NACE Paper No.

MECCOCT18-12367

Corrosion Performance and Mechanical Properties of Additive Manufactured Stainless Steel

316L using Selective Laser Melting

Omar S. Alabdulgader
Saudi Aramco
Dhahran 31311
Saudi Arabia

ABSTRACT

The corrosion performance and mechanical properties of additive manufactured 316L stainless steel
material have been studied. As a revolutionary manufacturing process, additive manufacturing creates
3D objects by the fusion of successive layers of metallic powder, using computer controlled heat
sources such as lasers or electron beams. Geometries with high complexity patterns can be produced
using this net-shape manufacturing process. It brings solutions to a wide spectrum of applications in
different industries such as aerospace, energy production, and medical devices. The material
properties produced by the repetitive powder deposition and curing process has a major impact on the
reliability of the additive manufactured devices; especially at aggressive environments. In this
experiment, the properties of 316L stainless steel parts manufactured using the Selective Laser Melting
(SLM) technique were studied. The cyclic potentiodynamic polarization test indicated that additive
manufactured materials had lower corrosion resistance than the wrought stainless steel parts of the
same grade. This was evident by the difficulty of regenerating a stable and protective passive oxide
layer at room temperature, as well as the instability of passivation at higher temperatures. This behavior
was attributed, mainly, to the higher surface roughness generated by the additive manufacturing
process, and to the chemical composition of the passive layer. Moreover, the additive manufactured
samples showed a higher yield strength than the wrought samples, but lower values for elongation and
ultimate tensile stress. The increased strength and reduced ductility of the additive manufactured
sample was likely a result of grain size strengthening.

Key words: Additive Manufacturing (AM), 3D Printing, 316L Stainless Steel, Selective Laser Melting
(SLM), Medical Implants, Orthopedic Implants, Cyclic Potentiodynamic Polarization, Corrosion
Characterization, Mechanical Properties.

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 INTRODUCTION

As a revolutionary manufacturing process, Additive Manufacturing (AM) creates 3D objects by the

fusion of successive layers of metallic powder feedstock, using computer controlled heat sources such
as lasers or electron beams. This net-shape manufacturing process produces the desired geometry of
components with high complexity patterns in a single step. Comprehensive integration of emerging
technologies from materials science, mechanical engineering, and laser technology is required to
achieve the favorable properties (1).

Different material properties produced by the repetitive powder deposition and curing process has a
major impact on the reliability of the AM devices, especially in applications under aggressive
environment. Therefore research is currently directed to promote the use of AM in several industries,
such as aerospace, energy production, and medical devices. The ultimate goal is to develop a
comprehensive analysis of the relationship between the AM operating parameters and the resulting
material properties of the end-product. (2)

The medical devices manufacturing industry is one of the highest demand downstream industries for
(3)
AM, representing 23.4% of total demand . Due to the increasing demand for manufacturing patient-
customized medical implants, AM has become the dominant technology to manufacture hearing aids,
and to create more than 30,000 orthopedic implants, 500 thousand dental implants, and countless other
devices (3).

The main AM processes include laser sintering (LS), laser melting (LM) and laser metal deposition
(2)
(LMD) . The main difference between these techniques is that LS involves partial melting of the
powder layer before depositing the next layer, while SLM and LMD involves complete melting of the
powder. That is why LS is more suited for pure metals, where achieving complete homogenization is
not required, while laser melting techniques are most suited for alloy powder to achieve the best
homogeneity. Since SLM is considered one of the most efficient AM for manufacturing functional, fully
(4)
dense metallic components , it has been successfully utilized to manufacture orthopedic implants,
such as fingers and zygomatic bones (3). Therefore, it was selected to be studied in this paper.

In line with the efforts of improving the reliability of AM medical devices, this paper focuses on studying
the corrosion, and mechanical properties of AM 316L stainless steel in simulated physiological fluid.

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 EXPERIMENTAL PROCEDURE

Corrosion Characterization
(3)
The cyclic potentiodynamic polarization test was performed to assess the corrosion behavior of
metallic implants under simulated physiological conditions. To understand the corrosion behavior of AM
implants compared to conventionally manufactured implants, four types of samples were tested:

1. Wrought 304 stainless steel at 23oC

2. Wrought 316L stainless steel at 23oC
3. AM 316L stainless steel at 23oC
4. AM 316L stainless steel at 37oC

The samples were immersed in a simulated physiological solution. The AM sample composition was
compliant to ASTM 3184 specifications for AM stainless steel alloy with powder bed diffusion. The
chemical composition of the different samples is shown in table 1.

