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L, I . ( ,'i. t* (' ', Tnans, fnd, Ceram. Soc,, vol,73, no. 4,pp.293-29{} (7()l'l)
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I f @ 2014 The lndian Ceramic Society
I tn
+aP-* * ;1
x oe alno : Basu, I rt
ISSN 0371-750X (Print), ISSN 2165-5456 (Online)
t-\ =r-. € http ://dx. d oi. org/ 1 0. 1 080 | 037 1 7 50X.20 1 4. 969773
)8).
7-/ i q. r. I11
.. !e and D Basu, i\
r). I
I
t
lnTtuence of Critical Parameters on the Properties of
Liu, Acta Biomater., Ir
l+rl,t I't Ju".',' Plasma Sprayed Coatings Prepared from
: and A. M. Rossi, i{t' * Spray Dried Alumina Powder
004).
d H. Begam, OPen
S. T. Aruna* and N. Balaji

J. A. Ohnsorge, Sufface Engineeing Division

iomater. Appl., 22, CS/R-Nafio n a I Ae ro sp a ce La bo rafon'es
HAL Airport Road, Bangalore - 560 017, lndia
Bone Mineral Res., [MS received Februa ry'l 9, 201 4; Accepted May 27, 201 4l

E. Geuze, J. D. de
B,16, Plasma sprayable o-alumina powder was prepared by spray drying process. The powder was characterized by field
rc Engg.: Part
emission scanning electron microscopy (FESEM), powderX-ray diffractometry, particle size analysis and flowabitity
measurement. In the present work, the influences of three different critical plasma spray parameter (GPSP) values
pp.99-117, Humana (675, 825 and 937.5 Wnl.pm) on the crystallographic forms, microstructure, microhardness, surface roughness,
wear and corrosion resistance of the plasma sprayed alumina coatings were investigated. The coatings were
characterized by X-ray diffractometry and the analysis revealed the presence of some traces of 7-alumina along
t419-1424 (1 994).
with a-alumina for the coating obtained at higher CPSP. The surface roughness, microhardness, corrosion and
<ley, J. Bone Mineral wear resistance of the coatings were evaluated. Plasma sprayed alumina coating obtained at the highest CPSP
exhibited improved wear and corrosion resistance compared to the other two coatings which is attributed to the
dense nature of the coating.
z and G. T. Chandler,
4). [Keywords: Alumina, Spray drying, Plasma spraying, Wear, Microstructure]

H. Deppe, S. Milz,
:1,
1-445 (2005).
., C. C. Kappert and
71-475 (1998).
Technol., 41, 57-60
cand. J. lnfect. Dis.,
obie, J. Bone Joint
bchnol., 46, 125-129
r, M. A. Simpson and
-173 (2011\.
A. Brown, Calcified
)rthop. Trauma, 16,
77 (1958).
Ochiai, T. Kobayashi,
LeGeros, Mater. Sci.
\.
Introduction
Corrosion and wear problems are still of great
rnlelvance in a wide range of industrial applications and
;rruducts as they result in the degradation and eventual
lrrilure of components and systems both in the processing
atrd manufacturing industries and in the service life of many
{;(}mponents. Various technologies have been used to
tk:posit the appropriate surface protection that can resist
lhr-r degradations. Among these, thermal spraying,
especially plasma spraying, is often considered as a
1xrlential alternative to traditional coating techniques (such
artc hard chrome electroplating) for the production of wear-
re$istant coatings.l{ Since the 1960s atmospheric plasma
apraying (APS) has been widely used in industry and found
npplications in many fields like automotive, aeronautical,
rnodical and paper milling.T-e As far as anticorrosion and
nntiwear applications are concerned, the most frequently
rused coating materials are oxide ceramic coatings.s
Aluminium oxide, Al2O3, more often referred to as
nlumina, is an exceptionally important ceramic material
which has many technological applications. Plasma
*prayed aluminium oxide (Al2O3) coatings offer excellent
wear resistance, corrosion resistance, heat and thermal
shock resistance, and have been widely used by the US
Navy and other industries.T Plasma sprayed alumina
(Al2O3) coatings have been used for many applications in
lextile, electronic, aerospace, and aircraft industries
because of their dielectric and wear resistance properties
+Corresponding author; e-mail: aruna_reddy@nal.res.in
and also in nuclear industry.lo'tl Alumina coatings have
several specaal properties like high hardness, chemical
inertness, wear resistance and high melting point. lt is
reported that the corrosion resistance of alumina coatings
is higher than that of cermet and metallic coatings.l2' 13
lmproved wear resistance has been reported for alumina
coatings deposited by low pressure plasma spraying.l4
The effects of substrate temperature on the hardness,
porosity and thermal expansion of AlrO. coatings prepared
by plasma spray process have been reported.ls Fernandez
et a1.16 studied the influence of sliding speed and normal
load on the wear behaviour of plasma sprayed Al2O3
coatings. Spraying conditions, such as critical plasma
spray parameter (CPSP) and distance between spraying
gun and substrate, which are wadely used as variables to
quantitatively identify the temperature of spray powders
inside the plasma flame, also affect the final coating
microstructures and consequently the wear resistance.
Critical plasma spraying parameter (CPSP) is expressed
as the plasma output power in the numerator and the
primary gas (Ar) flow rate in the denominator.lT'18 [ is well
known that when the plasma output power is increased,
the particle temperature increases due to increase in
plasma jet temperature as it is very sensitive to CPSP.
The decrease in argon flow rate, which leads to an increase
in powder in-flight time, has a similar effect on particle
temperature as that of the increase in plasma output power.
So CPSP can alter the coating microstructure And
properties. Our previous study provided an insight into the

