Materials Research Innovations

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Novel surface treatment for 316L stainless steel

using magnetisation technology

X. Q. Cheng, C. F. Dong, X. G. Li & W. D. Li

To cite this article: X. Q. Cheng, C. F. Dong, X. G. Li & W. D. Li (2013) Novel surface treatment
for 316L stainless steel using magnetisation technology, Materials Research Innovations, 17:7,
557-560, DOI: 10.1179/1433075X13Y.0000000101

To link to this article: http://dx.doi.org/10.1179/1433075X13Y.0000000101

Published online: 06 Dec 2013.

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 TECHNICAL NOTE
Novel surface treatment for 316L stainless
steel using magnetisation technology
X. Q. Cheng*, C. F. Dong, X. G. Li and W. D. Li
A novel surface treatment for 316L SS by using magnetisation was studied, and the effects on the
electrochemical behaviour and semiconductor properties were measured by potentiodynamic
polarisation, electrochemical impedance spectroscopy (EIS) and Mott–Schottky analysis in
3?5 wt-% NaCl solution. The results showed that the open circuit potential, corrosion potential Ecorr
and charge transfer resistance Rt of the specimen markedly increased after the magnetisation
treatment, while the passive current Ip decreased. Mott–Schottky analysis indicated that the donor
densities of the passive films on the treated and untreated specimen are 3?8361027 and
5?0961027 m23 respectively. In addition, the flat band potential of the treated specimen is more
negative than that of the untreated specimen. These parameters (Nd and Efb) are closely related
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to the effects of magnetisation treatment on the anodic dissolution process of 316L SS.
Keywords: Corrosion, Magnetisation, Electrochemical, Stainless steel

Introduction 12?58Ni–0?014C–0?073S (in wt-%). The specimen with

the size of 1061063 mm was soldered to a copper wire
The technology of magnetisation treatment on alloys was for electrical connection, using lead containing solder and
studied for many years;1–4 the researchers found that it phosphoric acid flux, and was mounted in epoxy resin
can affect the mechanical properties of alloys, such as with only 1 cm2 of surface area exposure to solution. The
hardness,5 friction,6 fatigue7 and fracture.8 It was believed working surface of the specimen was abraded to a mirror
that magnetic field can change the microstructure of finish with 2000 SiC paper, cleaned with distilled water
materials.2,9,10 However, the mechanism is still unclear. and acetone and then dried in cold air immediately.
Recently, some researchers noticed that magnetic field The magnetisation treatment apparatus (Fig. 1) con-
could affect corrosion resistance of some metals, such as sisted of magnetic poles and a current controller which
carbon steel and stainless steel, when they applied can adjust the magnetic field intensity. The specimens
magnetic field on these metals.11,12 However, it is also were treated to form a passive film at 0?35 T magnetic
anticipated to understand the mechanism. field intensity (the magnetic field perpendiculars to the
In this paper, we investigated the effect of magnetisa- surface of the specimen) for 80 s treatment time in
tion treatment on the corrosion behaviour of 316L SS in 3?5 wt-% NaCl solution.
3?5 wt-% NaCl solution by potentiodynamic polarisa- Electrochemical experiments were carried out on a
tion, electrochemical impedance spectroscopy (EIS) and 2273 advanced electrochemical system from Princeton
Mott–Schottky analysis and developed a novel surface Applied Research. A saturated calomel electrode (SCE)
treatment for 316L stainless steel. The donor density Nd and a large graphite plate served as the reference
and flat band potential Efb of the specimen by magnetisa- electrode and the counter electrode respectively. All
tion treatment were determined, which were found to be experiments in this paper were conducted in 3?5 wt-%
closely related to the corrosion resistance of the passive NaCl at 22uC.
film. The mechanism of the effect of magnetisation on the
corrosion behaviour of the specimen was discussed in Open circuit potential measurement in situ
terms of Nd and Efb. It is quite useful to understand the
The open circuit potential (OCP) of the specimen was
effects of magnetisation treatment on the properties of
recorded in static electrolyte until the OCP values were
passive film and improve its corrosion resistance.
stable enough.
Experimental Potentiodynamic polarisation and EIS
Electrodes and solutions measurements
The chemical composition of the 316L stainless steel was The potentiodynamic polarisation tests in solutions with
as follows: 0?60Si–0?80Mn–0?013P–2?28Mo–17?14Cr– different magnetisation treatment were carried out at a
scan rate of 1 mV s21 from the OCP to 0?5 V(SCE) to
evaluate the electrochemical corrosion behaviour. The EIS
Corrosion and Protection Center, University of Science and Technology experiment was conducted over the frequency from 100 kHz
Beijing, Beijing 100083, China to 2 mHz using a 10 mV sinusoidal potential modulation
*Corresponding author, email [email protected] (peak to peak) around the film formation potentials.

