Performance of Corrosion Resistant Arc Spray Coatings as a

Function of Spray Parameters

J. Cheney*, Ph.D.
Scoperta, San Diego, CA, USA
*E-mail: jcheney@scopertainc.com

G. Kusinski, Ph. D.
Chevron Energy Technology Company

Abstract environments in the oil and gas industry. However, due to

Twin wire arc spray (TWAS) coatings were produced under
varying spray conditions (spray angle, traverse rate, and spray
distance) to simulate on-site hand spraying operations
typically used to coat existing refinery vessels. Two materials,
Alloy C276 (commonly used for corrosion protection of
refinery vessels) and the newly developed Nicko-Shield™ 200
chemistry (designed to reduce porosity and oxide content
under arc spray conditions) were compared in the testing.
Alloy C276 coatings showed good coating performance (>40
MPa adhesion) when sprayed under ideal conditions, but
showed a sharp drop off in coating integrity (<20 MPa
adhesion) when sprayed at lower traverse rates, sharper
angles, and closer spray distances. Deviating from non-ideal
conditions resulted in increased porosity and oxide content
leading to increased permeability. It was concluded that non-
ideal conditions, which intermittently occur in hand spraying
operations on large surface areas, can lead to coating patches
with unacceptably low adhesion, potential spalling, and high
permeability when spraying Alloy C276. Patches of low
coating quality require additional maintenance or result in
coating failure, creating a lack of confidence in thermal spray
technology as a protective solution in the industry. This study
shows the results of an effort to develop an alloy solution
which is more reliable in spraying large surface areas by hand
for corrosion protection. The developed Ni-based material
showed improved adhesion (70+ MPa) and greatly reduced
permeability (as measured by ferroxyl exposure). This
performance was stable across the wide range of spray
conditions used in this study. This suggests that alloy design
can be used to increase the reliability for twin wire arc spray
coatings, and enable confidence for expanded use in this
industry.
Introduction
The nickel-chromium-molybdenum family of alloys has been
demonstrated as an effective tool against corrosive
their high cost, they are generally utilized in only the most
corrosive environments where Fe-based materials (400-series,
300 series stainless, or duplex steel) are still subject to
aggressive attack. Very often, aggressive corrosive conditions
are related to the extraction or processing of sour crudes and
gases, e.g. those containing H2S. Developing cost effective
solutions to function reliably in sour services can greatly
reduce the maintenance and downtime costs experienced in
the oil and gas industry.
Thermal spray processing is a cost effective method to deposit
corrosion resistant coatings for use in corrosive environments.
Nickel alloy chemistries such as those within the Hastelloy™
(Ref 1) and Inconel™ (Ref 2) alloy families, originally
designed and proven to be effective for use as bulk
components (plate, sheet, bar…), have been transitioned into
thermal spray materials for the variety of deposition options
(TWAS, HVAS , HVOF, HVAF). However, thermal spray
technology must overcome several processing challenges not
experienced in bulk forms. These challenges are well
documented and understood: in flight oxidation of the
particles (Ref 3) deposits oxide impurities in the coating
structure, coating porosity (Ref 2) results in some level of
permeability through the coating thickness, and finally the
relatively weak mechanical bonding to the substrate and
internal stresses resulting from the particle quenching process
can lead to spalling. Unfortunately, these challenges are
further magnified when coatings are sprayed by hand over
large surface areas.
Spray parameter variations such as spray angle (Ref 4),
traverse rate and spray distance can affect coating integrity.
Many applications in the oil and gas industry, including both
the initial application and reapplication of coatings in pre-
installed refinery vessels, require hand spraying to meet cost
and time constraints. An appropriate thermal spray solution
must deliver a reliable high performance coating within these
constraints in order to reduce maintenance costs.

