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Proceedings of the
International Thermal Spray Conference
Copyright 2013
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ORGANIZING COMMITTEE
iii
Contents
Organizing Committee ...........................................................................................................iii
Cold Spray
Corrosion Protection of 5xxx Series Aluminum-Alloy by Cold Spray Process ............. 126
K. Sridharan, B. Maier, B. Hauch, and D. Devan,
University of Wisconsin - Madison, Madison, WI, USA
Near-Net Shape Fins for Compact Heat Exchanger Produced by Cold Spray ............... 166
Y. Cormier1, P. Dupuis1, B. Jodoin1, and A. Corbeil2
(1) University of Ottawa, Ottawa, Ontario, Canada
(2) Brayton Energy Canada, Gatineau, Quebec, Canada
ix
Analysis of Thermal History and Residual Stress in Cold Sprayed Coatings ................ 269
Z. Arabgol1, H. Assadi1, T. Schmidt2, F. Grtner2, and T. Klassen2
(1) Tarbiat Modares University, Tehran, Iran
(2) Helmut Schmidt University, Hamburg, Germany
The Optional Facilities for the Low Pressure Cold Spray ................................................ 275
A. Shkodkin, A. Kashirin, O. Klyuev, and T. Buzdygar
Obninsk Center for Powder Spraying, Obninsk, Russia
Deformation and Adherence of Fe40Al- Particles in Cold Gas Spraying ....................... 297
N. Cinca1, A. List1, F. Grtner1, J. Fernndez2, J.M. Guilemany2, and T. Klassen1
(1) Helmut Schmidt University, Hamburg, Germany
(2) Universitat de Barcelona, Barcelona, Spain
Dense and High Purity Yttria Coatings by APS with a New Yttria Powder ..................... 307
A. Allimant1, D. Billires1, and H. Wallar2
(1) Saint-Gobain Coating Solutions, Avignon, France
(2) Saint-Gobain Coating Solutions, Worcester, MA, USA
x
Behavior of Ceramic Thermal Spray Coatings under Plasma Exposure ........................ 395
H. Yokota and M. Inaba, TOCALO Co., Ltd., Hyogo, Japan
xii
Structure and Properties of HVOF and Plasma Sprayed Ceramic AluminaChromia Coatings Deposited from Fused and Crushed Powders .................................. 465
P. Vuoristo1, K. Niemi1, V. Matikainen1, L. Hyvrinen1, H. Koivuluoto1, L.-M. Berger2,
S. Scheitz3, and I. Shakhverdova3
(1) Tampere University of Technology, Tampere, Finland
(2) Fraunhofer Institute for Material and Beam Technology, Dresden, Germany
(3) Dresden University of Technology, Dresden, Germany
Surface Engineering
3D Wear Analysis of Thermal Spray Coatings .................................................................. 487
W. Tillmann, W. Luo, and U. Selvadurai,
TU Dortmund University
Turbine Coatings
Impact of Impurity Content on the Sintering Resistance of Dysprosia and
Yttria Stabilised Zirconia Thermal Barrier Coatings ......................................................... 557
N. Curry1, Wyszomir Janikowski2, and N. Markocsan1
(1) University West, Trollhttan, Sweden
(2) University of Manchester, Manchester, UK
Poster
New Method for Carbon Nanofibers-Metal Powder Formation and
Their Use in Thermal Spray Coatings ................................................................................ 620
D.R. Vidal, I.G. Cano, J. Fernndez, and J.M. Guilemany,
Universitat de Barcelona, Barcelona, Spain
xvi
xvii
Wear Resistant Coatings on Ball Valves for Coal-Slurry Pipelines ................................. 712
L. Pershin1, J. Mostaghimi1, Afshin Maknoni2, Y.S. Ma3, Q. Gao3, Z.D. Chang3,
H.B. Liu3, and Q.M. Wu3
(1) University of Toronto, Toronto, Canada
(2) Metal Morphosis Specialty Metals Inc., Cambridge, ON, Canada
(3) Wuzhong Instruments, Wuzhong, China
Computational Simulation for Gas Heater of Cold Spray System ................................... 717
Huang Guosheng1, Gu Daming1, Li Xiangbo2, and Xing Lukuo2
(1) Harbin Institute of Technology, Harbin, China
(2) Science and Technology on Marine Corrosion and Protection Laboratory, Qingdao, China
xviii
Abstract
In recent years, the very low pressure plasma spraying
(VLPPS) process has been developed and implemented to
manufacture thin, dense and finely-structured ceramic coatings
for various applications, such as Y2O3 for diffusion barriers.
This paper aims at presenting developments carried out on
metallic coatings. Aluminum was chosen as a demonstrative
material due to its "moderate" vaporization enthalpy (i.e.,
38.23 KJ.cm-3) compared to copper (i.e., 55.33 KJ.cm-3),
cobalt (i.e., 75.03 KJ.cm-3) or even tantalum (i.e., 87.18
KJ.cm-3). The objective of this work is primarily to better
understand the behavior of a solid precursor injected into the
plasma jet leading to the formation of vapors and to better
control the factors affecting the coating structure. Nearly
dense aluminum coatings were successfully deposited by
VLPPS at 100 Pa with an intermediate power plasma torch
(i.e., Sulzer Metco F4 type gun with maximum power of 45
kW). Optical emission spectroscopy (OES) was implemented
to study and analyze the powder behavior into the plasma jet.
Simplified CFD modeling allowed better understanding of
thermo-physical mechanisms. The effect of powder size
distribution, substrate temperature and spray distance were
studied. Coatings were characterized by SEM observations
and Vickers microhardness measurements.
Introduction
The very low pressure plasma spray (VLPPS) process is an
emerging process allowing manufacturing ceramic and
metallic coatings. It is operated in an inert atmosphere (i.e.,
Ar) at unusually low pressures of typically between 100 and
1000 Pa. As a consequence, the deposition mechanisms are
different compared to the ones encountered with the
atmospheric plasma spray (APS) process since they result
mostly from the condensation of vapors instead of the stacking
of flattened particles. Depending upon spray operating
parameters, coating structures vary from nearly dense to
highly porous. As shown by K. Von Niessen et al. (Ref 1), M.
Gindrat et al. (Ref 2), A. Hospach (Ref 3), and J.-L. Dorier et
al. (Ref 4), the VLPPS process has an important potential.
Those authors proved that this process can be seen as
combining the high deposition rate of conventional spray
Experimental Methods
Feedstock and Substrates
Atomized aluminum 1050 powder particles manufactured at
IRTES-LERMPS, with a size distribution ranging from 25 m
(d10) and 65 m (d90) and an average size diameter (d50) of 45
m, were used as starting feedstock material (see Fig. 2). In
order to highlight the effect of the particles size on the coating
Set 1
Set 2
F4
6
650
73
45
0
10
15.0
100
650
64
17
33
5
31.4
100
1.5
3
650 to 800
200
200
950
1300
6
30
500
33.3
9.01
150
CFD Modeling
Figure 4 represents an example of computed fields (i.e.,
pressure, temperature, thermal conductivity, density, velocity
and effective viscosity) for the conditions depicted in effect) is
reduced and power vaporization is very likely more important
due to a better heat transfer to particles.
a)
Table 2.
