Applied Surface Science 410 (2017) 432–444

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

The effects of parametric changes in electropolishing process on

surface properties of 316L stainless steel
Zia ur Rahman a,b , K.M. Deen c,d , Lawrence Cano e , Waseem Haider a,b,∗
a
School of Engineering and Technology, Central Michigan University, Mt. Pleasant, MI 48859, USA
b
Science of Advanced Materials, Central Michigan University, Mt. Pleasant, MI 48859, USA
c
Department of Materials Engineering, University of British Columbia, Vancouver, BC V6T 1Z4, Canada
d
Department of Metallurgy and Materials Engineering, CEET, University of the Punjab, Lahore, 54590, Pakistan
e
Department of Mechanical Engineering, The University of Texas Rio Grande Valley, Edinburg, TX 78539 USA

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

Article history: Corrosion resistance and biocompatibility of 316L stainless steel implants depend on the surface features
Received 22 October 2016 and the nature of the passive film. The influence of electropolishing on the surface topography, surface free
Received in revised form 7 March 2017 energy and surface chemistry was determined by atomic force microscopy, contact angle meter and X-
Accepted 7 March 2017
ray photoelectron spectroscopy, respectively. The electropolishing of 316L stainless steel was conducted
Available online 12 March 2017
at the oxygen evolution potential (EPO) and below the oxygen evolution potential (EPBO). Compared to
mechanically polished (MP) and EPO, the EPBO sample depicted lower surface roughness (Ra = 6.07 nm)
Keywords:
and smaller surface free energy (44.21 mJ/m2 ). The relatively lower corrosion rate (0.484 mpy) and smaller
Electropolishing
Orthopedic
passive current density (0.619 ␮A/cm2 ) as determined from cyclic polarization scans was found to be
Impedance spectroscopy related with the presence of OH, Cr(III), Fe(0), Fe(II) and Fe(III) species at the surface. These species
Potentiodynamic assured the existence of relatively uniform passive oxide film over EPBO surface. Moreover, the relatively
Corrosion biomaterials large charge transfer (Rct ) and passive film resistance (Rf ) registered by EPBO sample from impedance
spectroscopy analysis confirmed its better electrochemical performance. The in vitro response of these
polished samples toward MC3T3 pre-osteoblast cell proliferation was determined to be directly related
with their surface and electrochemical properties.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction rounding tissues is considered extremely important for enhanced

Stainless steel is extensively used in various industrial appli-
cations such as automotive parts, in semiconductor industry and
biomedical devices [1–3]. The low-carbon stainless steel is consid-
ered biocompatible material and is mainly used in many orthopedic
devices and cardiovascular implants [4]. However, the mechani-
cal stability and corrosion resistance of 316L are the paramount
concerns for long-term applications. The in vivo utilization of this
material therefore demands high quality surface, structural and
biological properties [5].
In orthopedics, the bone/implant integration strongly depends
on the surface properties of the prosthetic device. Also the integrity
of implant/tissue interface and the biological response of sur-
∗ Corresponding author at: School of Engineering and Technology, Central Michi-
gan University, Mt. Pleasant, MI 48859, USA.
E-mail address: haide1w@cmich.edu (W. Haider).
osseointegration at the early stage of implantation [6]. Dissolu-
tion of ions from the implant surface and its accumulation at the
interface could be one of the main reasons causing inflammatory
reactions in the body [7].
The presence of body fluids, minerals, chlorides, amino acids
and proteins in the human physiological environment could pro-
mote corrosion of stainless steel implants. The ionic species such as
iron (Fe), chromium (Cr), nickel (Ni) and molybdenum (Mo) could
release and accumulate within the surrounding tissues or may be
transported through the blood stream to the various parts of body.
These ions may initiate inflammatory reactions within surrounding
tissues [7–10]. The build-up of metal debris in the soft tissues of the
body may lead to necrosis [11] and aseptic loosening of knee joint
(common example of implant failure), which can be life threatening
in older age [12]. Therefore, the formation of stable passive oxide
film over the implant surface is necessary which could limit the
release of metallic ions.

