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Electropolishing of medical-grade stainless steel in preparation for surface

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Article  in  Journal of Solid State Electrochemistry · April 2012

DOI: 10.1007/s10008-011-1539-9

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Citation:
Nazneen, Feroze and Galvin, Paul and Arrigan, Damien W.M. and Thompson, Michael and Benvenuto,
Pasquale and Herzog, Gregoire. 2012. Electropolishing of medical-grade stainless steel in preparation for
surface nano-texturing. Journal of Solid State Electrochemistry. 16 (4): pp. 1389-1397.

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 Electropolishing of medical-grade stainless steel in preparation for
surface nano-texturing

Feroze Nazneena, Paul Galvina, Damien W. M. Arriganb, Michael Thompsonc,

Pasquale Benvenutoc and Grégoire Herzoga*
a
: Tyndall National Institute, University College Cork, Lee Maltings, Cork, Ireland
b
: Nanochemistry Research Institute, Department of Chemistry, Curtin University, Perth,
Australia
c
: Department of Chemistry, University of Toronto, Toronto, Ontario, Canada

*Corresponding author: e-mail: gregoire.herzog@tyndall.ie

Abstract:
The purpose of this work is to investigate the electropolishing of medical grade 316L stainless
steel to obtain a clean, smooth and defect free surface in preparation for surface nano-texturing.
Electropolishing of steel was conducted under stationary conditions in four electrolyte mixtures:
A) 4.5 M H2SO4 + 11 M H3PO4, B) 7.2 M H2SO4 + 6.5 M H3PO4, C) 6.4 M glycerol + 6.1 M
H3PO4 and D) 6.1 M H3PO4. The influence of electrolyte composition and concentration,
temperature and electropolishing time, in conjunction with linear sweep voltammetry and
chronoamperometry, on the stainless steel surface was studied. The activation energies for
dissolution of steel in the four electrolyte solutions were calculated. The resulting surfaces of
unpolished and optimally-polished stainless steel were characterised in terms of contamination,
defects, topography, roughness, hydrophilicity and chemical composition by optical and atomic
force microscopies, contact angle goniometry and x-ray photoelectron spectroscopy. It was
found that the optimally polished surfaces were obtained with the following parameters:
electrolyte mixture A at 2.1 V applied potential, 80 °C for 10 minutes. This corresponded to the
diffusion-limited dissolution of the surface. The root mean square surface roughness of the
electropolished surface achieved was 0.4 nm over 2 x 2 m2. Surface analysis showed that
electropolishing led to ultraclean surfaces with reduced roughness and contamination thickness,
and with Cr, P, S, Mo, Ni and O enrichment compared to untreated surfaces.
Keywords: Medical-grade stainless steel (316L); Electropolishing; Anodic dissolution; Surface
analysis

1
1. Introduction
Electropolishing is an electrochemical process that is often employed in order to produce a well-

passivated, smooth, light-reflective, defect-free metal surface. A number of these properties are

considered to be crucial with regard to metal-based medical devices such as stainless steel stents.

These structures are used to support diseased atherosclerotic arteries subsequent to balloon

angioplasty [1, 2]. Although widely employed in this type of medical procedure, the

biocompatibility of the metal surface constitutes a key issue [3, 4]. One strategy for addressing

this problem is the nano-structuring of an electropolished surface in order to promote endothelial

cellular adhesion and proliferation [5-7]

Electropolishing of metals has a long history that began with the first patent published in 1930

[8]. Over the years, many studies of both practical and fundamental aspects of the process have

been conducted on various metals including biocompatiblity aspects of electropolished medical-

grade stainless steel [9-18]. Electropolishing involves anodic dissolution of the metal/alloy in a

suitable electrolyte. Parameters that influence the electropolishing process include: anodic

current density, applied potential, bath temperature, reaction time, composition and concentration

of electrolytes, and the anode-to-cathode surface area ratio [19]. Generally, electropolishing of

stents has been preceded by various surface cleaning and physical treatments [20, 21].