This study focuses on understanding the parameter constraints
around hand spray operations and how they affect coating
quality. A proper solution must deliver coatings with high
integrity (low porosity, low oxide content, low permeability,
and high adhesion) within an achievable spray parameter
window. Arc spray processes, whether TWAS or HVAS, are
widely used due to their ability to effectively coat large
surface areas. However, in order to reliably function in the
corrosive conditions found in the oil and gas industry, a
certain level of coating integrity must be maintained even
under hand spray operations. Alloy C276, a commonly used
material for corrosion protection, is compared with the Nicko-
Shield™ 200 chemistry. The Nicko-Shield™ 200 chemistry
has been designed to specifically function within the arc spray
process and as a result shows a greater level of reliability in
hand spray operations than Alloy C276.
Experimental Methods and Materials
Two alloys, Alloy C276 solid wire and Nicko-Shield™ 200
cored wire, were used in this study. Alloy C276 is a well-
known commercially available alloy. Nicko-Shield™ 200 is
a proprietary material jointly developed by Chevron ETC and
Scoperta Inc. Chromium and molybdenum are known to be
the key alloying elements to providing these nickel-based
materials with enhanced corrosion resistance, and the relative
concentrations of both are given in Table 1 for alloy C276 and
Nicko-Shield™ 200. Many of the secondary alloying
additions to Alloy C276 (Co, W, Fe, W, Si, and Mn) are added
to effect properties relevant to the bulk form such as ease of
fabrication, microstructure of wrought forms, etc.
The alloying additions/modifications of Nicko-Shield™ 200
have been added to improve the spray-ability and performance
of the material under the arc spray process specifically. For
example, the chromium content has been substantially
elevated to account for the preferential in-flight oxidation of
chromium during the spray process. Thus, the as-deposited
metallic component of the Nicko-Shield™ 200 coating closely
resembles the chromium and molybdenum levels found in
wrought alloy C276.
Table 1: Relative concentration of chromium and molybdenum
(given in weight percent) in Alloy C276 and Nicko-Shield™
200
Alloy Cr % Mo %
C276 16 16
NS200 20 12
Both alloys were sprayed under a series of identical conditions
utilizing a programmed 6-axis robot. The parameter variables
examined within this study include 1) traverse rate, 2) spray
distance, and 3) spray angle. The samples were sprayed with a
TAFA 8830 spray gun with a CP 302 power supply, and a
green short cross cap/positioner. All samples were sprayed
with 32V and 200A. A spray offset of 12.5mm was utilized in
all experiments, which reflected a roughly 50% overlap
between subsequent spray passes. A schematic for the test
configuration is shown in Fig. 1. 100mm x 100mm x3.175mm
rectangular carbon steel panels were used as the substrates for
all testing parameters.
Figure 1: Experimental Diagram for Spray Parameter Study
Each panel was coated with ~0.5mm of material, a standard
coating thickness for corrosion resistant thermal spray
coatings. In some cases, where the thickness per pass was
relatively high >0.25 mm/pass, slightly higher total coating
thickness were deposited. In each case, after the first coating
pass, the coating thickness and substrate temperature were
noted. Substrate temperature was measured using an optical
pyrometer and thickness measurements were taken with a
micrometer.
The adhesion strength of the coatings was measured using a
Positest AT-A automatic adhesion tester according to ASTM
D4541. The permeability of the coatings was evaluated using
ferroxyl exposure testing according to a modified ASTM
A967 standard. A 75mm x 150mm surface area of each
coated panel was exposed to the ferroxyl solution, with 25 g of
potassium ferricyanide and 15 g of sodium chloride dissolved
in 1 L of distilled water. Before the ferroxyl exposure, all
coatings were lightly grit blasted with Al2O3 to remove any
potential iron contamination. Samples were exposed to the
ferroxyl solution for 10 minutes and lightly washed with water
before examination. The exposure time was increased from
30 seconds (as called for in ASTM A967) to 10 minutes to
fully allow the ferroxyl time to penetrate through any potential
through-porosity.
