Surface & Coatings Technology 366 (2019) 86–96

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Surface & Coatings Technology

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

Effects of pack chromizing on the microstructure and anticorrosion T

properties of 316L stainless steel
⁎
Zhihao Donga, Tong Zhoua, Jie Liua, Xinwen Zhanga, Bin Shena, Wenbin Hub, Lei Liua,c,
a
State Key Laboratory of Metal Matrix Composites, School of Material Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
b
School of Material Science and Engineering, Tianjin University, Tianjin 300072, China
c
Collaborative Innovation Center for Advanced Ship and Deep-Sea Exploration, Shanghai Jiao Tong University, Shanghai 200240, China

A R T I C LE I N FO A B S T R A C T

Keywords: To extend the applications of 316L stainless steel in corrosive environments and correlate the corrosion re-
316L stainless steel sistance with composition and microstructure, homogeneous Cr-rich layer with the thickness of 75 μm was
Pack chromizing fabricated on 316L stainless steel by pack chromizing and post heat treatment. The chromizing layer was mainly
Corrosion resistance composed of FeeCr solid solution. Post heat treatment eliminated the precipitates and Cr-depletion in the
Electrochemical measurements
chromizing layer. The corrosion behaviors were studied by electrochemical measurements and corrosion mor-
phology observation. The pitting corrosion in Cl− containing solutions was avoided after chromizing treatment,
which was ascribed to the reduced sensitivity of Cr-rich surface to Cl− ions. The higher Cr concentration in the
modified layer also improved the long-term stability of corrosion resistance. After immersion in NaCl solution for
24 days, the charge transfer resistance of chromizing sample was higher than that of 316L by a factor of 8.19. In
addition, the free corrosion potential shifted to the positive direction after post heat treatment, and the corrosion
current density was also reduced to 0.066 μA/cm2. The further improvement on anticorrosion performance was
attributed to the homogeneous microstructure.

1. Introduction
Stainless steels (SS) have been widely applied in manufacturing,
nuclear power, transportation and biomedical facilities [1]. Corrosion is
a serious threat for the service of stainless steels. 316L SS is one of the
most commonly used industrial stainless steels. It can be used to fab-
ricate the turbine blades in power plants or marine equipment [2,3],
and also as the biomaterial implants due to the excellent biomedical
properties [4,5]. The steady service performance for long period is
crucial in industrial practices. However, 316L SS is susceptible to the
localized pitting corrosion after long-term exposure to corrosive en-
vironments, especially the Cl− containing solutions [1,6]. Therefore,
improving the anticorrosion property in typical corrosive mediums is
meaningful to extend the applications of 316L SS.
Surface modification is an effective approach for corrosion pre-
vention by changing the contact conditions between corrosive mediums
and the materials. Surface modifications such as micro-arc oxidation
[7,8], laser surface treatment [9–11] and surface mechanical attrition
treatment [12] have been studied for corrosion resistance improve-
ment. Modified layer can be deposited out of the matrix surface as
coatings or films, and can also be located beneath the original surface of
substrate through atom diffusion process. In lots of researches, ceramic
and amorphous protective coatings (e.g. TiN, TaN and ZrO2)
[4,5,13–17] as well as superhydrophobic coatings [18,19] were formed
on 316L SS matrix to improve the anticorrosion performance through
physical or chemical deposition. Harun et al. [20] fabricated a thermal
oxide film on 316L SS by high-temperature atmosphere heating. The
oxide film containing Cr2O3 provided obviously enhanced corrosion
resistance, whereas the film was thinner than 1 μm and cannot satisfy
the requirements under severe conditions. Furthermore, the weak
bonding strength between coatings/films and the matrix may cause
troubles in service. In addition to the coatings or films, the diffusion
layers are also investigated due to its metallurgical bonding with the
substrate. Nitrogen ions implantation [21–23] and solid cementation
[24] were applied to improve the pitting corrosion resistance of ma-
terials. However, the nitrogen ions collision might damage the crystal
lattice and conversely reduce the long-term corrosion resistance.
It is well known that the hard chromium (Cr) possesses outstanding
corrosion and wear resistances [25,26]. Thus, Cr-rich surface layer is an
appropriate choice for corrosion prevention, especially for resisting

⁎
Corresponding author at: State Key Laboratory of Metal Matrix Composites, School of Material Science and Engineering, Shanghai Jiao Tong University, Shanghai
200240, China.
E-mail address: anodic@sjtu.edu.cn (L. Liu).

