Critical review of corrosion protection by cold

spray coatings
S. M. Hassani-Gangaraj1,2, A. Moridi1,2 and M. Guagliano1∗

Cold spray distribution, surface oxidation15–18 as well as substrate

nature and properties.19,20
Cold spray is a high deposition rate coating process, in The exact bonding mechanism is still a matter of
which solid powder particles are accelerated to velocities debate. However, adiabatic shear instability is known as
ranging between 300 and 1200 m s − 1 through a de the predominant bonding precursor in cold spray. Adia-
Laval nozzle, impact and adhere to a substrate or pre- batic shear instability occurs at the particle substrate
viously deposited coating. The powder feedstock remains interface during impact. A strong pressure field is intro-
well below its melting temperature during deposition. duced as a result of particle impact on the substrate. Con-
Therefore, cold spray is categorised among solid state sequently, a shear load is generated, which accelerates the
deposition methods, and offer significant advantages as material laterally. This causes localised shear straining,
compared to other traditional thermal spray techniques. which, under critical conditions, leads to adiabatic shear
Particles/substrate interaction during high velocity instability. Experimental results show that the minimal
impact and the resultant bonding is fundamental, and particle impact velocity needed to produce shear localis-
determines physical and mechanical properties of the ation at the particles/substrate interface, correlates quite
coating/substrate system. Numerous experimental and well with the critical velocity for particle deposition by
computational efforts have been carried out to provide a the cold spray process in a number of metallic materials.
better understanding of the bonding mechanism in cold The initiation of adiabatic shear instability is usually
spray.1–12 These efforts raised the consciousness that described by thermal softening in competition with strain
adhesion only occurs when the powder particles exceed and strain rate hardening. During high strain rate defor-
a critical impact velocity. The knowledge of critical vel- mation, strengthening occurs as a result of dislocation
ocity is a key point to determine the optimised spraying generation and movement. On the other hand, heat gen-
parameters, and reduce the manufacturing cost by erated by plastic work softens the material. At a certain
increasing the deposition efficiency. Experimental investi- point, softening dominates the material response and
gations show that the critical velocity depends on the results in the flow stress breakdown and onset of adiabatic
spray material properties,13,14 particle temperature, size shear band formation.21 This phenomenon often leads to
material jet formation in the powder particle or both par-
ticle and substrate (shown in Fig. 1), that is a precursor of
1
Department of Mechanical Engineering, Politecnico di Milano, Milan adhesion in cold spray.
20156, Italy The success of the cold spray process mainly depends
2
Department of Materials Science and Engineering, Massachusetts Insti-
tute of Technology, Cambridge, MA 02139, USA on proper acceleration of the powders to an impact vel-
∗
ocity window, set by the critical and erosion velocities.3,22
Corresponding author, email [email protected]
 coatings, are shown in Fig. 2. Each circle demonstrates
a coating/substrate system whose electrochemical behav-
iour was examined. The materials on the axes represent
either pure metals or the main constituent of the exam-
ined alloys. The materials were sorted according to galva-
nic series data in sea water for both axes. A large interest
can be found in protecting steel either by more noble
materials or by zinc. In the former case, cold spray is
used to impart protective layer by presenting a more pas-
sive surface to the environment than the bare substrate,
steel in this case. The latter provides sacrificial protection
where zinc coating corrodes in preference to the steel sub-
strate. A significant interest can be also seen in protecting
Al, Mg and their alloys as they are highly active materials
1 Schematic deformation of particle and substrate in cold
and thus prone to corrosion. Al and its alloys have been
spray deposition
also considerably used as the coating. This is because of
their high tendency to form oxides and develop a passiva-
Erosion velocity is an upper limit for particle impact vel- tion layer such that corrosion protection is provided by
ocity beyond which erosion and rebound occur instead of inhibited kinetics.
adhesion. Main coating characteristics can be described Cold spray provides the possibility of exploring wide
as a unique function of the ratio of particle impact vel- variety of materials system for corrosion protection. In
ocity to the critical velocity.23 Optimisation of deposition the rest of this section, a few examples including protec-
parameters (gas pressure and temperature, substrate pre- tion of Mg alloys, application of Ti as the protective coat-
heating, etc.) and deposition strategy (single or multipass ing, sacrificial protection by zinc, use of glassy and Stellite
deposition) is the key to achieve better deposition effi- alloy powders are reviewed.
ciency and coating performance.23–25 Pure aluminium coating on AZ91 magnesium alloy
At the early stage of its emergence, cold spray was showed higher pitting corrosion resistance than the bulk
mostly conducted on selected metallic materials. Soon it pure aluminium in NaCl solution.34 Surface mor-
spread to other materials, and currently, a wide variety phologies of bulk and cold sprayed aluminium coating
of materials such as metals, metal matrix composites, cer- before immersion as well as 1 and 10 days after immersion
amics, polymers and nanostructured powders can be suc- are shown in Fig. 3. Smooth surface of bulk aluminium
cessfully deposited. For a detailed discussion on different converted to severely corroded regions in localised spots
material systems that have been cold sprayed and the after 1 day immersion. Coated surface characterised
potential applications, readers are referred to the recent with fish scales and pores did not change significantly
review paper.26 It is clear that cold spray is a versatile tech- after 1 day immersion. After 10 days, fish scales have
nique with multitude potential industrial applications. been corroded away, and signs of local corrosion were
However, the response of cold sprayed components to found. Nevertheless, no magnesium was found as the
the operating conditions and, in particular, fatigue,27,28 main constituent of corrosion product indicating suffi-
wear29,30 and corrosion,31,32 is an important aspect to be cient corrosion protection of aluminium coating. In the
explored in order to transfer the technology to in-service bulk material on the other hand, deeper corrosion pits
products. The aim of the present paper is to provide a criti- and local cracks indicated aggravated localised corrosion
cal assessment of cold spray for corrosion protection. after 10 days immersion. To provide a corrosion resistance
barrier coating for Mg alloys, high purity aluminium
coating resulted in the lowest galvanic corrosion rate
as compared with AA 5356, AA 4047, commercially
Cold spray to mitigate corrosion pure aluminium and Al–5Mg co-deposited powders.