Furthermore, to prevent the oxidation and deterioration of stent products, surface passivation has

been performed subsequent to the electrochemical process [21].

At present, the surface mechanisms associated with the electropolishing process are not yet fully

understood. However, it is generally considered to involve two discrete reactions at the anode

surface, that are termed anodic leveling and brightening [22-24]. Anodic leveling results from a

difference in the dissolution rate between peaks and valleys on a rough metal/alloy surface,

2
which depends on the current distribution or mass-transport conditions. This process is usually

associated with a decrease of roughness at the micron or larger range and can be achieved under

the ohmic (primary current distribution), activation (secondary), and mass-transport (tertiary)-

controlled metal dissolution reactions. Anodic brightening can be achieved only under the

conditions in which the metal dissolution is mass-transport-controlled, and where the formation

of a precipitated salt layer at the electrode surface is possible. The presence of a salt layer is

associated with suppression of the influence of metal micro-structure and surface defects on the

dissolution rate. This phenomenon would lead to specular reflectivity of the metals/alloys by

surface micro-smoothing at the sub-micron scale. Consequently, a smooth electropolished

substrate surface, which appears light-reflective, results from these two factors acting in unison

[22, 24].

The composition of the electrolyte employed in the electropolishing process has been the subject

of a number of studies [14, 22, 25, 26]. It is considered that electropolishing takes place in the

diffusion-limited current region under controlled mass transport conditions, and is favored by

high temperatures [25]. A similar result has been obtained by Datta and Vercruysse [27], who

suggested dissolved metal ions as the transport-limiting species, and also by the work of Singh

and Upadhyay [28], who studied the polarization behavior of stainless steel alloys in a

phosphoric-acetic acid mixture. Previous studies on the polishing behavior of various metals and

alloys in a phosphoric-sulfuric acid mixture have examined the effects of electrochemical

impedance [22], temperature and water concentrations [26], and varying volumetric ratios of acid

mixtures and polishing charge [29]. Furthermore, the effect of glycerol incorporation in the acid

mixture has also been investigated [30, 31]. Based on these various studies, several explanations

for anodic dissolution have been suggested. These include the models of duplex salt film

3
production [32], adsorbate-acceptor interaction [32], preferential adsorption of shielding

molecules [33, 34], and the role played by inter-molecular forces [35]. Finally, in an attempt to

avoid the use of an acid-based electrolyte in electropolishing, Abbott and coworkers [36, 37]

electropolished stainless steel in ethylene glycol-choline chloride. They demonstrated that a non-

acid based solution leads to higher current efficiencies and negligible gas evolution at the

anode/solution interface compared to an acid-based electrolyte solution. However, dissolution of

the oxide film is slower which led to pitting at lower current densities.

The specific goal of the present study is the optimization of electropolishing parameters to obtain

a clean, defect-free and smooth 316L stainless steel surface suitable for nano-texturing. The

electro-polishing behavior of flat austenitic type 316L stainless steel was studied in four different

electrolyte mixtures mentioned in literature [19, 20] under static conditions. Included are the

effects of electrolyte compositions and concentrations, temperature and time, in conjunction with

linear sweep voltammetry and chronoamperometry. The resulting surfaces were analyzed by

optical and atomic force microscopies, contact angle goniometry and x-ray photoelectron

spectroscopy (XPS).

2. Experimental
2.1 Steel substrate and reagents

Austenitic type 316L stainless steel foils with a thickness of 0.9 mm, annealed and mirror

polished on both sides, were obtained from Goodfellow Ltd., Cambridge, UK. These substrates

are composed of 69 % Fe, 18 % Cr, 10 % Ni and 3 % Mo. The foils were cut into 10 mm

squares. The samples were cleaned with acetone, ethanol and finally in ultrapure water via an

ultrasonic treatment for 10 min. The samples were then dried under a stream of nitrogen. Four

electrolyte solutions were prepared using H2SO4 (95-97 %), H3PO4 (85 %) and glycerol (99 %

4
purity) (All purchased from Sigma Aldrich): A, 11 M H3PO4 + 4.5 M H2SO4, B, 6.5 M H3PO4 +

7.2 M H2SO4, C, 6.1 M H3PO4 + 6.4 M glycerol and D, 6.1 M H3PO4. Freshly prepared

electrolyte solutions (50 ml) were used for all electropolishing experiments in the light of the

observation that a change in the metal ion concentration in the electrolyte may have an effect on

the electropolishing conditions [19, 38]. Purified water (18.2 M cm) used for all the aqueous

solutions was from an Option R15 system (Veolia Water Systems, Ireland).

