Microstructure and cavitation erosion behavior of WCCoCr coating on 1Cr18Ni9Ti

stainless steel by HVOF thermal spraying

Yuping Wu
a,

, 1
, Sheng Hong
a
, Jianfeng Zhang
b
, Zhihua He
a
, Wenmin Guo
a
, Qian Wang
a
, Gaiye Li
a
a
College of Mechanics and Materials, Hohai University, Nanjing 210098, China
b
Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan
a b s t r a c t a r t i c l e i n f o
Article history:
Received 4 October 2011
Accepted 7 January 2012
Keywords:
WCCoCr coating
HVOF thermal spray
Cavitation erosion
A WCCoCr coating was deposited by a high velocity oxy-fuel thermal spray (HVOF) onto a 1Cr18Ni9Ti
stainless steel substrate to increase its cavitation erosion resistance. After the HVOF process, it was revealed
that the amorphous phase, nanocrystalline grains (CoCr) and several kinds of carbides, including Co
3
W
3
C,
Co
6
W
6
C, WC, Cr
23
C
6
, and Cr
3
C
2
were present in the coating. The hardness of the coating was improved to
be 11.3 GPa, about 6 times higher than that of the stainless steel substrate, 1.8 GPa. Due to the presence of
those new phases in the as-sprayed coating and its higher hardness, the cavitation erosion mass loss eroded
for 30 h was only 64% that of the stainless steel substrate. The microstructural analysis of the coating after the
cavitation erosion tests indicated that most of the corruptions took place at the interface between the un-
melted or half-melted particles and the matrix (CoCr), the edge of the pores in the coating, and the bound-
ary of the twin and the grain in the stainless steel 1Cr18Ni9Ti.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
Cavitation erosion is a common phenomenon in the hydraulic
components such as valves, propellers, hydraulic pumps and diesel
engines, which are mostly made of metal/alloy materials [1]. In
their operation processes, these components are often kept in con-
tact with a fast-owing or vibrating liquid with a uctuating pres-
sure. Pressure uctuation results in generation and collapse of
bubbles, exerting stress pulses on solid surfaces nearby and leading
to cavitation erosion of the metal surface [2]. The preparation of
appropriate surface coatings on the metal/alloy substrates is often
necessary to reduce cavitation damage of the hydraulic components.
For example, the WC-based coatings can be used to increase the
wear, oxidation and erosioncorrosion resistance of the metal/alloy
materials [36]. The reason is that the hard WC particles in the coat-
ings lead to high coating hardness and high wear resistance, while
the metal binder (Co, Ni, or CoCr) supplies the necessary coating
toughness [7]. However, in the traditional thermal spray technolo-
gies, the WC phase tends to decompose into W
2
C with a low
hardness and a higher brittleness, which usually deteriorates the
hardness, oxidation and cavitation erosion resistance of the coatings
[4].
High velocity oxy-fuel (HVOF) technology has attracted much at-
tention for coating preparation in the past decades because it can pro-
vide a high quality coating with a good adhesion quickly. For the case
of WC- and Cr
3
C
2
-based coatings, it has more obvious predominance
over traditional plasma spray. The reason is that, with two great char-
acteristics of lower temperature (19003000 K) and higher velocity
of around 550 m s
1
, HVOF technology reduces efciently the phase
transformation and oxidization of carbide particles during the coating
process (decarburization) [810].
At present, a WCCoCr cermet coating is prepared by the HVOF
thermal spraying on a stainless steel 1Cr18Ni9Ti substrate, which is
widely used for hydraulic machinery. The microstructures, phase
composition and transformation of the carbide of coating are identi-
ed by X-ray diffraction (XRD), optical microscope (OM), scanning
electron microscopy (SEM) and transmission electron microscopy
(TEM). The Vickers microhardness of the coating and the substrate
is tested by the indentation method. The cavitation erosion behavior
of the WCCoCr coating and the reference austenite stainless steel
1Cr18Ni9Ti is investigated using vibratory cavitation apparatus. The
eroded surfaces are examined by means of SEM and the possible ero-
sion resistance mechanism is discussed.