Corrosion is the degradative loss of a material or its func-
tion due to interaction with the environment. Two main
approaches are used to deal with corrosion problems.
The first uses materials science and engineering to treat
design of bulk materials at microscopic level (composition
and microstructure) to increase the inherent resistance in
corrosive environments. The second strategy encompasses
the design and implementation of ‘engineered surfaces’ to
be applied on a less corrosion resistant base material to
impart superior corrosion resistance to critical surfaces
or to place a barrier between the metal and its environ-
ment.33 An engineered surface obtained by cold spray
deposition and its effect on corrosion behaviour of coat-
ing–substrate system is of central attention in this paper.
Cold spray with its unique advantages over traditional
family of thermal spray coatings gained an ever increasing 2 Selected coating–substrate systems used in literature to
attention for corrosion protection in the last decade. examine corrosion behaviour of cold spray coating: cir-
Some selected coating–substrate systems studied in the lit- cles represent either pure metals or main constituent of
erature, to examine corrosion behaviour of cold spray examined alloys; SS stands for stainless steel
3 Surface morphologies of cold sprayed pure Al coating and bulk pure Al a, b before immersion, c, d after 1 day and e, f after 10
days of immersion34

Nevertheless, when the objective is the overall perform- effects of less porosity. Corrosion performance of cold
ance including hardness, adhesion strength and corrosion, sprayed titanium coating in sea water was compared to
Al–5Mg powders appeared to provide the best barrier the performance of the bulk material by open circuit
coating for Mg alloys.35 potential (OCP) survey and potentiodynamic polarisation
Titanium can provide corrosion protection for steel. measurements.37 Lower circuit potential and higher cor-
Cold spraying titanium powders on carbon steel substrate rosion current were obtained for titanium coating. Pre-
in wide range of deposition pressures and temperatures sences of porosity in the coating resulted in more active
provided better corrosion resistance in NaCl solution as and less corrosion resistant surface.
compared to the substrate itself.36 Polishing as sprayed Zinc and its alloy coatings have been widely used for
titanium coating peeled the rough outer layer including cathodic protection of steel. Owing to its negative cor-
small pores and decreased the surface area leading to con- rosion potential, zinc coating corrodes in preference to
siderable improvement of corrosion resistance. Neverthe- the steel substrate. At the same time, it is crucial that
less, the corrosion current of the polished coatings was zinc coating demonstrates low corrosion rate such that
still larger than bulk titanium. Lower deposition pressure it could provide long term protection. Cold sprayed zinc
leads to more porous structure with less dissolved oxygen onto mild steel in as sprayed and heat treated (150°C
concentration in the pores than in the surrounding for 1 h) states were examined in NaCl solution.38 Poten-
environment. This promotes oxygen concentration differ- tiodynamic curves showed that heat treatment of the coat-
ence corrosion. Increasing deposition temperature of tita- ing reduced the corrosion current by a factor of 7–10 over
nium powders from 350 to 500 and 650°C decreased the the whole duration of exposure (72 h). Heat treatment
porosity level in the coating. Nevertheless, examinations also shifted the corrosion potential towards less negative
of the coated samples showed that the lowest corrosion value. The reason was that numerous weakly bonded
current in polarisation curves corresponded to 500°C. splats, cracks and pores observed in the as sprayed coat-
This was due to increased oxygen content in the coating ing converted to better bonded splats, lower and much
with increased temperature that dominated the beneficial thinner cracks in the heat treated sample.
 Glassy powder (Al90.05Y4.4Ni4.3Co0.9Sc0.35) was suc- Cold versus thermal spray: corrosion
cessfully cold sprayed onto Al6061 such that the coating
retained its amorphous structure with a few nanocrystals
behaviour
embedded in amorphous matrix.39 The potentiodynamic Several characteristics of cold spray as compared to ther-
polarisation curves of the coating and substrate were mal spray are of particular interest for its use in develop-
obtained in 0.01 and 0.1 N NaCl solutions. The coating ing corrosion resistant surface layer. Cold spray is
exhibited lower passive current as compared to the sub- deposited with feedstock particles in the solid state, and
strate. The corrosion rate of the substrate was five times no intrinsic defects due to the liquefaction and solidifica-
higher than that of coating, indicating excellent cor- tion processes are developed. This attribute leads to dense
rosion resistance of aluminium bulk metallic glass. Two coatings with low porosity that is desired for corrosion
main features of metallic glass coating were responsible protection. The tendency for high temperature reactions
for such high corrosion resistance. First, the amorphous and oxidation is also much lower in cold spray. This is
nature of the coating led to chemical homogeneity hin- an important consideration particularly in case of galva-
dering formation of localised galvanic cells and the nic protection, where it is desirable to have the superficial
onset of corrosion. Second, accelerated passive film for- layer in the form of pure and oxidisable elements. In
mation might have occurred due to enhanced diffusion addition, since the coating build-up is accompanied by
of passive elements in the nanocrystal containing amor- peening effect of incoming particles, compressive residual
phous structure. Moreover, the conventional phenom- stresses can be developed during cold spray, both in the
enon of pit formation for Al nanocrystallites was not coating and in the substrate. Thermal spray, on the
observed in the amorphous matrix. The reason is that other hand, imparts tensile residual stresses, and there-
amorphous matrix is rich in substitutional elements sur- fore, the tendency for delamination of the coating from
rounding the nanocrystals. Therefore, it requires a higher the substrate in thicker coating is higher. There are also
potential than pure Al to maintain stable pit growth some disadvantages for cold spray. These include non-
state. portability of many cold spray units, powder handling
Stellite alloy is a range of cobalt–chromium alloys to minimise the risk of combustion and cost efficiency
designed for wear resistance. It may also contain tungsten of the process. In this section, corrosion performance of
or molybdenum and a small but important amount of car- cold spray and thermal spray coatings are compared.
