Surface & Coatings Technology 203 (2009) 2912–2915

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Surface & Coatings Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s u r f c o a t

Study on formation of “easy to remove oxide scale” during mechanical descaling of

high carbon wire rods
A. Chattopadhyay a,⁎, P. Kumar b, D. Roy a
a
Research and Development Tata Steel, Jamshedpur, 831007, India
b
Indian Institute of Technology, Kharagpur, 721302, India

a r t i c l e i n f o a b s t r a c t

Article history: Oxide layer in high carbon wire rods are not completely removed by the mechanical descaling process.
Received 22 December 2008 Formation of hematite causes poor mechanical descaling whereas magnetite and wustite are found to be
Accepted in revised form 5 March 2009 non-adherent oxides which can be more readily removed. Oxide formation at high temperature has been
Available online 16 March 2009
studied using Gleeble simulation and it is found that a high laying head temperature (LHT) followed by faster
cooling reduces the formation of the hematite layer. Based on this observation, plant trails have been
Keywords:
High carbon wire rods undertaken and a lower amount of adherent oxide has been observed.
Gleeble simulation © 2009 Elsevier B.V. All rights reserved.
Oxidation
Raman spectroscopy
Mechanical descaling

1. Introduction
Oxide scales, which are deposited on the surface of the steel wire
rods during the process of wire rod rolling need to be removed before
any further processing like wire drawing. Initially the de-scaling
process was used by the pickling process using hydrochloric acid. But,
nowadays due to the stringency of laws favoring environmental
protection, the use of HCl is being discouraged. A lot of emphasis is
therefore being laid for employment of alternate methods of
descaling. One such process used is mechanical descaling. Other
modern methods are also employed today for mechanical descaling
purpose in wire rod mills like reverse bending procedure. [1,2].
It becomes essential for the mechanical descaled wire rods to have
scale free surfaces to be able to prevent wear and abrasion of dies
during the wire drawing operations. Subsequently, in order to meet
this requirement, engineering the development of desired scale
structures becomes a necessity. The laying head temperature (LHT)
and cooling rate at the Stelmor conveyor significantly influence the
formation of different oxide phases in the scale namely, wüstite (FeO),
magnetite (Fe3O4) and hematite (Fe2O3) as shown in Fig. 1 [1–5]. The
latter two types of oxide are not desirable for both mechanical
descaling and pickling point of view [6–9]. Though the mechanical
descaling process is mainly designed for low carbon wire rods, yet for
its application in high carbon wire rod detailed study on the oxide
formation at high temperature for high carbon wire rods is required.
Mechanical descaling process is unable to remove all the oxides
⁎ Corresponding author. Tel.: +91 9204058840.
E-mail address: bhoda29@yahoo.co.in (A. Chattopadhyay).
present at the surface of high carbon wire rod surface. As a result of
which of which die life gets affected during subsequent process.
The present paper aims at optimizing the process conditions
during the cooling of wire rods by simulated laboratory tests to favor
the formation of easily removable oxide scale during mechanical
descaling of high carbon wire rods. Although the transformation of
oxide under forced air cooling in simulated lab condition is known [1],
the literature on industrial process is very limited [10,11].
2. Experimental procedure
In order to determine the chemical composition of the adherent
oxides after mechanical descaling a sample wire rod (whose
composition is given in Table 1) from wire rod mill of Tata Steel was
taken. During mechanical descaling most of the oxides get removed.
These oxides are collected separately as powder which is analyzed
later on. In order to study the high temperature oxide formation on
the high carbon wire rods, the samples obtained from the plant were
cut into pieces of 5.5 cm length having 8 mm diameter. Subsequently
the samples were pickled in 15% HCl solution with 0.1% inhibitor
(polyamine based) to remove all the scales on the sample.
The oxide scale formation was simulated using Gleeble-1500. The
different thermal profile maintained at Gleeble-1500 is given in
Table 2. Initially the samples were heated to 1200 °C and hold for
austenitising (cooling rate not important) and then cooled to 1000 °C
in 20 s (rate not important). During heating process the Ar
atmosphere was maintained inside the simulator so that oxidation
during heating could be prevented. After reaching 1200 °C, air having
80–85% relative humidity is introduced into the chamber and Ar gas
was withdrawn simultaneously. After that, cooling from 1000° to 860°

0257-8972/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2009.03.006
 A. Chattopadhyay et al. / Surface & Coatings Technology 203 (2009) 2912–2915 2913

Table 2
Details of thermal profiles maintained in Gleeble.