2.2 Electropolishing procedure

To obtain clean, defect-free and smooth surfaces in an electrolyte bath, a 50 ml doubled-walled

glass jacketed beaker was used as an electropolishing cell. The inner compartment of the cell was

filled with electrolyte while thermostated water was circulated through the enclosed outer jacket

in order to maintain the desired temperature of the electrolyte. An opening was provided in the

cell, on to which a poly(tetrafluoroethylene) lid was placed, through which a three electrode

system was inserted into the polishing electrolytes. The three-electrode system featured a 1 cm2

316L stainless steel foil working electrode, a platinum wire mesh counter electrode and silver–

silver chloride (Ag/AgCl) in 3M KCl reference electrode. The distance between the counter and

working electrodes was fixed at 6 mm. Electrochemical measurements were performed at a scan

rate of 5 mV s-1 with a CHI1100 potentiostat (IJ Cambria, Scientific Ltd, UK) controlled by

software run on a personal computer. All the polishing experiments were executed without any

agitation of the electrolyte solutions. Electropolishing by linear sweep voltammetry was initiated

at the open-circuit potential once it had been stable for 8-10 minutes. Linear sweep voltammetry

was conducted to study the influence of electrolyte temperature, composition and concentration

to determine the potential range required for polishing in the diffusion-limited current region of

the current density versus potential curves in the four electrolyte mixtures. The polishing

5
temperature was controlled by a thermostated water circulation bath set at 50, 60, 70 or 80 °C.

Chronoamperometry was performed to investigate polishing time. After each electropolishing

experiment, the 1 cm2 316L stainless steel substrate was replaced with a fresh substrate.

Subsequent to electropolishing, the substrates were copiously rinsed with distilled water and then

dried under a stream of nitrogen. The counter electrode was rinsed with de-ionized water and

then treated in the blue flame of a bunsen burner to remove any impurities. The reference

electrode was dried with nitrogen and then stored in a 3 M KCl solution. Prior to, and after each

experimental run, the jacketed vessel was rinsed several times with acetone and then with

distilled water.

2.3 Surface characterization

An optical study was conducted to analyze surface defects of all the electropolished and

unpolished (as-received) 316L stainless steel substrates. The images were acquired with an

Olympus BX51 microscope equipped with an Olympus DP71 Camera. The pictures were taken

with a 2.5X magnification at sensitivity of ISO 800.

An atomic force microscope (AFM) was used to assess the surface topography and roughness of

the stainless steel surfaces. AFM examinations were performed in ambient air with a commercial

microscope (Dimension 3100 controlled by a Nanoscope IIIa controller equipped with a phase

imaging extender, Digital Instruments, Santa Barbara, CA, USA) in tapping mode. The silicon

cantilevers (Windsor Scientific Ltd, UK) had a <10 nm radius of curvature and a 40 N m-1 spring

constant (nominal values). Topographic images were recorded at a scan rate of 0.5 Hz and a

resonance frequency of 300 kHz. Surface roughness of the samples was evaluated over 20 x 20

µm2 and 2 x 2 µm2 images. The average roughness (Ra) (arithmetic average of the deviations

from the center plane) and root mean square roughness (Rq) (the average of height deviations

6
taken from the mean plane) were calculated using Veeco Nanoscope IIIa analyzing software

(version 7.12). Four unpolished and three 316L stainless steel surfaces electropolished with

electrolyte A were measured. On each of these surfaces, four topographic measurements were

performed.

