Mill scale Cargo Ground Study

Mill Scale

Mill scale is the product of oxidation which takes place during hot rolling. The oxidation and
scale formation of steel is an unavoidable phenomenon during the process of hot rolling which
involve reheating of steel in a reheating furnace, multi-pass hot rolling and air-cooling in the
inter-pass delay times and after rolling.  Mill scale is usually removed by process water used for
descaling, roll and material cooling, and by other methods. It is subsequently separated by
gravity separation techniques.

The formation of oxide scale not only results in a significant loss of yield of steel, but also
deteriorates the surface quality of the steel product caused by rolled-in scale defects or
roughened surface. In addition, the presence of a hard scale layer on the steel can have an
adverse effect on roll wear and working life. The amount of mill scale generated in a rolling mill
depends on the type of the reheating furnace and on the practice of rolling adopted in the mill. It
is generally in the range of 1 % to 3 % of the weight of the steel rolled.

Mill scale is a layered and brittle material, composed of iron oxides with wustite as a
predominant phase. It is normally considered as waste material. From the chemical and physical
analysis performed on the mill scale, and with respect to the environmental concerns, mill scale
is non-dangerous waste and normally considered as a green waste.

Scale formed during the heating of steel to rolling temperatures in the reheating furnace is known
as primary scale. This primary scale is removed generally by hydraulic descaling before hot
rolling. The removal of the primary scale formed during the reheating operation before hot
rolling is usually done for producing steel products with high surface quality and for reducing
roll wear. However, secondary scale continues to form on the descaled steel surface during the
inter-pass delay time in the roughing and intermediate rolling mills. The color of primary mill
scale is generally bluish black while that of the secondary scale is blue.  The secondary scale
gives the steel an appearance which is like that of a lacquer coating finish.

Properties of mill scale

Under visual inspection, mill scale appears as a black metal powder made up of small particles,
flake, and chips. Its physical state is solid and powdered. The bulk density of mill scale is in the
range of 5.7 tons/cum while the specific gravity is 6.2. The melting point of mill scale is around
1370 deg C and the boiling point is around 2760 deg C. It has a stable state. It is insoluble in
water and alkalis but soluble in most of the strong acids. It is normally classified as non-
dangerous waste material.
Mill scale particles, flakes, and chips are brittle and have low mechanical strength. They easily
break hence the stockpiles of mill scale are likely to be made up of varied particle sizes. Mill
scale is not combustible. Under normal conditions, fire and explosion hazards are not associated
with the mill scale.

The mill scale does not generally contain any dangerous, inflammable, radioactive or explosive
substances. The material is free of dirt, nonferrous metals, or foreign material of any kind, and
excessive rust and corrosion.

The iron in the primary mill scale is usually present in different chemical forms. The primary
scale has three layers of iron oxides consisting of wustite (mostly FeO), magnetite (Fe3O4), and
hematite (Fe2O3) from the metal surface outwards.

Wustite is the inner most phase of the scale which forms next to the metal and is the Fe rich
phase. It has the lowest O2. It is represented as FeO, and is not stable below around 570 deg C.
However, its content in the scale increases with increasing temperature and occupies around 95
% of the scale layer when the steel temperature is above 700 deg C. The density of wustite is
around 5.87 g/cu cm. Wustite exists as a thermodynamically stable, single phase structure, over a
wide range of composition. The non-stoichiometry of wustite increases with increasing
temperature and does not seem to reach the stoichiometric composition FeO. Compared to the
other scale phases and the steel itself, the wustite phase has a relatively low melting point, which
is from 1370 deg C to 1425deg C. Melting of the wustite layer (washing) accelerates the scale
formation rate and increases the grain boundary penetration. This not only reduces the surface
quality, but also increases the fuel consumption of the furnace and reduces the yield.

The magnetite phase, Fe3O4 is the intermediate phase of the scale. It is the main equilibrium
constituent of scale below 500 deg C. It has a density range of 5 g/cu cm to 5.4 g/cu cm. It exists
as a metal deficient oxide but at a much smaller level than wustite. It has been shown from
various studies that both cations and anions diffuse in Fe3O4. As the temperature increases to
around 700 deg C, wustite formation takes place at the expense of the magnetite phase and at
elevated temperatures, magnetite occupies only around 4 % of the total scale layer. Magnetite is
harder and more abrasive than wustite.