Laying head temperature Different cooling rates Corresponding Stelmor end

(LHT)(°C) used (°C/s) temperature (°C)
880 7.86 600
8.02 575
8.24 550
860 7.56 600
Fig. 1. Macrophotograph of mechanical descaled wire rod showing adherent oxides. 7.70 575
7.88 550
840 7.07 600
(precise rate 140 °C/s) is carried out. Finally, heat transfer model 7.16 575
7.27 550
predicted cooling rate is maintained and it is kept limited up to the 820 6.92 600
end of Stelmor cooling i.e. up to 600–550 °C, followed by conventional 7.02 575
forced air cooling. The Stelmor end temperature is restricted up to 7.11 550
550 °C because, as per the thermodynamic condition the possibility of
hematite formation is higher below 550 °C and the growth rate and
phase transformation of oxide scale are negligible. Prior to the thermal Fig. 3 depicts the typical thermal profile predicted by the heat
simulation in Gleeble, scale free rods were welded with two transfer model used in wire rod mill following which Gleeble
thermocouples made of chromel–alumel. Samples were heated and simulation is carried out. After the Gleeble simulation the oxide
cooled with the given thermal profile as predicted by heat transfer composition and their relative amount is measured by semi
model used in the wire rod mill. quantitative reitveld method using GAXRD and the result is shown
The oxide scales were formed on the surface of the wire rod in Fig. 4 a and b. The result of faster cooling rate is plotted in Fig. 4a.
samples are analyzed by using Raman Spectroscopic Analysis [12].
Laser Raman spectrometry was carried out on different samples with a
Renishaw Raman System RM 1000B coupled with a Leica DMLM
microscope. Excitation of the sample was achieved with a 20 mW
diode Laser source of 785 nm wavelengths and filtering of the Rayleigh
scattering was achieved through an edge filter at 200 cm− 1 cut off
that allows study of Raman scattering only on the Stokes side of the
spectrum. Power at incidence on the liquid surface was about 8 mW
with laser spot size of about 1.5 µm. For identification of the Raman
peaks obtained from Raman Spectroscopy study standard database
available is used [13]. The oxide layer is further analyzed by Glancing
angle X-Ray Diffraction (GAXRD) using Cu Kα. Phase quantification is
done by using semi quantitative reitveld method. The step size [°2Th.]
maintained in the X-Ray diffractometer is 0.1000 and scan step time
[s] is 1.0000. Scan type is continuous in nature and divergence slit size
[°] is 6.2899. In Reitveld method, each measured data point is
considered as an independent information parameter and least square
fitting is done on the whole pattern by high score plus software. Next,
refinement on crystal structure related information i.e. unit cell
parameters and atomic co-ordinates is carried out. Beside this
refinement due to instrument related parameters like peak profiles,
zero shift, sample height etc are also prepared.

3. Results and discussion

Wire rod sample (Fig. 1) taken just after mechanical descaling has
shown some adherent oxide scales at the surface. The adherent oxides
and oxides collected from below the mechanical descaler are both
analyzed under Raman Spectroscope and results are shown in Fig. 2a
and b respectively. Fig. 2 a shows that adherent oxide is hematite
(αFe2O3 and γ Fe2O3) in nature whereas Fig. 2 b shows that the oxides
powders collected from below the mechanical descaler are wustite
(FeO) and magnetite (Fe3O4) type of oxides. Later types of oxides are
non-adherent in nature. Formation of FeO and Fe3O4 type of oxides are
favorable for high carbon wire rods which pass through mechanical
descaler route.

Table 1
Chemical composition (wt.%) of the wire rod used for the experiments.

C Mn Si P S Cu Ni Cr Al
0.81 0.8 0.3 0.015 0.01 0.05 0.05 0.05 0.05 Fig. 2. Raman spectroscopy results (a) adherent oxide scale (b) powder scale collected
from mechanical descaler.
2914 A. Chattopadhyay et al. / Surface & Coatings Technology 203 (2009) 2912–2915

From Fig. 4a it is evident that at lower LHT, the amount of hematite has
increased significantly. As per the oxide stability diagram [9] it is
found that, only magnetite and wustite is stable at high temperature.
However, since during the cooling process, equilibrium diagram is not
maintained properly the hematite formation also takes place. But at
higher LHT it is observed that the formation of hematite is
significantly low. The variation of magnetite at different cooling rate
at different LHT is shown in Fig. 4 b where each data point corresponds
to a particular LHT followed by particular cooling rate as described in
Table 2. From Fig. 4 b it can be observed that at faster cooling rate the
amount of magnetite is almost always higher compare to other two
cooling rates. At high temperature as wustite and magnetite scales are
stable and dominant. As the cooling process progresses, the tendency
of these oxides to decompose to form hematite starts. If cooling rate is
maintained high then the time for decomposition of high temperature
scales to form hematite is very low and therefore, higher amount of
magnetite is observed. Whereas, for slower cooling rate chance of
hematite formation is higher and as a result of which lower amount of
magnetite is observed. Phase transformation in oxide scale depends
on various factors like availability of oxygen, cooling rate etc. As the
complete process takes place in normal air condition therefore the
availability of oxygen is not a critical factor to be considered. In this

Fig. 4. Quantitative analysis obtained from semi reitveld method (a) relationship
between % Fe2O3 with LHT for high cooling rate (b) relationship between % Fe3O4 with
LHT for various cooling rates.

type of condition, only cooling rate plays important role in determin-

ing the oxide scale composition.

4. Conclusions

So from the above made discussion following conclusions can be

derived:

1. Fe2O3 is responsible for adherent oxide formation. This type of

Fig. 3. Thermal profile maintained in Gleeble simulation to simulate LHT and stelmor
condition (a) LHT 860 °C and stelmor 550 °C (b) LHT 820 °C and stelmor 550 °C.
oxide causes problem during mechanical descaling process.
2. During Stelmor cooling faster cooling is preferable because at
higher cooling rates the amount of adherent oxides formed is less.
Fe2O3 forms as a decomposition of higher temperature oxides like
FeO and Fe3O4. Because of faster cooling the time needed for
decomposition is less as a consequence of which less Fe2O3 forms.
3. Laying head temperature should be kept near 880 °C because at this
temperature the oxide scales contain less of Fe2O3. At higher
temperature the chance of decomposition of high temperature
oxide is less and subsequently less Fe2O3 forms.
Based on the above observation one plant trail had been conducted
and the result of plant trail confirms the above observations. The
amount of Fe2O3 has come down significantly with higher LHT and
faster cooling rate.
 A. Chattopadhyay et al. / Surface & Coatings Technology 203 (2009) 2912–2915
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