https://doi.org/10.1016/j.surfcoat.2019.03.022
Received 3 December 2018; Received in revised form 26 February 2019; Accepted 11 March 2019
Available online 12 March 2019
0257-8972/ © 2019 Elsevier B.V. All rights reserved.
Z. Dong, et al.
pitting corrosion. Among the surface modifications aforementioned,
pack cementation holds the advantages of low cost and massive pro-
duction. In the open literature, the relevant properties of chromizing
carbon steels have been studied [27–31]. Nevertheless, few investiga-
tions were conducted on stainless steels. Lee et al. [32] briefly studied
the surface microstructure and polarization behaviors of chromizing
layer on SS. However, the correlation between microstructure and the
corrosion resistance was not discussed. Therefore, the detailed effects of
pack chromizing on the microstructure and anticorrosion property of
316L SS are necessary to be comprehensively investigated.
In this work, surface chromizing treatment was conducted on 316L
SS to improve the corrosion resistance. The corrosion behaviors in ty-
pical corrosive mediums were investigated in detail to comprehend the
correlation between composition/microstructure and anticorrosion
property. Post heat treatments were applied to further homogenize the
microstructure of chromizing layer, which was not discussed in pre-
vious studies.
2. Experimental
2.1. Materials and procedures
The chemical composition of substrate material 316L SS is listed as
follows (wt%): Cr-17.19, Ni-9.56, Mo-2.86, Mn-1.08, Si-0.31, Al-0.05,
C-0.03, Fe balance. All the specimens with the dimension of
10 mm × 10 mm × 6 mm were ground by #600, #1200 and #2500
waterproof SiC abrasive papers, and then polished with 2.5 μm and
1 μm diamond pastes.
The specimens for chromizing were packed in the chromizing
powders (commercial grade, Jingchun New Materials Co., Ltd., China,
purity: > 99 wt%) with the composition of 58 wt% Cr powders as the
chromizing source, 30 wt% Al2O3 powders as the inert additive and
12 wt% NH4Cl as the active additive. The average particle size of
chromizing powders was 40 μm. The specimens and powders were
sealed in a vessel using high-temperature refractory clay. The vessel
was heated in air atmosphere at 1070 °C for 12 h, and then cooled in
furnace. During the process, chromium atoms diffused into the lattice of
316L austenite grains and substituted certain iron atoms. After the
chromizing treatment, a Cr-rich thermal diffusion layer was formed on
the surface of 316L SS. The samples before and after chromizing
treatment were labelled as 316L and 316L/Cr, respectively. Parts of the
chromizing specimens were post heat treated under different conditions
to examine the evolution of microstructure and phase composition. The
detailed procedures and parameters of post heat treatment are given in
Table 1. The samples for post heat treatment were heated at the rate of
10 °C/min in air atmosphere. The post heat treated samples were la-
belled from Q1 to Q6. The chromizing and post heat treated specimens
were mechanically polished to remove the rough outer surface layer
and obtain mirror surfaces for the next experiments.
2.2. Surface characterization
The phase composition of top surface layer was characterized by
glancing angle X-ray diffraction (GAXRD, Bruker D8 Advance) with Cu-
target Kα radiation. The glancing incidence angle was set as 3° and the
scanning rate was 1°/min. The micro morphologies were observed by
scanning electron microscope (SEM, JEOL JSM-7800F) with the
Table 1
The procedures and parameters of post heat treatment.
Samples Q1 Q2
Temperature (°C) 900 900
Time (min) 30 60
Cooling mode Quenched Quenched
Surface & Coatings Technology 366 (2019) 86–96
accelerating voltage of 10 kV. The distribution and proportion of ele-
ment composition were determined by energy dispersive spectroscopy
(EDS, Thermo Scientific System 7), using the line scanning, mapping
and point analysis mode under the voltage of 15 kV. The 3-D surface
morphologies after polarization were observed and reconstructed by
ultra-depth of field optical microscope (Keyence VHX-1000) and atomic
force microscope (AFM, Nanonavi E-Sweep). The composition of pro-
tective film after long-term immersion was characterized by X-ray
photoelectron spectroscopy (XPS, AXIS Ultra DLD). The XPS peak fitting
was carried out by the CasaXPS software, and the binding energy of C 1s
peak was set as 284.8 eV for spectra calibrating. The cumulative mass
loss after immersion tests was measured by an analytical balance with
the accuracy of 0.1 mg. The tests were repeated for three times and
averaged to ensure the reliability.
2.3. Electrochemical measurements
Electrochemical measurements were conducted with a CHI660E
electrochemical workstation at the room temperature 25 °C. The stan-
dard three-electrode system was applied, consisting of a saturated ca-
lomel electrode as the reference electrode, a platinum electrode as the
counter electrode, and the tested samples with the exposed area of
1 cm2 as the working electrode. The electrolyte solutions included
0.1 M HCl and 3.5 wt% NaCl solutions.
The samples were immersed in electrolyte solution for about 2000 s
in advance to get a steady open circuit potential (OCP). Electrochemical
impedance spectroscopy (EIS) measurements were performed under the
sinusoidal voltage excitation with the amplitude of 5 mV around OCP
and the frequency range of 100 kHz to 0.01 Hz. Equivalent circuit fit-
ting was performed by ZView software to obtain the parameters of
electrochemical impedance. Polarization resistance (Rp) was measured
in the voltage range from −10 mV to +10 mV versus OCP by linear
potentiodynamic sweep. The scanning rate was set as 0.33 mV/s.
Potentiodynamic polarization (PDP) tests were conducted in the voltage
range from −0.6 V to +1.2 V versus OCP with the scanning rate of
1 mV/s. The free corrosion potential (Ecorr) and corrosion current
density (Icorr) were calculated from the PDP curves.
3. Results and discussion
3.1. Microstructure and phase composition of chromizing layer
3.1.1. Microstructure
The cross-sectional morphology of 316L/Cr after metallographic
etching is shown in Fig. 1(a). The chromizing layer was composed of
three layers (remarked as layer A, B and C) with the total thickness of
75 μm. Layer A and B were separated by a row of closed pores, which
might stem from the Kirkendall effect in diffusion process [30]. Some
closed pores also appeared inside layer A. Layer B and C were dis-
tinguished by the different microstructures. Layer B was flat and com-
pact, while layer C was etched in certain areas. The cross-sectional
element distribution along the depth direction is plotted in Fig. 1(b).
The content of Cr was higher than that of Fe in the chromizing layer. A
sharp decrease of Cr concentration appeared in the depth of 75 μm,
while the intensity of Fe increased rapidly at the same location, in-
dicating the interface between chromizing layer and the substrate.
Additionally, Ni concentration slightly fluctuated in the depth of 50 μm
Q3 Q4 Q5 Q6
1070 1070 1200 1200
30 60 30 60
Quenched Quenched Quenched Quenched
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Z. Dong, et al.
Fig. 1. 316L/Cr: (a)cross-sectional morphology; (b)element distribution along depth direction; top view of (c) layer A and (d) layer B.
to 75 μm. The top view of layer A is shown in Fig. 1(c). Some protru-
sions with the average size of about 40 μm were scattered on the rough
surface of layer A. The protrusions were identified as adherent Cr
powders according to the EDS spectrum in Fig. 1(c). The top view of
layer B after polishing and metallographic etching is presented in
Fig. 1(d). The morphology of layer B showed that the grain boundaries
were extremely wide, and some white precipitates appeared at the grain
boundaries. The wide grain boundaries usually existed together with
the white precipitates.
Layer B was the most compact one among the three layers according
to the cross-sectional morphology and was presumed to possess the best
anticorrosion performance. To investigate the detailed microstructure
of layer B, the element mappings are shown in Fig. 2. It was clearly
observed that the concentration of Cr and C in the white precipitates
were higher than the surrounding regions. Therefore, the white pre-