The hydrophobicity of the surface was assessed by measurement of de-ionized water contact

angles using an OCA contact angle system (Dataphysics Instruments GmbH, Germany). The

drop volume used was 1 µL. The contact angle between the drop and the substrate was measured

immediately after the contact was made in order to minimize evaporation. The reported results

are the average of five measurements taken at five different sites on 0.9 mm 316L stainless steel

surfaces prior to and after electropolishing at different temperatures.

Two stainless steel samples were analyzed by XPS. The first was an unpolished sample and the

second was a sample that has been electropolished with electrolyte A. The data were collected on

a ThermoFisher Scientific K-Alpha XPS facility located at the University of Toronto. All

samples were analyzed with a high pass energy (200 eV). This provides the highest sensitivity,

but also the lowest resolution. The take-off angle (angle of measurement) was performed at 90

degrees (perpendicular to the sample surface). The X-ray spot size was 400 µm.

Monochromatized aluminum K-alpha X-rays were used. The point spacing for the survey scan (a

scan across the entire energy spectrum) was 1 eV, while the point spacing for the regional scan

(individual element spectra) was 0.1 eV. The data acquisition and processing software was

Avantage. Peak integration was performed using the “Smart” method with a background average

at start and end set to 0.80 eV.

7
3 Results and Discussion

3.1 Electrochemistry

Figure 1 shows the anodic linear sweep voltammograms obtained for electropolishing solutions

A, B, C and D at 70 °C with a scan rate of 5 mV s-1 under unstirred conditions. It is clear from

Figure 1 that scanning in a positive direction from the open circuit potential produces

voltammograms with four distinct regions in the anodic curve: active dissolution (I-II region),

passive (II-III region), diffusion-limited current (III-IV region) and oxygen evolution (IV-V

region). In the active dissolution region, the steep increase in current is the result of breakdown

of the oxide layer on the surface of the stainless steel sample. The passive region is associated

with the buildup of a fresh oxide layer. The diffusion-limited current region is connected to the

mass-transfer control of anodic metal dissolution. The further final rise in current with increased

potential is caused by oxygen evolution. The high applied potentials of the oxygen evolution

region are generally not selected for electropolishing purposes because of the formation of

bubbles which cause surface pitting and the obstruction of current passage [9, 39]. Similar active

dissolution, passive and gas evolution behaviors of stainless steel were also reported elsewhere

[40, 41]. An absence of the passive oxide film was observed with electrolyte solutions C and D

as the current did not reached a maximum. The current measured for electrolyte D was much

higher than the ones observed for electrolytes A, B and C. Electrolyte D contains only H3PO4,

whereas the other electrolytes contain, additionally, sulfate (A, B) and glycerol (C). The latter

may adsorb on the stainless steel surface and result in lower currents.

The scan rate dependence of the electropolishing behavior was investigated (Figure 2). The peak

current increased linearly with the square root of the scan rate, indicating diffusion-controlled

behavior, as shown in the inset of Figure 2 for electrolyte A at 80 °C. However the peak potential

8
also shifted to higher values with increasing scan rate, indicative of uncompensated resistance

and/or electrode kinetic limitations. Nevertheless, at sufficiently high applied potentials, the

electrode process can be driven in a diffusion-controlled manner. For subsequent experiments,

the lowest scan rate was employed so as to achieve a slow increase of anodic dissolution and to

avoid pitting.

Figure 3 shows the influence of temperature on the anodic linear sweep voltammetry of 316L

stainless steel substrates in electropolishing solution A. In these experiments, electropolishing

was conducted with a scan rate of 5 mV s -1 under unstirred conditions at temperatures of 50, 60,