AN CERAMIC SOCIEry voL.73 (4) OCTOBER - DECEMBER 20t4

 wear behaviour of plasma sprayed Al2O, coatings prepared provides the parameters used for plasma spraying
ysing coprecipitation synthesized alumina powders.ls spray
dried alumina powders. To improve the aOneJion ot
However, such a study has not been reported for alumina
alumina coatings to stainless steelsubstrates, Amdry g62
coatings prepared using spray dried alumina powder.
(Sulzer Metco) bondcoat material was sprayed before
The main aim of this work was to prepare plasma
spraying alumina powder. Energy dispersive X_iay analysis
sprayable alumina powder by spray drying'process and
showed the following composition for the bondcoai
obtain coatings with three different crititaipiasma spray
Al 9.07 wt%, Cr 23.22wt%, Ni 67.39 M% and y 0.33
parameters using the spray dried alumina powders. wt%
lt was Prior to spraying, the substrates were grit blasted (the
also aimed at studyinE the effect of CpSp on the
average size of commercial alumina grit was about 25
microstructure,wear and corrosion resistance of the lrrn)
plasma sprayed alumina coatings. The obtained
and degreased ultrasonically in aietone, The plasmr.r
results sprayed alumina coatings sprayed at 675, g2S and g37.s
were compared with those of the reported plasma sprayed
CPSP (Wnl.pm) were assigned as alumina_1, alumina_2
al um ina coatin gs prepa red from co-precipitation
meinoi. r t and alumina-3 respectively.
Experimentai Buehler microhardness testerwas used for measurinE
Plasma sprayable grade alumina powderwas prepared the microhardness of the cross-sections of the prasmi
.
ytllg a laboratory type tal! spray dryer (SM Scientech, sprayed coatings. A load of 50 gf was used for
microhardness measurement at ten different praces
India) as foliows: 350 g alumina powder (_45 prm sieve, on
the cross-section and its standard deviation was arso i;
Alcoa) was dispersed in 1 L water and s0 mL of 6% pvA
(Loba Chemie), and was milled for 4 h ustng pot reported. For wear studies, spray dried alumina powdei
a mill was plasma sprayed on stainless steel substrates with
and alumina balls. The spray dryer was operated with
an
inlet temperature of -300oC, outiet temperature of 35 x 20 x 4 mrn3 dimension. A TR_28S M, DUCOM
-1S0"C reciprocating wear tester was used for wear testing
and air pressure of 2 bars. The obtained spray dried against
alumina powder was sieved (-2g to +gg pm) to i"rou" 6.rT diameter Al2O3 ball. The wear test was pJrfo-rmed
larger and smaller sized particles before plasma spraying. with 2 N load, 1 Hz frequency, and 15 mm stroke length
The spray dried powder was not subjected'to'ariy for 3Y, h. Wear rate was obiained by dividing the wJar
calcination before prasma spraying. phaie formation volume by the product of road appried and sriding distance.
ot The weight loss of both the coating and the ciunterpart
alumina powders was confirmed byl_ray diffraction (XRD)
using D-8 Bruker Advance X-ray diffractometer. particre alumina balls was measured using jn electronic weighing