2. Experimental procedure
2.1. Materials and HVOF thermal spraying process
The starting powder used for the coating on the austenitic stain-
less steel (1Cr18Ni9Ti) in the present study was about 2050 m in
grain size with a composition of 40 wt.% W36 wt.% Cr20 wt.% Co
Int. Journal of Refractory Metals and Hard Materials 32 (2012) 2126
Corresponding author. Tel./fax: +86 25 83787233.
E-mail address: wuyphhu@163.com (Y. Wu).
1
Present address: College of Mechanics and Materials, Hohai University, Xikang
Road 1, Nanjing 210098, China.
0263-4368/$ see front matter 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijrmhm.2012.01.002
Contents lists available at SciVerse ScienceDirect
Int. Journal of Refractory Metals and Hard Materials
j our nal homepage: www. el sevi er . com/ l ocat e/ I JRMHM
and a balance of C. Fig. 1 shows the SEM morphology of this starting
powder at a low magnication of 100 (Fig. 1(a)) and a high magni-
cation of 1000 (Fig. 1(b)), respectively. Fig. 1(b) shows that the
powder was composed of several small particles about 15 m in an
agglomerated and a slightly sintered state.
Before the coating process, the screw specimen made of stainless
steel (1Cr18Ni9Ti) was degreased and grit blasted to get a roughness
of 17 m. Then the screw was coated by the WCCoCr coating from
the above starting powder using a JP5000 spray system. Kerosene and
oxygen were used as the fuel gases with ow rates of 0.02 m
3
min
1
and 1.85 m
3
min
1
, respectively, whereas argon was used as the car-
rier gas with a ow rate of 0.01 m
3
min
1
. The powder feed rate was
xed at 10 g min
1
with the aid of a computerized powder feeder
station. After 15 passes of the spray gun, a coating was obtained
with a deposit thickness of 500 m.
2.2. Cavitation erosion test
Cavitation erosion tests were carried out using a vibratory cavita-
tion apparatus, the detailed procedure of which can be found else-
where in literature [11]. In brief, before the cavitation erosion tests,
the screw specimen with the WCCoCr coating on it was pretreated
by grinding and mechanical polishing. Then, the coated sample was
attached to the free end of the horn. The tip of the screw was im-
mersed about 3 mm in the water held in a 1000 ml beaker and the
system kept in a resonant condition with a frequency of 191 kHz
and double amplitude of 605 m by controlling the output power
of the ultrasonic generator. In the testing process, the beaker was sur-
rounded by the owing cooling water to keep the water inside it at
2530 C. In every 30 min, the well-handled water in the beaker
would be replaced by unused water. After the set time of erosion
(1.5 h), the samples were cleaned and weighted by a balance with
an accuracy of 0.1 mg. The reference austenitic stainless steel
1Cr18Ni9Ti was also tested in the same condition for comparison.
2.3. Microstructural characterization
The crystal phase of the starting powder and the coating were
identied by X-ray diffraction (XRD; Geigerex, Rigaku Corp.) with
CuK radiation. The microstructure of the uneroded and eroded coat-
ing was observed by scanning electron microscopy (SEM, Hitach:
S-3400N). Some ner-scale microstructure features of the coating
were investigated using a transmission electron microscopy (TEM,
JEOL: 2000EX)). Vickers hardness (H
v
) at roomtemperature was eval-
uated by a hardness tester (HXD-1000TC) at a load (P) of 1.96 N for
15 s and was averaged by 20 measurements along the medium
cross-sections of the coating and the austenitic stainless steel
(1Cr18Ni9Ti).
3. Results and discussion
3.1. Phase composition
The X-ray diffraction patterns for the starting powder and the as-
sprayed coating are shown in Fig. 2. In the WCCoCr coating and the
starting powder, different phases of Co
3
W
3
C, Co
2
C, WC, CrCo and
chromium carbide were detected. The results indicate that higher
ame velocity and lower ame temperature of the HVOF process
would effectively limit WC decomposition process [12]. Fig. 2 also
shows the presence of a distinct diffuse diffraction halo centred
around 243 and 65 in the traces suggested that there is a certain
proportion of amorphous phase within the powder and the coating,
and it is more intense in the XRD data from the coating.