70 and 80 °C. Various studies have proposed that electrochemical polishing generally occurs at

the potential in the limiting-current region and is favored by high temperatures [9, 25]. From the

results obtained in the present work, the anodic curve contains an obvious diffusion-limited

current peak, with current rising with the polishing temperature. This temperature dependence

suggests that the anodic dissolution in this potential region followed a mass-transport-controlled

mechanism, as expected [22, 25, 42, 43] and in agreement with the sweep rate dependence

presented above. From Figure 3, the diffusion-limited current region is in the potential range

between 2.1 and 2.2 V in the temperature range from 50 to 80 °C. In addition, a clear yellow-to-

green color was observed in the solution at the vicinity of the exposed anode area during the

polishing process. This indicates that the transport-limiting species could be dissolved metal ions

such as Fe3+, Cr(IV), Cr(VI) (yellow) and Ni2+, Ni6+ / Mo(IV) (green) transferred from the

anodic metal surface to the bulk electrolyte (salt film mechanism), or an acceptor limited species.

The latter species could be H2PO4- or its complex or water for the dissolved metal ions in

polishing solutions [9, 22, 44]. In this study, the anodic dissolution mechanism was evaluated

via XPS.

9
A bright and reflective surface was observed visually on both sides of the stainless steel substrate

following electropolishing at temperatures above 60 °C. Dull surfaces were observed for

temperatures below 60 °C. Although a diffusion-limited current was achieved at temperatures

lower than 60 °C, an electropolished surface was not achieved, which is consistent with other

studies which found that the observed mass transport-controlled region at these temperatures was

insufficient for polishing [22, 26]. Therefore optimum electropolishing conditions are probably

obtained at high temperatures when an increased rate of anodic dissolution is achieved by

temperature-enhanced mass transport [9, 25]. This is in contrast to a process which is dominated

by charge transfer kinetics at lower temperatures [14] and is consistent with the fact that

macroscopic “smoothing” and brightening is more efficient at higher temperatures.

Figure 4 presents the optical micrographs of stainless steel substrates before and after the anodic

linear sweep voltammetry in each of the electrolytes. Figures 4a to 4d show the steel surfaces

after anodic dissolution studies at 5 mV s -1 with solution A and B at 80 °C, and solution C and D

at 70 °C, whereas Figure 4e shows the unpolished steel surface. An obvious disparity in surface

topographies is clear from Figure 4. The unpolished surface (Figure 4e) shows lines, pits and

scratches resulting from the fabrication process. Figure 4d shows the surface following

electropolishing in the presence of phosphoric acid (solution D), which produced high anodic

dissolution currents. Electropolishing in electrolyte D did not lead to a smooth surface. Addition

of glycerol (Figure 4c) and sulfuric acid (Figure 4b) to the electrolyte solution improved the

surface morphology. Glycerol slows down the rate of anodic dissolution but does not remove

completely the scratches on the surface of the stainless steel sample. The presence of sulfuric

10
acid in electrolyte B helped improve the surface smoothness in parts of the sample. However,

pitting of the surface is also apparent.

Previous studies have reported the achievement of bright and smooth stainless steel surfaces

using electrolyte C. However, Haidopoulos et al. performed electropolishing with a galvanostatic

method and obtained a smooth surface after polishing for 5 minutes at room temperature[19],

while in another study, acid pickling and annealing pre-treatment methods were applied and

polishing was carried out in solution C at 90-95 °C at applied potential in the region of 10-12 V

for 1 min [20]. These results were achieved at currents or applied potentials much higher than

used in our study.

A yellow-green color was observed in the solution close to the stainless steel anode for all

electrolyte solutions except solution C, where no change in colour was noticed. This implies that

mass transfer-control is common to all electropolishing systems, but that the amount of elemental

species released from the metal surfaces varies with the electrolyte composition.

Overall, these results imply that the polishing temperature, the applied potential (located in the

diffusion-controlled current region) and the electrolyte composition and concentration all play

essential roles in achieving the best polishing results. The best electropolishing result was

obtained with electropolishing solution A at 80 °C at 5 mV s-1. This led to a smooth and

reflective surface with reduced pitting. Using this electrolyte composition, the influence of

polishing time on surface topography and roughness parameters was evaluated using AFM. The

evolution of the chemical composition of electropolished substrates was studied with XPS to

determine the chemical species eliminated or formed on the steel surface during the polishing

process.