bon. Despite the difficulty of its plastic deformation, Hot corrosion/oxidation test by aqueous solution of
optimisation of cold spray parameters was shown to be Na2SO4 and NaCl at 705°C was performed on cold and
able to deposit stellite-6 coating with minimised porosity plasma sprayed tantalum on steel substrate. While orig-
and excellent adhesion to low alloy carbon steel sub- inal homogeneous fine grained structure of the cold
strate.40 Plastic strains in stellite powder were mainly sprayed substrate was unchanged, remarkable microstruc-
accommodated by twining rather than dislocation slip tural alteration (grain coarsening) of the plasma sprayed
and phase transformation. High temperature oxidation substrate occurred due to infiltration of air and corrosive
test in air atmosphere showed that the hexagonal phase salt. Almost identical polarisation behaviour with clear
starts to appear at 600°C, and coexists with the cubic passivation in KOH solution was reported for bulk and
phase up to 900°C. Cr2O3 with excellent protective prop- cold spray coated tantalum on aluminium, copper and
erties were observed to start growing at 700°C. The coat- steel substrates.41 However, the curves shifted towards lar-
ing did not show signs of spallation at 900°C and ger current density values and lower potentials without
maintained its integrity despite oxidation at the particle passivation for inert atmosphere plasma sprayed coating.
boundaries. Potentiodynamic behaviour of the coating This was due to the presence of defects and intercon-
in the NaCl solution also exhibited ameliorated corrosion nected porosity.
performance as compared to the bare substrate. Open cell potential measurements of WC–12Co coat-
This introductory section was aimed at discussing the ing onto carbon steel by high velocity oxygen fuel
ability of cold spray for corrosion protection by exempli- (HVOF)42 and onto Al7075 by cold spray43 in the same
fying the widely used materials such as Al, Ti, Mg and Zn testing conditions in NaCl solution revealed more noble
and also the less used materials such as Stellite and glassy behaviour for the cold sprayed coating. The metal/cer-
powders. For a material based classification of cold spray amic interfaces are the preferable paths for the electrode
coatings, the readers are referred to the available to corrode the coating. The peening effect of the particles
reviews.26,32 What comes in the rest of this paper is a pro- in cold spray tends to less porous structure of the coating
cess based classification of cold spray coatings to mitigate and, hence, fewer paths for the electrode to penetrate in
corrosion that is concluded with possible prospects for the case of cermet deposition. The similar results were
further research and development. The section ‘Cold ver- also obtained in Ref. 44, where cold spraying WC–Co
sus thermal spray: corrosion behaviour’ compares cold onto Al7075 resulted in better performance as compared
and thermal spray coatings in terms of corrosion protec- to HVOF, not only in electrochemical test, but also in
tion. The section ‘Considerations to obtain higher cor- abrasive wear test (rubber wheel) and sliding wear test
rosion resistance by cold spray’ reviews the effect of (ball on disc). Nevertheless, deposition efficiency of
deposition temperature and pressure, particle size, carrier HVOF was found to be higher (∼70%) than cold spray
gas, post-treatment, and co-deposition of metals and cer- deposition.
amic on corrosion behaviour of cold spray coatings. The Ni–20Cr coatings deposited on boiler steel by HVOF,
section ‘Applications and industrial examples’ highlights detonation gas spray and cold spray along with the bare
applications of cold spray to improve corrosion behaviour substrate were subjected to molten salt at 900°C for 50
in different fields. A critical discussion and future path for cycles. The mass change data were recorded as indicator
research and development is given in the last section ‘Path of corrosion rate.45 HVOF, detonation gas and cold
forward’. spray have significantly (61, 88 and 64% respectively)
reduced the mass gain observed for the bare substrate. X- area, and leading to more active sites for corrosion. A
ray diffraction analysis revealed the presence of NiCr2O4 similar trend was also found for corrosion performance
after corrosion test of the detonation gas sprayed sample of Ti coating onto carbon steel where corrosion resistance
and very weak intensity of this phase for HVOF sample. increased by increasing deposition temperature from 350
This mixed oxide phase was found to be absent for the to 500°C, and then decreased at deposition temperature of
cold sprayed specimen. NiCr2O4 exhibits superior cor- 600°C.36
rosion resistance, and its formation was mentioned to be Open circuit potentials of cold sprayed free standing
the reason for better protection offered by detonation titanium in as sprayed and heat treated conditions, in
gas spray. NaCl solution, were more negative as compared to the
Erosion–corrosion tests of HVOF and cold spray bulk titanium. This illustrates more active surface and
coated Ni–20Cr powder on boiler steel were conducted higher thermodynamic tendency to corrosion in the for-
in actual boiler environment as well.46 While the bare mer case.48 Increasing deposition temperature from 600
steel showed an overall weight gain, the HOVF and to 800°C decreased porosity level to almost half and
cold sprayed coating demonstrated an initial weight loss reduced the corrosion current density by an order of mag-
followed by a marginal weight gain. High velocity oxygen nitude. Heat treatment of the two free standing specimens
fuel resulted in lower erosion–corrosion rate and better at 1050°C for 60 min further decreased the corrosion rate
performance as compared to cold spray. This behaviour by one to two orders of magnitude. Heat treatment did so
was attributed to the continuous presence of Cr2O3 in by eliminating smaller pores, surface oxides and produ-
the HVOF coating as opposed to discontinuous streaks cing more homogeneous structure. Open circuit potential
of Cr2O3 in cold spray coating. Chromium has high affi- of titanium coating on carbon steel substrate lied in
nity for oxygen and forms more stable oxide, inhibiting between the corresponding values for bulk titanium and
oxidation of substrate by blocking diffusion of reacting carbon steel, showing solution percolation through the
species. coating. Open circuit potential of the coating deposited
In the light of the reported direct comparisons, and as a at higher temperature was closer to that of bulk titanium
result of the mentioned advantages of cold spray depo- for the first few hundred seconds, and then, the OCP
sition, it can be concluded that cold spray more likely, decreased. However, with the coating deposited at low
but not necessarily, tends to superior corrosion protection. temperature, the OCP value decreased to that of carbon
Nevertheless, thermal spray can lead to better perform- steel within few tens of seconds of immersion. This was
ance when oxides formation is the predominant protective attributed to larger pores distributed through the coating
mechanism. deposited at lower temperature and higher interconnected
porosity.