The various coating parameter sets were then evaluated
microstructurally to quantify porosity and oxide content. The
corrosion resistance of both coatings, when sprayed under
optimal conditions, was evaluated according to ASTM G31 in
hot (175oC) sulfuric acid (83%). Hot (near boiling) sulfuric
acid condensation is an environment typically experienced in
refinery vessels associated with desulfurization and other sour
service processes, and is very aggressive on carbon steels (~90
mm/year corrosion rates).

Results and Discussion
Table 2 summarizes the parameters used in this study and the
measured adhesion results. Parameters were varied around an
‘ideal’ set of spray conditions: 175mm spray distance, 300
mm/s traverse rate, and a 90o spray angle. In the case of spray
distance, smaller (125mm) and larger spray distances
(225mm) were used to study the parameter range an operator
might oscillate between when hand spraying a vessel. 300
mm/s, although determined to be an ideal coating traverse rate,
is relatively fast for an applicator to hand spray large surface
areas for a long period of time. Thus, slower traverse rates
were evaluated to simulate realistic conditions including the
possibility of applicator fatigue. Finally, spray angle
parameters were varied from 90o, the optimal condition, to
30o, a non-optimal condition which can occur even when
spraying flat surfaces, but will certainly occur when the need
to spray in tight spaces arises.
Figure 2 is a plot of coating adhesion versus two parameters:
traverse rate (x-axis) and spray distance (as specified in the
legend). As expected, slower traverse rates and smaller
coating distances generally resulted in very fast material build
up rates (reaching up to 0.25-0.4 mm/pass, Table 2), and
resulted in lowered coating adhesion in Alloy C276 coatings.
In the worst case scenarios, Alloy C276 coatings appear to be
in danger of spalling off immediately when traverse rates fall
near 40 mm/s. The Nicko-Shield™ 200 coatings, however, do
not show the adverse effect of traverse rate or spray distance.
The coatings maintain a relatively constant >55 MPa ->70MPa
adhesion strength over the span of these parameters.

Table 2: Spray parameters used [traverse rate (Trav.) in

mm/s, spray distance (Dist.) in mm] and spray results [coating
adhesion of Nicko-Shield 200 (NS200) and Alloy C276 in
MPa and average recorded thickness per pass(thick/pass) in
mm/pass] Figure 2: Coating adhesion in Alloy C276 and Nicko-Shield™
200 (NS200) coatings as a function of spray distance and
Trav. Dist. Angle NS200 C276 thick/pass traverse rate [number next to alloy designation in legend
(mm/s) (mm) (o) (MPa) (MPa) (mm) denotes spray distance in mm]
40 125 90 61.9 0.0 0.4
125 125 90 62.1 31.3 0.15
In general, the C276 coating process was hotter, resulting in
200 125 90 58.6 37.6 0.13 surface temperatures roughly 10oC-40oC higher than the
300 125 90 70* 42.1 0.08 surface temperature of the Nicko-Shield™ 200 coating under
40 175 90 63.8 37.2 0.4 similar spray conditions. It is possible that the elevated oxide
125 175 90 70* 54.7 0.15 content found in Alloy C276 coatings lowers the thermal
conductivity of the coating and reduces its capacity to
200 175 90 66.1 60.2 0.13 dissipate heat into the substrate. In the optimum spray
40 225 90 70* 49.5 0.4 parameter regime, where resulting parameters lead to a 0.075-
125 225 90 65.5* 60.8 0.15 0.15 mm/pass build up, the C276 material formed strongly
200 225 90 68.4 64.9 0.13 adherent coatings approaching the high adhesion levels of the
Nicko-Shield™ ™ 200 material. Alloy C276 also showed
125 175 30 70* 59.1 0.15
some tendency to produce lower adhesion values as the spray
200 175 30 70* 32.6 0.10 angle decreased, although the effect was less consistent. As
shown in Fig. 3, the spray angle reduction from 90o to 30o
Coating Adhesion generates a 24MPa drop in adhesion values, when the traverse
The measured adhesion strength for Alloy C276 was 44.2 rate is 200mm/s, but does not appear to affect the adhesion
MPa on average, varying from 0 MPa to 64.9 MPa. The values when the traverse rate is 125mm/s. The result is
measured adhesion strength for Nicko-Shield™ 200 was 65.0 unexpected as the slower traverse rate should produce lower
MPa on average varying from 58.6 MPa to 70+ MPa (glue adhesion values. The Nicko-Shield™ 200 material formed
failure). In general, the Alloy C276 coatings tended to exhibit consistently strong (>65MPa) levels of adhesion as spray
adhesive failure (separation of coating from steel coupon), angle and traverse rate were varied.