cipitates were suggestive of chromium carbides [33]. At the concave
areas, the mass concentration of Cr was relatively lower than that in the
rest regions. Thus, the concave areas were characterized as Cr-depletion
regions. Additionally, the enrichment of Fe at the broad grain bound-
aries could also be observed. Due to the high stoichiometric ratio of Cr/
C in chromium carbides (e.g. Cr23C6), the intergranular precipitates
would cause the Cr-depletion in the vicinity of chromium carbides and
result in the enrichment of Fe at the grain boundaries [34,35]. The
observation of element concentration difference was also verified by
EDS analysis: the mass ratio of Cr/Fe in normal grains was 1.71, while
the ratio at the Cr-depletion areas was only 1.28.
3.1.2. Phase composition
Before characterization, the chromizing layer of 316L was thinned
to different thicknesses which were corresponding to the depth of layer
B, C and the substrate by mechanical polishing, and then examined by
glancing angle X-ray. The GAXRD patterns of different layers are shown
in Fig. 3. As observed, the phase composition of layer A was compli-
cated. Chromium carbides including Cr23C6 (JCPDS No. 35-0783) and
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Surface & Coatings Technology 366 (2019) 86–96
Cr7C3 (JCPDS No. 11-0550) and chromium nitrides including Cr2N
(JCPDS No. 35-0803) and CrN (JCPDS No. 65-2899) were detected in
layer A. The appearances of chromium carbides and chromium nitrides
were consistent with the results reported in the literature [27,33]. The
FeeCr solid solution phase (JCPDS No. 34-0396) was detected in layer
A as well. Although the C content in 316L stainless steel was low, the C
atoms could uphill diffuse onto the surface due to the activity gradient
of C element [36]. The C atoms gathered on the surface and formed
chromium carbides with Cr atoms. In addition, the N atoms in chro-
mium nitrides originated from NH4Cl active additive instead of the
substrate [27,29,30]. As seen in layer B, the main phase turned into
FeeCr solid solution and little Cr2C (JCPDS No. 14-0519) was also
detected. The chromium nitrides disappeared in layer B because of the
few contents of NH4Cl. Although the mass ratio of Fe/Cr at the grain
boundaries was slightly different with that in the normal grains, the
lattice types were identical. Both of the two areas were characterized as
FeeCr solid solution phase due to the substitution structure of FeeCr
solid solution and the tiny atomic size difference between Fe and Cr. In
addition, it was noteworthy that the Cr23C6 and Cr7C3 evolved into Cr2C
as the depth increased, which was ascribed to the lower formation
enthalpy of Cr2C in Cr-deficient conditions [33]. Therefore, it was de-
termined that layer B mainly consisted of FeeCr solid solution phase
and the white precipitates were chromium carbides. As for layer C, the
main phase was still FeeCr solid solution. Additionally, the FeeNi
(JCPDS No. 26-0790) and CreNi (JCPDS No. 26-0429 and 26-0430)
solid solution phases appeared in this layer, which was in agreement
with the Ni concentration fluctuation. The matrix of 316L/Cr was
completely composed of γ-Fe phase (JCPDS No. 33–0397) and the same
as 316L samples.
3.2. Corrosion resistance in HCl solution
3.2.1. Corrosion behavior in 0.1 M HCl solution
In chemical industry, 316L SS suffers severe threat from corrosive
Z. Dong, et al.
Fig. 2. The SEM image and element distribution of magnified area in layer B of 316L/Cr.
Fig. 3. GAXRD patterns of different layers in 316L/Cr.
substances such as HCl. To investigate the corrosion behaviors of 316L
and 316L/Cr in mediums containing Cl− and H+ ions, the electro-
chemical measurements were performed in 0.1 M HCl solution. The
results and corrosion morphologies after polarization are shown in
Fig. 4. The diameter of capacitance arc of 316L/Cr in Fig. 4(a) was
significantly bigger than that of 316L, implying the higher charge
transfer resistance (Rct) and better corrosion resistance. In other words,
the transformation of metallic atoms into metallic ions was restricted on
the surface of 316L/Cr. The potentiodynamic polarization curves are
shown in Fig. 4(b). The higher free corrosion potential (Ecorr) and lower
corrosion current density (Icorr) were observed in 316L/Cr. Generally,
Ecorr is relevant to the initiation of corrosion while Icorr corresponds to
the corrosion rate after starting. The improvements on Ecorr and Icorr
indicated the higher corrosion resistance of 316L/Cr compared with
316L. At the polarization potential of 0.45 V, the corrosion current
density of 316L sharply increased, which was well known as the char-
acteristic of pitting corrosion caused by Cl− ions. However, no pitting
corrosion was observed in the curve of 316L/Cr. Consistent with the
pitting corrosion feature in the polarization curve, remarkable corro-
sion pits with the diameter of > 100 μm were observed on the surface
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Surface & Coatings Technology 366 (2019) 86–96
of 316L in Fig. 4(c). Pitting corrosion usually resulted from the Cl− ions
in corrosive environments, and recent research also revealed the
breaking mechanism of passive film under the attack of Cl− through
experimental observation [37]. No corrosion pits appeared on the sur-
face of 316L/Cr in Fig. 4(d). Usually, higher Cr concentration in steels
could move the pitting potential to the more positive direction. If the Cr
concentration reached a certain value, the pitting corrosion would not
take place any more [26]. In addition, the broad grain boundaries of
316L/Cr were clearly observed in Fig. 4(d). The grain boundaries were
preferentially corroded compared with the normal grains and the pre-
cipitates, which could be attributed to the Cr-depletion in grain
boundaries [34,35,38]. The intergranular etching of 316L/Cr was much
less serious than the corrosion pits in 316L, indicating the resistance to
H+ and Cl− ions was significantly improved due to the higher surface
Cr concentration.
3.2.2. Mass loss measurements in 1 M HCl solution
To accelerate the corrosion process and verify the results of elec-
trochemical measurements, the mass loss was measured after immer-
sion in 1 M HCl solution. The cumulative mass losses of 316L and 316L/
Cr versus immersion time are shown in Fig. 5(a). The mass loss of 316L/
Cr was significantly less than that of 316L at all the measuring points.
After 48 h immersion, the cumulative mass loss of 316L/Cr was
0.217 mg/cm2 and was 3.78 times lower than that of 316L. The cu-
mulative mass loss rate of 316L/Cr in Fig. 5(b) was also lower than that
of 316L during the immersion test. Although the Cl− ions kept at-
tacking the material surfaces, the protective film still came into effect
and gradually reduced the mass loss rate. In conclusion, the cumulative
mass loss and mass loss rate of 316L/Cr were both significantly lower
than 316L, which was in agreement with the improved corrosion re-
sistance aforementioned.
3.3. Corrosion resistance in NaCl solution
3.3.1. Corrosion morphology after polarization
To investigate the sole influence of Cl− ion without H+ ions, the
corrosion tests were conducted in the neutral 3.5 wt% NaCl solution.
The corrosion morphology of 316L after polarization was shown in
Z. Dong, et al.
Fig. 4. (a) Electrochemical impedance spectroscopy, (b) polarization curve and corrosion morphology of (c) 316L and (d) 316L/Cr after polarization test in 0.1 M HCl
solution.
Fig. 6(a) and (b), the 3-D photo was taken by ultra-depth of field optical
microscope. The pitting corrosion caused by Cl− ions was observed on
the surface of 316L. The depth and diameter of the corrosion pit was
38 μm and 20 μm, respectively. It was noteworthy that the size of pits
was several times smaller than that formed in 0.1 M HCl solution
(Fig. 4(c)) though the Cl− concentration was about 6 times higher,
indicating the significant role of synergism between Cl− and H+ ions.
The cathodic processes of corrosion in HCl and NaCl solution are well
known as H2-production and O2-consuming reactions, respectively
[39]. The high concentration of H+ ions in HCl solution accelerated the
cathodic reaction. Therefore, the corrosion process in HCl solution was