Open circuit potential measurements in NaCl solutions
Considerations to obtain higher were conducted for low and high pressure cold sprayed
corrosion resistance by cold spray copper coating on Fe52 substrate in as sprayed and heat
treated conditions.49 Fully dense, impermeable coating
In order to draw a general guideline towards improved
structure of high pressure cold spray coating in both as
corrosion resistance understanding the effects of cold
sprayed and heat treated states led to OCP values similar
spray parameters and conditions on corrosion behaviour
to that of bulk Cu. The OCP value of the low pressure
is essential. In this section, cold spray parameters and
conditions are correlated to the resultant corrosion behav- cold spray coating was close to that of substrate, reflecting
the existing of through porosity in this case. Heat treat-
iour in a systematic manner. The effect of deposition
ment was also performed after low pressure cold spray,
temperature and pressure, particle size, coating thickness,
but did not succeed in improving the denseness due to
carrier gas, post-treatment and co-deposition of metals/
the presence of excessive interconnected porosity.
alloys with ceramics/intermetallics are reviewed in details.
Addition of ceramic particle (alumina), on the other
hand, densified the coating structure. Addition of alumina
Deposition temperature and pressure particle in low pressure cold spray followed by post-heat
Increasing deposition temperature of 304 stainless steel treatment resulted in similar OCP behaviour to that of
powders onto interstitial free steel, from 450 to 500 and bulk copper. The coating experienced higher work hard-
550°C, was shown to have a great contribution in enhan- ening in high pressure deposition, hammering effect in
cing bonding between the particles, increasing cohesion co-deposition with ceramic particles and void reduction
strength and decreasing porosity from 6 to 3 and 2%.47 during heat treatment. All these effects have shown to
Potentiodynamic polarisation test in NaCl solution lead to denser and more corrosion resistant copper coat-
showed lower corrosion current density and higher cor- ing. Similar effect of pressure level was found in cold
rosion potential for all the coatings as compared to the spray deposition of titanium powders onto carbon steel.
substrate. Increasing the deposition temperature from Lower deposition pressure led to higher oxygen concen-
450 to 500°C improved the corrosion resistance by chan- tration difference corrosion due to the formation of
ging the rate from 0.47 to 0.02 mm/year. The beneficial more porous structure with less dissolved oxygen concen-
effect reduced for the deposition temperature of 550°C, tration in the pores.36
that resulted in corrosion rate of 0.17 mm/year. The In general, increasing deposition temperature and
weak performance of the 450°C deposited coating was pressure results in higher impact velocity and higher
attributed to the higher porosity leading to sever pitting induced plastic deformation of the powders. These are
of the coating. The decline of the performance from 500 beneficial in terms of obtaining less porous coating, and
to 550°C was attributed to higher degree of plastic defor- thus better corrosion performance. However, corrosion
mation at higher deposition temperature, changing the performance was observed to decline at extremely high
chemical potential of the metal atoms in the deformed deposition temperatures. This is attributed to
predominant softening of the powders at extremely high μm, demonstrating a critical thickness of the coating
temperature and induced localised deformation in such required to avoid the formation of interconnected poros-
cases acting as the preferential sites for corrosion. ity from the coating surface to the substrate via localised
attack.
Three types of 316L stainless steel powders of different
Particle size and coating thickness granulometry (fine, − 18+5; medium, − 28+7; and
Two sets of standard and improved tantalum powders coarse, − 36+15) were cold sprayed onto aluminium sub-
were deposited on carbon steel.50 Improved powders con- strate.52 No significant effect of the powder size on the
sisted of finer powders with narrower size distribution and coating adhesion and microhardness was observed,
less oxygen content, and were deposited at higher temp- whereas the porosity level increased by increasing the par-
erature. Open cell potential of the coating with improved ticle size. The anodic polarisation behaviour in NaCl sol-
conditions approached to that of bulk tantalum, while ution resulted in least noble potential and highest
standard coating behaved similar to the substrate. The corrosion current density for the coarse powders. Decreas-
reason was that existing through porosity in standard ing particle size led to slight decrease in the corrosion cur-
coating allowed the test solution to penetrate into the rent density. However, the polarisation curve of the
coating/substrate interface. Such behaviour was also the coating deposited with the finest powders was still far
reason to provide instability of passivation layer in stan- from the curve of the bulk stainless steel. Application of
dard coating, and poor corrosion protection in NaCl surface laser post treatment was shown to shift the polar-
and H2SO4 at room temperature as compared to bulk tan- isation behaviour towards bulk stainless steel. Laser post-
talum and improved high quality coating. The high qual- treatment was able to do so by eliminating interparticle
ity coating, on the other hand, showed similar discontinuity borders, and decreasing the porosity, lead-
polarisation behaviour to the bulk material. It got passi- ing to significant improvement of corrosion.
vated rapidly with stable passive layer testified to a very In summary, using big powder particles in cold spray
low corrosion rate in the passive area at both room and deposition leads to poor corrosion resistance. Finer pow-
elevated temperature (80°C). ders tend to result in a more compact coating and improve
Figure 4 shows anodic polarisation behaviour of cold the corrosion properties. Increasing coating thickness also
sprayed 316L stainless steel coatings of the same thick- appears to be beneficial in terms of corrosion perform-
ness, but with different powder particle sizes, on AZ91 ance. It seems that a lower band thickness exists for the
as well as the bulk material.51 The largest set of the par- coating to ensure protection of the substrate by preventing
ticles resulted in the least noble potential and the highest corrosion attack via interconnected porosity.
corrosion current density. The corrosion rate decreases by
reducing the powder size due to less porous structure of
the coating with smaller particles. Nevertheless, a mixture Carrier gas
of large and small particles ( − 22 and − 10 μm) exhibited Two different carrier gases, i.e. helium and a mixture of
the closest corrosion performance to that of the bulk helium and nitrogen, were used to deposit 1100 alu-
material. The improved quality of interparticle bonding minium onto the same substrate.53 Comparing electroche-
in this case played an important role to reduce the effect mical behaviour of the coating with the substrate in
of localised corrosive attacks. In the same study, coatings H2SO4 demonstrated faster protective layer formation in
with different thicknesses obtained by the same particle the coating as a result of porosity and residual stress.