The hematite phase, Fe2O3 is the outer most layer of the scale and has the highest oxygen
content. It forms at temperatures above around 800 deg C. The density of hematite is around 5.24
g/cu cm. Hematite occupies around 1 % of the total scale layer at high temperatures. As with the
magnetite phase, hematite is hard and abrasive.

The secondary mill scale is composed of iron oxides which predominantly consist of ferric oxide
(Fe2O3). The thickness of this oxide layer is normally less than 0.1 mm. It initially adheres to the
steel surface and protects it from atmospheric corrosion provided no break occurs in this layer.
Since secondary scale layer is electro-chemically cathodic to steel, any break in this scale layer
causes accelerated corrosion of steel exposed at the break. The secondary scale layer is thus a
boon for a while since it protects the steel against corrosion. However, this protection disappears
when the coating breaks due to handling of the steel product or due to any other mechanical
cause.
Mill Scale has been classified has an UVCB material (unknown or variable compositions,
complex reaction products and biological material) since it is made of many constituents and its
composition can change according to the steel plant production (reinforcement bar, special steel
etc.). It can contain C, Si, Ca, Na, Al, Mn and other metal oxides. The allowable limit for oil
content in the mill scale is less than 1 % for all uses except batteries and melting charge for
which up to 3 % is allowed. Typical average chemical analysis of mill scale is given in Tab 1.

Tab 1 Typical average chemical composition of mill

scale
Sl.
Element Unit Value
No.
1 Fe % 71.1
2 P % max 0.06
3 S % max 0.1
4 Al2O3 % max 1
5 SiO2+CaO % max 1.5
6 MgO % 0.2
7 Na + K % 0.3
8 Si % 0.61
9 Ca % 0.44
10 Ti % max 0.05
11 V % max 0.05
12 Cr % 0.072
13 Mn % 0.059
14 Co % max 0.05
15 Ni % 0.0034
16 Cu % 0.0011
17 Nb % max 0.05
18 Mo % 0.0008
19 Sn % max 0.05
20 Mg % 0.12

The components and the micrograph of mill scale is shown in Fig 1

 Fig 1 Components and micrograph of mill scale

The size of Mill scale normally varies from dust size in microns up to usually 6 mm. The typical
size analysis of mill scale is given in Tab 2.

Tab 2 Typical size analysis of mill scale

Sl.No. Size Unit Value
1 More than 8 Mm 0.4
2 6 to 8 Mm 0.6
3 4 to 6 Mm 3.8
4 2 to 4 Mm 27.2
5 0.5 to 2 Mm 32.0
6 Less than 0.5 Mm 36.0

Mill scale is a nuisance when the steel is to be processed. Any coating applied over it is wasted,
since it comes off with the scale as moisture laden air gets under it. All mill scale needs to be
removed to present a uniform and clean surface of the substrate steel for any application of any
coating on the steel.

Removal of mill scale is virtually impossible by hand. It is extremely tedious and time-
consuming using power tool cleaning methods. Neither of these two methods gives a good base
to start. Steel from the hot rolling mills has no surface profile, which is most important to the
overall adhesion strength and integrity of the coating system. Mill scale is normally removed
from steel surface by flame cleaning, pickling or abrasive blasting. These methods remove the
mill scale and provide a surface profile that gives the coating system its design requirements.
Coating over mill scale, however tempting, is a futile exercise, as the presence of mill scale on
the steel surface accelerates the corrosion of the underlying steel.

Uses and recycling of mill scale

Mill scale though has a high-level content of iron (68 % -72 %) yet it is still considered as an
industrial waste in the form of iron oxide mainly because it gets contaminated with water and oil
during the process of rolling. Most of the mill scale in a steel plant is recycled in the production
of either iron ore sinter or iron ore pellets which are used either for reduction in iron making
furnace. It is also used as a coolant in a steel making furnace. Mill scale recycling is also being
done by briquetting it after mixing with a binder.

Mill scale is also used as a raw material in granular refractory. When this refractory is cast and
preheated, mill scale provides escape route for the evaporating water vapor, thus preventing
cracks and resulting in a strong monolithic structure.