3.2. Characterization of the coating
Fig. 3(a)(d) presents the polished transverse surfaces of the coat-
ing. Fig. 3(a) shows that the coating is very dense and has a good con-
tact with the substrate. This indicates that the coating does have a
tight adherence to the substrate due to the higher velocity of HVOF
thermal spraying (Fig. 3(a)). The porosity value for as-sprayed WC
CoCr coating is less than 1% from Fig. 3(b), which correlates with
the results of the Fe-based coating by HVOF [11] and high velocity
axial plasma spraying (HVAPS) [13]. Scrivani et al. [14] proposed
that the high impact velocity of the coating particles, which caused
high density and high cohesive strength of individual splats, may
lead to the low value of porosity and high density of the coating.
Fig. 3(b) shows the presence of the un-melted or half-melted particle
in the coating with a near spherical morphology. A similar
Fig. 1. SEM micrographs of the powder morphology at a magnication of (a) 100 and
(b) 1000.
Fig. 2. XRD patterns of the as-powder and as-sprayed coating.
22 Y. Wu et al. / Int. Journal of Refractory Metals and Hard Materials 32 (2012) 2126
morphology has been observed in our previous investigations of Fe-
based alloy coatings [11, 15, 16]. It is proposed here that the metal
binder (CoCr) was partly or fully melted, while the most of the car-
bide particles remained in the solid state during the HVOF thermal
spraying [17]. Fig. 3(c) and (d) shows that the coating also consisted
of the matrix (CoCr) and carbide particles. A small amount of oxide
appears with the lightest grey contrast, whereas no oxide formation
has been observed in the coating by the XRD analysis due to the
very low oxide content. A similar result has also been observed by
Magnani et al. [18].
TEM was also used to obtain more detailed information about the
microstructure of the WCCoCr coating in the present study. The
corresponding TEM images were shown in Fig. 4, from which it can
be detected that the coating consists of carbides, nanocrystalline
phase and amorphous phase. The diffraction patterns, taken with
the selected area aperture centered over the amorphous region,
showed the expected diffuse halo with diffuse diffraction spots aris-
ing from crystalline grains within the selected area (Fig. 4(b)).
These diffuse characters present in the TEMcoincide with the XRD re-
sults in Fig. 2. The size of the nanocrystalline grains in the coating is in
the range of 10 to 30 nm shown in Fig. 4(c), and the nanocrystalline
grains were identied as the bcc Cr-based phase fromthe polycrystal-
line selected area diffraction (SAD) pattern shown in Fig. 4(d). Be-
cause the cooling rate of a droplet could be high enough to give a
high rate of nucleation and the recrystallization of the originally
amorphous region during successive passes of the thermal spraying,
the nanocrystalline grains are able to form. The latter explanation
was the same as the literature [19]. The WC phase noted in the XRD
spectrum of Fig. 2 was also observed by TEM shown in Fig. 4(e) and
(f), which has an orthogonal structure with a massive shape and a
hexagonal lattice structure.
The amorphous phase formation of the WCCoCr system is
closely related to the atomic structure besides the high cooling
velocity of ~10
7
K s
1
[20], which is suitable for forming amor-
phous phase. The base composition in the present coating is the
CoCrWC system, the effective addition of Co, Cr, W and C
causes the sequential change in the atomic size in the order of
W(1.41 ) >Cr(1.30 ) >Co(1.25 ) >C(0.91 ) as well as the gen-
eration of new atomic pairs with various negative heats of mixing. The
topological structure and chemical short-range order are increased,
leading to the formation of a highly dense, random packed structure
with low atomic diffusivity in the super cooled liquid [21]. That is to
say, the formation of the amorphous phase was attributed to the high
cooling velocity of molteddroplets and the proper powder composition.
This view is similar to that in the literature [20].