The plasma jet structure is highly affected by the low
surrounding pressure and presents a succession of
compression and expansion areas. Expansion areas correspond
to thermodynamic properties decreasing except for velocity
field which suddenly increases and vice-versa. According to
Figure 4, axial gradients strongly decreased after 40 cm from
the nozzle exit indicating the full expansion of the flow.
Indeed, a spray distance equal to or longer from 40 cm can be
considered to deposit coatings.
b)
c)
d)
e)
30000
Intensity (u.a)
3000
20000
15000
10000
5000
0
0
2500
Intensity (u.a)
394.6 nm (Al I)
396.2 nm (Al I)
25000
100
200
300
400
2000
1500
1000
500
0
0
100
200
300
400
500
600
700
800
Intensity (u.a)
16000
14000
12000
10000
8000
6000
4000
2000
0
100 m
100 m
396.2 nm (Al I)
394.6 nm (Al I)
c)
100 m
0
100
200
300
400
500
600
700
800
12000
Intensity (u.a)
b)
a)
394.6 nm (Al I)
396.2 nm (Al I)
10000
8000
6000
4000
2000
0
0
Microhardness(HV0.025)
a)
b)
c)
d)
b)
100 m
50 m
c)
Figure 13: Surface morphology SEM observations for (a) no
cooled coating (950 K), (b) cooled sample (400 K), (c) spray
distance of 650 mm, and (d) spray distance of 800 mm.
Table 3: Coatings characteristics.
50 m
Characteristics
Surface roughness (m)
Average maximum peak-to-valley ratio
(m)
Microhardness (HV0.025g.f)
Void content estimation (%)
Spray distance
(mm)
650
800
11
8
119
78
78
> 10
90
<1
a)
3.
b)
4.
Conclusion
5.
6.
7.
8.
9.
Acknowledgements
The authors gratefully thank S. Lamy, A. Lamraoui and O.
Ribet (IRTES-LERMPS) for their contributions to the coating
characterizations, L. Dembinski (IRTES-LERMPS) for the
manufacturing of the aluminum feedstock.
10.
11.
Literature
12.
13.
14.
Abstract
The presented work compares a new WC-FeCrAl-matrix
feedstock powder with a standard WC-Co powder. The
investigation covers the powder analysis, spray jet properties,
splat flattening and coating properties, as well as, XRD
analyses of the feedstock powders and as sprayed coatings. As
the formation of single splats sets up the foundation for any
thermal spray coating, this step was chosen as the major
subject of investigation in this paper. A new method to create
a footprint of splats from a spray jet with an extremely short
exposure time was used to perform these splat examinations
(Ref. 1). It was found, that the interdependencies between
spray parameters and coating properties are generally the same
for both materials. Differences occurred in the phase stability
of the materials during the spraying process. In XRD
measurements the standard WC-Co material did not exhibit
any recognizable phase transformations of the WC, while a
significant formation of W2C and oxidation of the matrix was
observed for the WC-FeCrAl powder.
Experimental Procedure
Feedstock Powder
Two agglomerated and sintered cermet powders were used for
the experiments. The first one was a new WC-FeCrAl material
from H.C. Starck (Ref. 6). The second feedstock material was
a standard WC-Co powder of the type WOKA 3102 from
Sulzer Metco. The chemical compositions of the powders are
given in Tab. 1. The particle size distribution was determined
by laser scattering and sieve analysis with a Microtrack S3500
for both materials (Fig. 1). The carbide size was measured to
be between 0.5 and 4 m for the standard WC-Co and
between 0.2 and 2 m for the WC-FeCrAl by means of digital
picture analysis on SEM pictures at backscatter electron (BE)
mode. The inner porosity was measured using digital picture
analysis on SEM pictures at secondary electron (SE) mode
(Fig. 2). The average inner porosity of the powder particles
was approx. 26 vol.-% for both powders.
Introduction
WC-Co powders were introduced as a wear protection
material for thermal spray applications in the 1980s (Ref. 2).
Since Co proved to be hazardous, applications in the food
industry were inaccessible for this coating system. Thus, WCbased cermets with alternative matrix compositions have been
developed to avoid the toxic effect of Co. Fe-based matrix
materials are one promising group of materials, which is under
recent development (Ref. 3-5). The two powders compared
here are a standard WC-Co 88/12 and a new WC-FeCrAl
85/10/4/1 material. The aim of this investigation is to discover
differences in the processability of the new alternative powder
material compared to standard WC-Co feedstock powder.
Therefore, extensive investigations on the processing
parameters and the resulting properties of the microstructures
and mechanical properties were necessary and are presented
here. These cover the powder analysis, spray jet properties,
coating properties and splat flattening. One focal point is the
formation of single splats. They form the foundation of any
thermal spray coating. The results are used to help
understanding the correlation between the particle in-flight
properties and the coating morphology. The splat capturing
device is a new development of the TU-Dortmund and has
been first presented at the International Thermal Spraying
W
82.3
79.2
C
5.5
5,3
Co
12.1
Fe
0.1
Cr
0
Al
0
9.8
4,2
1,5
WC-Co
Oxygen/fuel ratio ()
Kerosene [l/h]
Stand-off distance [mm]
Powder feed rate [g/min]
-2
1.0
15
200
8.5
-1
1.075
17,5
225
32
0
1.15
20
250
55.5
1
1.225
22,5
275
79
2
1.3
25
300
102.5
WC-FeCrAl
Oxygen/fuel ratio ()
Kerosene [l/h]
Stand-off distance [mm]
Powder feed rate [g/min]
-2
0.9
15
250
8.5
-1
1,0
16.75
300
32
0
1,1
18.5
350
55.5
1
1,2
20.25
400
79
2
1,3
22
450
102.5
Figure 4: Response surface plots for particle temperature of WC-Co (a) and WC-FeCrAl material (b) as a function of kerosene level
and stand-off distance
10
3Fe+2O2 Fe3O4
4Fe3O4+O2 6Fe2O3
2WC+2O2 W2C+2CO2
2W2C+O2 2W+2CO
Figure 6: Particle velocities for WC-Co (a) and WC-FeCrAl powder in dependency of Stand-off distance and kerosene level.
11
Figure 7: Plot of the relative numbers of mountain-like and pancake-like splats plotted against corresponding particle velocities
(upper graphs) and particle temperatures (lower graphs) for the WC-Co standard powder (left) and WC-FeCrAl (right).