http://dx.doi.org/10.1016/j.apsusc.2017.03.081
0169-4332/© 2017 Elsevier B.V. All rights reserved.
 Z. ur Rahman et al. / Applied Surface Science 410 (2017) 432–444
For cardiovascular devices, the chemical composition, rough-
ness and surface energy are the most important properties of
stainless steel for its better thrombogenicity and electrochemical
stability [13]. The non-homogenous surfaces could initiate adhe-
sion and aggregation of platelets which may activate the plasmatic
coagulation and immunological responses [14]. The intrinsic coag-
ulation of proteins and platelets at the implant surface could induce
clotting and thrombosis [15]. Furthermore, the surface characteris-
tics could influence neointimal hyperplasia, which may result in the
disruption of endothelial layer and triggers the cellular response
at the wall of vascular muscle. Thus, rapid proliferation of the
smooth muscle cells could promote restenosis [16]. Therefore, in
order to reduce inflammation and immunological response at the
implant/tissue interface, surface modification of implant materials
(such as stainless steel) is considered extremely important [17].
The electropolishing is an electrochemical surface treatment
process involving anodic dissolution of metal or alloy in an
appropriate electrolyte to restore defect free and smooth surface
[18]. During electropolishing, the simultaneous surface dissolu-
tion and brightening effect could generate smooth mirror-like
surface. In this way the deleterious influence of surface defects,
microstructural variations and preferred crystallographic orienta-
tions on the electrochemical properties and biological response
could also be minimized. It is therefore considered that the elec-
tropolishing of 316L stainless steel implants could be an effective
method to improve corrosion resistance, biocompatibility and ser-
vice longevity [19].
In this research work, the electropolishing of 316L stainless steel
was carried out under optimized conditions. The current–voltage
(V–I) curves for electropolishing could be divided into two regions
as ‘below oxygen evolution’ and ‘at oxygen evolution’ potential as
shown in Fig. 1. Mechanistically, below the oxygen evolution
potential, the electrochemical reactions during electropolishing
are under pure kinetic controlled regime resulting in the syner-
gistic dissolution and passivation of the surface whereas at the
oxygen evolution potential the electropolishing is carried out dur-
ing the dissociation of aqueous electrolyte [20]. The produced
surfaces were characterized to examine their topographical, chem-
ical, structural and electrochemical properties in the simulated
body environment. Furthermore, their biological response was also
Fig. 1. Anodic polarization scan for 316L stainless steel showing two regions of electropolishing.
433
Table 1
Chemical composition of 316L stainless steel (wt.%).
C Mn Cr Ni Mo N P S Fe
0.03 2.00 17.0 11.5 2.00 0.02 0.045 0.030 Balance
investigated to evaluate the proliferation behavior of MC3T3 pre-
osteoblast cells.
2. Experimental
2.1. Sample preparation
The circular disks, 1.6 cm in diameter and 0.5 cm thickness were
cut from a commercial grade 316L stainless steel rod. The stainless
steel rod was purchased from onlinemetals.com and its chemical
composition is given in Table 1 as provided by the supplier. The
®
disks were ground sequentially on a Buehler abrasive belt grinder
by using silicon carbide papers of 240, 320, 400, 600, 800 and 1200
grit size. These disks were washed in deionized water followed by
ultrasonic cleaning in ethanol for 15 min. The ground disks were
electropolished both below and at oxygen evolution potential at
®
Electrobright (Macungie, PA, USA) facility. Briefly, 85% phosphoric
acid (H3 PO4 ) mixed with 93% sulfuric acid (H2 SO4 ) in a volume ratio
of 7:3 at 60 ◦ C was used for electropolishing at the oxygen evolution
potential (EPO). On the other hand, electropolishing below the oxy-
gen evolution plateau (EPBO) was carried out in 100 ml methanol
(CH3 OH) containing 300 ml of 93% sulfuric acid solution at 25 ◦ C.
In both cases of electropolishing, 10 V DC potential was applied
for 5 min and copper (Cu) was used as cathode. In the following
discussion, mechanically polished and electropolished disks at and
below the oxygen evolution potentials are designated as MP, EPO
and EPBO samples, respectively.
2.2. Surface characterization and X-ray photoelectron
spectroscopy
The surfaces of MP, EPO and EPBO samples were examined
by a scanning electron microscopy (SEM) (Sigma VP Carl Zeiss,
Germany). The surface roughness was measured by atomic force
microscopy (AFM) (Nanoscope IV MultiMode, Digital Instruments,
USA) operated under tapping mode and scanning 10 ␮m × 10 ␮m
434 Z. ur Rahman et al. / Applied Surface Science 410 (2017) 432–444

surface area. The interfacial free energy, contact angle, surface free
energy (SFE) and work of adhesion were calculated from sessile
drop method using Kyowa contact angle meter (DM-CE1, Japan).
The surface chemistry of each sample was analyzed by X-
ray photoelectron spectroscopy (XPS) (Thermo Scientific K-Alpha).
Themonochromatic Al K␣ radiation source (1486.67 eV) was used
and the photoelectron were detected at 90◦ take-off angle. The
base pressure was adjusted to 2 × 10−9 mbar. Survey spectra were
recorded in the binding energy scale from 0 to 1350.0 eV with a pass
energy of 200 eV, step size of 1.0 eV and dwell time of 10 ms. High
resolution spectra for O 1s, Cr 2p and Fe 2p were obtained at a fixed
analyzer transmission mode with a pass energy of 10.0 eV, step size
of 0.1 eV and dwell time of 50 ms. Binding energies in the survey
and high-resolution spectra were calibrated with respect to C 1s
(285.0 eV) adventitious peak. The acquired data was analyzed by
using the ThermoScientific Avantage XPS software package. Peak
fitting was performed using mixed 80% Gaussian–20% Lorentzian
deconvolution function after subtracting the background by Smart
method.

2.3. Electrochemical analysis

The electrochemical behavior of MP, EPO and EPBO was eval-

uated by using potentiodynamic cyclic polarization (PCP) and
electrochemical impedance spectroscopy (EIS) in phosphate buffer
saline (PBS) solution. The phosphate buffer saline solution was
prepared by dissolving one tablet (Part # P4417-50TAB, Sigma
®
Aldrich ) in 200 ml deionized water. The PBS solution was com-
posed of NaCl (0.8 g/L), Na2 HPO4 (0.06 g/L), NaHCO3 (0.35 g/L),
KH2 PO4 (0.06 g/L), MgSiO4 (0.2 g/L) and CaCl2 (0.14 g/L).
The three-electrode cell setup was used in this study for elec-
trochemical analysis. The saturated calomel electrode (SCE) and
graphite rod were used as reference and counter electrodes, respec-
tively. 316L stainless steel samples were used as working electrodes
in this setup. Both PCP and EIS experiments on this cell were
conducted under 5% CO2 environment in the incubator and tem-
perature was maintained constant at 37 ◦ C. The cell was connected
with Gamry potentiostate reference 3000 for electrochemical test-
ing.
Before each experiment, the open circuit potential (OCP) was
measured for 24 h in order to achieve 0.01 mV/s potential stability.
For PCP tests, the scan rate was adjusted to 1 mV/s. The surface
area of working electrode samples (MP, EPO, EPBO) exposed to
the electrolyte was 2.02 cm2 . To obtain EIS spectra, the poten-
tial perturbation of 10 mVrms (0 Vdc vs. OCP) was applied within
0.01 Hz–100 kHz frequency range.