Fig. 5 shows the microstructure of stainless steel 1Cr18Ni9Ti,
which presents typically twin austenite. The microhardness of the
coating is 11.3 GPa at a load of 1.96 N, which is signicantly higher
than that of the comparing material stainless steel 1Cr18Ni9Ti,
1.8 GPa at the same load of 1.96 N. The high hardness of the coat-
ing is attributed to the complex structures of amorphous phase,
nanocrystalline grains and several kinds of the carbide hardened
phases, such as Co
3
W
3
C, Co
6
W
6
C, WC and chromium carbide, as
shown in Fig. 2 and Fig. 4. On the other hand, the lower porosity
content is benecial to the high hardness value of HVOF deposited
WCCoCr coating [4].
3.3. Cavitation erosion characteristic
The cavitation erosion cumulative mass loss curves of the HVOF
deposited WCCoCr coating and reference stainless steel
(1Cr18Ni9Ti) are shown in Fig. 6. It is shown that the HVOF-sprayed
WCCoCr coating exhibits apparently higher resistance than the ref-
erence stainless steel 1Cr18Ni9Ti. After being eroded for 30 h, the
mass loss of the coating was 17.5 mg, only 64% that of reference stain-
less steel 1Cr18Ni9Ti (27.4 mg).
Fig. 3. SEM images of a transverse section of the as-sprayed coating: (a) a lamellar morphology; (b) pores and half-melted particles; (c) and (d) CoCr matrix, oxide and carbide
grain.
23 Y. Wu et al. / Int. Journal of Refractory Metals and Hard Materials 32 (2012) 2126
Fig. 7 shows the surface SEM micrographs of the stainless steel
1Cr18Ni9Ti samples after being eroded for 30 h. There is some defor-
mation in the reference stainless steel 1Cr18Ni9Ti after the cavitation
test. Fig. 7(a) shows the central part of the sample that presented the
most severe cavitation erosion characteristic and some particles from
plastic deformed material were torn off. But the perimeter of the sam-
ple surface showed no trace of erosion characteristic. Therefore, there
is a dividing region between the eroded and uneroded regions, which
Fig. 4. TEM images (bright eld) of typical microstructure of coating: (a) a region of amorphous phase, (b) SAD ring pattern of amorphous region, (c) a region of nanocrystalline
grains, (d) SAD ring pattern of nanocrystalline region, (e) carbide, nanocrystalline grains and amorphous phase, (f) SAD ring pattern of WC phase.
Fig. 5. Microstructure of stainless steel 1Cr18Ni9Ti, at a magnication of 1600. Fig. 6. Cumulative mass losses vs. cavitation erosion time.
24 Y. Wu et al. / Int. Journal of Refractory Metals and Hard Materials 32 (2012) 2126
is shown in Fig. 7(b). The characters of slip bands and twins were
more obvious than that of original structures (Fig. 5). The microcracks
are initiated at the connection part of the twin lamella and the aus-
tenitic grain boundary.
Fig. 8 shows the cavitation erosion characteristic of the coating
sample eroded 30 h. There is no obvious damage phenomenon on
the coating surface in the SEM image (Fig. 8(a)). The surface of the
coating only shows little material desquamation, and there are still
some polished regions undamaged. As shown in Fig. 8(b, c), the
mass loss began at the interface between the un-melted or half-
melted particles and the matrix or the edges of pores, then extend
to the general edges of the pores and even over the surface, which
is in agreement with the result of HVOF spraying Fe-based coating
in our previous investigation [11]. A larger magnication morphology
(Fig. 8(d)) shows that the coating was removed by delamination.
Fractography (Fig. 8(d)) seems to have a fatigue character, which is
because of the presence of fatigue strip.
The materials subjected to the cavitation erosion can be destroyed
by repeated short-time impacts. Therefore, cavitation erosion of
metals in some previous works was interpreted as a particular case
of cyclic microimpact-load destruction [22]. For the sake of repeated
impact load and very small contact area, degradation mechanism
caused under the action of cavitation erosion could be also described
by repeated nanoindentation loading [23, 24]. The WCCoCr HVOF
coating in the present study also had a fatigue character, as shown
in Fig. 8. In our experimental procedure, the cavitation erosion was
interrupted for weight measurement. After that, the cavitation ero-
sion continued until the next weight measurement. This may contrib-
ute to the fatigue character in Fig. 8.