size distribution of the spray dried powder was anaryzed balance (0.0001 g accuracy). The average of three weal"
using Mastersizer 2000 which works on the principie tes{s was reported. A roughness profilometer (Taylor
of
laser light scattering method. Frowabirity of the spray Hobson) was used for obtaining the surface roughnlss
ori"J (&) of the coatings.
alumina powderwas measured as perASTM B21d_gi.
fiun Corrosion behaviour of plasma sprayed alumina
emission scanning electron microscope (FESEM,
Cari
Zeiss) was used to examine the morphoiogyof the powOer, coatings deposited at three different
cpsp; on stainless
and surface and cross-sectionar microstruitures of prasma steel coupons were studied using CHI 604 2D
sprayed alumina coatings. Sutzer Metco_gM air plasma electrochemicar workstation and the details have been
spray system was used for plasma spraying spray dried reported in a previous study.le
alumina powders on stainless steel substrates. iable
I Results and Discussion
Table | : Plasma spray parameters used for bondcoat
Characterization of Spray Drted Alumina powder
and
spray dried alumina powder The spray dried alumina powder has a flowability of
70 s/0.050 kg which is stighily lower than that of
Plasma spray parameters
coprecipitation synthesized prasma sprayabre arumina
Bond coat Alumina powder (a6 s/0.05 kg). The variation in thL
frowabirity is
Argon flow (NLpM) 40
attributed to the rower density of spray dried powder than
40
tf'3t of co-precipitation synthesized powder. The spray
Hydrogen flow (NLpM) 9 7 dried afumina powder possesseO mosily spherical shaped
Amps (A)A/otts (V) 550/60 450, 550, 625 / 60 particles as shown in the FESEM images (Figs.
1a and
cPsP (NLPM) 1b). A higher magnification of the FESEM imagle (Fig.
825 675, 825, 937.5 1c)
shows smaller sized particres which indicate thatLach
Carrier gas ftow (SCFH) 15 15 particle was composed of smaller sized particles.
Pre heaUspray passes
The
2t5 2t14 particle size distribution curve of the spray
dried alumina
Powder feed rate (g/min) powder (Fig. 2) shows a narrow size distiibution
10 15 with an
average agglomerated particle size of 41 pm. The particle
Cooling air pressure (bar) 2 2 size distiibution was very apt for plasma spraying as
Spray distance (cm)
the
25 15 d*was below 50 pm compared to d5s of 126pm, iporteO
for co-precipitation synthesizeO alumina. e Fi gure
Gun speed (mm.s-1) 800 800
1
3;h;;
the powderX-ray diffraction pattern of spray dried arumina

TRANSACTIONS OF THE INDTAN CERAMIC

SOCIETY
 F4r llFi#plrqq :.q'F'-*-'ry

ftes, Amdry 962

s sprayed before
rsive X-ray analysis
for the bondcoat:
.o/o a'od Y 0.33 wt%.
e grit blasted (the
t was about 25 prn)
tone. The plasma
i75,825 and 937.5 Fig' 1 - FESEM images of spray dried alumina particles taken
at various magnifications: (a) 1.5 KX (b) 5 Kx (c) 30 KX
rmina-1, alumina-2
1B
rsed for measuring 16 particles; exploded splats were not observed as in the other
rns of the plasma ". 14 two coatings (Fig. 4c). Higher magnification FESEM
gf was used for ;F 12 :,1 : :,.. /I : r '. images of the splats showed some cracks and pores typical
'
.