Table 1. Stainless steel specimens composition (wt%)

Sample Fe Cr Ni C Mn S Mo Si

Wrought 0.08 2.0 0.03 0.75

Balance 18- 20 8.0-10 -
304 max max max max

Wrought 0.03 2.0 0.03 2.0- 0.75

Balance 16- 18 10- 14
316L max max max 3.0 max

AM 0.03 2.0 0.03 2.0- 1.0

Balance 16- 18 10- 14
316L max max max 3.0 max

The electrochemical measurements were performed in a three-electrode electrolyte cell with a standard
calomel Ag/AgCl as reference electrode (SCE), platinum as the counter electrode, and the metal
specimen as the working electrode. Ringer’s solution (3)
was used to simulate orthopedic metallic
implants environment; composition is provided in table 2. The samples exposed surface area was
measured to be 133mm2. The specimens were left in the solution and the open circuit potential was
recorded until the corrosion potential (Er) stabilized. The potentiodynamic scan was then started at 100
mV lower than Er in the positive or noble (forward) direction. The potentiostat was set on a scan rate of
1 mV/s. The scan was reversed after the potential voltage has reached 1000 mV. The reverse scan
was stopped after the current has become less than that in the forward direction, and the anodic-to-
cathodic transition potential was determined. The data was plotted with the potential voltage in mV on

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the x axis (linear scale) versus the current density in mA/cm2 on the y axis (logarithmic scale). The
experimental setup is shown in Figure 1.

Table 2. ASTM specifications for Ringer's solution composition

Substrate Composition (g/L)

NaCl 8.69
KCl 0.33
CaCl2 0.3
pH 7.4

Figure 1: Schematic illustration of the potentiodynamic polarization test setup. (Materials

Evaluation & Engineering, INC)

Mechanical Testing

Quasi-static tensile testing was performed on dog bone tensile samples that have been produced using
the same additive manufacturing technique, SLM, as well as samples that have been cut from a
wrought stainless steel plate, as shown in Figure 2.

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 Figure 2: The wrought (left) and additively manufactured (right) tensile samples

An Instron Tensile tester was used to conduct the mechanical testing. The testing was done on a
standard tensile frame with a 100 kN load cell and a 6 mm/min extension rate. Due to concerns of
damaging equipment at the time of fracture, the tests were conducted without the use of an
extensometer and thus results are presented with grip extension only.

RESULTS & ANALYSIS

Corrosion Characterization
The results of the cyclic potentiodynamic polarization tests were obtained from monitoring the behavior
of the current in response to the applied voltage in forward and reverse directions; Figures 3-6 show the
obtained curves from each test.

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Figure 3: Potentiodynamic polarization curve of the Wrought 304 SS at 23oC

Figure 4: Potentiodynamic polarization curve of the wrought 316L SS at 23oC

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 Figure 5: Potentiodynamic polarization curve of the additive manufactured 316L SS at 23oC

Figure 6: Potentiodynamic polarization curve of the additive manufactured 316L SS at 37oC

Five main features were extracted from the polarization curves, to understand the corrosion behavior of
each material. A brief explanation for each feature follows:
 Pitting and repassivation potentials

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Pitting potential is identified by the point at which the current starts to increase dramatically after the
passive region. Repassivation potential was identified by the point where the current in the reverse
direction becomes less than current in the forward direction.
 Hysteresis loop
As the current density varies between the forward and reverse scans, a hysteresis loop is formed. If the
current density in the reverse scan was lower than the forward, the hysteresis becomes positive, and
vice versa.
 Active-passive transition
Some materials showed this behavior where the current showed a maximum value close to the
corrosion potential, and then decreased to a low value forming an “anodic nose.”
 Anodic-to-cathodic transition potential
This potential was determined by the value where the current changed from anodic to cathodic during
the reverse scan.
A summary of the extracted features from each test is provided in table 3.

Table 3. Results summary of the cyclic polarization tests

Active- Anodic to
Corrosion Breaking Repassivation Maximum
Hysteresis Passive Cathodic
Samples Potential Potential Potential Current
Loop Transition Transition
Er (mV) Eb (mV) Ep (mV) (mA/cm2)
(mV) (mV)
Wrought
More
304 SS (-175) 180 (-75) Negative No 9.7
Anodic
(23oC)
Wrought
More
316L SS (-400) 90 120 Negative (-10)-88 38.7
Anodic
(23oC)
AM
More
316L SS (-355) 110 (-15) Negative (-15)-100 37.3
Anodic
(23oC)
AM
More
316L SS (-180) 175 -10 Negative No 27.1
Cathodic
(37oC)

To characterize the corrosion behavior of AM 316L stainless steel samples, comparison with wrought
304 and 316L stainless steel at room temperature was performed and followed by studying the effect of
increasing the temperature up to human body temperature on the AM 316L.