Splat Formation and Coating Properties
The selected properties of interest are primarily the coating
hardness and the coating porosity. Fig. 8 shows the
corresponding curves in dependency to the relative number of
pancake-like splats. The tendency for both materials shows
that an increasing percentage of pancake-like splats correlates
with an increasing coating hardness and decreasing coating
porosity, although the porosity appears to be generally much
lower for the WC-FeCrAl powder. It can be seen that the
maximum of 1420 HV 0.3 for the coating hardness of the WCFeCrAl material is a little higher than that of the WC-Co
standard powder. Still, the difference is negligible with regard
to the average standard deviations of hardness measurements,
which are about the same dimension.
12
Figure 8: Correlation graphs of coating hardness and porosity versus relative number of pancake-like splats on the substrate
Spray Parameters and Phase Reactions
In the previous graphs the most significant correlations have
been shown in each step, from the spray parameters to the
particle properties, to the splat morphologies and coating
morphologies. Yet, critical phase transformations inside the
powder material and the coating can be further relevant factors
for the evaluation of the coating quality. The generation of
brittle intermetallic phases is just one possible undesired
reaction that could take place during the thermal spray process
with an HVOF spray gun. As already mentioned during the
interpretation of the particle temperatures in the spray jet,
XRD investigations were conducted, using the high-intensity
synchrotron radiation of the electron accelerator DELTA at
the TU-Dortmund.
13
(Ref. 9-10) calculated for Fe2O3, Fe3O4 and W2C. The slope of
the Fe2O3 curve reveals that most of the energy could be
released due to the formation of Fe2O3. Still, the Fe3O4 phase
is needed as a preliminary oxidation phase before Fe2O3 can
exist. Interestingly, the curves of Fe3O4 and W2C have a point
of intersection, indicating that above 1750 K the WC W2C
reaction is preferred. The lower the temperature, the more
likely is the generation of Fe3O4, which is needed for Fe2O3
formation. This supports the assumption that the WC W2C
reaction is more likely to happen at high temperatures, while
Figure 10: Response surfaces for W2C and Delta Fe2O3-peaks as quadratic fits versus stand-off distance and kerosene level
14
4.
5.
Summary
In this study a new WC-FeCrAl and a common WC-Co
standard HVOF feedstock powders were compared. It was
found that the range of spray parameters for the new WCFeCrAl material had to be altered to slightly higher stand-off
distances and slightly lower kerosene levels to obtain
reasonable coating results. A significantly higher particle
temperature for the WC-FeCrAl powder was recorded during
spraying, which is supposed to be an effect of phase reactions
during the particle dwell-time in the spray jet. XRD graphs
revealed W2C and Delta-Fe2O3 formations. Calculations of the
free Gibbs energy propose that energy is being released during
the formation of these phases. Comparable correlations
between particle in-flight measurements and splat
morphologies were found for both feedstock powders.
Resulting coating hardness values ranged between 1100 to
1400 HV 0.3 for both powders, whereas, the porosity of the
coating reached significantly lower values for the WC-FeCrAl
powder than for the WC-Co standard powder within the
chosen field of parameters. This effect was attributed to the
smaller carbide grain size of the new powder, which might
promote a lower viscosity of the molten particles at impact. A
response surface analysis of the XRD measurements indicates
that the W2C formation occurs during the particle flight time
in the spray jet, while the Delta-Fe2O3 formation is supposed
to take place on the surface of the substrate after the particle
deposition.
6.
7.
8.
9.
10.
11.
12.
Acknowledgement
The authors gratefully acknowledge the financial support of
the DFG (German Science Foundation) within the
collaborative research center SFB 823 B1
13.
14.
References
1.
2.
3.
15.
16.
17.
15
Hysteresis
Phenomenon,
International Journal of Heat and Fluid Flow, 2007,
28(6), p1492-1506
I.M. Mahbubul, R. Saidur, M.A. Amalina, Latest
Developments on the Viscosity of Nanofluids,
International Journal of Heat and Mass Transfer, 2012,
55(4), , p 874-885
H. Reiss, Methods of Thermodynamics, 1965, Dover
Publications, ISBN 0-486-69445-3
Abstract
Deposition of two types of oxide-dispersed bond coats and
their oxidation behavior were examined. CoNiCrAlY powder
and nano-size -alumina powder were milled by a highenergy-attrition ball-mill, resulting in an oxide-dispersed
powder with a mixed structure of metal and alumina in each
particle. The oxide-dispersed bondcoat powder was deposited
under the deposition condition of a fine CoNiCrAlY powder
by HVOF. Pores, however, were observed in the coating since
the dispersed alumina was deposited without a high degree of
melting. Isothermal oxidation tests were carried out for the
bondcoat specimens at a temperature of 1373 K up to 1000
hours in air. As a result, oxidation proceeded not only at the
surface but also inside the coating, since oxygen penetrated
through pores created by the dispersed alumina. Another
deposition was performed using higher power levels. This
produced a bond coat without pores. A commercially available
oxide-dispersed CoNiCrAlY powder was also deposited by
HVOF and VPS, and isothermal oxidation tests were
performed in air. The HVOF bond coat exhibited the thinnest
thermally grown oxide than those of the VPS bond coat and
conventional metallic bond coat. The internal oxidation,
however, proceeded in the HVOF-sprayed coating since the
powder particles due to particle cohesion issues. Furnace
cycling tests were conducted using the specimens with an
additional ceramic thermal barrier coating. The specimen with
the bond coat sprayed by VPS using commercial oxidedispersed powder exhibited almost same number of cycles to
delamination compared with the specimen with the
conventional metal bond coat.
Introduction
The chemical composition of the CoNiCrAlY powder (Sulzer
Metco, Wohlen, Switzerland) used to prepare Powder HB was
Co-32Ni-21Cr-8Al-0.5Y (wt.%). Figure 1a shows the
morphologies of the particles of this powder. The oxide
powder was -alumina (io-li-tec, Heilbronn, Germany), and
its nominal particle size is 80 nm, as shown in Fig. 1b. The
CoNiCrAlY and alumina powders were placed in the highenergy-attrition ball mill in an 80/20 ratio and the mixture was
milled at the maximum rotational speed of 1600 rpm for 1 h.
Powder HB was deposited by high-velocity oxy-fuel (HVOF)
16
20m
50m
50m
Figure 1: Morphologies of starting powders for oxidedispersed powder manufactured by high-energy-attrition ball
milling.
Condition 2
HB-2
CA-H
Nitrogen (nlpm)
450
300
460
Oxygen (nlpm)
155
395
230
-
Methane (nlpm)
245
Hydrogen (nlpm)
630
690
200
250
200
500
500
300
Spraying distance
(mm)
Robot velocity
(mm/s)
Specimen
CA-V
Current
750
Process pressure
(mbar)
60
Argon (nlpm)
50
Hydrogen (nlpm)
Spraying distance
(mm)
Robot velocity
(mm/s)
275
440
17
20m
50m
Figure 4: Morphology of cross section of Bondcoat HB-1.