while the Nicko-Shield™ 200 coatings exhibited cohesive
failure (separation within the coating), glue failure, or a mixed Coating Permeability: Ferroxyl Testing
mode between the two. Ferroxyl exposure detects the presence of free iron and is a
very sensitive technique for evaluating permeability. The
ferroxyl solution is a yellow-orange color, but turns blue
rapidly when in contact to free iron, Fe2+ ions. Although
Alloy C276 contains 4-7% iron in the chemical composition,
the solution does not turn blue in the presence of Alloy C276
alone. For example, ferroxyl solutions are most typically used
to detect cracks or dilution in Fe-based welds and do not turn
blue when in contact with stainless steels. Ferroxyl does turn
blue rapidly in the presence of mild steel, the substrate
material used in all tests. Figure 4 shows the ferroxyl
exposure results for 4 different coating types; 1) Nicko-
Shield™ 200 sprayed under optimal conditions, 2) Nicko-
Shield™ 200 sprayed under non-optimal conditions, 3) Alloy
C276 sprayed under optimal conditions, and 4) Alloy C276
sprayed under non-optimal conditions. Optimal conditions are
defined as 175mm spray distance, 200mm/s traverse rate, and
90o spray angle. Non-optimal spray conditions are defined as
125mm spray distance, 125mm/s, and 90o spray angle.
Figure 3: Coating adhesion in Alloy C276 and Nicko-Shield™
200 (NS200) coatings as a function of spray angle and
traverse rate [number next to alloy designation in legend
denotes traverse rate in mm/s]
Figure 4: As-Sprayed coatings of Nicko-Shield™ 200 and
Alloy C276 exposed to ferroxyl solution for 10 minutes and
washed off with running water.
In all coatings, there is evidence of porosity as expected, the
ferroxyl solution is absorbed into pockets of high porosity and
is not washed clean in the running water. The Alloy C276
coatings do show extensive permeability under both optimal
and non-optimal spray conditions as indicated by the presence
of blue tint on the coating surface. The ferroxyl solution
appears to have penetrated most effectively in bands running
lengthwise across the surface concurrent with the traverse
direction. Although the sample appeared macroscopically
uniform in thickness and quality, the microstructural integrity
of the Alloy C276 coating appears highly variable even when
sprayed under optimal condition. The optimal spray
conditions were constructed such that the spray patterns of
each pass overlapped by 50% over the spray pattern of
previous passes. It is interesting to note that even when the
spray path is controlled to this level of precision, coating
permeability clearly varies across the surface of the 100mm x
100mm test specimen. Such bands of lowered coating
integrity likely exist in a hand sprayed application across
hundreds or thousands of square feet. The Nicko-Shield™
coating sprayed under non-optimal conditions (#2) also shows
bands of high porosity in line with the spray direction.
However, in contrast to the Alloy C276 specimens very little
through porosity is indicated (i.e. the ferroxyl solution remains
its original color, yellow-orange). Under optimal conditions,
the Nicko-Shield™ 200 coating shows a more uniform
distribution of porosity across the sample surface and no
indication of through porosity.