ß W. S. Maney & Son Ltd. 2013

Received 9 December 2012; accepted 17 February 2013
DOI 10.1179/1433075X13Y.0000000101 Materials Research Innovations 2013 VOL 17 NO 7 557
 Cheng et al. Surface treatment for 316L SS using magnetisation technology

1 Schematic diagram of magnetisation treatment experimental set-up

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Mott–Schottky measurements potential value around 20?18 V(SCE). It suggests that

Mott–Schottky analysis was employed to characterise the the magnetisation treatment has significant effect on
semiconducting properties of the passive film with different the OCP values due to the modification of the passive
magnetisation treatment. Potential sweeps are carried out film.
at a scan rate of 50 mV s21 from 20?3 to 0?5 V(SCE), with The value of OCP is defined as the potential drop in
amplitude signal of 10 mV. Considering the influence of Helmholtz double layers, and the surface state of passive
measured frequency, the very commonplace frequency films formed on specimens strongly influences the value.
value 1000 Hz was used in this investigation because many The OCP keeping a stable value for 1500 s means that
documents indicated that the electronic properties of the both sides of Helmholtz double layers were equally
passive layer do not change with the frequency at 600– occupied by negative and positive charges respectively.
6000 Hz.13,14 The magnetisation treatment modified the structure of
passive film. It further makes equilibrium distribution to
Results and discussion another state at which the potential drop in Helmholtz
double layers is more positive. It is because magnetisa-
Open circuit potential measurement in situ tion treatment could decrease the vacancies in the
Figure 2 shows the OCP plots of the specimens with and surface of passive film, which would be demonstrated
without magnetisation treatment in 3?5 wt-% NaCl in the following evidences. Such vacancies serve as a
solution. It is obvious that the OCP values of specimen kind of trap accumulating positive charges in the surface
without magnetisation treatment are stable enough of passive film, which causes the more positive potential
around 20?353 V(SCE) during the immersion period drop in Helmholtz double layers. This leads to the
of 1500 s. However, for the specimen with magnetisation increase in OCP values of 316L stainless steels with the
treatment, the OCP values markedly increase to a stable magnetisation treatment.