Figure 3: Morphology of the particles of Powder HB.
The test specimens were cut at the center before or after the
tests, and their cross sections were polished for microstructural
observations, which were made using optical microscopy and
scanning electron microscopy (SEM).
Isothermal Oxidation Test and Furnace Cycle Test
Isothermal oxidation tests were performed using the
Bondcoats HB-1, CA-V, CA-H and Standard Bondcoat in an
electric furnace. The tests were performed in air at the
temperature of 1373 K with the test time of 100 h, 500 h and
1000 h.
20m
Figure 5: Morphology of cross section of Bondcoat HB-2.
18
30m
(a) Bondcoat CA-V
30m
30m
(b) Bondcoat CA-H
Figure 6: Morphologies of cross section of Bondcoats CA-V and CA-H and Standard Bondcoat before test.
30m
(a) Before test
30m
(b) 100h
30m
(c) 500h
Figure 7: Morphologies of cross section of Bondcoat HB-1 after isothermal oxidation test at the temperature of 1373K in air.
Isothermal Oxidation Test
Figure 7 indicates the microstructure of Bondcoat HB-1 before
and after the isothermal oxidation test. A gray-colored oxide is
formed after 100 h, and it grows within the coating. X-ray
diffraction analysis of the surface of the bondcoat after the test
shows the presence of spinel oxides, such as the mixed oxide
of Co, Ni, and Cr, and of alumina. The mixed oxide is formed
by the oxidation of the metal part of the bondcoat since
oxygen can penetrate into the coating through the pores
described in the previous section. Thus, in order to prevent the
internal oxidation of the metal part, it is necessary to spray a
dense coating of the TBC using higher-temperature flames.
Figures 8a, b and c show the microstructures of Bondcoat CAV, Bondcoat CA-H and Standard Bondcoat, respectively, after
500 h of the isothermal oxidation test. Internal oxidation
occurs only in Bondcoat CA-H since the sprayed particles do
not adhere due to the insufficient melting, resulting in oxygen
penetrating into the coating. Deposition under spraying
19
100m
100m
100m
Figure 8: Morphologies of cross section of bondcoats after 500h at the temperature of 1373K in air.
30m
(a) Bondcoat CA-V
30m
30m
(b) Bondcoat CA-H
Figure 9: Magnified views of cross section of bondcoats after 500h at the temperature of 1373K in air.
oxide in TGO in Bondcoat CA-H. Figure 10 shows the
relationship between TGO thickness and the test time. The
thickness increases with the test time in all the bondcoats. No
significant difference in the thickness between Bondcoat CAV and Standard Bondcoat is found. On the other hand, the
thickness in the case of the Bondcoat CA-H specimen was half
that of the other specimens. The fine oxides dispersed within
the coating can hinder elemental diffusion. In addition, the
smaller amount of the Y-rich oxide in TGO also can reduce
the growth.
20
15
CA-H bondcoat
CA-V bondcoat
Standard CoNiCrAlY
10
200
400
600
Test time (h)
800
1000
Standard
4.
2.
3.
HB-1
1.
CA-V
21
Abstract
The quality of bond coat and the top coat of thermal barrier
coatings (TBCs) have strong influences on their lifetime at
high temperature. Especially, the oxygen content level and the
surface roughness of the bond coat have been demonstrated to
play an important role in the thermal behavior of TBCs. In this
study, dry-ice blasting was used during the preparation of
TBCs which were composed of air plasma sprayed
CoNiCrAlY bond coat and air plasma sprayed YSZ top coat.
Three sets of TBCs deposited with different treatments of dryice blasting were compared with respect to the coating
microstructure evolution, the growth behavior of thermally
grown oxide (TGO), crack propagation and thermal shock
behavior during thermal exposure. It was interesting to find
that different microstructures of bond coat and top coat were
obtained under different conditions. Moreover, the results
showed that CoNiCrAlY bond coats continue to be oxidized
during the deposition process of YSZ top coats which were
plasma-sprayed without dry-ice blasting. These three sets of
TBCs have different thermal shock lifetime. TBC with APS
dry-ice blasted bond coat and APS dry-ice blasted top coat
was the most durable and exhibited much improvement in
lifetime.
Introduction
Thermal barrier coatings (TBCs) are highly advanced material
systems, which were usually thermally insulating materials
with a relatively low thermal conductivity coated on hightemperature-exposed components, such as gas turbine and
aeronautical engine components (Ref 1-4). These coatings can
allow for extending part life by reducing oxidation and
thermal fatigue. Therefore, thermal barrier coating technology
is one of most important technologies for perfectly
manufacturing the entire gas turbine system. At present,
plasma-sprayed TBCs, composed of yttria-stabilized zirconia
(YSZ) ceramic top coat (TC), an oxidation-resistant MCrAlY
bond coat (BC), where M = Fe, Ni, Co, CoNi, or NiCo, are
commonly used (Ref 5-7). The oxidation-resistance of bond
T
22
Taking into account that dry ice blasting has a better cooling
effect during the coating deposition process, and its peening
effect as reported in our previous studies (Ref 21, 22), dry ice
blasting in this study was used to prepare thermal barrier
coatings. The primary objective of this study was to
systematically investigate the influence of dry-ice blasting on
the microstructure of as-sprayed bond coat and top coat. Then,
the thermal cycle lifetimes of the various types of TBCs were
compared by furnace cycling at an elevated temperature
(1150C) to accelerate the coating degradation process.
CoNiCrAlY
600
66.9
60
11
2.0
YSZ
630
65.0
30
11
3.0
CoNiCrAlY
APS without dry-ice
blasting
APS with dry-ice
blasting
APS with dry-ice
blasting
YSZ
APS without dry-ice
blasting
APS without dry-ice
blasting
APS with dry-ice
blasting
Characterization
The morphologies of the as-sprayed coatings were examined
using an optical microscope (OM). The porosities and oxide
contents of the as-sprayed coatings were then estimated using
an image analysis of the OM micrographs. More than 5 photos
randomly observed in the polished cross-section were
averaged to evaluate the porosity and oxide contents.
Surface roughness profiles of the three types of bare
CoNiCrA1Y bond coats on 316L steel substrates were
measured for their average surface roughness (Ra) using a
AltiSurf 500 roughness tester produced by Altimet. Three
measurements of 17.5 mm length were made at random
23
(a)
(b)
(c)
(d)
Figure 1: Optical micrographs of cross section of asdeposited TBCs (sample AA) with APS bond coat and APS top
coat (a) over view, (b) CoNiCrAlY bond coat with porosity
and oxide inclusions and BSE images showing (c) CoNiCrAlY
bond coat, (d) YSZ.