Comparison of Coating Macro and Micro Structures
Differences in coating integrity between Nicko-Shield™ 200
and Alloy C276 specimens can be detected with simple visual
inspection. The Nicko-Shield™ 200 coating (Fig. 7) tends to
have a lighter more metallic appearance, and the Alloy C276
(Fig. 8) appears darker (an indication of higher oxide
concentration). This increased level of oxides within the
coating contributes to the reduced adhesion and increased
permeability of Alloy C276. Under certain non-optimal spray
conditions, the difference in coating integrity between the two
chemistries is more pronounced as shown in Fig. 6. These
spray conditions result in coating build up in the range of
0.25-0.4 mm/pass. The build-up conditions are out of the
typical specified range (typically 0.08 mm/pass is desired).
However, the non-optimum conditions nevertheless occur in
on-site applications due to a slowing traverse rate or
decreasing spray distance. The Alloy C276 coating spalls off
immediately under these conditions. Nicko-Shield™ 200
shows nearly 62 MPa adhesion strength. In both alloys
sprayed under non-optimal conditions, striations can be seen
occurring along the horizontal traverse direction creating a
banded appearance.
Both adhesion and permeability are a function of the impurity
level (porosity and oxide content) in the coatings. Figure 7
shows Nicko-Shield™ 200 and Fig. 8 shows Alloy C276,
both coatings sprayed under optimal conditions. Both
samples were metallographically prepared simultaneously
under similar cutting, mounting, and polishing conditions to
remove any preparation technique variability in the evaluation
of coating integrity. Alloy C276 shows an increase in the
overall impurity content (porosity + oxides) in comparison to
the Nicko-Shield™ 200 coating. The preferential oxidation
of chromium in Alloy C276 accounts for the majority of
embedded oxides in the coating. In general, each ‘splat’
particle in the Alloy C276 coating is encased in a thin oxide
layer. The Nicko-Shield™ 200 chemistry is designed to
prevent the formation of chromium oxides, which results in a
lower overall oxide concentration. This contrast is magnified
under increasingly non-optimum spray conditions. The
impurity content (porosity + oxides) in Nicko-Shield™ 200
remains steady at below 10% when the spray angle is changed
from 90o to 30 o. The impurity content of Alloy C276 under a
similar angle change increases from >20% to just under 35%.
Figure 5: Photograph of Alloy C276 (left) and Nicko-Shield™
200 (right) coatings sprayed under similar optimal conditions
Figure 6: Photograph of Alloy C276 (left) and Nicko-Shield™
200 (right) coatings sprayed under similar optimal conditions
Sulfuric Acid Corrosion Results
ASTM G31 hot acid corrosion testing showed that both
coatings provided significant protection to the underlying mild
steel after 1 week of testing. For reference, bulk alloy C276
has a reported rate of 5 mm/year and low carbon steel has a
reported rate of >100 mm/year in 83% H2SO4 at 175oC.
Therefore, a properly applied Ni-Cr-Mo chemistry can be used
to extend the lifetime or reduce the maintenance of a vessel
significantly. The corrosion rate of Nicko-Shield™ 200
remained steady at roughly 2-2.25 mm/year over two weeks of
exposure. Alloy C276 saw an increase in the corrosion rate
after week one from 2.25 mm/year to up to over 3.75
mm/year, a 66% increase. The measured corrosion rates are
shown in Fig. 9 with the coating surfaces after 2 weeks of
exposure shown in Fig. 10 for both Nicko-Shield™ 200 and
Alloy C276. As shown, the sample panels around (but not
including) the intended exposure areas were ground such that
an effective seal could be retained. To prevent any smearing
effects, the exposed coating area was left as-sprayed, and no
sealant was applied. Both coatings saw measurable thickness
loss as a result of the exposure (roughly 0.1-0.2 mm for
Nicko-Shield™ 200 and 0.125-0.2 mm for Alloy C276.) The
alloy C276 coating was noticeably smoother after exposure
than the exposed Nicko-Shield™ 200 coupon. The adhesion
values of each coating was tested on the exposed area,
however, glue adhesion was insufficient to create coating
failures in either material. Each surface was lightly blasted
with Al2O3 to remove any scale formed during the exposure.