2.4. Cell adhesion

The MC3T3-E1 (Subclone-4) cells were cultured in the ␣-

modified minimum essential medium (␣-MEM) (HyCloneTM ) Fig. 2. SEM micrographs of 316L stainless steel, (a) MP, (b) EPO and (c) EPBO.

containing 10% fetal bovine serum (FBS) (ThermoScientificTM ) and

®
1% Penicillin–Streptomycin (Sigma–Aldrich ). The cells were cul-
tured in controlled humidified atmosphere having 5% CO2 at 37 ◦ C.
200 ␮l of growth media containing 15,000 cells was spilled over
MP, EPO and EPBO samples to fully cover the surfaces. After 24 and
®
48 h of incubation periods, cell staining was done using NucBlue
Live Cell Stain Ready Probes (Invitrogen Inc.) for the nuclei, and
ActinRedTM 555 Ready Probes Reagent (Thermofisher) for F-actin
filaments of cytoskeleton. Overlay fluorescent images of nuclei
®
and cytoskeleton were captured by EVOS FL Cell Imaging System
(AMF4300, Invitrogen Inc.).
3. Result and discussion
The surface morphology of mechanically polished and elec-
tropolished 316L is shown in Fig. 2. The grinding marks over the MP
sample (Fig. 2a) were clearly visible as unidirectional parallel lines
across the entire surface. The mechanical grinding of stainless steel
samples could increase the roughness, influences surface energy
by distorting the subsurface microstructure [21]. These effects may
enhance the susceptibility of pitting corrosion at the metal surface
even in the mild aggressive environments. On the other hand, by
 Z. ur Rahman et al. / Applied Surface Science 410 (2017) 432–444 435

Fig. 3. XPS Survey spectra of 316L stainless steel samples, (a) MP, (b) EPO and (c) EPBO.

improving surface finish without disturbing surface or subsurface
microstructures such as electropolishing could be an effective way
to improve corrosion resistance. The dissolution characteristics of
these surfaces are also strongly dependent on the stability of pas-
sive film which in the adverse case could increase the chances of
toxic elements i.e. Fe, Cr and Ni release into the human body beyond
the tolerance level. However, the significant improvement in the
surface smoothness could be observed after electropolishing (EPO
and EPBO) as shown in Fig. 2b and c respectively.
3.1. XPS analysis
X-ray photoelectron spectroscopy analyses of the MP, EPO and
EPBO surfaces were carried out to investigate and compare the
compositional variations at the surfaces. XPS survey spectra of
mechanically polished and electropolished 316L are shown in Fig. 3.
The chemical composition of elements (wt.%) within the surface
film is provided in Table 2. It was observed that the oxygen O1s
concentration was dominant within the surface film of all MP, EPO
and EPBO samples. The slightly lower concentration of oxygen in
the EPO and EPBO when compared to MP could be related with the
polishing procedure. The relatively stronger S2p and P2 peaks on
EPO sample when compared to EPBO might be attributed to the
adsorption of phosphates and sulfates anions within the passive
film. The surface species i.e. C, Na and Si could also be originated
from the grinding and electropolishing process or during handling
and/or storage as minor contaminants. The relatively higher Si con-
tents on MP sample could be expected after grinding over silicon
carbide papers.
Fig. 4 shows the high resolution XPS spectra of O1s, Cr2p and
Fe2p species present at the surfaces of MP, EPO and EBPO samples.
The dashed lines represent the sum of the deconvoluted XPS spec-
tra. In case of MP sample, three major peaks at 530.4 eV, 532.4 eV
and 533.5 eV were observed and associated with O1s in the form
of OH or some organic contaminants respectively. Peak “a” and
peak “b” could be assigned to the metal oxides and hydroxides,
whereas the peak “c” corresponded to organic carbonate impuri-
ties phase at the surface [22]. On the other hand, in the case of EPO
and EBPO samples the satellite peak at 533.5 eV did not appear. The
OH peak was intensified in EPO whereas in EPBO, the peak related
with metal oxide was dominant. The formation of chromium oxide
and/or iron oxides on the surface may be attributed to the for-
mation stable oxide film after electropolishing. Furthermore, the
chromium (Cr2p) spectra of the MP sample indicated that the exis-
tence of chromium Cr(0) but the dominancy of Cr(III) in the form
of Cr2 O3 and Cr(OH)3 was evident in EPO and EPBO samples. From
the peaks analysis, it was also observed that the surface of EPO and
EPBO was enriched with hydrous chromium (III) oxide film and its

Table 2
Elemental composition of 316L obtained from XPS survey spectra.