It should be pointed out nally that the erosion resistance was ex-
tremely sensitive to the quantity of microstructural defects [25].
Some literatures have proved that the strength and hardness of mate-
rials decreased as the porosity increases [26]. It may thus suggest that
the pores and un-melted particles could weaken the capability of ma-
terial. Therefore, cavitation erosion resistance can be improved by the
Fig. 7. Cavitation erosion characteristic of 1Cr18Ni9Ti stainless steel (eroded 30 h):
(a) cavitation erosion region, magnication: 2500; (b) the boundary of the cavitation
erosion region, magnication: 500.
Fig. 8. Cavitation erosion characteristics of the WCCoCr coating: (a) magnication: 100; (b) and (c) un-melted or half-melted particles and pores, magnication: 2000;
(d) fatigue strip, magnication: 10,000.
25 Y. Wu et al. / Int. Journal of Refractory Metals and Hard Materials 32 (2012) 2126
optimization of spray parameters for a more homogeneous coating
with a smaller number of un-melted particles and pores. Such work
is still underway and will appear in a further paper.
4. Conclusion
A WCCoCr coating is obtained by HVOF spraying for cavitation
erosion resistance applications. The main conclusions are as follows:
(1) The HVOF-sprayed WCCoCr coating has a uniform micro-
structure and tight metallurgical bonding to the substrate.
The phases of the coating consist of the amorphous phase,
the nanocrystalline grains and several kinds of carbide. The
Vickers hardness values of the coating (11.3 GPa) are much
higher than that of the stainless steel 1Cr18Ni9Ti (1.8 GPa).
(2) The cavitation erosion resistance of the coating is higher than
that of 1Cr18Ni9Ti stainless steel as a result of its high hardness
and ner structure.
(3) The mass loss took place at the interfaces of different compo-
nents. In the coating, the mass loss began at the interface be-
tween the un-melted or half-melted particles and the matrix,
the edge of the pores and the interface of different phases.
The microcracks in austenitic stainless steel 1Cr18Ni9Ti are ini-
tiated at the connection part of the twin lamella and austenitic
grain boundaries.
Acknowledgements
The research was supported by the Innovation Foundation of
Hohai University, China Postdoctoral Science Foundation (No.
20100471371) and the Fundamental Research Funds for the Central
Universities (No. 2009B16314).
References
[1] Stella J, Schuller E, Heing C, Hamed OA, Pohl M, Stover D. Cavitation erosion of
plasma-sprayed NiTi coatings. Wear 2006;260:10207.
[2] Cheng FT, Shi P, Man HC. Correlation of cavitation erosion resistance with
indentation-derived properties for a NiTi alloy. Scripta Mater 2001;45:10839.
[3] Stachowiak GB, Stachowiak GW. Tribological characteristics of WC-based clad-
dings using a ball-cratering method. Int J Refract Met Hard Mater 2010;28:
95105.
[4] Murthy JKN, Venkataraman B. Abrasive wear behaviour of WCCoCr and Cr
3
C
2

20(NiCr) deposited by HVOF and detonation spray processes. Surf CoatTechnol

2006;200:264252.
[5] Barletta M, Bolelli G, Bonferroni B, Lusvarghi L. Wear and corrosion behavior of
HVOF-sprayed WCCoCr coatings on Al alloys. J Therm Spray Technol
2010;19(12):35867.
[6] Gant AJ, Gee MG. Structureproperty relationships in liquid jet erosion of tungsten
carbide hardmetals. Int J Refract Met Hard Mater 2009;27:33243.
[7] Zhao LD, Maurer M, Fischer F, Dicks R, Lugscheider E. Inuence of spray parameters
on the particle in-ight properties and the properties of HVOF coating of WCCoCr.
Wear 2004;257:416.
[8] Stewart DA, Shipway PH, McCartney DG. Abrasive wear behaviour of conventional
and nanocomposite HVOF-prayed WCCo coatings. Wear 1999;225229:78998.
[9] Picas JA, Xiong Y, Punset M, Ajdelsztajn L, Forn A, Schoenung JM. Microstructure
and wear resistance of WCCo by three consolidation processing techniques. Int
J Refract Met Hard Mater 2009;27:3449.