The Alloy C276 saw glue failure at around 7 MPa, likely due
to the smoothed contour of the corroded surface. The Nicko-
Shield™ 200 coating saw glue failure at 35 to 41 MPa,
indicating that it is unlikely that the acid had penetrated the
coating thickness to attack the substrate/coating interface
directly.
Figure 7: Optical micrographs of ~0.5mm Nicko-Shield™ 200
coatings at 100X
Figure 8: Optical micrographs of ~0.5mm Alloy C276
coatings at 100X

Figure 9: Corrosion rate of Nicko-Shield™ 200 and Alloy
C276 coatings on mild steel in hot (175oC) dilute sulfuric acid
(83%) after 2 weeks of exposure
A micrograph of the Nicko-Shield™ 200 coating cross
section after exposure is shown in Fig. 11. This cross-
sectional micrograph shows the interface between the exposed
(left portion of figure) and the un-exposed region (right)
portion of the corrosion coupon. The corrosion damage
appears to exist only on the surface of the coating, and the
through thickness integrity and coating/substrate bond appears
unaffected by the acid exposure.
Figure 10: Alloy C276 panel (left) and Nicko-Shield™ 200
panel (right) after2 weeks exposure. Blue circular pattern is
the area of the coating which was subjected to the acid
solution. The Alloy C276 coating saw a higher level of
corrosive attack and a smoother surface finish.
Summary and Conclusions
Nicko-Shield™ 200 and Alloy C276 coatings were deposited
onto steel substrates under a range of spray parameters
designed to simulate the operational window experienced
when spraying large surface areas by hand. Oil and gas
equipment, particularly refinery vessels, are often subject to
both high temperatures and corrosive conditions, eliminating
the potential to use epoxies or other more conventional coating
techniques. An understanding of hand spray performance is
relevant to the corrosion protection of oil and gas equipment.
The Nicko-Shield™ 200 chemistry demonstrated a higher
level of consistency within the ‘hand spray’ parameter
window, exhibiting adhesion typically above or approaching
70 MPa in all conditions. While such a strong adhesion is not
necessary in many environments, high levels of adhesion are
indicative of dense high integrity coatings, which are expected
of HVOF or HVAF coatings. Thus, it was expected to see a
lower oxide and porosity content in the Nicko-Shield™ 200
coatings and therefore less permeability than in the Alloy
C276 coatings. These results show that properly designed
alloys, such as Nicko-Shield™ 200, can be formulated to
produce effective corrosion resistant arc spray coatings.
Figure 11: Optical micrographs of Nicko-Shield™ 200 at
100X after exposure to sulfuric acid testing
Acknowledgments
This work was supported by Chevron Energy Technology
Company. Special thanks to Lisa Watson for her contribution
to the naming of the Nicko-Shield alloy family.
References
1. N. Ahmed, M.S. Bakare, D.G. McCartney, and K.T.
Voisey, The Effects of Microstructural Features on the
Performance Gap in Corrosion Resistance between Bulk
and HVOF Sprayed Inconel 625, Surface Coatings and
Technology. 2010, 204(14), p 2294-2301
2. E. Lister, R.N. Wright, P.J. Pinhero, and W.D. Swank,
Corrosion of Thermal Spray Hastelloy C-22 Coatings in
Dilute HCl, J. Therm. Spray Technol., 2002, 11(4), p 530-
535
3. D.P. Guillen and B. Williams In Flight Oxidation of
Aluminum in the Twin-Wire Electric Arc Process, J.
Therm. Spray Technol., 2006, 15(1), p 63-71
4. M.P. Kanouff, R.A. Neiser Jr., and T.J. Roemer, Surface
Roughness of Thermal Spray Coatings Made with Off-
Normal Spray Angles, J. Therm. Spray Technol., 1998,
7(2), p 219-228