severe and the corrosion pits enlarged rapidly. However, in neutral
NaCl solution the corrosion mechanism turned from H2-production to
O2-consuming. The low content of dissolved O2 in NaCl solution re-
strained the cathodic reaction. Consequently, the corrosion pits were
smaller compared with that formed in HCl solution. In both HCl and
NaCl solutions, small corrosion pits initiated under the attack of Cl−
ions, whereas the further growth of corrosion pits was controlled by
different cathodic processes shown above. As a consequence, the high
Fig. 5. (a) Cumulative mass loss and (b) cumulative mass loss rate of 316L and 316L/Cr during the immersion test in 1 M HCl solution.
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Surface & Coatings Technology 366 (2019) 86–96
concentration of H+ ions resulted in the significant enlargement of the
initial corrosion pits.
Fig. 6(c) and (d) displays the corrosion morphology of 316L/Cr after
polarization in 3.5 wt% NaCl solution. Since the micro precipitates were
hard to be observed by optical microscope, AFM was used to char-
acterize the corrosion topography. As seen in the photos, chromium
carbide precipitates were salient compared with the rest areas. The
morphology implied that chromium carbides were the noblest phase in
NaCl solution. In addition, the height difference between normal grains
and the grain boundaries was not remarkable, indicating that the slight
composition discrepancy showed no significant influence on the cor-
rosion behavior in neutral NaCl solution. The absence of pitting cor-
rosion in 316L/Cr implied the enhanced pitting resistance of Cr-rich
surface. In conclusion, the corrosion resistance of 316L/Cr in 3.5 wt%
NaCl solution was much higher than that of 316L.
3.3.2. Electrochemical impedance spectroscopy analysis
The samples were also immersed in static 3.5 wt% NaCl solution for
several days to simulate the natural corrosion and investigate the
Z. Dong, et al.
Fig. 6. (a) Corrosion morphology and (b) 3-D reconstruction of 316L characterized by ultra-depth of field optical microscope; (c) corrosion morphology and (d) 3-D
reconstruction of 316L/Cr characterized by AFM after polarization in 3.5 wt.% NaCl solution.
evolution of electrochemical behavior. Fig. 7 shows the Bode diagrams
of electrochemical impedance spectroscopy after immersion for 0, 5 and
24 days. In the phase angle-peak diagrams (Fig. 7(a–c)), the higher
phase angle and wider peak represented the better corrosion resistance.
The maximum phase angle of 316L experienced the initial increase
followed by a decrease, whereas the value of 316L/Cr kept at 84°
without fluctuation in Fig. 7(a–c). Thus, 316L/Cr exhibited the en-
hanced stability compared with 316L. Generally, the electrochemical
behaviors in high and low frequency regions are corresponding to the
charge transfer and mass transport processes, respectively [40–42].
According to Fig. 7(c), the phase angles of 316L/Cr after 24 days im-
mersion were higher than that of 316L in both high and low frequency
regions. The enhancement demonstrated the higher resistance to en-
vironmental interference in a broad frequency range. The impedance
moduli |Z| of 316L/Cr and 316L were close to each other before im-
mersion in Fig. 7(d). After the immersion started, |Z| of 316L/Cr kept
stable while the value of 316L declined. After 24 days immersion, |Z| of
316L/Cr in Fig. 7(f) was obviously higher than 316L, indicating the
better protective effect provided by the chromizing surface [43]. As a
result of the electrochemical impedance spectroscopy analysis, the
chromizing treatment endowed 316L with the enhanced anti-inter-
ference and anticorrosion properties during long-term immersion in
NaCl solution.
3.3.3. Equivalent circuit fitting
Equivalent circuit fitting was performed to investigate the evolution
of electrochemical parameters after long-term immersion in 3.5 wt%
NaCl solution. The measured data and fitting curves are represented by
symbols and solid lines in Fig. 7, respectively. The equivalent circuit
model of 316L and 316L/Cr is given in Fig. 8. Two time constants were
introduced to get the best fitting results since the broad phase angle
peak was most probably superposed by two peaks. Rs is the resistance in
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Surface & Coatings Technology 366 (2019) 86–96
electrolyte solution. Rf is the resistance of surface film and Rct re-
presents the charge transfer resistance of double electric layer. CPE is
the constant phase angle element similar to capacitance.
The fitting electrochemical parameters are listed in Table 2. The Rf
of 316L initially increased followed by a remarkable decline and was
surpassed by that of 316L/Cr after 24 days, implying the more protec-
tive film on the surface of 316L/Cr [43]. The Rct of 316L was reduced
by two orders of magnitude during the immersion test. However, the
value of 316L/Cr increased after initial decline and was 8.19 times
higher than that of 316L after 24 days. The parameters CPE-T and “n”
represent the capacitance value and capacitive exponent of CPE, re-
spectively. The CPE degenerates to pure resistance as n = 0 while pure
capacitance as n = 1 [41]. The bigger value of “n” usually suggests the
lower porosity of surface [43]. The n1 of 316L kept reducing during the
test, indicating the degradation of protective film on 316L after im-
mersion for several days. On the contrary, the increased n1 of 316L/Cr
represented the enhanced stability of protective film. In conclusion,
316L obtained improved corrosion resistance in the early immersion
stage, whereas the property started decreasing subsequently, which was
consistent with the conclusion reported by Heakal et al. [44]. However,
the anticorrosion property of 316L/Cr kept outstanding and steady after
the long-term immersion in NaCl solution, indicating the significant
improvement compared with 316L.
3.3.4. XPS analysis
XPS analysis was performed to further investigate the composition
of protective films after immersion in 3.5 wt% NaCl solution for
24 days. The results of spectra fitting are shown in Fig. 9 and Table 3.
The binding energies used for peak fitting were determined according
to the NIST database. The O 1s spectra in Fig. 9(a) showed that the
protective films on both 316L and 316L/Cr were mainly composed of Cr
(OH)3, Cr2O3 and Fe2O3, whereas the relative quantities were different.
Z. Dong, et al.
Fig. 7. Bode diagrams after immersion in 3.5 wt.% NaCl solution for (a) (d) 0 day; (b) (e) 5 days; (c) (f) 24 days. (a) (b) (c) are phase angle-frequency diagrams and
(d) (e) (f) are impedance modulus-frequency diagrams.
Fig. 8. Equivalent circuit model of 316L and 316L/Cr used for EIS fitting.
The content of chromium compounds including Cr(OH)3 and Cr2O3 on
316L/Cr was 89.83%, while the percentage on 316L was only 69.67%.
It was previously proved that 316L/Cr possessed the higher corrosion
resistance after immersion, and the improvement could be attributed to
the higher content of chromium compounds in the protective film of
316L/Cr. The fitting results of Fe 2p3/2 spectra in Fig. 9(b) revealed the
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Surface & Coatings Technology 366 (2019) 86–96
higher percentage of zero-valent iron in 316L/Cr. The more reserva-
tions of original Fe also verified the enhanced protective effect of
chromizing surface.
3.4. Post heat treatment
3.4.1. Microstructure and phase composition evolution
The post heat treatments were conducted to homogenize the mi-
crostructure and further improve the corrosion resistance. The thick-
ness and element composition of chromizing layers were not changed
after the post heat treatments. Fig. 10 shows the microstructures of all
the samples after polishing and metallographic etching. 316L was
completely composed of austenite in Fig. 10(a). The microstructure of
316L/Cr in Fig. 10(b) was discussed in Section 3.1.1. Obvious pre-
cipitates were still observed in Q1 (Fig. 10(c)) and Q2 (Fig. 10(d)) after
treated at 900 °C, indicating that the low temperature could not offer
enough activation energy for precipitates to decompose. The micro-
structures of Q3 and Q4 were shown in Fig. 10(e) and (f), respectively.
Z. Dong, et al. Surface & Coatings Technology 366 (2019) 86–96