Jifferent places on
10
B ''''':';' I..''i :' t
: ,,, . ,: ',,t, I' I of plasma sprayed coatings. Figure 5 shows the Cross,
leviation was also 6 :i:t..........: : ,i.,.,,
"I
, l, .:l '
,.:,.-.
r
sectional FESEM images of plasma sprayed alumina
4 coatings. From the images it is observed that the density of
rd alumina powde;'
2
rel substrates with the coatings varied as: alumina-3 > atumina_2 > alumina_1
0
'.-285 M, DUCOM o.ol 0.1 1 10 100 1000 30oo
Alumina-1 coating had more unmerted/ partiaily merted
year testing against PARTICLE S|ZE (pm) regions than alumina-2 and alumina_3 coatings. The
esi was performed coating thickness was also slighfly higher for arimina-3
l'lg ? - Particle size distribution of spray dried alumina powder
, mm stroke length xlrowing a narrow size distribution coating and this may be attributed to complete melting of
' dividing the wear most of the alumina particles in high temperature plasma.
nd sliding distance. All the coatings showed bimodal distribution containing
nd the counterpart :
d
fully melted and unmerted or partiaily merted zones and
>lectronic weighing o decreased with increasing CpSp.
j
rage of three wear d
ofilometer (Taylor t*
@

surface roughness a d
UJ o
F. o
sprayed alumina z I
dl
;PSPs on stainiess 6.I
NN

ng CHI 604 2D -ll

details have been 30 40 50 60 70 80

20 (degree)

Fig. 3 - XRD pattern of spray dried alumina powder

mina Powder
ras a flowability of . peiwder. The pattern confirmed the formation of 100%
rwer than that of r-alumina. The pattern matched exacfly with the starting
;prayable alumina sfumina powder and the diffraction peaks were sharper.
in the flowability is
dried powder than characterization of plasma sprayed coating Deposited
rowder. The spray Using Spray Dried Alumina
y sphericalshaped Microstructure of the Coatings
rges (Figs. 1a and Figure 4 shows the FESEM surface images of the
:M image (Fig. 1c) plasma sprayed alumina coatings. Some sflatJappeared

I'I.u r custard apple containing well fused particles

indicate that each
zed particles. The
rray dried alumina
listribution with an
tl pm. The particle
ra spraying as the
f 126 pm, reported
r.le Figure 3 shows
pray dried alumina
(Fig. 4a). The appearance of such features may be
attributed to the exprosion of finer and smailer sized
particles due to insufficient plasma power available
for
melting- The presence of such features could have resulted
in porous and rougher alumina-1 and alumina_2
coatings.
However, the extent of such features was reduced in
alumina-2 (Fig. 4b) and finer atumina particles were
obberved- on the other hand alumina-3 coating exhibited Fig- 4 - FESEM surface images of ptasma sprayed
atumina
mostly fully melted splats along with very few alumina coatings at different CpSps: (a) alumina_i, (bi allmina_2
and
(c) alumina-3

\N CERAMIC SOCIETY
vol. 73 (4) OCTOBER - DECEMBER 2014

@**1'
Fig. 5 - FESEM images of plasma sprayed alumina coating cross-sections at different CPSPs: (a) alumina-1, (b) alumina-2 and
(c) alumina-3

X-ray Analysis of Plasma Sprayed Alumina Coatings
Figure 6 shows the XRD patterns of plasma sprayed
alumina coatings prepared from spray dried cr-alumina
powderat different CPSPs. The coating formed with lower
CPSP retained cr-form of alumina. Interestingly, the coating
obtained with highest CPSP (alumina-3) showed the
presence of y-alumina (400) peak. Commonly y-Al2O3
nucleates in preference to a-Al2O3 during rapid solidification
of liquid droplets.20-22 With increasing CPSq the intensity
of 100o/o a-alumina (113) and (024) peaks increased.
However, c-Al2O3 (208) peak intensity decreased with
increasing CPSP.
to the complete melting of the alumina particles at higher
CPSP. lh general, higher microhardness values wer€
obtained for plasma sprayed alumina coatings preparec
from spray dried powder compared to co-precipitatior
synthesized powderle and this may be due to the better
melting of spray dried powder. The lower microhardness
of alumina-1 is attributed to the presence of higher fractior
of unmelted or partially melted zones present in the
microstructure of the plasma coating. The surface
roughness of alumina-1 coating was the highest and thal
of alumina-3 was the least (Fig. 8). This is attributed to the
presence of more completely melted zones in alumina-3
coating compared to atumina-1 coating.