3.2 Surface characterization

11
Figure 5 shows the three-dimensional AFM images of 316L stainless steel surfaces before and

after electropolishing in solution A. The electropolishing procedure was conducted in two steps

at 80 °C and 5 mV s-1. The first step involved scanning of the potential from the open circuit

potential up to the point where the diffusion-limited current region was reached. The linear

sweep voltammetry was then stopped and the selected potential was maintained for 0, 3, 5 or 10

min using chronoamperometry. In the AFM images, the untreated surface appears rough

presenting irregularities with deep valleys, peaks and bumps on a scanned area of 2 × 2 µm2

(Figure 5a). After 10 min of electropolishing, a much smoother surface was achieved (Figure

5b).

Normalized Ra and Rq values are shown in Figure 6 as a function of the electropolishing time for

two surface areas: 20 × 20 µm2 and 2 × 2 µm2. A normalized value for Ra and Rq was used since

there was some variability from sample to sample. This normalized parameter is defined as the

final roughness divided by initial roughness of the specimen. It is apparent that the surface

roughness of the specimens decreased with the increased duration of polishing. After 10 minutes

of electropolishing, a Rq value of 0.4 nm over 2 x 2 m2 was achieved. Initially, an abrupt

decrease in surface roughness occurred, while a further reduction in surface roughness was

observed subsequently for longer polishing times on both surface areas. Similar results were also

found by Rao et al. in H3PO4, H2SO4 and chromic acid at room temperature [46], and in H3PO4,

glycerol and water mixtures at both room and elevated temperatures [19].

Contact angle results show that unpolished steel surfaces are hydrophobic with an average

contact angle of 82° ± 4° (N = 3). This result is likely associated with carbonaceous

contamination on the sample surfaces, as verified by XPS examination (discussed later). After

electropolishing in solution A at temperatures of 50, 60, 70 and 80°C, the hydrophobic

12
unpolished steel surface becomes completely hydrophilic (contact angle < 10°). This suggests the

removal of the surface contaminants and reduction in roughness.

The XPS surface analysis data for two samples are presented in Table 1. When comparing the

unpolished and electropolished stainless steel surfaces under optimal conditions (polishing

solution A, 5 mV s-1, 80 °C and 2.1 V for 10 min), an increase in the atomic percentages of Cr, P,

S and O are observed after the polishing procedure. The increase in Cr is likely the result of Cr

enrichment in the surface oxide layer of the steel substrate. This phenomenon is associated with

the electropolishing process and has been previously reported in the literature [19]. The change in

the Fe content after polishing is small and remains fairly constant. This may simply reflect that

Fe is either more evenly distributed within the oxide layer, or is unaffected during the

electropolishing process. The increases in P and S after electropolishing can be attributed to the

incorporation of various P and S oxides onto the surface of the steel substrate from the

electrolyte solution. The electrolyte solution is the most likely source since the contents of P and

S in the unpolished steel substrate are negligible. Moreover, the higher content of P when

compared to S on the electropolished sample may be indicative of the higher concentration of

phosphoric acid relative to sulfuric acid in this electrolyte solution. This would further support

the notion that P and S on the electropolished surface originates from the the electrolyte solution.

The S contamination on the stainless steel surface from a sulfuric acid bath has been reported in

the literature [21]. The increase in O after electropolishing is due to the formation of various

metallic and non-metallic oxides (indicating the formation of fresh passive layer). With regards

to carbon, its atomic percentage decreases dramatically after polishing. This decrease can be

attributed to the removal of adventitious carbon from the surface of the steel substrate. Mo shows

a slight increase after polishing. This may simply be due to Mo becoming more exposed as

13
surface layers are removed during the polishing process. The Ni content is very low and changes

very little from the unpolished to polished substrates. This is probably because Ni is confined to

depths at which XPS cannot probe. As such, there may be other possible explanations for the low