MP EP EPBO

Elem. Binding energy (eV) Con. (wt.%) Elem. Binding energy (eV) Con. (wt.%) Elem. Binding energy (eV) Con. (wt.%)

O1s 531.37 43.92 O1s 532.00 36.51 O1s 531.19 38.75

C1s 285.55 33.15 C1s 285.45 30.23 C1s 285.45 32.09
Si2p 102.61 3.16 Fe2p 723.99 10.51 N1s 398.48 3.68
Fe2p 710.67 13.89 Cr2p 586.97 7.55 Fe2p 721.16 11.5
N1s 400.06 1.90 Cr 44.32 5.65 Cr2p 586.56 8.55
P2p 133.18 0.54 N1s 399.81 3.33 Cr2p3 577.04 1.23
Mn2p3 640.90 0.76 P2s 191.4 0.44 P2p 191.4 0.47
Ni2p3 870.27 0.61 S2p 165.57 0.64 Ni2p3 853.36 1.28
Cr2p 586.38 1.86 S2p3 166.08 0.32 S2p 165.57 0.69
Mo3d3 231.80 0.15 Ni2p3 854.20 0.67 Mn2p3 640.17 1.25
S2p 165.57 0 Mn2p3 638.94 3.43 Si2p 101.08 0.00
436 Z. ur Rahman et al. / Applied Surface Science 410 (2017) 432–444

Fig. 4. High resolution spectra of 316L samples before and after electropolishing.

intensity was found to be higher on EPBO sample. The formation of
the Cr(OH)3 indicated the presence of thick passivated oxide film.
Similarly, iron peaks at 706.88 eV and 710.58 eV were attributed to
metallic state Fe(0) and Fe(III) (Fe2 O3 ) respectively [23]. The EPBO
has two satellite peaks at 714.78 eV and 716.38 eV indicating the
presence of both Fe(II) and Fe(III) species which corresponds to
FeO and Fe2 O3 respectively. The iron oxide peaks dominancy in
both EPO (69.15 at.%) and EPBO (65.26 at.%) were attributed to the
stable surface which could improve the corrosion resistance. Fur-
thermore, the EPBO sample showed relatively stronger Fe(0) peak
than other samples. This peak could influence the surface wettabil-
ity properties and protein adhesion [24]. The formation of PO4 2−
and SO4 2− complexes with the Cr(III), Fe(II) and Fe(III) species at
the electropolished samples could be possible. However, the elec-
tropolishing at high applied DC potential (10 V) and at low pH also
suggested the limited activity of PO4 2− and SO4 2− ionic species in
the electrolyte under applied conditions [25,26].
The phosphorus and sulfur in the metallurgical composition of
316L stainless steel could possibly be oxidized at the surface dur-
ing electropolishing and the formed passive film may contain these
species. The deconvoluted P2p and S2p spectra were identified as
shown in Fig. 5. The splitting of P2p high resolution spectra into
doublet peaks at 133.40 eV and 135.50 eV binding energies could
be associated with the Cr(III)–PO4 and P2 O5 species respectively.
Both EPO and EPBO showed similar behavior and indicated the
formation of phosphate species. The prominent signatures of phos-
phate species within the passive film could also be affiliated with
the adsorption of H3 PO4 and or H2 PO4 − species present in the elec-
trolyte during electropolishing process. The sulfate species within
the surface passive film were also identified as presented in Fig. 5b.
 Z. ur Rahman et al. / Applied Surface Science 410 (2017) 432–444 437

Fig. 5. P2p and S2p XPS high resolution deconvoluted spectra of (a) EPO and (b) EPBO.

The high activity of cationic species (H+ ) and aggressively oxidizing Table 3
Average values of contact angle in degrees (n = 3).
conditions during electropolishing could also promote the dissolu-
tion and oxidation of Fe into Fe(II) and Fe(III). These species could Contact angles
physically adsorb at the surface and could possibly form sulfates as
MP EPO EPBO
confirmed from the S2p peak splitting analyses. The following elec-
DI water 67.16 ± 5.99 66.35 ± 0.39 53.51 ± 2.44
trochemical reactions (1) and (2) could occur at the surface during
Ethylene glycol 26.30 ± 4.74 36.07 ± 0.40 36.63 ± 4.48
electropolishing [25]. Diiodomethane 25.40 ± 11.95 27.43 ± 0.11 30.04 ± 7.33

4Fe + [4H2 SO4 ]ads → [3FeSO4 ]ads + FeS + 4H2 O (1)