Table 2
Parameter values of the electrochemical impedance spectroscopy fitting.
Samples Immersion time (days) Rs (Ω·cm2) Rf (kΩ·cm2) CPE1-T (μF·cm−2) n1 Rct (kΩ·cm2) CPE2-T (μF·cm−2) n2

316L 0 6.65 330.8 18.77 0.947 1154.8 9.84 0.883

5 6.71 357.8 36.73 0.945 135.6 165.48 0.892
24 6.48 160.8 34.08 0.938 37.1 133.04 0.868
316L/Cr 0 10.11 703.7 25.57 0.921 1932.8 8.77 0.861
5 8.42 306.9 25.62 0.927 150.3 45.89 0.886
24 11.61 323.4 20.88 0.930 303.7 31.22 0.903

The Cr-depletion areas in Q3 still existed, whereas both the precipitates Table 3
and Cr-depletion in Q4 were eliminated. The grain boundaries in Q4 Fitting parameters and relative quantity of compounds in surface film after
also became narrow and straight. The heat treatment temperature for immersion in 3.5 wt.% NaCl solution for 24 days.
Q3 and Q4 (1070 °C) reached the decomposition temperature of chro- Spectra Samples Species Binding energy (eV) Relative quantity (%)
mium carbide precipitates, thus the precipitates disappeared. However,
the discrepancy of Cr concentration in different regions still existed and O 1s 316L Cr(OH)3 531.6 47.93
Cr2O3 530.8 21.74
it would take lots of time for Cr diffusion from Cr-rich areas to Cr-
Fe2O3 529.8 30.32
depletion areas. The heat treatment time for Q3 (30 min) was not en- 316L/Cr Cr(OH)3 531.6 75.57
ough for the homogenization of Cr concentration. As a consequence, the Cr2O3 530.8 14.26
Cr-depletion areas remained in Q3. Nevertheless, under the longer heat Fe2O3 529.8 10.17
treatment time, the Cr concentration difference was eliminated in Q4. Fe 2p3/2 316L Fe 706.7 0.81
Fe2O3 710.8 99.19
The microstructures of Q5 and Q6 were shown in Fig. 10(g) and (h), 316L/Cr Fe 706.7 8.42
respectively. The precipitates and Cr-depletion in Q5 and Q6 were Fe2O3 710.8 91.58
eliminated as well, since the temperature was high enough for micro-
structure homogenization, regardless of the heat treatment time.
The XRD patterns in Fig. 11 verified the microstructure evolution The electrochemical impedance spectroscopy measurements were
under different heat-treated temperatures and time. The chromizing conducted in 3.5 wt% NaCl solution and the results are shown in
layers of Q1 and Q2 were mainly composed of carbides and FeeCr solid Fig. 12(a). The capacitance arc diameter of Q2 and Q3 showed no su-
solution, which was consistent with the morphologies in Fig. 10. Q4, Q5 periority to that of 316L, implying the decreased corrosion resistance
and Q6 were entirely composed of FeeCr solid solution phase and no after heat treatment compared with 316L/Cr. The capacitance arc of Q1
carbide precipitates were detected in the three samples. According to was close to that of 316L/Cr, which indicated the values of Rct were
the phase composition and microstructure analysis, the homogeneous similar. In addition, the Rct of Q4, Q5 and Q6 were raised compared
surface states were obtained after appropriate heat treatment process. with that of 316L/Cr, among which Q5 possessed the biggest diameter
During the heat treatment, enough temperature and time offered the of capacitance arc. The improvements on Q4, Q5 and Q6 strongly
activation energy for precipitates decomposition and Cr-depletion corresponded to the homogeneous microstructures in Fig. 10, verifying
elimination. Namely, the microstructure homogenization was achieved the higher corrosion resistance after post heat treatment.
through thermodynamic or kinetic approaches. The potentiodynamic polarization curves are shown in Fig. 12(b).
The parameters Ecorr, Icorr and Rp of each sample are listed in Table 4.
The characteristic of pitting corrosion was shown in 316L at the po-
3.4.2. Corrosion resistance in 3.5 wt% NaCl solution tential of 0.323 V due to the damage of Cl− ions to passive film. No
The corrosion resistance of chromizing layer could be significantly sharp increase in current density was observed from the curves of 316L/
influenced by the microstructure. Due to the disparity in crystal struc- Cr and the post heat treated samples, showing the lower sensitivity to
ture and chemical composition, the relative nobility of each region in Cl− ions of Cr-rich surface. According to Table 4, Q5 and Q6 possessed
corrosive medium is different [43]. The areas with lower corrosion the most positive Ecorr indicating the most difficult initiation of corro-
potentials are easier to be corroded, which is known as galvanic cor- sion. The Icorr of Q5 was the lowest among all the samples. Additionally,
rosion. The corrosion behaviors of samples after post heat treatments the polarization resistance Rp of Q5 and Q6 also showed superiority to
were investigated to comprehend the relationship between corrosion the other samples. As a conclusion, Q5 possessed the best anticorrosion
resistance and the microstructure.

