka,

Just some ideas to your question for de-oiling mill scale:

There are really many different processes. One method is using water to separate the oil content from the solid by high shear agitation. I refer you to the following US patent for details: US Patent 5047083, "Process for de-oiling mill scale".

Another patent suggests a mixing the mill scale with calcined lime followed by a burning process to form pellets. Please see US patent 4326883.

Regards,

Amir Moezzi
engineering - Sydney, Australia



October 4, 2012

Q. What is the effect of steel mill scale on shear blade if the steel plate is sheared without pickling or shotblasting.

Mohankrishna G
- Jamshedpur, India

December 19, 2012

Q. Hello: I want to briquette Mill Scale Dust removed from a Shot Blasting Operation. Can these briquettes be used as material to be remelted for Industrial Steel Manufacturing in EAF type of process? What are the pros and cons?

Brian Lehane
- Ramos Arizpe, Coahuila, Mexico


July 3, 2014

All about mill scale . . .

Mill scale immediately starts at the steel making stage of casting hot metal steel grades and steel alloys when the metal is in a liquid stage. The mill scale chemistry will be the exact makeup of the steel and/or steel alloys being made. It is the outer skin of the casting and is formed by the rusting of the iron as it is exposed to the humidity and Oxygen of the air. Steel makers allow this to occur as it will form a protective coating from further rusting to occur for a period, normally 1 mm per year under normal ambient conditions. Sometimes it is forced to occur by a light spray of moisture. As indicated it will slow the development of further rusting but will not stop it and an additional 1mm per year will be expected on normal high carbon steel. Any crack or hole in the mill scale to reach the base metal will continue the rusting effect. Salt air will hasten rusting.

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I am continuing my response on mill scale, if I may . . . In addition to the explanation on where mill scale comes from and how it forms -- mill scale is sold on the commercial and international exchange mainly to the Chinese steel makers that use low quality iron ores either domestically mined or purchased. The Chinese steel makers then mix the mill scale with the low quality iron ore and prepare it for feed to a sinter plant, whereas the iron ore is mostly less than 60% Fe and the mill scale is around 70% Fe. How much they add is dependent on their steel making processes. Mill scale can be used in other iron ore preparation for steel making but it may require crushing and grinding it to very specific sizes and too expensive or it can be briquetted and used directly. If it is used directly the further preparation and processes to use it would have to be scrutinized to ensure that it would be efficient and economic to do so. It would be beneficial to use it as it is the highest quality iron oxide available. Mill scale production is equal to 1% of all cast steel in the world. Today on an annual basis with1.4 billion tons of steel cast worldwide, that means there is produced around 10 million tons of mill scale per year. Today only about 1/2 million to 1 million tons or so are commercially exchanged. It should be noted to remember that all mill scale will include the exact makeup of the cast metal or steel and alloys. Meaning that if there are any other ingredients in the steel, carbon, any alloy or additive it will also be in the mill scale. Another question I noted was about finishing: it absolutely must be removed prior to any use of the steel and/or finishing. As it starts out to be a protectant it is also the beginning of rusting and over time the steel must be protected from itself. From the casting metal it is removed before further processing, rolling or drawing as the mill scale will damage other equipment in the processes and can cause early failure of any component.

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Further to my previous 2 blogs on mill scale, I seem to find more information in my aged brain, therefore, I wish to explain what it looks like after it is removed from the steel and what to do with it. In a rolling mill where the steel will be stretched and squished the mill scale will first be removed mostly by water jets, or by sand blasting in some shops or by vibrating rolls in others and the mill scale will fall into a pit below the equipment where it will also be joined by rolling mill lubricants and bearing oils and water. From there it will be pumped to a holding pond, where companies like Harsco will be paid by the steel mill to clean out the pond once in awhile and get rid of the mill scale. In the U.S. in the past, and only a few short years ago it was dredged up and let drip dry and sold to a bidder, normally a cement plant who bought it for a very low amount and processed it to use in cement making since they require a little amount of iron in their processing and mill scale hit the mark. However a few years ago the EPA found that some of the ingredients, mostly from the lubricants from the rolling mill oils, caused the mill scale to be a hazardous material. The cement plants looked for other sources of the iron and mill scale became a personna non-grata. As the international market place for mill scale was taking off with China purchasing it as previously indicated, it is now an out to send the hazardous waste there and let them deal with it. This is not very neighborly, to say the least, so a few companies have come up with alternatives. One is to compress the mill scale into giving up the oils and lubricants and water to an acceptable level for the feed to the sinter plant where the mill scale is mixed with other iron ores and hydrocarbons from coke plants and bake it at 2500 °F. The squished out oils and lubricants by the way are recycled to be used once again. As far as recycling it to make other steel, the answer is yes it is being done at steel mills that employ a sinter plant. There are 7 in the U.S. and almost all steel mills in Europe, China and other places like India employ them with the use of the blast furnace to make steel. Other plants that use the EAF (electric arc furnace) cannot use them as it would take an ungodly amount of energy to extract the iron from the mill scale unless it were put through a major amount of preparation and chemical reduction first. There is also the consideration of what are the elements that are in the mill scale. Remember, I indicated that every bit of mill scale represents the product being made at the steel mill whether it is construction grades of steel like rebar or high quality alloys and stainless for example. Therefore if a steel mill wants to make rebar and they buy mill scale from the open market and it comes from an alloy shop what do they do with the other elements and how do they get it out? That costs money and lots of it for the procedures and the equipment and the chemicals to eliminate the unwanted stuff. So, further processing and experimentation and trials and tribulations must be done to be able to recycle and use all of the 10 million tons per year and growing.

Thomas J Coyne jr
T.C.Inc. - Estacada, Oregon, USA


July 2014

thumbsup2 Wow! Finishing.com has received thousands of helpful postings, but this is the most thorough and exhaustive in many years. Thanks!

Regards,

pic of Ted Mooney Teds signature
Ted Mooney, P.E. RET
finishing.com
Pine Beach, New Jersey

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