− + −
2Fe + [3HSO4 ]ads → [Fe2 (SO4 )3 ]ads + 3H + 6e
The XPS high resolution spectra of S2p shows strong peaks of
Fe2 SO4 , Fe2 (SO4 )3 and other metal sulfides in both cases i.e. EPO
and EPBO samples. Furthermore, SO2 peaks might be attributed
to the partly immerged anions in the passive oxide layer during
electropolishing.
3.2. Wettability and surface roughness
The solid surface and liquid molecular interaction was studied
in order to investigate the wettability of surfaces after mechani-
cal and electro-polishing. Wettability of the implant surface could
(2)
influence the cell proliferation due to protein adhesion which could
influence the implant/tissue integration. Therefore, the surface
energetics and wettability are considered as the key factors influ-
encing the integrity of implant materials in the aggressive biological
environment. The quantitative detail about contact angle (CA) of
MP, EPO and EPBO sample is displayed in Table 3. The CA measured
from water droplet at the surface of MP (67.16◦ ) and EPO (66.35◦ )
samples was almost similar, whereas EPBO sample represented rel-
atively small contact angle (53.51◦ ). The statistical analysis showed
that there was no significant difference in wettability of MP and
EPO whereas; EPBO was significantly different than MP and EPO
(P < 0.05). Table 3 also displays the contact angles with non-polar
438 Z. ur Rahman et al. / Applied Surface Science 410 (2017) 432–444
Table 4
Surface free energy (SFE) components measured by using acid–base theory.
LW AB Acid (+)
MP 48.50 ± 0.50 3.31 ± 0.07 0.3
EPO 45.25 ± 0.16 2.29 ± 0.05 0.1
EPBO 44.21 ± 0.09 0 0
(diiodomethane) and dipolar (ethylene glycol) which are the essen-
tial reagents for calculating the total surface free energy (SFE). The
total surface free energy was calculated from the polar components
(AB) and dispersive component (LW).
The detailed experiments to separate individual contribution of
surface polarity and dispersive component (LW) were conducted
based on the acid/base theory and quantitative results are given in
Table 4. It was evident that the major contribution to the total SFE
was arising because of LW component as their values were almost
close to the total SFE. High energy surfaces could supports better
cell adhesion and mineralization compared to low energy surfaces
[27]. The results indicated that MP has comparatively higher SFE
(51.81 mJ/m2 ) when comparison with EPO (47.52 mJ/m2 ) and EPBO
(44.21 mJ/m2 ). However, the surface polarity was very low for both
MP and EPO and became zero for EPBO. The low value of surface
polarity is considered beneficial for optimal cellular adhesion and
growth [28]. It has been reported previously that fibroblast attach-
ment and their spreading was more pronounced over hydrophilic
surfaces compared to hydrophobic ones [29]. Hence the surface
energetics could significantly influence the performance of perma-
nent prosthetic devices. On the other hand, the hydrophobic (large
contact angle) surfaces could limit electrochemical charge transfer
reactions and the challenge of achieving better cell adhesion and
corrosion resistance properties at the same time is still an active
area of research. Here it could be suggested that the modification
of implant surface should be based on the targeted function and
location of implant in the body. In bone prosthetics, hydrophilic
(small contact angle) surfaces are favorable as these could support
cell adhesion and osseointegration. In case of coronary stent and
blood contacting devices, hydrophobic surfaces may promote pro-
tein adsorption and blood coagulation which may ultimately lead
to thrombosis [30].
On the other side, wettability is sensitive to surface rough-
ness therefore, the long term integrity of implant materials depend
on the compromise between osseointegration and electrochemi-
cal dissolution of metal ions at the bone/implant interface [31–33].
AFM micrographs and the roughness parameters measured for MP,
EPO and EBPO are provided in Table 5. The MP sample presented
relatively large average roughness (Ra = 33.51 nm) compared to
EPO (Ra = 11.50 nm) and EBPO (Ra = 6.07 nm) samples which can
be expected depending upon the surface preparation method. The
topographical features (Ra and Rq) were found to be directly related
with the contact angle as discussed above. This behavior could be
associated with the competition between the surface tension of
the stainless steel samples and cohesive forces of the interacting
electrolyte. The higher micro scale surface roughness is consid-
ered beneficial for cell adhesion, osseointegration and for improved
biomechanical integration. Although, increased surface roughness
could enhance the localized corrosion behavior of the surface. In
other words, the relatively smooth surfaces (EBPO) would promote
the spreading of electrolyte (lower contact angle). However, the
active passive nature of stainless steel and complex electrochem-
ical reactions would also depend on the surface free energy and
composition of the interacting species in the electrolyte. Therefore,
PCP and EIS tests were conducted to evaluated the effect of surface
properties on their electrochemical performance in the simulated
biological environment.
Base (−) Total SFE (mJ/m2 ) Fractional polarity, AB/(LW + AB)
9.12 ± 0.20 51.81 ± 0.70 0.06
12.70 ± 0.37 47.52 ± 0.18 0.05
28.58 ± 0.16 44.21 ± 0.09 0
3.3. Electrochemical analysis
The open circuit potential trends of MP, EPO and EBPO samples
are shown in Fig. 6. It was determined that upon immersion of MP
in the PBS solution presented more negative value (−0.3 V vs. SCE)
compared to EPO and EBPO. The rapid shift in OCP toward more
positive (noble) direction in initial 4 h could be associated with the
relatively higher surface roughness of MP sample. On the other
hand, EPO sample represented similar trend but attained a con-
stant potential value (−0.145 V vs. SCE) in the initial 2 h. The OCP of
MP and EPO approached to the constant values after 16 h whereas
EBPO remained constant during immersion. The negligible change
in potential of MP and EPO samples was observed in the following
8 h. However, it could be seen that initial OCP of EBPO observed
in the PBS solution was more noble (112.8 mV) than MP and EPO
samples. Finally, after 24 h all the polished samples achieved stable
OCP values and followed the EBPO > EPO > MP sequence represent-
ing higher to the least noble corrosion tendency in the PBS. The
stabilization of OCP and slight difference in the final values of
mechanically and electrochemically polished samples suggested
that electropolishing above the oxygen evolution regime could oxi-
dize the elemental phosphorus and sulfur present at the surface.
Also the presence of phosphate ions (H2 PO4 − , HPO4 2− and PO4 3− )
in the electropolishing electrolyte could modify the properties of
passive film as discussed above. These ions may greatly influence
the electrochemical properties of stainless steel sample whereas in
case of EBPO sample it was expected that electropolishing condi-
tions remained within water stability region without dissociation
into O2 which could promote the formation of homogeneous and
uniform surface passive film at the sample surface. To confirm this
behavior, the PCP scans were initiated from very negative cathodic
potential (−1.0 V vs. SCE) (reducing conditions) to eliminate the
possible effect of inherent passive film and to determine purely,
the electrochemical response related with surface topography. The
relatively higher current density below −0.8 V vs. SCE observed in
case of MP compared to EPO and EBPO was in support with higher
surface roughness. The lower current density (about 3 order of
decades) observed in case of EBPO sample at relatively negative
potential could be associated with the limited dissolution of pas-
sive film compared to higher current density observed in case of
MP and EPO samples. This could be due to the presence of rela-
tively thick passive oxide film over EBPO sample which may have
not been dissolved during cathodic polarization. Also the compro-
mised or corrosion potential (Ecorr ) was more negative (active) in
case of MP than EPO and EBPO as shown in Fig. 7. The intersection
of cathodic polarization curves of EPO and EBPO with the anodic
trend of MP in forward scan at the same point could be associated
with the preferential dissolution of active sites within the passive
film. The estimation of kinetic parameter in the Tafel region of each
curve also validated the higher corrosion rate (1.866 mpy) of MP
than EPO (0.717 mpy) and EBPO (0.484 mpy). The corrosion rate of
MP, EPO and EBPO samples under similar conditions were relatively
lower than the values reported elsewhere [34,35].
In the real biological environment number of other factors such
as effect of oxidant (i.e. dissolved oxygen, low pH etc.) and presence
of chloride ions could also affect the stability of passive film. To
investigate the stability of passive film in the PBS the anodic polar-
ization scans up to 2.5 V vs. SCE or current density limit 10 mA/cm2
 Z. ur Rahman et al. / Applied Surface Science 410 (2017) 432–444 439