Fig. 9. High resolution XPS of (a) O 1s and (b) Fe 2p3/2 after immersion in 3.5 wt.% NaCl solution for 24 days.

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Z. Dong, et al. Surface & Coatings Technology 366 (2019) 86–96

Fig. 10. Microstructures of (a)316L; (b)316L/Cr; (c)Q1; (d)Q2; (e)Q3; (f)Q4; (g)Q5; (h)Q6.

composed of FeeCr solid solution and chromium carbide pre-

(2) The pitting corrosion of 316L/Cr in Cl− containing environments
(3) Post heat treatments further eliminated the chromium carbide
Fig. 11. Phase composition of the samples after post heat treatment.
performance among all the samples, and the corrosion resistance of Q6
was also improved on the basis of 316L/Cr. The Cr-rich chromizing
layer endowed the samples with higher resistance to pitting corrosion,
and the further homogenized microstructure eliminated the galvanic
corrosion.
4. Conclusions
(1) A Cr-rich diffusion layer with the thickness of 75 μm was fabricated
on the surface of 316L SS through pack chromizing treatment. The
modified layer consisted of three layers. The interlayer was mainly
cipitates. The Cr-depletion caused by carbide precipitates was also
observed at the grain boundaries.
was avoided. The reduced sensitivity to Cl− ions was ascribed to the
high concentration of Cr on the chromizing surface. The cumulative
mass loss of 316L/Cr in 1 M HCl solution was lower than that of
316L by a factor of 3.78. The stability of anticorrosion performance
of 316L/Cr in NaCl solution was also enhanced compared with
316L. After immersion for 24 days, the Rct and Rf of 316L/Cr were
8.19 and 2.01 times higher than those of 316L, respectively. The
improved anticorrosion property of 316L/Cr could be attributed to
the better protective effect of the film containing up to 89.83%
chromium compounds.
precipitates and element concentration difference in 316L/Cr. The
samples after appropriate treatment process were entirely com-
posed of FeeCr solid solution phase. The heat treatment parameters
1200 °C/30 min endowed Q5 with the best corrosion resistance. The
sample Q5 possessed the lowest corrosion current density
(0.066 μA/cm2) among all the samples, which was 1.48 times lower
than that of 316L/Cr. The pitting corrosion and galvanic corrosion
were restricted by the homogeneous microstructure with higher Cr
concentration. The results verified the prominent improvement on
anticorrosion property triggered by homogeneous microstructure
and established the correlation between corrosion resistance and
the surface microstructure.

Fig. 12. (a) Electrochemical impedance spectroscopy and (b) potentiodynamic polarization curves of 316L, 316L/Cr and the post heat treated samples.