2040 o
U'
- ?
2
o
2000

I rsoo E
F f ^ rsoo
-.t
zlu P^-
F
1000
3 E tooo
at
= o.
500 8
z
soo
Y

30 40 50 60 70 80 ALUMINA-l ALUMINA.2 ALUMINA.3

20 (degree|
Fig. 7 - Histogram showing the Knoops microhardness of the
Fig. 6 - XRD patterns of plasma sprayed alumina coatings at alumina coatings, plasma sprayed at different CPSPs
different critical plasma spray parameters: (a) alumina-l,
(b) alumina-2 and (c) alumina-3

Microhardness and Roughness of Plasma Sprayed

Alumina Coatings e7
Alumina-1 exhibited the lowest microhardness followed frs
o
urE
zv
by alumina-2, and alumina-3 exhibited the highest I
microhardness (Fig. 7). The properties of the coatings were g4
o
affected by the high incidence of semi-molten/unmelted
particles. Porosity was higher at lower spraying energies,
r3
where the semi-molten particles are less deformed. At Bz
E
higher spraying energies, the particles are melted to a dt
greater extent and the molten material can fill the asperities
and gaps of the previously deposited layers, leading to ALUMINA-I ALUMINA-2 ALUMINA-3

lower porosities. The microhardness increased with

Fig. 8 - Histogram showing the surface roughness of the surface
spraying power (Fig. 7), possibly as a result of the and worn out regions of APS alumina coatings, plasma sprayec
decreased porosity.23 The higher hardness is attributed at different CPSPs

296 TRANSACTIONS OF THE INDIAN CERAMIC SOC|EN

 rr,i'.rr /?esrstance of Plasma Sprayed Alumina Coatings Table lll : Potentiodynamic polarization data of
I lre weardata obtained for all the three plasma sprayed plasma sprayed alumina coatings
.rlrirrrtn? coatings and the counterpart alumina balls are
t,rliulat€d in Table ll. Alumina-3 coating and its Samples ocP (v) E"on (v) l"o' R"
' {lr,f:;ponding alumina ball counterparts exhibited the (pA.cm-2) (Q.cm')
lirvv1,r..;l wear loss. The wear rates of plasma sprayed
Substrate -0.177 -0.199 9.717 3661
'tlununa coatings obtained from spray dried powder and
i r, prccipitation powder (reported in literature) were in the Alumina-1 -o.294 -0.331 0.6864 51 399
,i;lilr{: order but were slighily lower for the former
Alumina-2 -0.236 -0.212 0.3647 54702
ra-l, (b) alumina-2 and ,,rirtul!lS.le Larger wear rates are usually caused by the
{'n ri )virl of entire lamellae or part of them. The low cohesive
Alumina-3 -0.310 -0.214 0.1129 340454
r