[10] Thiele S, Sempf K, Roessler KJ, Berger LM, Spatzier J. Thermophysical and micro-
structural studies on thermally sprayed tungsten carbidecobalt coatings. J Thermal
Spray Technol 2011;20(12):35865.
[11] Wu YP, Lin PH, Chu CL, Wang ZH, Cao M, Hu JH. Cavitation erosion characteristics
of a FeCrSiBMn coating fabricated by high velocity oxy-fuel (HVOF) thermal
spray. Mater Lett 2007;61:186772.
[12] Sidhu HS, Sidhu BS, Prakash S. Mechanical and microstructural properties of HVOF
sprayed WCCo and Cr
3
C
2
NiCr coatings on the boiler tube steels using LPG as the
fuel gas. J Mater Process Technol 2006;171:7782.
[13] Liu XQ, Zheng YG, Chang XC, Hou WL, Wang JQ, Tang Z, et al. Microstructure and
properties of Fe-based amorphous metallic coating produced by high velocity
axial plasma spraying. J Alloys Compd 2009;484:3007.
[14] Scrivani A, Ianelli S, Rossi A, Groppetti R, Casadei F, Rizzi G. A contribution to the
surface analysis and characterisation of HVOF coatings for petrochemical applica-
tion. Wear 2001;250:10713.
[15] Wu YP, Lin PH, Xie GZ, Hu JH, Cao M. Formation of amorphous and nanocrystalline
phases in high velocity oxy-fuel thermally sprayed a FeCrSiBMn alloy. Mater
Sci Eng A 2006;430:349.
[16] Wu YP, Lin PH, Wang ZH, Li GY. Microstructure and microhardness characteriza-
tion of a Fe-based coating deposited by high-velocity oxy-fuel thermal spraying. J
Alloys Compd 2009;481:71924.
[17] Berger LM, Saaro S, Naumann T, Wiener M, Weihnacht V, Thiele S, et al. Micro-
structure and properties of HVOF-sprayed chromium alloyed WCCo and WC
Ni coatings. Surf CoatTechnol 2008;202:441721.
[18] Magnani M, Suegama PH, Espallargas N, Dosta S, Fugivara CS, Guilemany JM, et al.
Inuence of HVOF parameters on the corrosion and wear resistance of WCCo
coatings sprayed on AA7050 T7. Surf CoatTechnol 2008;202:474657.
[19] Dent AH, Horlock AJ, McCartney DG, Harris SJ. Microstructure formation in high
velocity oxy-fuel thermally sprayed NiCrMoB alloys. Mater Sci Eng A
2000;283:24250.
[20] Moreau C, Cielo P, Lamontagne M, Dallaire S, Krpez JC, Vardelle M. Temperature
evolution of plasma-sprayed niobium particles impacting on a substrate. Surf
CoatTechnol 1991;46:17387.
[21] Inoue A, Shinohara Y, Gook JS. Thermal and magnetic properties of bulk Fe-based
glassy alloys prepared by copper mold casting. Mater Trans JIM 1995;36:142733.
[22] Zhang XB, Liu CS, Liu XD, Dong J, Yu B. Cavitation erosion behavior of WC coatings
on CrNiMo stainless steel by laser alloying. Int J Miner Metall Mater 2009;16:
2037.
[23] Cairney JM, Tsukano R, Hoffman MJ, Yang M. Degradation of TiN coatings under
cyclic loading. Acta Mater 2004;52:322937.
[24] Ma LW, Cairney JM, Hoffman M, Munroe PR. Deformation mechanisms operating
during nanoindentation of TiN coatings on steel substrates. Surf CoatTechnol
2005;192:118.
[25] Tomlinson WJ, Kalitsounakis N, Vekinis G. Cavitation erosion of aluminas. Ceram
Int 1999;25:3318.
[26] Coble RL. Effect of microstructure on mechanical properties. In: Kingery WD, editor.
Ceramic Fabrication Process, New York; 1958. p. 223.
26 Y. Wu et al. / Int. Journal of Refractory Metals and Hard Materials 32 (2012) 2126