Long term performance of atomic layer deposition
coatings for corrosion protection of stainless steel
E. Marin*, A. Lanzutti, L. Paussa, L. Guzman and L. Fedrizzi
The use of atomic layer deposition (ALD) for the corrosion protection of metallic
substrates was speculated for the irst time in the 1990 s. Since then, a lot of
research has been carried on to investigate the application limits of this
technique. ALD has been ef iciently used to deposit conformal oxide layers on
different metallic substrates, which were used as insulators and diffusion
barriers to prevent contact between aggressive electrolytes and metal. In this
work, a complete morphological and compositional characterization of some
ALD coatings has been carried out using atomic force microscopy and glow
discharge optical emission spectrometry. Electrochemical impedance
spectroscopy and potentiodynamic polarizations have been used to evaluate
the over-time performance of three different ALD deposits on AISI 316 stainless
steel, namely TiO
2
, Al
2
O
3
and AlN, and the results have been compared to
previous literature data. It has been observed that, in contrast with the
previous literature results, Al
2
O
3
layers deposited on AISI 316 do not suffer
premature failure. On the contrary, a lower and time-dependent corrosion
protection was observed when using TiO
2
coatings and a decrease of corrosion
protection over time due to oxidative phenomena of the protective layer has
been observed in the case of the AlN coatings.
1 Introduction
In the ield of engineering, when a balanced combination of
corrosion resistance and mechanical performances is requested,
austenitic stainless steels of the AISI 300 series, such as AISI 304
and AISI 316, are often the best candidates. Thanks to their high
chromium and nickel contents, austenitic stainless steel are
corrosion resistant in a wide range of industrial and domestic
applications, such as pressure vessels, cutlery, turbine blades,
civil structures and biomedical components. From a composi-
tional point of view, the only difference between 304 and 316 is
the latter containing molybdenum, which further improves
pitting and crevice corrosion resistance, in particular in presence
of high amounts of chlorides. For this reason, 316 has been
widely applied also for naval components.
The presence of a spontaneously formed, conformal
chromium oxide layer on the surface of austenitic stainless steel
is not only protective against corrosion, but also an effective
diffusion barrier that prevents diffusion of potentially dangerous
or toxic elements, such as nickel. For this reason, 316 and, in
particular 316 low carbon (L) has been widely applied in
aggressive biological environments for high performance
prosthetic implants [1–5]. Additional uses of AISI 316 L also
include high temperature applications thanks to its natural
immunity to sensitization [6–10].
Even if AISI 316 L is characterized by a balanced
combination of mechanical properties and corrosion resistance,
less mechanically performing titanium alloys such as Ti-6Al-4V
are still preferentially used in biomedical components because of
their superior corrosion resistance, in particular for not highly
stressed parts.
A great number of innovative treatments are nowadays
under intensive study to further improve stainless steel corrosion
resistance, such as plasma detonation techniques [11], arc-ion
plating [12], sol-gel deposition [13,14], chemical conversion layers
of cerium [15], chromium [16] or other elements, chemical vapor
deposition (CVD) [17], high-velocity oxy-fuel spray [18], plasma-
nitriding [19], and lately atomic layer deposition (ALD) [20–25].
Using ALD, a wide array of materials can be deposited,
including chemical compounds, metal oxides, nitrides, sulides,
carbides, luorides, pure metals, biomaterials and even polymers
[26,27]. The main advantages of ALD technologies when
compared to CVD and PVD are the higher process control and
the possibility to deposit more conformal layers even on complex
3 d shaped substrates. It has been observed in literature that ALD
is one of the few techniques that can conformally coat the inner
surface of nanotubes with high form factors [28,29]. As
conventional CVD, ALD practical industrial applications on
metals are in reality strongly limited due to the required process
temperature. If the chamber temperature exceeds the
E. Marin, A. Lanzutti, L. Paussa, L. Guzman, L. Fedrizzi
University of Udine, via Cotonificio 108, Udine 33100, (Italy)
E-mail: elia.marin@uniud.it
Materials and Corrosion 2015, XXX, No. XXX DOI: 10.1002/maco.201408012 1
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