(a)
(b)
(c)
(d)
Figure 2: Optical micrographs of cross section of asdeposited TBCs (sample CA) with APS-dry-ice blasted bond
coat and APS top coat (a) over view, (b) CoNiCrAlY bond
coat with porosity and oxide inclusions and BSE images
showing (c) CoNiCrAlY bond coat, (d) YSZ.
24
(a)
(b)
(c)
(d)
Figure 3: Optical micrographs of cross section of asdeposited TBCs (sample CC) with APS-dry-ice blasted bond
coat and APS-dry-ice blasted top coat (a) over view, (b)
CoNiCrAlY bond coat with porosity and oxide inclusions and
BSE images showing (c) CoNiCrAlY bond coat, (d) YSZ.
25
(a)
(a)
(b)
(b)
(c)
(a)
(b)
(c)
(c)
(a)
26
(b)
References
1. R.A. Miller, Thermal Barrier Coatings for Aircraft Engines:
History and Directions, J. Thermal. Spray. Technol., 1997,
6(1), p 35-42
2. C.T. Sims, Non-Metallic Materials for Gas Turbine
EnginesAre They Real?, Adv. Mater. Process., 1991,
139, p 32-39
3. R. Vaen, S. Giesen, D. Stover, Lifetime of PlasmaSprayed Thermal Barrier Coatings: Comparison of
Numerical and Experimental Results, J. Thermal. Spray.
Technol., 2009, 18(5-6), p 835-845
4. B.H. Kear, E.R. Thompson, Aircraft Gas Turbine Materials
and Processes, Science, 1980, 208, p 847-856
5. N.P. Paduture, M. Gell, E.H. Jordan, Thermal Barrier
Coatings for Gas-Turbine Engine Applications, Science,
2002, 296, p 280-284
6. A. Scrivani, G. Rizzi, U. Bardi, C. Giolli, M. Muniz
Miranda, S. Ciattini, A. Fossati, and F. Borgioli, Thermal
Fatigue Behavior of Thick and Porous Thermal Barrier
Coatings Systems, J. Thermal. Spray. Technol., 2007,
16(5-6), p 816-821
7. J.A. Haynes, M.K. Ferber, W.D. Porter, Thermal Cycling
Behavior of Plasma-Sprayed Thermal Barrier Coatings with
Various MCrAIX Bond Coats, J. Thermal. Spray. Technol.,
2000, 9(1), p 38-48
8. L.D. Xie, D.Y. Chen, E.H. Jordan, Formation of Vertical
Cracks in Solution-Precursor Plasma-Sprayed Thermal
Barrier Coatings, Surf Coat Technol, 2006, 201, p 10581064
9. R. Va en, G. Kerkhoff, D. St over, Development of a
Microme-Chanical Life Prediction Model for Plasma
Sprayed Thermal Barrier Coatings, Mater. Sci. Eng. A, 2001,
303(1-2), p 100-109
10. K.W. Schlichting, N.P. Padture, E.H. Jordan, M. Gell,
Failure Modes in Plasma-Sprayed Thermal Barrier
Coatings, Mater. Sci. Eng., A, 2003, 342, p 120-130
11. R.V. Hillery, B.H. Pilsner, R.L. McKnight, T.S. Cook,
M.S. Hartle, Thermal Barrier Coating Life Prediction
Model Development, Final Report, NASA CR 180807,
1988, National Aeronautics and Space Adminis-tration,
Washington, DC
12. A.G. Evans, D.R. Mumm, J.W. Hutchinson, Mechanisms
Controlling the Durability of Thermal Barrier Coatings,
Prog Mater Sci, 2001, 46(5), p 505-553
13. S. Kuroda, T.W. Clyne, The Quenching Stress in
Thermally Sprayed Coatings, Thin Solid Films, 1991,
200(1), p 49-66
14. T.S. Hille, T.J. Nijdam, A.S.J. Suiker, S. Turteltaub, W.
Sloof, Damage Growth Triggered by Interface
Irregularities in Thermal Barrier Coatings, Acta Mater,
2009, 57, 2624-2630
(c)
27
28
Abstract
Introduction
The fundamental feature of any thermal spray coating is its
lamellar microstructure formed by the rapid solidification of
impinging molten droplets and cohesion among splats.
Formation of this lamellar microstructure is a stochastic
process and is associated with interdependent processing
variables such as the feedstock size, feedstock material, flame
jet temperature, and particle velocity (Ref 1, 2). An illustration
of a typical ceramic thermal spray microstructure was depicted
in Fig. 1. Due to the cumulative interactions of variables
within the spray stream, discriminating features such as splat
dimensions, pore sizes, crack density, inter-splat coalescence,
and associated artefacts can be ascertained.
The lamellar splat structure also gave rise to highly anisotropic
mechanical properties of thermal spray coatings. Thus, the
coating material properties depended on the direction
measured as opposed to an isotopic bulk material. The
anisotropic nature of a thermal sprayed microstructure has
been specifically defined as transversely isotropic because the
architecture has two orthogonal planes of symmetry: i.e., (i) a
29
In this work, the standard TAT was used while a TCT setup
was adapted as shown in Fig. 2. These tests allowed the
evaluation of plasma sprayed yttria stabilised zirconia (YSZ)
coatings mechanical strength for in plane as well as the
perpendicular orientations. The in plane orientation is
parallel to the substrate surface whereas the perpendicular
orientation refers to the coating thickness cross section. In
addition, the anisotropic behaviour of YSZ coatings was also
tested using orientated Knoop hardness measurements
Experimental Methods
The use of YSZ ceramics in the context of this work are for
thermal barrier coating (TBC) applications. TBCs can be
found in advanced gas turbine engine components operating
above 1,000C (Ref 6).
YSZ powder (Metco 204NS, Sulzer Metco Inc., USA) with a
composition of ZrO2-8wt% Y2O3 was used for this work. The
powders were manufactured by the HOSP method and were
spherical with good flowability and chemical homogeneity.
The particle cut was from +16 -125 m and the mean particle
size was 71.5 m. For TAT specimen, a metallic bond coat of
Amdry 365 (Sulzer Metco Inc., USA) was used. Amdry 365 is
a proprietary NiCrAlY alloy powder with a particle size cut
between +5 -45 m. It is manufactured by a gas atomization
route and a spheroidal powder is produced.
30
A universal joint design was used for the tensile testing rig as
recommended by the ASTM C633 Standard. An
electromechanical-type universal testing machine: (Uniaxial
MTS Criteron Model 43, MTS Systems Corporation, MN,
USA) with measuring capabilities rated at 50 kN was used to
apply the tensile load for TAT. After a TAT sample had been
assembled in the loading devices via the threaded couplings,
the machine program was activated. A pre tensile load of 30 N
was applied to remove any slack in the load train. No data was
recorded when the preload was applied. Subsequently, the
tensile load was applied, at constant crosshead rate of
0.015 mm/s, to each TAT specimen until rupture occurred.
