Volume 20 Preprint 101
The Influence of TiN-Sputtering on Hardness and Corrosion Rate of AISI 304 for Biomaterials Application
H.P. Priyambodo, V. Malau, P.T. Iswanto, T. Sujitno and Suprapto.
Keywords: Sputtering, Hardness, Corrosion Rate, AISI 304
This study examines the effect of hardness and corrosion resistance of Titanium Nitride (TiN) sputtering treatment on AISI 304 as alternative biomaterials. TiN sputtering was done a 25-30 mA, 2.5-3 kV and a distance between the substrate with a target of 10 mm. The variations of the ratio between argon gas (Ar) and nitrogen gas (N2) were 70:30; 80:20 and 90:10. The variations in the duration of the sputtering process were 30, 60, 90, 120 and 150 minutes. The Vickers hardness test was performed with 5 grams of load for 10 seconds. The corrosion test was performed on a bovine serum solution as a substitute for human body fluids. Hardness and corrosion resistance increased by sputtering. The hardness of the treatment material with the 70:30 ratio of Ar and N2 for 150 minutes is 48% higher than the hardness of non treatment material. The corrosion rate of the material with the 70:30 ratio of Ar and N2 for 120 minutes is 875% lower than the corrosion rate of non treatment material.
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The Influence of TiN-Sputtering on Hardness and Corrosion
Rate of AISI 304 for Biomaterials Application
Bambang Hari Priyambodo
Viktor Malau b, Priyo Tri Iswanto b, Tjipto Sujitno c, Suprapto c
Teknik Mesin, Akademi Teknologi Warga Surakarta, Indonesia,
Departemen Teknik Mesin dan Industri, Universitas Gadjah Mada, Indonesia
Pusat Sains Dan Teknologi Akselerator Batan, Indonesia
This study examines the effect of hardness and corrosion resistance of Titanium Nitride
(TiN) sputtering treatment on AISI 304 as alternative biomaterials. TiN sputtering was done
a 25-30 mA, 2.5-3 kV and a distance between the substrate with a target of 10 mm. The
variations of the ratio between argon gas (Ar) and nitrogen gas (N2) were 70:30; 80:20 and
90:10. The variations in the duration of the sputtering process were 30, 60, 90, 120 and
150 minutes. The Vickers hardness test was performed with 5 grams of load for 10
seconds. The corrosion test was performed on a bovine serum solution as a substitute for
human body fluids. Hardness and corrosion resistance increased by sputtering. The
hardness of the treatment material with the 70:30 ratio of Ar and N2 for 150 minutes is 48%
higher than the hardness of non treatment material. The corrosion rate of the material with
the 70:30 ratio of Ar and N2 for 120 minutes is 875% lower than the corrosion rate of non
Keywords: Sputtering, Hardness, Corrosion Rate, AISI 304
TiN-Sputtering is the process of inserting TiN atoms on the surface of the substrate by
firing high-energy ions on the target surface causing the target surface atoms to
decompose and insert on the surface of the substrate . The TiN layer deposition has hard
properties, corrosion resistance, abrasion resistance, high temperature resistance, low
friction coefficient, biocompatible and has good mechanical properties [2-5]. The increased
hardness occurs when there is a change in the residual stress tension that can inhibit the
dislocation movement [6-7].
The process of thin film formation is influenced by various parameters. As follows interelectrode voltage, distance between electrode, gas pressure, deposition time and substrate
temperature. The electrode voltage affects the amount of ionic energy to strike the target
surface. The distance between the electrodes affects the number of atoms attached to the
surface of the substrate. The gas pressure affects the collision of pound ions with air
particles which is still present in the vacuum chamber. It affects of the rate of deposition of
the atoms in the sputtering process. The length of deposition time greatly affects the
thickness of the resulting film. Increasing temperature causes the number of vacancies to
increase rapidly. It allows foreign atoms to infiltrate deeper between the atomic spaces, so
that can occupy an existing void.
TiN belongs to an inert ceramic material, which is widely used as a surface coating material
and has an advantage in terms of hardness . It is resistant to high temperature, wear
resistant and has good mechanical properties . The majority of this layer is a nano
crystalline compound obtained by layer deposition by sputtering or arc evaporation
process. A thin layer of TiN on the surface of the specimen is formed by depositing
titanium. The N2 gas is inserted at the same time, so that a chemical reaction occurs Ti +
1/2 N2 TiN .
The effect of new coating in terms of hardness, corrosion rate, and microstructure for
alternative biomaterials applications is investigated.
Austenitic stainless steels AISI 304 was used as material. The material composition was
presented in Table 1 and the mechanical properties are shown in Table 2. The specimens of
plate-shaped 3 mm thick were cut in a circle of 14 mm in diameter and polishing on the
TiN Sputtering was done by adjusting the current parameters of 25-30 mA, 2.5-3 kV
voltage, the distance between the substrate and the target of 10 mm, and the ratio of Ar
and N2 was 7: 3. Ar used as a gas sputter and N2 as reactant gas. Pure titanium was used as
a target coating material. The duration of the sputtering process was varied 30, 60, 90,
120, and 150 minutes.