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Table 4
Potentiodynamic polarization parameters of samples in 3.5 wt.% NaCl solution.
Samples 316L 316L/Cr Q1
Ecorr(mV) −166 −151 −136
Icorr(μA·cm−2) 0.172 0.092 0.195
Rp(kΩ·cm2) 783.79 1012.23 852.38
Acknowledgement
This research is supported by National Natural Science Foundation
of China [grant number 51771117] and Collaborative Innovation
Center for Advanced Ship and Deep-sea Exploration (Shanghai Jiao
Tong University).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.surfcoat.2019.03.022.
References
[1] P. Dhaiveegan, N. Elangovan, T. Nishimura, N. Rajendran, Corrosion behavior of
316L and 304 stainless steels exposed to industrial-marine-urban environment: field
study, RSC Adv. 6 (2016) 47314–47324, https://doi.org/10.1039/c6ra04015b.
[2] Z.L. Lu, D.C. Li, Z.Q. Tong, Q.P. Lu, M.M. Traore, A.F. Zhang, B.H. Lu, Investigation
into the direct laser forming process of steam turbine blade, Opt. Lasers Eng. 49
(2011) 1101–1110, https://doi.org/10.1016/j.optlaseng.2011.05.016.
[3] M. Vieira, A. Sarmento, L. Reis, Failure analysis of the guide vanes of the pico wave
power plant wells turbine, Eng. Fail. Anal. 56 (2015) 98–108, https://doi.org/10.
1016/j.engfailanal.2015.04.004.
[4] H. Ghorbani, A. Abdollah-zadeh, F. Bagheri, A. Poladi, Improving the bio-corrosion
behavior of AISI316L stainless steel through deposition of Ta-based thin films using
PACVD, Appl. Surf. Sci. 456 (2018) 398–402, https://doi.org/10.1016/j.apsusc.
2018.06.154.
[5] G.S. Kaliaraj, V. Vishwakarma, K. Alagarsamy, A.M.K. Kirubaharan, Biological and
corrosion behavior of m-ZrO2 and t-ZrO2 coated 316L SS for potential biomedical
applications, Ceram. Int. 44 (2018) 14940–14946, https://doi.org/10.1016/j.
ceramint.2018.05.103.
[6] T. Xi, M.B. Shahzad, D.K. Xu, Z.Q. Sun, J.L. Zhao, C.G. Yang, M. Qi, K. Yang, Effect
of copper addition on mechanical properties, corrosion resistance and antibacterial
property of 316L stainless steel, Mater. Sci. Eng. C Mater. Biol. Appl. 71 (2017)
1079–1085, https://doi.org/10.1016/j.msec.2016.11.022.
[7] T.S.N.S. Narayanan, I.S. Park, M.H. Lee, Strategies to improve the corrosion re-
sistance of microarc oxidation (MAO) coated magnesium alloys for degradable
implants: prospects and challenges, Prog. Mater. Sci. 60 (2014) 1–71, https://doi.
org/10.1016/j.pmatsci.2013.08.002.
[8] H.B. Wu, X.Y. Zhang, Z.H. Geng, Y. Yin, R.Q. Hang, X.B. Huang, X.H. Yao, B. Tang,
Preparation, antibacterial effects and corrosion resistant of porous Cu-TiO2 coat-
ings, Appl. Surf. Sci. 308 (2014) 43–49, https://doi.org/10.1016/j.apsusc.2014.04.
081.
[9] V.K. Balla, S. Dey, A.A. Muthuchamy, G.D.J. Ram, M. Das, A. Bandyopadhyay, Laser
surface modification of 316L stainless steel, J Biomed Mater Res B Appl Biomater
106 (2018) 569–577, https://doi.org/10.1002/jbm.b.33872.
[10] K. Geenen, A. Rottger, W. Theisen, Corrosion behavior of 316L austenitic steel
processed by selective laser melting, hot-isostatic pressing, and casting, Mater.
Corros. 68 (2017) 764–775, https://doi.org/10.1002/maco.201609210.
[11] B. Krawczyk, P. Cook, J. Hobbs, D.L. Engelberg, Corrosion behavior of aqua-blasted
and laser-engraved type 316L stainless steel, J. Mater. Eng. Perform. 26 (2017)
6167–6181, https://doi.org/10.1007/s11665-017-3053-4.
[12] N.N. Li, S.Q. Shi, J.L. Luo, J. Lu, N. Wang, Effects of surface nanocrystallization on
the corrosion behaviors of 316L and alloy 690, Surf. Coat. Technol. 309 (2017)
227–231, https://doi.org/10.1016/j.surfcoat.2016.11.052.
[13] W.H. Kao, Y.L. Su, J.H. Horng, Y.T. Hsieh, Improved tribological properties, elec-
trochemical resistance and biocompatibility of AISI 316L stainless steel through
duplex plasma nitriding and TiN coating treatment, J. Biomater. Appl. 32 (2017)
12–27, https://doi.org/10.1177/0885328217712109.
[14] M. Kazazi, M. Haghighi, D. Yarali, M.H. Zaynolabedini, Improving corrosion re-
sistance of 316L austenitic stainless steel using ZrO2 sol-gel coating in nitric acid
solution, J. Mater. Eng. Perform. 27 (2018) 1093–1102, https://doi.org/10.1007/
s11665-018-3202-4.
[15] Y. Wang, M.Y. Li, L.L. Sun, X.Y. Zhang, J. Shen, Environmentally assisted fracture
behavior of Fe-based amorphous coatings in chloride-containing solutions, J. Alloys
Compd. 738 (2018) 37–48, https://doi.org/10.1016/j.jallcom.2017.12.150.
[16] K. Shukla, R. Rane, J. Alphonsa, P. Maity, S. Mukherjee, Structural, mechanical and
corrosion resistance properties of Ti/TiN bilayers deposited by magnetron sput-
tering on AISI 316L, Surf. Coat. Technol. 324 (2017) 167–174, https://doi.org/10.
1016/j.surfcoat.2017.05.075.
[17] F. Jiang, T.F. Zhang, B.H. Wu, Y. Yu, Y.P. Wu, S.F. Zhu, F.J. Jing, N. Huang,
Surface & Coatings Technology 366 (2019) 86–96
Q2 Q3 Q4 Q5 Q6
−145 −174 −147 −121 −115
0.151 0.131 0.163 0.066 0.098
259.61 110.43 935.48 1195.77 1275.01
Y.X. Leng, Structure, mechanical and corrosion properties of TiN films deposited on
stainless steel substrates with different inclination angles by DCMS and HPPMS,
Surf. Coat. Technol. 292 (2016) 54–62, https://doi.org/10.1016/j.surfcoat.2016.
03.007.
[18] Q.L. Huang, Y. Yang, R.G. Hu, C.J. Lin, L. Sun, E.A. Vogler, Reduced platelet ad-
hesion and improved corrosion resistance of superhydrophobic TiO2-nanotube-
coated 316L stainless steel, Colloids Surf. B: Biointerfaces 125 (2015) 134–141,
https://doi.org/10.1016/j.colsurfb.2014.11.028.
[19] H.C. Qian, M.L. Li, Z. Li, Y.T. Lou, L.Y. Huang, D.W. Zhang, D.K. Xu, C.W. Du, L. Lu,
J. Gao, Mussel-inspired superhydrophobic surfaces with enhanced corrosion re-
sistance and dual-action antibacterial properties, Mater. Sci. Eng. C Mater. Biol.
Appl. 80 (2017) 566–577, https://doi.org/10.1016/j.msec.2017.07.002.
[20] W.S.W. Harun, R.I.M. Asri, F.R.M. Romlay, S. Sharif, N.H.M. Jan, F. Tsumori,
Surface characterisation and corrosion behaviour of oxide layer for SLMed-316L
stainless steel, J. Alloys Compd. 748 (2018) 1044–1052, https://doi.org/10.1016/j.
jallcom.2018.03.233.
[21] S.O. Chong, S.J. Kim, Optimum temperature on corrosion resistance for plasma ion