:,:lrr:nt;lh and the presence of inter-lamellar cracks could

ra particles at higher f rrrvr: cr:ntributed to largerwear rate of alumina-1.iAt
higher
rdness values were t.f ';;;t most of the particles are fully melted in the spray implying better corrosion resistance of the coating
compared to the other coatings. The improved corrosion
ra coatings prepared ;t=l lrr r:ase of coatings sprayed with medium CpSp, there
resistance of alumina-3 is attributed to the dense nature
I to co-precipitation elttt $rrfficient numbers of partially melted or unmelted
of the coating. The corrosion protection obtained by plasma
be due to the better rrltii(xt$ that resemble the constituent alumina particles of
ile it(lqlomerates. sprayed alumina coatings of the present study is superior
ower microhardness
to that reported for coatings obtained from co-precipitation
nce of higher fraction
synthesized powder.
)nes present in the Table ll : Wear rate of plasma sprayed spray
ating. The surface ' dried alumina coatings Conclusions
the highest and that Plasma sprayable grade alumina powderwas prepared
ris is attributed to the Volume loss (mm3) Wear rate (mm3.N-l.m-l; by spray drying process. The powders were plasma
I zones in alumina-3 r-.j rrt t lJ rlc lD sprayed at three different critical plasma spray parameters
Ing. Coating Ball Coating Ball (CPSP). From this study it is evident that CpSp inftuences
the microstructure, microhardness and wear behaviour of
Alirrrrrrt;t
na-1 1.859 0.507 1.259 x 10-3 1.052 x 10{
the plasma sprayed alumina coatings. The surface
Ahrrrrrnit
nir-2 0.728 0.126 5.09 x 104 8.76 x 10-5 roughness decreased with increasing CpSp and the
{lurrrirra
rra-3 0.452 0.101 3.15 x 10{ 7.01 x 10-5 density of the coatings increased with increasing CpSp.
The wear and corrosion resistance of alumina coatings
increased with increasing CpSp. The coating that was
I lr* wear resistance of plasma sprayed coatings is plasma sprayed at higher CpSp showed traces of
Inlirreneed by microhardness, microstructure, ductility, y-alumina along with o-alumina. The microhardness of the
Iuuglrness and pores present in the coating. In general, coatings increased with increasing CpSp and was in the
r;ilgltrrlf$ with higher hardness will exhibit higher wear range of 1000-2100 HKsosr. The alumina coating, plasma
rr$irslflnce. The coefficient of friction (COF) was -0.7 for sprayed at the highest CPSR showed lower wear rate and
2 ALUMINA3 gflllrn ltrree coatings irrespective of different CpSps used higher corrosion resistance compared to the other two
frrr plnsma spraying and matches well with the reported coatings, which is attributed to the dense nature of the
; microhardness of the likrrnture.le The predominant wear mechanism was of coating. The surface roughness of the coatings decreased
fferent GPSPs atttaerve type and caused the material to delaminate owing with increasing plasma power. In general., the
iti llre high pressure exerted by the ball on the coating. microhardness, wear and corrosion resistance exhibited
lher values of the corrosion potential (E"o) and the by plasma sprayed alumina coatings were superior for tfre
*firf{lsion current density (i"o) were extracted from the coatings obtained from spray dried powder when
{irfiver} using Tafel extrapolation method. The corrosion compared to those obtained from co-precipitation
[ullenlial, corrosion current density and the polarization synthesized powder.
tasislance (Ro) obtained for the plasma sprayed alumina
i:fidfings by potentiodynamic polarization studies are Acknowledgements: The authors acknowledge the financial
assistance received from the Network project on Nanostructured
tebulaled in Table lll. Lower the corrosion current density, Advanced Materials (NWP-00-51-01) from CSIR-NML. The authors
lrlgher will be the corrosion resistance. The corrosion thank the Director, NAL and Head, SED for their constant
enrenl density followed the order: alumina-3 < alumina-2 encouragement. The authors thank Dr Geetha Manivasagam, VlT,
'., €lulnina-1 < stainless steel substrate. The corrosion vellore for the wear studies. Help received from Siju in FESEM study is
{:Urrdnt density for the alumina-3 coating was very low acknowledged.
r#rlch also indicates superior corrosion resistance of the References
ALUMINA-3
$$Htrng. fn general, the E"oovalues shifted to more negative 1 . Handbook of Thermat Spray Technotogy, pp. 171-20g, ASM
*ure eompared to the substrate indicating improved Internationat, Materials park, OH, USA (2004).
rughness of thesurface
ffltTosron resistance of the coatings over the substrate.
atings, plasma sprayed 'fhe lto value of alumina-3 coating was the highest, 2. K. Anup Kumar and A. Agarwal, J. Thermat Spray Technot.,
20,1217-1230 (2011).

IDIAN CERAMIC SOCIETY Yflt rs (41 ocToBER - DECEMBER 2014