Table 5
AFM 3D surface topography of 316L Stainless steel.

Surface AFM analysis

Topography Surface roughness, Ra (nm) RMS of roughness, Rq (nm)

MP 33.51 ± 5.54 48.28 ± 8.65

EPO 11.50 ± 1.61 14.79 ± 1.90

EPBO 6.07 ± 0.73 7.91 ± 0.73

Fig. 6. Open circuit potential of 316L before and after electropolishing.

440 Z. ur Rahman et al. / Applied Surface Science 410 (2017) 432–444

Fig. 7. Cyclic potentiodynamic polarization scans of 316L before and after electropolishing.

Table 6
Quantitative analysis of potentiodynamic polarization scans and comparison with literature.

Icorr (A/cm2 ) Ecorr vs. ref (mV) Passive potential, Breakdown Protection Corrosion rate Corrosion rates
Ipass (mV) potential, Eb potential, Ep (mpy)a from other
literature (mpy)

MP 5.610e−6 −410.0 −297.4 239.9 −149.7 1.866 51.18 [34] b

EPO 2.370e−6 −353.0 −248.6 319.8 −73.9 0.717 4.069 [35] c
EPBO 1.290e−6 −288.0 −187.2 308.4 −60.31 0.484
a
This work.
b
Mechanically polished 316LSS (corrosion rate was measured by weight loss).
c
Electropolished 316LSVM SS.

were obtained. The potential was reversed to the negative (ini-
tial) potential to evaluate the pitting tendency of samples. It was
observed that passive current density (ipass ) of MP (4.436 ␮A/cm2 )
was higher than EPO (3.24 ␮A/cm2 ) and EBPO (0.6194 ␮A/cm2 ) as
given in Table 6. All the samples represented large positive hys-
teresis during reverse of anodic polarization scan suggesting strong
pitting susceptibility of samples. The XPS analyses also ensured the
presence of chromium (III) and oxygen species at the surface of
these samples which are the principle ingredient of passive film
on stainless steel and may hydrolyzed in aqueous environment
(reactions (3) and (4)).
The possible reactions which may occur at the breakdown
potential (Eb ) of passive film and may initiate pitting in the presence
of chloride ions could provide insight of the corrosion process.
Cr2 O3 + 3H2 O → 2Cr(OH)3
Cr2 O3 + H2 O + 2H+ → 2Cr(OH)2 +
Cr(OH)2 + + Cl− → Cr(OH)2 Cl
Reaction (3) could also be possible reaction at the defect site
(high surface energy region) where Cr2 O3 could hydrolyzed to
Cr(OH)2 + . This could further promote the ingress of chloride ions
toward the defect site (reaction (5)) and my initiate the pit forma-
tion.
To compare the pitting resistance (Eb − Ecorr ) and pitting sus-
ceptibility (Ep − Ecorr ) quantitatively, the passive film breakdown
potential (Eb ) and protection potential (Ep ) values were also deter-
mined. It was calculated that pitting resistance of EPO (672.8 mV)
was slightly higher than the MP (649.9 mV) and EBPO (596.4 mV)
sample. The increase in potential or the presence of oxidants in the
electrolyte could also enhance the pitting susceptibility of stain-
less steel by breakdown of passive film at ‘Eb ’ corresponding to the
following reaction (6) and the behavior is evident from the large
positive hysteresis loop (Fig. 7) [36].
Cr2 O3 + 5H2 O → 2CrO4 2− + 10H+ + 6e− (6)
Another useful parameter which determines the pitting sus-
ceptibility was also calculated for these samples from PCP scans.
The comparable value exhibited by EBPO (227.69 mV) than MP
(260.3 mV) and EPO (279.1 mV) samples was attributed to relatively
to their higher pitting susceptibility in PBS solution. This situation
(3) could be simulated with the shift of surface potential toward Epit
from Ecorr and may only arise in the presence of oxidants such as
(4) dissolved oxygen and Fe(III) ions in the electrolyte.
The electrochemical behavior of inherent passive film devel-
(5)
oped over MP, EPO and EBPO samples at OCP was also determined
by EIS. The small potential amplitude (10 mVrms ) was applied to
avoid the occurrence of any faradaic irreversible reactions at the
surface and to evaluate the intrinsic characteristics of inherent pas-
sive film. The Nyquist and Bode plots of the samples are shown
in Figs. 8 and 9 respectively. The impedance spectra were ana-
lyzed and simulated with the equivalent electrical circuit models
(EEC) as shown in Fig. 8(b). The impedance as a function of fre-
quency was dependent on the current response associated with
 Z. ur Rahman et al. / Applied Surface Science 410 (2017) 432–444 441