size also showed different polarisation behaviours. The The corrosion resistance of the coating deposited with
curves followed a trend from behaviour dominated by helium was less than the one deposited with the mixed
the substrate (AZ91) towards the behaviour of the bulk carrier gas. Higher specific heat ratio and lower mass den-
stainless steel as the coating thickness increased from 40 sity of helium lead to higher induced plastic deformation
to 305 μm. A transition from non-passivating to passivat- in the particles and highly stressed regions in the coating.
ing behaviour was also observed at the thickness of 105 Accordingly, more preferential sites were present to

4 a anodic polarisation behaviour of 316SS cold spray coatings using different powder particles sizes and b anodic polarisation
behaviour of 316SS cold spray coatings of different thicknesses, compared to bulk type 316SS and AZ91E tb6 substrate
material; coatings were sprayed using − 22 μm powder51
undergo rapid corrosion kinetics, eventually leading to Codeposition of metals/alloys with ceramics/
localised extensive pitting and oxide layer cracking after intermetallic
corrosion test. Different volume fraction (0, 15, 30 and 60%) of silicon
The surface reactivity of the powders with oxygen carbide particles were mechanically blended with Al
might also vary with different carrier gases. For instance, 5056 powders and cold sprayed on aluminium substrate.57
using air increased the reactivity and thus doubled the Porosity of the Al 5056 coating decreased from 2.25%
porosity of the titanium coating deposited with com- to < 1% for all the composite coatings. It was found
pressed air as compared to the one deposited with that pores always appeared in the interparticle boundaries
nitrogen.36 between ceramic and metallic powders or within the clus-
It should be mentioned that helium is known to pro- ter of the ceramic particles due to poor deformability of
duce high quality coating with satisfactory mechanical SiC particles. Compared to the bulk aluminium, the
properties. The reason that using helium was not as effec- OCP values of all coatings shifted to cathodic values in
tive as the mixture of helium and nitrogen in the reviewed Na2SO4 solution. SiC content did not have any effect on
example could be attributed to ‘high end’ condition of the stabilised potential value due to its inert properties.
spraying experienced in this specific case, leading to loca-
Volume fraction of SiC particles also showed no signifi-
lised plastic deformation. Using helium in cold spray cant effect on the anodic polarisation behaviour of the
deposition as compared to nitrogen can potentially lead composite coatings. A crevice-like phenomenon due to
to better corrosion performance if the processing par- coating roughness, was found to be responsible for the
ameters are optimised such that localised severe defor- corrosion initiation. Propagation was promoted by acidi-
mation is avoided.
fication of localised corrosion in the particle boundaries.
The dissolution network finally ensures the particle
removal that can be considered as uniform degradation
of the coating.
Post-treatment Successful isolation of the magnesium alloy substrate
Cold sprayed stainless steel (316L) on mild steel substrate (AZ91) in NaCl solution was reported by cold spray
could provide higher corrosion resistance as compared to deposition of aluminium powders in pure state, alloyed
the bare substrate. However, the corrosion potential of (6061) and co-deposited with alumina particles.30,58 Cor-
stainless steel coating was lower than its bulk material. rosion current densities of the pure and composite coating
Heat treatment of the coated specimens at 400, 800 and were three orders lower than that of the bare substrate,
1100°C succeeded in increasing the corrosion potential indicating much higher anti-corrosion ability.58 No pas-
and shifting it towards the corrosion potential of the sive effect on anti-corrosion ability of the composite coat-
bulk material.54 This is due to the improvement in the ing was found as compared to that of pure Al coating.
quality of bonding especially in weakly bonded intersplat However, more reliable long term protection of the sub-
boundaries that were present in as sprayed condition. strate was speculated for the aluminium co-deposited
Laser post-treating of cold sprayed titanium was shown with alumina, due to less coating porosity.58 Figure 6
to be a successful technique to densify the coating by compares the cross-section of cold sprayed Al coating
melting top surface layer and releasing the porosities to onto AZ91D with that of Al–25 vol.-%Al2O3.59 The Al
the free surface with the subsequent solidification.55 Elec- coating shows a porous structure, whereas the co-depo-
trochemical tests in NaCl solution were conducted on
sition with ceramic particles significantly reduced the
titanium coating on carbon steel substrate in as sprayed coating porosity.
and laser post-treated conditions. The carbon steel sub- Addition of alumina particles to Ni–Cu powders has
strate was corroded, being less noble, and corrosion pit
been shown to have a two-side benefit to achieve higher
formed. The laser post-treatment, on the other hand, corrosion resistance.56 First, it improved the denseness
resulted in a shift of OCP and corrosion potential values of the coating by the hammering effect of ceramic par-
close to the level attained by bulk titanium (see Fig. 5) and ticles. Second, addition of hard alumina particle in the
a decrease in corrosion current by two orders of magni- metallic based powder enabled achieving higher depo-
tude compared to as sprayed condition. For a detailed dis- sition gas temperature (without nozzle clogging), and
cussion on the application of laser post-treatment after thus enhanced density and improved quality of the
cold spray, readers are referred to the review paper written coating.
in the field.29 Co-depositing alumina particles with Ni–20Cr on car-
There are also cases where heat treatment of the cold bon steel resulted in less through porosity in the coating
spray coating leads to slightly less noble behaviour as as shown by the salt spray test.60 The through porosity
compared to as sprayed coating. For instance, cold of the coating decreased with increasing alumina particles
sprayed nickel on carbon steel showed such behaviour size and fraction. Hard alumina particles also induced
in NaCl, NaOH and KOH solutions due to slight oxi- higher plastic deformation onto Al powders, making
dation of the coating during heat treatment.56 them packed and dense.30 Corrosion examination showed
In summary, post-heat or laser treatment improves that neither the alumina content nor the post-spray heat
bonding quality and diminish interparticle boundaries,
treatment had any significant effect on polarisation behav-
which are preferential sites for corrosion. Therefore, it is iour of the coating.30 Post-spray heat treatment, neverthe-
a recommended process as far as corrosion performance less, increased stability against formation of metastable
of cold spray coating is regarded. However, one should pits by increasing electrical conductivity, reducing inter-
mind oxidation of the coating during post-heat treatment. face contact resistance and reducing dislocation density.