The time to failure, crosshead displacement and maximum
failure load were recorded at 50 Hz for analysis. A total of
thirty five YSZ coupons were plasma sprayed and evaluated
using TAT.
Due to the relatively small cross sectional area tested for the
TCT specimen, a table-top electromechanical-type universal
machine Z010/ TN2S (Zwick GmbH & Co, Ulm, Germany)
was used. The Z010/ TN2S crosshead was screw driven with a
500 W DC actuator and was equipped with an interchangeable
load cell capable of measuring up to 1 kN. The constant
crosshead speed of 0.008 mm/s was selected as the testing
condition for all samples. This test speed was almost twice
less than that used for the conventional ASTM C633 standard
since the intention was to maintain the strain rate range within
the quasi-static or pseudostatic mode of tensile testing; i.e.,
between 10-5 to 10-1 s-1. A total of thirty five YSZ coupons
was also used for TCT.
31
Tensile adhesion
strength (MPa)
Tensile intersplat
strength (MPa)
Transverse rupture
strength of bulk
dense ceramic (MPa)
(Ref 7)
APS / YSZ
Porosity (%)
23.45
(4)
8.46
(2)
20.43
(11)
600-700
32
23.45
4.78
2.30
Conclusion
The mechanical strength of plasma sprayed YSZ coatings
were measured by performing TAT, TCT and Knoop
microhardness indentation test.
The adhesion strength of YSZ-bond coat system measured by
TAT was 8.46 MPa while the TCT tests, measuring the
coatings intersplat strength parallel to the spray direction
without the use of any adhesive, yielded strength of up to
20.43 MPa. In both datasets, the failure strength of the
coatings from the respective tests can be approximated to a
Weibull distribution and also indicated the anisotropic
behaviour of YSZ plasma sprayed coatings. The average
coating strength parallel to the spray direction is
approximately 1.5 times greater than the bond strength
perpendicular to spray direction. The anisotropic behaviour of
YSZ coatings have also been verified by the Knoop
microhardness measurements. It was found that the
33
34
Y2O3 and Yb2O3 Co-doped Strontium Hafnate as a New Thermal Barrier Coating
Material
W. Ma*, P. Li, H.-Y. Dong, Y. Bai, J.-L. Zhao, X.-Z. Fan
Inner Mongolia University of Technology, Hohhot, Inner Mongolia, P.R. China
*E-mail: wma66@163.com
Abstract
Y2O3 and Yb2O3 co-doped strontium hafnate powder with
chemistry of Sr(Hf0.9Y0.05Yb0.05)O2.95 (SHYY) was synthesized
by a solid-state reaction at 1450oC. The SHYY showed good
phase stability not only from 200oC to 1400oC but also at a
high temperature of 1450oC for a long period, analyzed by
differential scanning calorimetry (DSC) and X-ray diffraction
(XRD), respectively. The coefficient of thermal expansion
(CTE) of the sintered bulk SHYY was recorded by a hightemperature dilatometer and revealed a positive influence on
phase transitions of SrHfO3 by co-doping with Y2O3 and
Yb2O3. The thermal conductivity of the bulk SHYY was
approximately 16% lower in contrast to that of SrHfO3 at
1000oC. Good chemical compatibility was observed for
SHYY with 8YSZ or Al2O3 powders after a 24 h heat
treatment at 1250oC. The phase stability and the
microstructure evolution of the as-sprayed SHYY coating
during annealing at 1400oC were also investigated.
750 C
1130 C
Cmcm
I 4/ mcm
Pm 3m
Introduction
In recent years, much effort has been devoted to the
development of new ceramics as thermal barrier coating (TBC)
materials, in order to increase the efficiency of gas turbines
(Ref 1, 2). The current state-of-the-art TBCs are usually based
on 7-8 wt.% Y2O3-stabilized ZrO2 (8YSZ) due to its low
thermal conductivity, phase stability at temperatures below
1200oC and chemical inertness in combustion atmospheres
(Ref 3). However, YSZ cannot be operated long-term at
~1200oC because of phase transition and accelerated sintering
(Ref 4-6).
Experimental Procedure
Solid-state synthesis of SHYY was carried out through ball
milling using the starting powders of Y2O3 (99.99%, Grirem
Advanced Materials Co. Ltd., China), Yb2O3 (99.99%, Grirem
Advanced Materials Co. Ltd., China), SrCO3 (>98%, Shanghai
35
Dth (T )C p (T ) (T )
(Eq 1)
/ 0 1 4 / 3
(Eq 2)
36
37
'
38
39
40
Abstract
Introduction
Thermal spraying is a material processing technique, which is
based on the combination of thermal and kinetic energy. The
feedstock used is heated by one of the following heat sources:
chemically (by combustion), physically (by gas ionization), or
electrically (by employing arc ignition) (Ref 1). The materials
of the feedstock are accelerated, melted and then atomized by
means of atomization or process gases. These processes differ
not only in their thermal source but also in their feedstock
type. The three major categories of feedstock materials used
are powders, massive wires and cored wires. The main
properties of the thermal sprayed coatings are considered as
the sum of the parameters which directly or indirectly
influence the particle formation, particle in-flight
characteristics and the flattening behavior of droplets on the
41
42
Experiments
Results
Conventional Spraying Nozzles
The tests have shown that the highest particle velocities can be
produced with the nozzle 60 (168 5 m/s). The increase of
the secondary gas pressure leads to an increase in the particle
velocity. The behavior of the particle velocity in case of 4H
nozzle is different. The 4H nozzle has a detrimental effect on
particle velocity especially at higher spraying distance. The
particle velocity decreases at higher spraying distances with
increased gas pressure. Nevertheless, the measurements show
that the 4H nozzle has the narrowest spraying plume. The
focusing effect of the secondary gas is also obvious at 60
nozzle, as shown in Fig. 3 using Schlieren images. The nozzle
with 60 has a higher effect on the plume focusing than the
one with 30. In both cases the gas flow is more dominant
from the upper side of the nozzle, directly beneath the
secondary gas inlet. The images reveal no gas flow from the
wire side for both nozzle configuration 30 and 60. The
diamond shocks in the secondary gas flows are more obvious
for the outlet holes located at the nozzle upper side directly
below the gas inlet.
Wires
intersection
Secondary
gas inlet
Secondary
gas inlet
43
44
The slot form of the secondary gas outlet has a negative effect
on the achieved particle velocity as illustrated in Fig. 9. At
increased secondary gas pressure a significantly decrease in
particle velocity was obtained. The decline in particle velocity
is more obvious at a primary gas pressure of 6 bar. The
combination 6 bar - 6 bar shows a lower velocity than the
combination 4 bar - 6 bar.
45
Reference
11.
1.
12.
13.