nitrided 316L stainless steel in sea water solution, Jpn. J. Appl. Phys. 56 (2017)
01AC04, https://doi.org/10.7567/jjap.56.01ac04.
[22] A.F. Yetim, M. Yazici, Wear resistance and non-magnetic layer formation on 316L
implant material with plasma nitriding, J. Bionic Eng. 11 (2014) 620–629, https://
doi.org/10.1016/s1672-6529(14)60073-1.
[23] J. Biehler, H. Hoche, M. Oechsner, Nitriding behavior and corrosion properties of
AISI 304L and 316L austenitic stainless steel with deformation-induced martensite,
Surf. Coat. Technol. 324 (2017) 121–128, https://doi.org/10.1016/j.surfcoat.2017.
05.059.
[24] Y. Kayali, A. Buyuksagis, I. Gunes, Y. Yalcin, Investigation of corrosion behaviors at
different solutions of boronized AISI 316L stainless steel, Prot. Met. Phys. Chem.
Surf. 49 (2013) 348–358, https://doi.org/10.1134/s2070205113030192.
[25] B. Jegdic, D.M. Drazic, J.P. Popic, Open circuit potentials of metallic chromium and
austenitic 304 stainless steel in aqueous sulphuric acid solution and the influence of
chloride ions on them, Corros. Sci. 50 (2008) 1235–1244, https://doi.org/10.1016/
j.corsci.2008.01.012.
[26] J.Y. Xiong, G. Manjaiah, D. Fabijanic, M. Forsyth, M.Y. Tan, Enhancing the localised
corrosion resistance of 316L stainless steel via FBR-CVD chromising treatment,
Corros. Eng. Sci. Technol. 53 (2017) 114–121, https://doi.org/10.1080/1478422x.
2017.1402513.
[27] F.A.P. Fernandes, S.C. Heck, C.A. Picon, G.E. Totten, L.C. Casteletti, Wear and
corrosion resistance of pack chromised carbon steel, Surf. Eng. 28 (2012) 313–317,
https://doi.org/10.1179/1743294411y.0000000079.
[28] J.J. Hu, C.P. Ma, X. Yang, H.B. Xu, N. Guo, H.B. Yu, Microstructure evolution during
continuous cooling in AISI 5140 steel processed by induction heating chromizing, J.
Mater. Eng. Perform. 26 (2017) 5530–5537, https://doi.org/10.1007/s11665-017-
2942-x.
[29] J.-W. Lee, J.-G. Duh, Evaluation of microstructures and mechanical properties of
chromized steels with different carbon contents, Surf. Coat. Technol. 177-178
(2004) 525–531, https://doi.org/10.1016/j.surfcoat.2003.08.031.
[30] J.-W. Lee, J.-G. Duh, S.-Y. Tsai, Corrosion resistance and microstructural evaluation
of the chromized coating process in a dual phase Fe-Mn-Al-Cr alloy, Surf. Coat.
Technol. 153 (2002) 59–66.
[31] X.J. Lu, Z.D. Xiang, Formation of chromium nitride coatings on carbon steels by
pack cementation process, Surf. Coat. Technol. 309 (2017) 994–1000, https://doi.
org/10.1016/j.surfcoat.2016.10.047.
[32] S.B. Lee, K.H. Cho, W.G. Lee, H. Jang, Improved corrosion resistance and interfacial
contact resistance of 316L stainless-steel for proton exchange membrane fuel cell
bipolar plates by chromizing surface treatment, J. Power Sources 187 (2009)
318–323, https://doi.org/10.1016/j.jpowsour.2008.11.064.
[33] S. Iorga, M. Cojocaru, A. Chivu, S. Ciuca, M. Burdusel, P. Badica, C. Leuvrey,
G. Schmerber, C. Ulhaq-Bouillet, S. Colis, Influence of the carbo-chromization
process on the microstructural, hardness, and corrosion properties of 316L sintered
stainless steel, Metall. Mater. Trans. A Phys. Metall. Mater. Sci. 45 (2014)
3088–3096, https://doi.org/10.1007/s11661-014-2247-8.
[34] K.T. Kim, J.H. Lee, Y.S. Kim, Effect of ultrasonic nano-crystal surface modification
(UNSM) on the passivation behavior of aged 316L stainless steel, Materials 10
(2017) 713, https://doi.org/10.3390/ma10070713.
[35] J. Qian, C.F. Chen, H.B. Yu, F. Liu, H. Yang, Z.H. Zhang, The influence and the
mechanism of the precipitate/austenite interfacial C-enrichment on the inter-
granular corrosion sensitivity in 310S stainless steel, Corros. Sci 111 (2016)
352–361, https://doi.org/10.1016/j.corsci.2016.05.021.
[36] C.Z. Chi, Z.Y. He, Y. Gao, Z. Xu, Thermodynamic analysis of carbon migration in
W1-1.0C steel in plasma surface chromizing, J. Univ. Sci. Technol. Beijing 13
(2006) 131–134, https://doi.org/10.1016/s1005-8850(06)60029-7.
[37] B. Zhang, J. Wang, B. Wu, X.W. Guo, Y.J. Wang, D. Chen, Y.C. Zhang, K. Du,
E.E. Oguzie, X.L. Ma, Unmasking chloride attack on the passive film of metals, Nat.
Commun. 9 (2018) 2559, , https://doi.org/10.1038/s41467-018-04942-x.
95
Z. Dong, et al.
[38] K.H. Anantha, C. Ornek, S. Ejnermark, A. Medvedeva, J. Sjostrom, J.S. Pan,
Correlative microstructure analysis and in situ corrosion study of AISI 420 mar-
tensitic stainless steel for plastic molding applications, J. Electrochem. Soc. 164
(2017) C85–C93, https://doi.org/10.1149/2.0531704jes.
[39] J.F. Gou, Y. Wang, X.W. Li, F.F. Zhou, Effect of rare earth oxide nano-additives on
the corrosion behavior of Fe-based hardfacing alloys in acid, near-neutral and al-
kaline 3.5 wt.% NaCl solutions, Appl. Surf. Sci. 431 (2018) 143–151, https://doi.
org/10.1016/j.apsusc.2017.06.203.
[40] T.K. Chaitra, K.N. Mohana, D.M. Gurudatt, H.C. Tandon, Inhibition activity of new
thiazole hydrazones towards mild steel corrosion in acid media by thermodynamic,
electrochemical and quantum chemical methods, J. Taiwan Inst. Chem. Eng. 67
(2016) 521–531, https://doi.org/10.1016/j.jtice.2016.08.013.
96
Surface & Coatings Technology 366 (2019) 86–96
[41] R.S. Gonçalves, D.S. Azambuja, A.M.S. Lucho, Electrochemical studies of propargyl
alcohol as corrosion inhibitor for nickel, copper, and copper/nickel (55/45) alloy,
Corros. Sci 44 (2002) 467–479, https://doi.org/10.1016/S0010-938X(01)00069-5.
[42] Z.B. Qin, Z. Wu, X.S. Zen, Q. Luo, L. Liu, W.J. Lu, W.B. Hu, Improving corrosion
resistance of a nickel-aluminum bronze alloy via nickel ion implantation, Corrosion
72 (2016) 1269–1280, https://doi.org/10.5006/2097.
[43] Z.B. Qin, Q. Luo, Q. Zhang, Z. Wu, L. Liu, B. Shen, W.B. Hu, Improving corrosion
resistance of nickel-aluminum bronzes by surface modification with chromium ion
implantation, Surf. Coat. Technol. 334 (2018) 402–409, https://doi.org/10.1016/j.
surfcoat.2017.11.066.
[44] F.E. Heakal, O.S. Shehata, N.S. Tantawy, Integrity of metallic medical implants in
physiological solutions, Int. J. Electrochem. Sci. 9 (2014) 1986–2004.