Post-heat treatment did not show significant improvement Al 7075 particles mixed with B4C and SiC reinforce-
in case of co-deposited coatings, which will be discussed in ments were deposited onto 6061-T6 alloy using cold
the next section.
5 Open circuit potential in aerated 3.5%NaCl of bulk Ti, carbon steel, as sprayed Ti coating (on carbon steel) and laser treated Ti
coating55

spray.61 Open circuit potential of the bare substrate in WC–Co cermet powders were shown to successfully
NaCl solution tended to increase first as a result of surface provide corrosion protection for Al 7075 and carbon
passivation, by the formation of more protective oxide. It steel substrates.43,63 It should be mentioned that cold
then decreased, indicating that the substrate reached the spraying of WC–Co cermet is not co-deposition of metals
pitting potential, and simultaneously localised corrosion and ceramics but deposition of metal–ceramic composite
occurred. Al coatings (Al 7075, Al 7075+20 vol.-%B4C powders. A certain degree of ductility of the particles is
and Al 7075+20 vol.-%SiC), on the other hand, showed required for the successful deposition and coating build-
stable and lower potential, suggesting that stable oxide up in cold spray, justifying addition of ductile binder to
film have already formed before exposure or within a the ceramic. Open cell potential curves of WC–12Co,
few seconds of exposure. Unreinforced Al 7075 coating WC–17Co and WC–25Co coating on Al 7075 in NaCl
exhibited much more noble corrosion potential and solution initially decreased due to dissolution of oxides
lower corrosion current density as compared to the cer- and penetration of electrolyte; and then stabilised. Com-
amic reinforced coatings. Higher level of plastic defor- paring the potential values of the coatings and substrate
mation experienced in the composite coating was showed that the electrolyte did not reach the substrate
mentioned to lead to more active sites of corrosion. in any of coatings. As the fraction of ductile binder
Different powders, i.e. aluminium, aluminium–alumina increases, the coating shows less noble behaviour. By
and aluminium–alumina–zinc, were deposited onto increasing fraction of ductile binder, the metal/ceramic
Al2024 and were exposed to salt spray test corrosion interfaces increase. Therefore, more preferable paths are
test.62 Corrosion of aluminium–alumina coating intensi- provided for the electrode to corrode, leading to the less
fied as ceramic particle concentration increased in the noble electrochemical behaviour.
coating. The best performance was obtained for pure alu- Aluminium blended with 50 and 70 vol.-%Mg17Al12,
minium coating. The process of degradation was acceler- and cold sprayed on AZ91, was shown to successfully
ated for aluminium–alumina–zinc by the aluminium–zinc decrease the corrosion current density in NaCl solution,
galvanic couple, suggesting it as a suitable sacrificial as compared to the bare substrate. In fact, the corrosion
anode material. current density and corrosion potentials of both

6 Coating structure: a Al and b Al+alumina59

composite coatings were closer to pure Al rather than the is thermodynamically most stable in Hanks' solution.
substrate. The anti-corrosion performance was degraded Lowest corrosion current was also obtained for 50 wt-%
as the hard intermetallic particle fraction in the Al matrix HAP/Ti. The 20 wt-% HAP/Ti coating demonstrated
increased from 50 to 70 vol.-%. One explanation could be higher corrosion current than pure Ti coating due to the
that the bonding among Al and Mg17Al12 particles is fact that HAP promotes the formation of new apatite
mechanical interlocking rather than metallurgical bond- layer. The lowest corrosion current in case of 50 wt-%
ing. Interfaces in the composite coatings experienced HAP/Ti coating was possibly attributed to the presence
higher strain rate, and could act as preferential reaction of long and narrow cracks in the coating. Heat treatment
site for pitting or galvanic corrosion especially when of the 20 wt-%HAP/Ti coating decreased the corrosion
some defects are present at the interface.64 current as compared to pure Ti. It was also able to
In general, corrosion behaviour of co-deposited metals/ remarkably increase the ultimate shear strength and
alloys with ceramic/intermetallics is influenced by two microhardness of the coating recommending HAP/Ti
main phenomena. On the one hand, tamping effect of composite coating, as an effective candidate for load bear-
hard particles increases particle deformation and ing biomedical implants.
decreases the porosity level of the coating. On the other Co–Cr alloys and stainless steel are also extensively
hand, the interface between the hard phase and the binder used in biomedical implants. While corrosion resistance
promotes the localised corrosion at particle boundaries. of Co–Cr alloys is higher than stainless steel, its manufac-
These two competing phenomena might be the reason turing is much more problematic due to higher melting
for controversial results (improvement and deterioration temperature and strength. A reasonable compromise,
of corrosion resistance) reported in the literature. The therefore, might be expected by making a metal matrix
other important issue in co-deposition is considering the composite combining the two materials. Cold spray was
fraction of the hard phase in the initial blend in connection used to deposit stainless steel and 25, 33.3 and 50 vol.-%
with the amount entrapped in the coating. It seems that Co–Cr alloy L605 onto mild steel substrate.67 Potentiody-
there is a limit for the maximum amount of the second namic polarisation curves of the co-deposited stainless
phase after which the deposition efficiency decreases. steel/Co–Cr alloy as well as cold sprayed pure stainless
Co-deposition of metals/alloys with ceramics/intermetal- steel in Hanks' solution demonstrated higher corrosion
lics enables attaining higher deposition temperature, with- resistance for 25 and 33%Co-Cr as compared to the
out nozzle clogging issues, that could be beneficial in terms pure stainless steel coating. The corrosion resistance of
of the resultant corrosion resistance of the coating. 50%Co–Cr was lower than that of pure stainless steel
coating. Such behaviour could have been attributed to sig-
nificantly increased porosity and induced cracks in the
Applications and industrial examples stainless steel matrix for 50%Co–Cr as compared to 25
A wide variety of materials such as metals, metal matrix and 33%. The 25 and 33%Co–Cr coating exhibited
composites, ceramics, polymers and nanostructured pow- lower porosity than pure stainless steel coating as a result
ders have been successfully deposited by cold of stronger tamping effects of denser Co–Cr particles. As
spray.26,32,33,65 This provides the opportunity of exploring the proportion of Co–Cr increased, the deposition effi-
a wide range of coating/substrate systems with specific ciency decreased. The amount of Co–Cr in the nominally
functions in different fields of applications. However, the 50% powder blend decreased to 33.3% entrapped in the
industrial applications of cold spray aimed at contrasting coating; 33.3% could be, therefore, interpreted as the
corrosion are not so numerous. In this section, the most maximum amount of Co–Cr that could be added to stain-
relevant examples for potential applications of this kind less steel for cold spraying with the applied parameters.
are presented and critically discussed. The loss of the Co–Cr particle in 50%, and thus increased
interactions of in-flight particles, was perhaps responsible
for the jump in porosity level and the deterioration of cor-
Biomedical rosion resistance.