14.
15.
16.
17.
18.
19.
20.
46
Abstract
In high-temperature industrial furnaces metallic components
are used for radiation shields, muffles, protective tubes and
high-temperature recuperators. In these cases, the application
of metals instead of ceramics is advantageous, mainly due to
the greater thermal dynamics that allow a faster and more
precise control of the furnace and work load temperatures. For
these components, the operation under oxidizing atmospheres
is normally limited to temperatures of up to about 1450 K. It is
also known that molybdenum disilicide works well in a
temperature range from 950 to 1900 K under these conditions.
Therefore the aim of this work is the characterization and
optimization of molybdenum disilicide coatings for the hightemperature oxidation protection of metallic substrates.
Thermal spraying of agglomerated/sintered powder was
carried out by the APS process. Feedstock and coatings were
characterized by means of optical and scanning electron
microscopy. Coating porosity was determined by digital image
analysis.
Introduction
A lot of furnace linings consist of refractory materials like
Al2O3 or SiC with additional radiation shields, subdivisions or
muffles. These metallic parts are widely used in furnaces that
are operating in inert atmospheres. Especially because of the
better thermal dynamics, metallic components have
advantages over the conventional high-temperature-resistant
ceramics. Nevertheless these parts cannot be utilized when an
oxidizing atmosphere and high temperatures occur at the same
time.
47
Results
100
25
MoSi2 -45+20 m
20
15
80
10
40
20
cumulated [%]
distribution density
MoSi2 -20+5 m
10
100
(a)
-20+5 m
Ar [slpm]
H2 [slpm]
spray distance [mm]
-40+25 m
40
2,5
10
(b)
Figure 3: Optical micrographs of MoSi2-layers processed by
APS (a) MoSi2 -45+20 m (b) MoSi2 -20+5 m.
48
30
porosity [%]
20
15
10
25
20
15
10
5
-45+20 m
5 slpm H2
0
-20+5 m
2.5 or 5
5 or 10
10 slpm H2
100
125
150
(a)
porosity [%]
20
15
10
5
2.5 slpm H2
0
5 slpm H2
100
125
150
(a)
(b)
Figure 4: Measured porosity of the coatings:
(a) MoSi2 -45+20 m;
(b) MoSi2 -20+5 m.
600
HV 0.3
500
400
(b)
300
200
100
5 slpm H2
0
10 slpm H2
100
125
150
49
References
1. Y.A. Chang, Oxidation of Molybdenum Disilicide, J.
Mater. Sci., 1969, 4, p. 641-643
2. W. Schulle, Feuerfeste Werkstoffe, Deutscher Verlag fr
Grundstoffindustrie, 1991
3. Y.L. Jeng and E.J. Lavernia, Processing of Molybdenum
Disilicide, J. Mater. Sci., 1994, 29, p. 2557-2571
4. K. Bundschuh and M. Schtze, Materials for Temperatures
above 1500 C in Oxidizing Atmospheres - Part I: Basic
Considerations on Materials Selection, Mater. Corr.,
2001, 52, p. 204-212
5. N.S. Stoloff, C.T. Liu and S.C. Deevi, Emerging
Applications of Intermetallics, Intermetallics, 2000, 8, p.
1313-1320
6. Z.J. Yao and T.S. Stiglich, Molybdenum Silicide Based
Materials and Their Properties, J. Mater. Eng. Perf, 1999,
8, p. 291-304
7. J.K. Yoon, J.Y. Byun, G.H. Kim, J.S. Kim and C.S. Choi,
Growth Kinetics of Three Mo-Silicide Layers Formed by
Chem. Vapor Deposition of Si on Mo Substrate. Surf.
Coat. Techn., 2002, 155, p. 85-98
8. S. Govindarajan, J.J. Moore, B. Mishra and D.L. Olson,
Physical Vapor Deposition of Molybdenum and Silicon
Thin Films. Surf. Coat. Techn., 1994, 68-69, p. 45-50
9. M. Fukumoto, T. Ueda and I. Okane: Gas Permeability of
Plasma Sprayed MoSi2 Coating. J. Mater. Sci. Lett., 1994,
13, p. 656-657
10. S. Motojima, A. Fujimoto, and K. Sugiyama, Molybdenum
Disilicide Coating on Steel and its Oxidation Resistance, J.
Mater. Sci. Let., 1982, 1, p. 19-22
Acknowledgement
Part of the research was carried out within the scope of the
project # 16858 BG/1 funded by the Bundesministerium fr
Wirtschaft
und
Technologie
(BMWi)
via
the
Arbeitsgemeinschaft fr Industrieforschung (AiF). The
authors thank the BMWi for financing this project and the
Fraunhofer IKTS for supplying the powders.
50
Abstract
Materials based on the cubic hard phase TiC are a highly
promising extension and alternative to existing hardmetal
coating solutions, such as WC-Co, WC-CoCr and Cr3C2-NiCr.
TiC-based compositions, alloyed with Mo and N, consist of
two core-rim-structured hard phases embedded in metal binder
phase of Co and/or Ni, for example. These materials can be
sprayed with various methods, such as plasma spray,
detonation gun and HVOF, resulting in competitive coating
properties. For example, HVOF sprayed (Ti,Mo)(C,N)hardmetal coatings show variable friction properties where the
coefficient of friction (CoF) is lower when sprayed by gas fuel
type whereas liquid fuel type gives higher CoF. However, this
conclusion needs to be confirmed, since feedstock powders
and measurement equipment have been different that makes
prevent simple comparison. In this work, comprehensive
studies have been conducted by preparing powder feedstock
with Ni and Co binders retaining same manner for various
HVOF methods as well as unified measurement conditions for
CoF and wear properties.
Introduction
Thermal spray coatings have been continuously advanced,
enabling the expansion of their practical applications in a
range of industries. High velocity oxy-fuel (HVOF) spraying
technology has played an important role in the development of
functional surfaces with a high wear resistance. (Ref 1) This is
a critical factor for many machinery parts in industrial
applications. (Ref 1, 2) Their required wear resistance is
continuously increasing, and a matched improvement of
51
Experimental
(Ti,Mo)(C,N) Hardmetal Powders and HVOF Spraying
Four kinds of (Ti,Mo)(C,N) powders were produced by
agglomeration and sintering by Fujimi Incorporated (Japan) as
summarized in Table 1. Ni and Co were used as binder metal,
whose content was around 26~28wt%. Their volume ratio of
metal and ceramics was almost same as WC-12wt%Co (Ref 5).
Two different particle size distributions (PSD) of -45+15 and 30+10 m were prepared for kerosene- and gas-fuel HVOFs,
respectively. Scanning electron microscopic images of typical
powders are shown in Fig. 1.
The D6037 abrasion test, shown in Fig. 2 was tested under the
following conditions. The abrasive was silicon carbide (SiC)
sand paper (F180, +63 m, D50% of around 90 m). Specimens
had dimensions of 50 70 5 mm. The load was 30.1 N.