Besides the above uses, several other uses for mill scale have been developed. The main uses of
mill scale include (i) negative electrode for alkaline storage batteries, (ii) preparation and use of
catalysts, (iii) in the production of cement clinker, (iv) in the preparation of heavy concrete and
heavy weight aggregates, (v) composite counterweights for washing machines, (vi) in the
production of ferro phosphorus and ferro molybdenum, (vii) in steel foundry and heat treatment
of castings, (viii) in making flux for welding electrode coating, (viii) synergistic agent for mixed
fertilizer and material for phosphate fertilizer, (ix) in the production of iron powder for powder
metallurgy, (x) in the production of friction materials, (xi) in the manufacture of colored glass,
(xi) in the production of Iron oxide pigments, (xii) in the method of making mineral wool, (xiii)
in the iron oxide paint pigment precursor, (xiv) as an electromagnetic radiation shielding
material, (xv) as a component of materials for road construction, (xvi) in the preparation of some
refractory mixes, (xvii) in the treatments of water and soil, (xviii) in the production of
exothermic powders. The different uses of the mil scale are shown in Fig 2.

Fig 2 Different uses of mill scale

Matters associated with the shipping of mill scale

Mill scale is being increasingly exported as a bulk cargo in 5he international trade. However, in
order to have mill scale fit for sea carriage, the stockpile is always typically accumulated at the
port from different sources. This mill scale, having different particle sizes due to the way the
material has been previously handled results into the individual stockpile at the port not
homogeneous. This indicates that no two consignments do have same characteristics, even if
these consignments have come from the same port or shipper. Further, mill scale is also a cargo
which tends to drain water easily, accumulating at the bottom of a stockpile to form a wet base?

Mill scale is traded effectively in the same way as primary mined iron ore fines since the
physical nature of mill scale is like primary mined iron fines.  However, it is to be noted that the
mill scale is not a proper? bulk cargo shipping name? (BCSN) under the IMSBC (International
Maritime Solid Bulk Cargoes) Code. It is a cargo that is not listed in the IMSBC Code.  IMO
(International Maritime Organization) Circular DSC.1/Circ.63 of 12 October 2010 states that
iron ore fines are a cargo that may liquefy and are therefore a? Group A? cargo.? Group A?
cargo under the IMSBC code is a cargo that may liquefy if shipped at moisture content in excess
of its transportable moisture limit (TML). The terms of this circular also apply to mill scale even
though mill scale is normally carried in a dry condition with moisture content below its TML.

Though the mill scale cargo is not listed in the IMSBC Code, Section 1.3 of the IMSBC Code
specifies that unlisted cargoes, such as mill scale, should only be accepted for loading provided it
is accompanied by a certificate issued by the national competent authority, stating the
commodities suitability for seagoing carriage, of the country of the port of loading.

The IMSBC Code also warns about the potential liquefaction hazard of all fine-grained mineral
cargoes shipped with inherent moisture content, regardless of whether the cargo is specifically
identified as a Group A? cargo in the Code.  Appendix 3, Para 2.1 of the Code states; “Many
fine-particle cargoes if possessing a sufficiently high moisture content are liable to flow”.  Thus,
any damp or wet cargo containing a proportion of fine particles should be tested for flow
characteristics prior to loading.

Mill scale does have fine particle sizes with significant inherent moisture content and fall
therefore within the scope of this provision.  Therefore, mill scale cargoes are treated as cargoes
that may liquefy unless testing shows otherwise.  For Group A? cargoes, SOLAS (safety of life
at sea) and the IMSBC Code require shippers to provide the Master with a certificate of the
moisture content and the TML prior to loading.

Mill scale frequently shows a wet base.  This occurs when the material drains well and
accumulates water at the bottom of the stockpile.  Because of this drainage, the upper sections
can appear quite dry. The wet base nature of mill scale makes it vital that any moisture sampling
prior to loading does not just focus on the surface area of any stockpiles, and that a fully
representative sample is taken. The need for representative sampling is also vital for the
determination of the TML, particularly due to the variable nature of the material.  In order to
sample stockpiles mechanical excavators are necessary as manually digging into the piles is
impossible.
Also, because of the high density of mill scale cargo, the trimming requirements as detailed in
the Code are that it should be trimmed flat for the voyage to distribute the weight evenly across
the tank top.  Wet base cargoes are prone to cargo shift as the bottom liquefies and the top of the
high-density stow becomes free to slide around over the wet base.  The only remedy for this is to
trim the cargo properly.