Owing to its remarkable corrosion resistance, good bio- Magnesium has been suggested as an alternative bio-
compatibility and high mechanical strength, titanium material due to several reasons. Magnesium is biodegrad-
has been widely used for many years in biomedical able; it can promote the growth of new bone tissues; its
implants. High corrosion resistance and biocompatibility mechanical properties are compatible to those of bone tis-
of titanium originate from titanium oxide (TiO2) forming sues, and Mg2+ is an essential element to the human body.
on the surface. The lack of formation of apatite layer in However, it suffers from poor corrosion resistance and
bony tissues, nevertheless, deteriorates implant fixation tends to be degraded rapidly. In order to control the
and hinders its long term stability. To overcome this degradation rate, HAP was successfully cold sprayed on
issue, co-deposition of titanium with a bioactive material the Mg substrate without any phase change.68 While the
can be considered. 20 and 50 wt-% Hydroxyapatite bare substrate showed considerable degradation from
(HAP)/titanium powders were successfully deposited the very first day of immersion in simulated body fluid,
onto titanium substrate.66 Electrochemical corrosion HAP started dissolving after 1 day and showed signs of
behaviour of composite coating was examined in simu- regeneration after 10 days. The results confirmed that
lated body fluid, Hanks’ balanced salt solution with pH the coated sample was both biodegradable and bioactive,
= 7.25 ± 0.15, and compared to that of pure titanium and suitable for possible use in orthopedic implants.
coating. Hydroxyapatite (20 wt-%) was successfully
entrapped in the Ti matrix, and a dense and homogeneous
coating was obtained, whereas 50 wt-%HAP led to for- Hot corrosion
mation of voids and crack in the coating. The corrosion Metallic components working at high temperature are
potential values indicated that 50 wt-%HAP/Ti coating vulnerable to hot corrosion, that is an accelerated form
of oxidation in the presence of sulphate deposits. Such Naval
working condition mostly occurs in boilers where Ni Cavitation erosion is often a central problem in the rud-
based coatings could provide sufficient protection. Cyclic ders of ships that travels at high speeds. Cavitation is
corrosion test of boiler steel in molten salt at 900°C the formation of vapour cavities in liquids, that occurs
showed intense spalling, peeling of the scale and enor- when a liquid is subjected to rapid changes of pressure
mous weight gain due to rapid diffusion of oxygen at the points where the pressure is relatively low. When
through the molten salt layer.69,70 Ni–20Cr coating on subjected to higher pressure, the voids implode and
steel in the same testing condition, on the other hand, cause high localised loads and cyclic stress on the exposed
was found to reduce the weight gain by 87.269 and material surface. Material deformation and microstruc-
78%70 for two boiler steels, SA 516 and SA 213 respect- tural defects lead to initiation and growth of small cracks
ively. Further examination revealed formation of unpro- and eventually to local surface material removal. Cavita-
tective Fe2O3 oxides in the bare steel and protective tion test was performed on the classified ship building
NiO and Cr2O3 in the coating. A comparison of ero- steel GL-A (equivalent to S235) and also the same sub-
sion–corrosion rate of Ni–20Cr and Ni–50Cr coatings strate cold spray coated with CuAl10Fe5Ni5 bronze pow-
on the boiler steel in actual environment of coal fired boi- ders.75 Figure 7 shows the development of mean
ler showed that Ni–50Cr provided higher resistance to the cavitation erosion depths for coated samples with differ-
corroding species (58 and 72% reduced rate as compared ent parameters (as atomised or annealed powders, differ-
to bare substrate).71 This was correlated to the higher ent substrate temperatures, different ratios of impact to
amount of chromium along with oxygen (thermodynami- critical velocity shown by lowercase eta). The behaviours
cally stable chromium oxide) and higher microhardness of of the bulk substrate and bulk cast CuAl10Fe5Ni5 material
the Ni–50Cr coating. are also shown. Steady state cavitation rate of the coatings
Superfer 800H superalloy showed poor performance occurred at lower rate than that of the bulk steel. Higher
with 157.95 mpy degradation rate at high temperature cavitation resistance was obtained by optimising the cold
erosion–corrosion condition for 1000 h, in a medical spraying conditions. It was found that annealed powders
waste incinerator plan where the temperature is about form more cavitation resistant coating than as atomised
800–1000°C.72 Super alloy cold spray coated with NiCo- powders at the same impact conditions. This was due to
CrAlY, on the other hand, was able to significantly reduce lower porosity and thus more bonded interfaces obtained
the degradation rate to 36.56 mpy. The poor performance by annealed powders. Small variations of impact/critical
of the bare substrate was due to active oxidation in pres- velocity ratio had minor effect on cavitation rate. Increas-
ence of chlorine and formation of porous, fragile and non- ing substrate temperature increased deformability and
protective Fe2O3. The reduced degradation rate of the resulted in higher bond strength, coating cohesion and
coating was attributed to the formation of protective thus cavitation resistance, reaching to an optimum at
Al2O3 with some spinels of Co–Cr and Ni–Cr at top 300°C. Further increase in substrate temperature pro-
scale and also dense structure of the coating. These pro- motes surface oxidation and decreased cavitation
tective oxides did not allow oxygen to penetrate further, resistance.