Fig. 8. (a) EIS Nyquist plots of 316L before and after electropolishing and (b) electrical equivalent circuit (EEC) diagram.

Fig. 9. EIS bode plots of 316L before and after electropolishing.

the reversible charge transfer characteristics when small AC poten- response. The high frequency regime of impedance spectra could
tial perturbation was applied. The distribution of charge could be be related with the surfacial charge relaxation in the double layer
divided into the double layer and interfacial charge transfer pro- represented by Ydl and transport through Rct . The intermediate and
cesses associated with the adsorption/desorption and passive film low frequency behavior could be affiliated with the intrinsic char-
442 Z. ur Rahman et al. / Applied Surface Science 410 (2017) 432–444
Table 7
Kinetic parameters obtained after simulating of experimental EIS spectra with EEC models.
Rs ( cm2 ) Ydl( ␮S sn /cm2 ) n1
MP 93.40 53.51 0.889
EPO 104.2 55.13 0.920
EPBO 100.8 27.13 0.923
acteristics of passive film. The EEC model is presented in Fig. 8(b)
which describes the individual parameters and their quantitative
information is given in Table 7.
The impedance spectra of MP, EPO and EBPO represented
differentiable potential distribution across the interface and elec-
trochemical response was dependent on the charge transfer
process (faradaic reactions) associated with the possible adsorp-
tion/desorption of electrolyte species i.e. PO4 3− , Cl− , H+ and OH−
etc. which may either help in the healing of defects in the pas-
sive film or may enhance localized dissolution. The very high film
resistance (Rf ) (12420 M cm2 ) was presented by EBPO sample
compared to MP and EPO. This could be related with the better
barrier properties of passive film developed after electropolish-
ing below the oxygen evolution regime. Similarly, the relatively
larger Rf of (EPO (8.097 M cm2 ) sample than MP 14.5 k cm2 also
suggested the beneficial effects of electropolishing compared to
mechanical polishing. But very small charge transfers resistance
(Rct ) provided by EPO sample could be attributed to the instability
of passive film in the PBS solution. This behavior may be correlated
with the defective structure of the passive film on EPO sample. The
existence of Fe(II) and Fe(III) species in the passive film of elec-
tropolished samples was confirmed from the XPS analysis and these
could be beneficial for the development of non-crystalline passive
film on 316L stainless steel. Also the surface smoothness could sig-
nificantly influence the stability of passive film. The relatively lower
surface roughness of EBPO compared to EPO and MP could be the
reason for the its higher Rct and Rf values. Also the deficiency of iron
species (as found in the XPS spectra) in the passive film developed
over MP sample could also be the possible cause for its lower Rf
in PBS solution. The relatively higher constant phase element (Yf )
for the MP (7.73 × 10−3 S sn /cm2 ) and EPO (2.16 × 10−5 S sn /cm2 )
than EBPO (2.396 × 10−6 S sn /cm2 ) samples also indicated the large
amount of charge relaxation in the least resistive oxide passive film
which could be due to their higher surface roughness and defec-
tive structure respectively [37]. The existence of higher oxidation
state Fe(II) and Fe(III) species could also promote the adsorption of
OH− ions at the surface by forming FeOOH and/or Fe(OH)3 . These
species could enhance the barrier properties of passive film. Dur-
ing polishing samples above the oxygen evolution plateau (as EPO
sample), the electropolishing solution could be depleted with OH−
ionic species by reaction (7), and may produce defective oxide pas-
sive film. This behavior was confirmed by the very low Rct value
(279.7  cm2 ) provided by the EPO and could be simulated with the
rapid ingress of anionic species (OH− , PO4 3− etc.) available in the
PBS solution toward the film. The higher charge transfer through
double layer via adsorption processes is found to be dependent on
the nature of passive film. The higher values of Ydl and Yf as calcu-
lated from the simulation of impedance spectra of MP and EPO were
directly related with the charge transport through the distributed
double layer and defective structure of the passive film respectively
as given in Table 7. The very low Rct and relatively higher Rf , by the
EPO than MP sample could therefore be associated with the pref-
erential adsorption of ionic species and the thickening of the oxide
passive film respectively.
4OH− → 2H2 O + O2 + 4e−
Rct ( cm2 ) Yf (␮S sn /cm2 ) n2 Rf ( cm2 ) Goodness of fit
1.57 × 10 6
0.00773 0.624 1.45 × 104 4.859 × 10−3
279.7 21.63 0.909 8.097 × 106 7.404 × 10−3
1.316 × 106 2.396 0.4248 1.242 × 1010 7.204 × 10−3
The relatively high Rct values of both MP and EBPO but higher
charge transport through the double layer (Ydl ) in the former sam-
ple further validated the adverse effect by surface roughness. It can
be deduced from the impedance analyses that the nature of pas-
sive film and surface roughness are the critical parameters to ensure
electrochemical integrity of the 316L stainless steel in the PBS solu-
tion. The impedance analyses confirmed the resistive properties of
passive film developed over EBPO sample and the results were in
agreement with its low corrosion rate and relatively smaller passive
current density in PBS solution as determined from PCP curves.
3.4. Cell proliferation study