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Wrought 304, 316L and AM 316L at room temperature (23oC)
Stainless steel alloys are known of their corrosion resistance because of their self-passivation property
to form a protective passive oxide layer. Therefore, the values of the breaking (Eb) and repassivation
(Ep) potentials compared to the corrosion potential (Er) of each material provides a measure of the
protectiveness of its passive layer; refer to Figure 7. All tested materials have showed more noble Eb
and Ep compared to Er, as shown in table 3, which indicated resistance to pitting and general
corrosion. The wrought 316L showed the highest difference between Er and Eb, demonstrating the
most protective oxide layer among the three materials. It was followed by AM 316L and then 304.
Moreover wrought 316L showed the highest tendency to repassivate during the reverse scan, followed
by AM 316L and then 304. Furthermore, only wrought and AM 316L showed high resistance to crevice
corrosion, because of the high difference between Er and Ep of more than 200mV.

Figure 7: Pitting resistance and repassivation tendency comparison between test specimens

The hysteresis analysis provides a measure of the surface chemistry disruption that occurred by the
forward potential scan, which results in the current density difference at the same potential. The larger
the hysteresis loop, the greater the surface passivation disruption, the greater the risk of localized
corrosion. Although all tested materials showed negative hysteresis, indicating the decrease in passivity
by pitting initiation, wrought 316L was the fastest to restore its passivity, forming the smallest hysteresis
followed by AM 316L and then 304. That indicated that AM 316L has exhibited more disruption to the
surface passivity by localized corrosion than the wrought 316L; the passive film was unstable. The
disruption activity can be observed by the small peaks in the passive region of the AM 316L curve,
between -200 to 0 mV.

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AM and wrought 316L exhibited the active-passive transition feature. The sudden decrease in current
density by an order of magnitude in the passive region, forming the “anodic nose,” indicated that the
material might has undergone a different passivation process from Fe2O3 to Fe3O4. Another possibility
was that due to the lack of an effective surface treatment step prior to the test, some foreign materials
— on the surface — dissolved in the solution during the test, leading to the formation of a more
effective chromium oxide protective film.
The difference between the anodic-to-cathodic potential during the reverse scan and the Er provides a
measurement of the persistence of surface passivity. All materials have exhibited more noble anodic-to-
cathodic potentials compared to Er, which indicated that the passivity was reduced at the corrosion
potential. Due to the easily oxidizable/reducible surface species, the materials might experience
general corrosion.

AM 316L at human body temperature (37oC)

A noticeable variance was observed on the AM 316L corrosion behavior when tested at human body
temperature of 37oC. The passive oxide film was more easily broken, as indicated by the lower
difference between Eb and Er, compared to the higher difference at 23oC. Moreover, the tendency to
repassivate was slower, which indicated more pitting corrosion has taken place during the anodic scan.
A similar hysteresis loop was formed that was negative and had comparable size to AM 316L at 23 oC.
It did not exhibit the active passive transition feature, which might have been overcome by the increase
in current density due to the increase in temperature. Finally, a remarkable difference was observed by
having the anodic-to-cathodic transition potential more cathodic to the Er. This provided an indication of
a more persistent passivity as the scan returns through Er. A more stable passive layer might have
been developed by greater enrichment of chromium oxide.
Mechanical Properties
The mechanical properties of the wrought and additively manufactured were obtained from the stress-
extension curve shown in Figure 8.

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 Figure 8: Baseline stress-extension curves for wrought and AM 316L stainless steel

Examining these results, it is noted that the AM samples showed a higher yield strength than the
wrought samples, but lower values for elongation and ultimate tensile stress. Table 2 below
summarizes key values obtained from the test. The increased strength and reduced ductility of the AM
sample is likely a result of grain size strengthening. Since the layers of the printed samples are on the
order of 200 μm thick, the grains within those layers will also be on the same size scale, resulting in
relatively high strength.