2 Open circuit potential plots of specimens 3 Polarisation curves of 316L SS in 3?5 wt-% NaCl solution

Materials Research Innovations 2013 VOL 17 NO 7 558

 Cheng et al. Surface treatment for 316L SS using magnetisation technology

4 Nyquist diagrams measured on 316L SS in 3?5 wt-%

NaCl solution 5 Mott–Schottky plots for 316L SS in 3?5 wt-% NaCl solution

Potentiodynamic polarisation
Figure 3 displays the polarisation curves for untreated where Efb is the flat band potential; e0 is the vacuum
and treated specimens in NaCl solution. From Fig. 3, we permittivity with the value of 8?85610214 F cm21; e is
can clearly figure out the following results. First, Ecorr2, the relative dielectric constant of the specimen, 15?6
the corrosion potential of treated specimen, is more as in the literature;16 K is the Boltzmann constant
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positive than that of untreated specimen Ecorr1. This (1?38610223 J K21); T is the absolute temperature; N
means that magnetisation treatment is found to increase (m23) is the donor density Nd or accept density Na; and
the potential remarkably in the positive direction and A is the surface area of the sample (cm2).
is corresponding to the OCP measurements above. In this paper, it is assumed that the measured
Second, the passive current Ip of the treated specimen capacitance corresponds to the space charge capacitance
is smaller than the untreated specimen. Third, the pitting and that extra series capacitance, such as the Helmholtz
potential Ep of treated specimen is almost the same with capacitance and surface state capacitance, can be
untreated specimen. In sum, the magnetisation treat- ignored.17,18 This assumption is reliable because the
ment increases the corrosion potential Ecorr and Helmholtz capacitance with a value of 30–50 mF cm22
decreases the passive current Ip. for the smooth metallic/solution interface is much higher
than the capacitances of the passive film formed on the
Electrochemical impedance spectroscopy specimens.
Figure 4 shows the EIS of treated and untreated Figure 5 displays the Mott–Schottky plots for the
specimens. A common characteristic exists for the two passive films formed on the treated and untreated
curves in Fig. 4. They both contain one capacitive specimens in NaCl solution. From Fig. 5, a linear
semicircle in the test frequency range. However, the size relationship can be observed between C22 and E for
of the semicircle for treated specimen is much larger than both treated specimen and untreated specimen in the
that of untreated specimen. It indicates that only one time potential range from 20?25 to 0?5 V(SCE), from which
constant exists in the corrosion process. This electro- the slopes can be identified to be positive. According to
chemical process on the oxide films/solution was always equation (1), the positive slopes indicate all the passive
related to an equivalent electrical circuit. The equivalent films formed on specimens perform n type semiconduc-
electrical circuit shown in Fig. 4 is used to fit the tor. The appearance of peak values in Fig. 5 represents
impedance data, where Rs is the solution resistance, C is an inversion from n to p type semiconductor property.
the double layer capacitance and Rt represents the charge We should notice that the passive films possess almost
transfer resistance. The fitting results presented that the the same slope values.
charge transfer resistance Rt (59 300 V cm22) of the Moreover, the donor density Nd can be calculated from
oxide film formed on treated specimen is larger than the the slope of Mott–Schottky plots; the results list as
untreated specimen (10 600 V cm22). All these results 5?0961027 m23 for untreated specimen and 3?836
indicated that the corrosion resistance of the oxide film 1027 m23 for treated specimen. Nd value decreased after
was greatly enhanced by magnetisation treatment. magnetisation treatment. Most researchers19,20 believe that
the carrier density closely relates with the occasion of the
Semiconductor properties corrosion reaction because the carrier density corresponds
Based on the Mott–Schottky theory,15 the relationship to the point defects and the non-stoichiometry of the space
between the space charge capacitance C and the applied charge region. Therefore, the variability of donor densities
potential E can be written as indicates the modification of structure in the passive film by
the magnetisation treatment. Many previous works19,20
1 2 suggested that the smaller Nd would cause the lower
~ ðE{Efb {KT=eÞ n type (1)
C 2 ee0 eNA2 possibilities of film breakdown or pitting initiation because
these point defects in the film are potential sites where
1 {2 corrosion process are more likely to occur. Thus, magne-
~ ðE{Efb {KT=eÞ p type (2)
C 2 ee0 eNA2 tisation treatment could alleviate the probability of pitting

Materials Research Innovations 2013 VOL 17 NO 7 559

 Cheng et al. Surface treatment for 316L SS using magnetisation technology

initiation by decreasing the donor densities in the passive 3. The enhancement of corrosion resistance of 316L
film. It was well corresponding to the left shift of the anodic SS by magnetisation treatment was closely related to the
polarisation curves in Fig. 3. decrease in the donor density Nd and flat band potential
The Nernstian expression for the Efb of a semicon- Efb.
ductor is
Acknowledgement
Efb ~{EF0 =qzDWH (3)
The authors acknowledge the support of China National
where EF0 is the Fermi level of a semiconductor material Natural Science Foundation (grant no. 51271023).
and DWH is the potential drop in Helmholtz layer. From
equation (3), Efb varies with EF0 and DWH . It is assumed References
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Materials Research Innovations 2013 VOL 17 NO 7 560