The proliferation and morphology of MC3T3 pre osteoblast
cells were investigated on 316L stainless surfaces. The study was
intended to examine topographic and wettability features of the
passive film on cell proliferation. Topographic alterations could
affect the roughness, wettability, surface energetics and surface
chemistry, which could further affect the protein adsorption behav-
ior over the surface [38]. These parameters could also affect the cell
morphology, organization, cell adhesion and osseointegration [39].
Generally, cell attachment and its standard morphology is the ini-
tial step in a cascade of cell–implant interaction and determine the
biocompatibility of the implant.
In Fig. 10, the cell proliferation rate on MP, EPO and EPBO after
24 h was almost equal, however it can be observed that on MP, the
cells morphology showed peculiar structure in comparison with
the cells on EPO and EPBO. This might be attributed to the rel-
ative higher surface roughness (33.51 ± 5.54) of the MP sample.
It has been previously studied that rough surfaces could release
higher amount of ions in comparison with smooth surface [40].
The leached ions from biocompatible material at low concentra-
tion are considered non-toxic but they could significantly influence
the cell proliferation [41]. It is worthy to mention that the surface
roughness could provide better focal contact [42] and may lead to
better adhesion while surfaces with lower roughness below 10 ␮m
may influence the biological interactions and protein adsorption
[43]. Hence, the EPO and EPBO presented better cell proliferation
and morphology in initial 24 h incubation period compared to MP.
The cells also indicated the healthy and stellar morphology with
pronounced protrusion at the surface of EPO and EPBO samples.
This could be due to the limited release of metal ions which could
adversely affect the cell morphology and proliferation as is the
case with MP sample. The low corrosion rate registered by EBPO
than MP and EPO also validated this behavior and PCP scans were
in agreement with the cell proliferation character which followed
the EPBO > EPO > MP trend. The relatively higher corrosion rate of
MP sample adversely affected the cell morphology as shown in
Fig. 10. The surface wettability is also another important factor
which could also influence the cell response. It has been previously
investigated that SFE was an important surface characteristic for
cellular adhesion strength and proliferation [44]. From our wetta-
bility data, it is calculated that the acidic components are lower
than basic components. These polar components could influence
the cell adhesion and proliferation. The lower fractional polarity
(7) (AB/(LW + AB)) might be expected to provide better cell prolif-
 Z. ur Rahman et al. / Applied Surface Science 410 (2017) 432–444
Fig. 10. MC3T3 Cell proliferation on 316L SS for 24 h and 48 h.
eration and optimal cytocompatibility [28]. In comparison EPBO
provided lowest fractional polarity which could be attributed to its
better response toward cell proliferation than MP and EPO sam-
ples. This could also be the reason for enhanced bioactive behavior
of electropolished surfaces than the mechanically polished one.
After 48 h of incubation the relatively higher proliferation rate was
observed on all samples with no obvious difference and the surfaces
are almost covered by the cell monolayers.
4. Conclusions
Electropolishing of 316L stainless steel at the oxygen evolu-
tion and below the oxygen evolution potentials was carried out
to improve its surface roughness, topography and corrosion resis-
tance. The oxidation of 316L samples in the presence of H+ , H3 PO4
and H2 SO4 during electropolishing could significantly modify the
surface passive film. The XPS analysis of the core peaks of O1s, Cr2p,
Fe2p, P2p and S2p elements confirmed the existence of Cr (III) Fe (II)
and Fe(III) species at the surface of MP, EPO and EPBO samples. The
phosphate and sulfate species within the passive film were found
to be related with the possible oxidation of phosphorus or sulfur
content in the material and/or due to the adsorption of H3 PO4 ,
H2 PO4 − , H2 SO4 and HSO4 − species during the electropolishing pro-
cess. The relatively higher surface free energy provided by MP
(51.81 mJ/m2 ) than EPO (47.52 mJ/m2 ) and EPBO (44.21 mJ/m2 ) was
in accordance with the decrease in surface roughness in the order
of MP > EPO > EPBO as measured by AFM. The relatively positive
OCP, lower corrosion rate (0.484 mpy) and significantly large pas-
sive film resistance (12430 M cm2 ) provided by EPBO sample than
EPO and MP in the PBS solution confirmed the improvement in the
electrochemical stability of passive film.
In comparison, EPBO also provided the lowest fractional polarity
and surface roughness which could be beneficial for the cell prolif-
eration and to increase the bioactivity of the surface. The enhanced
protrusion and stellar morphology of the cell was observed on the
EPO and EPBO samples during initial 24 h incubation period. The
443
relatively higher corrosion rate of MP sample and release of metal
ions could be the possible reasons of its limited cell proliferation
characteristics.
Acknowledgement
Z. Rahman would like to acknowledge financial support from
Science of Advanced Materials program at Central Michigan Uni-
versity.
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