Table 4 Summary of mechanical properties of wrought and AM 316L stainless steel

Yield Strength Ultimate Tensile Extension at

Samples
[MPA] Stress [MPA] Fracture [mm]

AM 316L 510 583 15.6

Wrought 316L 360 632 19.2

The difference in ductility was also observed in the fracture surface of the bars. Figure 9 shows both the
wrought bar and AM bar fracture surfaces after tensile testing. It is observed that while each surface
exhibit features characteristics of a ductile fracture, the wrought sample showed considerably more
necking than the AM sample, which was consistent with the stress extension curves.

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 Figure 9: A fracture surface comparison between wrought 316L and AM 316L

Based on above corrosion results, the AM 316L stainless steel showed lower corrosion resistance than
the wrought 316L stainless steel at a similar environment. That was evident by the lower breaking and
repassivation potentials. More importantly, AM 316L showed even lower corrosion resistance when
tested at human body temperature, which was also evident by the lower breaking and repassivation
potentials; refer to Figure 7. This demonstrates how 316L stainless steel susceptibility to general and
localized corrosion is largely affected by two factors: surface topography and the chemical composition
of the passive oxide layer.

The rough surface produced by the additive manufacturing has provided more pitting initiation sites
leading to a less stable oxide layer. Microscopic images of the different samples showed how the AM
surfaces are not only rougher than the wrought surfaces, but contain much more crevice locations for
pits nucleation; refer to Figure 10. The pitting initiation activity can be characterized by the small peaks
in the passivation region of the AM 316L polarization curve. More importantly, the material
repassivation tendency of most of these nucleation sites was shown to be suppressed by existing
surface flaws such as inclusions and defects. The longer time taken to repassivate a disrupted surface,
the more metal dissolution into the solution takes place.

The chemical composition of the oxide layer was shown to play an important role in determining the
corrosion resistance of AM 316L. As the temperature was increased up to 37oC, more metal dissolution
has occurred. That is attributed to the passivity stability; the oxide layer formation process, as a
kinetically controlled process, was affected by the increase in temperature resulting in lower chromium
content. Therefore, a more stable passive oxide layer has formed during the reverse scan as evident by
the noble anodic to cathodic transition as a result of the polarization activity.

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Figure 10. Microscopic images show the difference in surface topography between wrought and
AM Samples. (a) Pristine wrought 316L surface. (b) Pitted wrought 316L surface. (c) Pristine AM
316L surface. (d) Pitted AM 316L surface.

To overcome the aforementioned challenges, corrosion mitigation measures should play a pivotal role
in the additive manufacturing of biomedical implants, alongside optimizing the AM design parameters.
Surface modification treatment is considered to be the best solution to control corrosion of implants, as
the use of inhibitors is not possible. Examples of proven surface treatment techniques are chemical
passivation by nitric acid, laser surface modification to produce more homogenous surface, UV
irradiation during passivation, plasma source ion implantation, and laser nitration (6).

CONCLUSIONS

The corrosion behavior of AM 316L stainless steel was characterized by performing the
potentiodynamic cyclic polarization test “ASTM F-2129” on stainless steel specimens in a simulated
physiological environment. The susceptibility to pitting/crevice corrosion was qualified, based on
analyzing the features of the polarization curves of each test. The AM samples showed lower corrosion
resistance than conventionally manufactured samples of the same grade. That was evident by the
lower breaking and repassivation potentials, as well as the instability of the passive oxide layer at
human body temperature. That can be attributed to the surface topography generated by the AM and

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the chemical composition of the oxide layer. Surface modification techniques can be utilized as a
beneficial solution to overcome those challenges.

Also, the mechanical properties of AM 316L stainless steel samples were tested and compared to
conventionally manufactured samples. It was noticed that the AM samples had a higher yield strength
than the wrought samples, but with reduced ductility. That was attributed to the increase in material
strength as a result of grain size strengthening, due to the powder deposition process of AM.

More research is needed to further improve corrosion resistance in AM implants. There is a need to
establish a relationship between microstructure, mechanical and corrosion properties, and AM
operating design parameters. Furthermore, studying fatigue-induced corrosion of AM materials,
corrosion behavior of different implant applications, and AM microstructure using advanced
characterization techniques, will further improve the reliability of AM implants.

ACKNOWLEDGEMENTS

The author would like to thank the project team members who actively contributed to the outcome of
this research, Quinlin Hamill and H.R. Shashank. I would like also to thank my management at Saudi
Aramco for allowing me to submit and present this work.

REFERENCES

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(2013). Laser additive manufacturing of metallic components: materials, processes and
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