The Vickers hardness test is used to determine the hardness of the specimen's surface .
The indentation load was used 5 gf for 10 seconds.
The corrosion rate test was performed with a cell type three potentiometric electrode type
M 273 electrode instrument . The serum bovine solution was used as a Simulated Body
Fluid (SBF) with a 25% bovine serum composition and 75% sterile aquades [12-14]. The
corrosion test parameters were performed with scan properties: Step Height (4 mV); Step
Time (2 s) and Scan Rate (2 mV/s).
Microstructure test was performing using optical microscope 200 x magnifications. Cross
section cross-sectional observations were also performed to determine the effect of
sputtering on the surface of the specimen.
Results and Discussion
Mechanical properties of AISI 304
The constituent elements of the material are shown in Table 1. The element is used as a
basis for corrosion test data. The corrosion rate is also affected by the alloying elements in
the material. Mechanical properties of AISI 304 are shown in Table 2. This data is used as a
comparison with the material already treated.
Table 1. Composition test
Table 2. Mechanical properties
Tensile Strength (MPa)
Yield Strength (MPa)
The effect of sputtering duration and composition on the hardness of AISI 304 is shown in
Figure 1. The TiN coated AISI 304 has a higher hardness than non-treatment material. AISI
304 hardness value without treatment is 248 HV. The highest hardness increased to 366 HV
or about 48% at the composition of 70:30 (Ar:N2) with a duration of 150 minutes.
The more duration on the sputtering increased hardness. As the sputtering duration
increases, more and more TiN atoms are inserted on the surface of AISI 304. The depleted
TiN atoms fill in the blank space on AISI 304 so that the surface density increases.
Figure 1. Effect of duration and sputtering layer composition against hardness of AISI 304
TiN layer composition was affected by nitrogen gas amount as reactant gas in sputtering
process. Nitrogen atoms which react with titanium atoms formed TiN. Hardness increased
by adding nitrogen atoms that are illuminated with Titanium atoms .
AISI 304 anodic polarization curve in serum bovine solution is shown in Figure 2. Analysis
of Tafel slope values indicates the corrosion current (Icorr) value of the specimen. The
smaller the Icorr value, the smaller the corrosion rate . Similarly, corrosion rate decrease
with increasing corrosion potential value (Ecorr). Ecorr values increase with increasing duration
of sputtering. It can be observed that treated AISI 304 tends to be more corrosion resistant
than AISI 304 non treatment. Ecorr of AISI 304 non treatment is -0.1923 V, while AISI 304
with TiN sputtering (70:30) duration of 120 minutes has the highest value Ecorr is -0.0267 V.
The corrosion resistance of stainless steels can be enhanced by the presence of nitrogen
elements [15-18]. Nitrogen can be a direct passivation or indirect it can stabilize
passivation . TiN thin layers was proved to be able to protect the the substrate from
surface corrosion attacks.
Figure 2. The anodic polarization curves of TiN sputtering film on AISI 304 of (a) Ar:N2
(90:10), (b) Ar:N2 (80:20) and (c) Ar:N2 (70:30) in bovine serum solution
The effect of sputtering duration on AISI 304 corrosion rate is shown in Figure 3. Corrosion
rate decreases with increasing duration of sputtering. Deposition time is an important
parameter in the sputtering process. The longer the sputtering process, the more target
quantity (Ti) splashed onto the surface of the substrate. However, the time of sputtering
deposition had an optimum limit. Maximum sputtering duration was 120 minutes. If the
duration was added it can increase its corrosion rate. AISI 304 non treatment corrosion rate
was 0.35 mpy and the best value of 0.04 mpy on the TiN specimen (70:30) was 120
minutes. This result shows relative corrosion resistant is outstanding . Comparison of
the initial specimen with the treatment specimen decreased the corrosion rate about 875%.
Figure 3. Corrosion rate ratio of AISI 304 and AISI 304-TiN (70:30; 80:20 and 90:10) with
duration of (0; 30; 60; 90; 120 and 150 minutes)
The observation of the microstructure was performed by 200X enlargement of the cross
section of the specimen shown in Figure 4. The TiN atoms in the sputtering process
diffused into the specimen surface and formed a thin layer with a thickness of about 5μm.
The vacancies on the surface of the specimen are inserted with TiN atoms, thereby
increasing the density of the specimen's surface. The TiN thin film is hard and serves as a
protective film layer of oxidation on the surface of the substrate. This is in accordance with
the results of hardness tests and corrosion tests, that TiN coating can increase hardness
and corrosion resistance.
Figure 4. Cross-section microstructure of sputtering (70:30) 120 minutes AISI 304
Sputtering TiN can increase the surface hardness and decrease the corrosion rate
significantly in AISI 304. The best AISI 304 corrosion rate is treated 8 times lower than AISI
304 non treatment. The surface hardness can also be increased by 48%.
The authors are thankful to Pusat Sains dan Teknologi Akselerator Batan for their sputtering
facility and Departemen Teknik Mesin dan Industri Universitas Gadjah Mada for their
microstructure tester, micro hardness Vickers tester and corrosion tester facility.
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