and prevented corrosion of the substrate. The same
phenomenon was responsible for the better performance
of NiCoCrAlY coating, as compared to NiCrAlY coat-
ing, in hot corrosion condition in Na2SO4 solution.73
Path forward
Having a highly compact coating with as much less poros-
ity as possible is crucial in majority of cold spray appli-
Electronics cations. It is widely accepted that the conditions leading
Sintered neodymium–iron–boron (NdFeB) is a new gen- to higher level of plastic deformation of the particles
eration of permanent magnetic material that is widely upon impact could result in more compact and less por-
used in electronics, acoustics, automation, communi- ous coating. Mechanical properties of the coating such
cation and magnetic resonance imaging. The presence as hardness, cohesion and adhesion are also often
of the rare earth Nd in the magnet, nevertheless, signifi- enhanced when high level of plastic deformation is
cantly decreases its corrosion resistance and limits its induced during impact. Higher deposition temperatures
application in humid environments. A dense coating of and pressure, peening effect of hard co-deposited ceramics
pure aluminium with no cracks and other defects at the or intermetallics and using lighter carrier gas are all poss-
interface was successfully deposited onto NdFeB using ible strategies for inducing higher plastic deformation,
cold spray to address this problem.74 The corrosion beha- and thus obtaining better mechanical properties. Electro-
viours of the bare and coated substrates were determined chemical response and corrosion resistance, on the other
by potentiodynamic polarisation in NaCl solution. The hand, was shown not to be necessarily improved in such
corrosion current of the coated substrate without immer- conditions. Corrosion resistance increases as far as higher
sion was less than one-third of the bare substrate. The cor- level of plastic deformation results in closing the pores
rosion current of the coating after 24 h immersion became and reducing the porosity. However, extreme localised
higher than that of without immersion possibly due to deformation appeared to provide preferential sites for
damage of the oxide film already formed in the air. rapid corrosion kinetics by changing the chemical poten-
With further immersion, the corrosion current gradually tial of the atoms in the deformed area. It eventually might
decreased, suggesting interaction of Al and the solution lead to localised extensive pitting and oxide layer crack-
to form a new oxide barrier that prevents penetration of ing. Viewing from this standpoint, finding a criterion to
the solution ions. Therefore, long-term protection of the carefully compromise between mechanical and electro-
NdFeB substrate could be expected by the cold sprayed chemical characteristics of cold spray coating seems
Al coating. essential in the field; as in many applications, satisfactory
7 Cavitation–erosion depth for differently processed coatings and bulk reference material overexposing time75

performance of the coating is required in both aspects. It corrosion products can accelerate pit formation and
was shown in this review that increasing deposition temp- growth through the surface. Excluding this inherent dis-
erature and pressure, finer powder particles, thicker coat- advantage of coating could lead to more illustrative com-
ings, post-heat or laser treatment and co-deposition of parison of corrosion behaviour of cold spray coating and
metals/alloys with ceramic/intermetallics are all capable bulk material of the same type. A thin layer could be
of potentially improving corrosion behaviour. removed from the coating surface to exclude the draw-
The dominant point of view in corrosion protection by backs of high surface roughness in corrosion studies. Per-
cold spray is to apply this technique to provide protective forming post-treatments such as grinding, machining or
layer for an unfinished component. However, one pro- electropolishing on the cold spray coatings and studying
spect of cold spray could be repairing the corroded the effects on corrosion performance are worth examin-
parts of the components that are already in service. Cor- ing. This can improve the corrosion behaviour of the coat-
rosion-related maintenance and failures cost the aircraft ing to approach to that of the bulk material, and more
industry billions of dollars annually. Therefore, on pro- importantly, this can reveal how corrosion mechanisms
spect of cold spray could be in situ repairing the aeronau- might change from bulk material to the coating when
tical components made of Al or Ti alloys, given the the roughness effect does not intervene.
successful performance of such coatings against corrosion Cold spraying of titanium offers an attractive avenue
reviewed in this work. Because cold spray process is highly for designing against aqueous corrosion as well as biome-
collimated, it is potentially suitable for localised corrosion dical applications. Nevertheless, some level of difficulty
protection and restoration, without the need for excessive has been often reported in cold spraying of titanium
masking. It can also eliminate the need to pre-surface and its alloys. High levels of Porosity as well as intercon-
treatments such as sand blasting, as it can bring the peen- nected pores significantly deteriorate corrosion perform-
ing effect of the particles itself. Adding the capability of in ance of titanium coatings. A comprehensive
situ repair to cold spraying would significantly increase its optimisation of deposition parameters is, therefore,
coverage in the field of corrosion protection. To achieve needed to exploit the full advantage of titanium as cold
this goal, portability of cold spray unit is a central chal- spray coating. As a rule of thumb, ‘high end parameters’
lenge to be overcome. Although the technology of design- should be set in cold spraying of titanium particles to
ing portable cold spray systems is currently available in obtain compact coatings. Preheating of the powders and
the limited industries, the widespread application of the substrate, high temperature deposition, 1000°C for
such units depends on the ability of making competitive instance, impact velocities far higher than the critical vel-
deposition with stationary counterparts, in particular, ocity (1100 m s − 1 for instance) and as much less deviation
for high pressure deposition regime. Therefore, design from perpendicular impact as possible are some key sug-
considerations of the basic elements in cold spray such gestions towards successful deposition of titanium par-
as supersonic nozzle, pressure vessel and heater should ticles. Nevertheless, some limitations of available devices
be carefully revisited and optimised. should be addressed first in this regard.
Cold spray coating, whether or not able to protect the A primary application of thermal spray coatings for
substrate, was not found to be able to retain the corrosion over half a century has been the galvanic protection of
properties of the bulk material of its type. It is known that steel structures. In the majority of cold spray deposition
cold spray significantly increases the surface roughness. onto steel substrates, reviewed here, the objective was
Rough surfaces decrease the corrosion resistance, because not to provide sacrificial protection but to provide less
of high ion release rate, plastic deformation under loading active layer to the environment. Zinc and aluminium
and promoting the risk of pit formation. Presence of sur- can provide sacrificial protection for steel. Zinc is a low
face defects entrapping corrosion causing species and melting temperature metal with low critical velocity
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