Ni content. The presence of Si and N are more difficult to interpret. Given the contact angle

measurements discussed above, it is very likely that the Si content is the direct result of

contamination since it is present before electropolishing and decreases after this treatment. The

increase in N after polishing may be associated with the polishing procedure itself. The analysis

of the unpolished and electropolished samples by XPS has shown that the composition of the

stainless steel surfaces was enriched with Cr, P, S, Mo, Ni oxides layers, but with less relative Fe

content after the polishing process. This suggests that the yellow-green color noticed in the

solution at the vicinity of the exposed steel substrate area may be due to the removal of Fe

content from the surface into the solution (salt film mechanism) (as mentioned earlier in section

3.1). A similar finding was also reported elsewhere after the electropolishing of steel substrates

in a sulfuric-orthophosphoric acid mixture [47].

4. Conclusions

We reported here the electropolishing of medical grade 316L stainless steel surfaces with a view

to the preparation of these surfaces for nano-texturing. For such applications, obtaining a smooth

surface is crucial. Among the four electrolyte solutions tested, electrolyte A was identified as the

best one as it led to a smooth and relatively defect-free surface when a potential of 2.1 V was

maintained for 10 minutes at 80 °C. The composition of this electrolyte solution was 11 M

H3PO4 + 4.5 M H2SO4 in water. XPS analysis of the electropolished surface has shown that the

stainless steel was enriched with Cr, P, S, O, Mo and Ni elements. The clear yellow to green

color noticed in the solution after the electropolishing process was attributed either to the

14
acceptor species (P and S oxides rich surface) or salt film formation (release of relative low Fe

content in the solution). The surface smoothness achieved will allow nano-texturing of steel.

5. Acknowledgements

This work was supported through the National Biophotonics and Imaging Platform, Ireland,

(NBIPI) and the Integrated NanoScience Platform for Ireland (INSPIRE) initiatives funded by

the Irish Government’s Programme for Research in Third Level Institutions, Cycle 4, National

Development Plan 2007-2013. MT and PB are grateful for support from the Natural Sciences

and Engineering Research Council of Canada. These authors also thank Surface Science Ontario,

University of Toronto for the provision of XPS data.

15
Figure Captions
Figure 1: Anodic linear sweep voltammograms of electrolyte solutions A, B, C and D at
temperature of 70 °C. Potential regions: I-II: active dissolution, II-III: passive region, III-IV:
diffusion limiting-current region, and IV-V: oxygen evolution region. Table in inset summarises
the different electrolyte compositions.

Figure 2: Anodic linear sweep voltammograms of electrolyte solutions A conducted with scan
rates in the range 5, 20, 50, 100, 200 and 500 mV s-1 at temperature of 80 °C. Inset represents
square root of scan rates vs peak current graph conducted with electrolyte solution A at 80 °C

Figure 3: Influence of temperature on the anodic linear sweep voltammograms of electrolyte

solution A conducted at 5 mV s-1.

Figure 4: Optical micrographs of 316L stainless steel surfaces after linear sweep studies at 5 mV
s-1 with: (a, b) solution A, B at 80 °C, and (c, d) solution C, D at 70 °C, and (e) unpolished
sample

Figure 5: AFM morphologies of 316L steel surfaces: a) unpolished (scale: 5 nm and bar 2µm),
and b) electropolished for 10 min at 5 mV s-1, 2.1 V and 80 °C (scale: 2 nm and bar: 2µm).

Figure 6: Normalized surface roughness of 316L stainless steel surfaces as a function of

electropolishing time.

16
Figure 1

17
Figure 2

18
Figure 3

19
Figure 4

20
Figure 5

21
Figure 6

22
Table 1: Relative atomic percentage of selected elements for various substrate treatments

Sample Relative Atomic Percentage (%)

C Cr Fe O S P Ni N Si Mo
( 1s) (2p) (2p) (1s) (2p) (2p) (2p) (1s) (2p) (3s)

1. Unpolished 58.37 1.31 3.33 27.32 0.18 0.26 0.15 1.67 2.79 0.34

2. Electropolished 32.05 3.73 3.07 44.40 2.57 5.36 0.22 3.02 1.14 1.18

23
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