Reciprocating velocity and total reciprocation at one test cycle
(run) was 40 DS/min and 400 DS, respectively. After weight
measurement, specimens were tested again. Wear area was
approximately 30 12 mm. Wear length was estimated to be
24 m/run. Each specimen had 5 run (total wear length of 120
m).
PSD
[m]
DTS-T10-45/15
DTS-T11-30/10
DTS-T14-45/15
DTS-T15-30/10
-45+15
-30+10
-45+15
-30+10
(a) T10
Co
27.8
27.1
reciprocation
Load: 3.15kgf (30.9N)
Coating
SiC abrasive paper (F180)
(b) T11
52
200m
(c) Co-DJ
200m
(d) Ni-DJ
500m
(e) Co-DJ, 6.1%
500m
(f) Ni-DJ, 3.0%
200m
(g) Co-JP, 11.6%
200m
(h) Ni-JP
200m
20 m
53
Wear Properties
Results of wear tests G65 (dry rubber wheel with quartz sand
0.1-0.6 mm), D6037 (dry abrasive with SiC F180 sand paper)
and G99 (PoD, against alumina ball) are shown in Fig. 5.
Wear track in G99 against steel ball is too small to estimate
the wear rate. Volume loss of G65 and D3067 has been
estimated using weight loss and theoretical density of the
material about 6.16 g/cm3.
40
30
Co-K2
Ni-K2
Co-DJ
Ni-DJ
Co-JP
Ni-JP
The K2 coatings show the best wear resistance in all tests. K2Ni has better wear resistance in D6037 and G99 than K2-Co.
The DJ samples have comparable properties to K2 only in
G99. In G65 these have slightly lower resistance. The JP
samples are the worst in G99 and G65 in this work. Co-JP is
the worst. Although large lateral crack is seen in Ni-JP,
mechanical properties of Co-JP coating are much lower than
Ni-JP, suggesting that Co-JP should have weaker bonding
between lamellae in the coating totally.
Worn out
around 4.7 km
Considering that the trend in all samples, G65 and G99 seems
to be quite similar: K2 is the best, DJ is not far from K2 and
JP is the worst. On the other hand, D6037 shows different
tendency that JP is better than DJ. The result of D6037 seems
to be consistent with hardness where harder coating simply
increase D6037 wear resistance. That suggests G65 and G99
are influenced by not only hardness but other factors, such as
toughness. Another possible factor is size of counter materials.
When large sized particles attack coating surface, these should
affect large area. Bonding among particles (lamellar
boundary) may be strongly affected than inside particles.
Media size in G65 and G99 seems to have significantly larger
than splat size that may enhance the wear from the lamellar
boundaries dominantly. In D6037, on the other hand, its media
size is smaller than other tests and is probably comparable to
splats and Vickers indent size of about 20 m. Small SiC
particle should attack smaller region, probably inside particles.
This difference of major factor on wear may affect the
tendency.
20
10
(a)
0
0
3
4
Distance [km]
15
Co-K2
Ni-K2
Co-DJ
Ni-DJ
Co-JP
10
20
(b)
0
0
0.003
(c)
2
3
Run [times]
0.128
0.002
0.001
Ni-JP
Co-JP
Ni-DJ
Co-DJ
Ni-K2
Co-K2
54
1.2E-07
1.1E-06
JP-steel
0.8
0.7
JP-alumina
0.6
COF
2.1E-07
1.5E-07
(a) Co binder
0.9
3.9E-08
1.E-07
6.9E-08
1.6E-07
1.E-06
K2-steel
0.5
DJ-alumina
K2-alumina
0.4
0.3
DJ-steel
0.2
WC-12Co/JP
Ni-JP
Co-JP
Ni-DJ
Co-DJ
Ni-K2
1.E-08
Co-K2
1.E-05
0.1
JP-Co-steel
DJ-Co-steel
K2-Co-steel
JP-Co-Al2O3
DJ-Co-Al2O3
K2-Co-Al2O3
0
0
1
5000
10000
15000
No. of cycles
20000
25000
30000
(b) Ni binder
0.9
JP-steel
0.8
0.7
K2-steel
COF
0.6
JP-alumina
DJ-alumina
0.5
0.4
K2-alumina
0.3
DJ-steel
0.2
0.1
JP-Ni-steel
DJ-Ni-steel
K2-Ni-steel
JP-Ni-Al2O3
DJ-Ni-Al2O3
K2-Ni-Al2O3
0
0
5000
10000
15000
No. of cycles
20000
25000
30000
0.7
JP-RT
0.6
K2-RT
DJ-600
K2-600
COF
0.5
JP-600
0.4
DJ-RT
0.3
Figure 8: Progression of the CoF of the Ni-DJ, Ni-K2 and NiJP coatings against alumina ball at room temperature and
600 C in the air
0.2
Ni-DJ-600
Ni-DJ-RT
0.1
Ni-K2-600
Ni-K2-RT
Ni-JP-600
Ni-JP-RT
0
0
55
5000
10000
15000
20000
No. of cycles
25000
30000
6.
7.
8.
Conclusion
Comprehensive studies have been carried out by preparing
powder feedstock of (Ti,Mo)(C,N) hardmetal with Ni and Co
binders retaining same manner for three HVOF methods of K2,
Diamond Jet and JP-5000. Coating specimens are evaluated by
microstructure, hardness, bonding strength, wear and friction.
K2 coatings showed higher hardness than others. All coatings
have higher bonding strength more than adhesives of 80 MPa.
In all wear tests, K2 showed the higher wear resistance, which
is comparable to Cr3C2-NiCr in G65 and D6037 as well as 10
times better than Cr3C2-NiCr in G99. Ni binder coatings by DJ
and K2 have stable CoF around 0.45-0.55 from room
temperature to high temperature of 600 C, where drastic
difference between the coatings are unclear. Considering that
wear and sliding properties, Ni binder by K2 is the best within
this study.
10.
References
12.
1.
2.
3.
4.
5.
9.
11.
13.
14.
15.
16.
56
Abstract
Introduction
Thermal spray coatings offer various customized surface
properties, such as resistance to corrosive atmosphere,
abrasion, erosion, high temperature and high heat flux.
Recently, these properties of the spray coatings have been
greatly progressed by development of spray processes, such as
high-power plasma spraying and high velocity oxygen-fuel
(HVOF) spraying, (Ref. 2, 3) as well as by development of
feedstock (Ref. 2) including customization for the equipments.
Durable spray coatings in molten metals are one of the
important applications practically. (Ref. 4)
57
Name
Powder
Combustion
conditions
1
1s
2
2s
3
4
4s
5
6
6s
7
8
8s
9
10
11
11s
12
13
14
14s
(a)
Experimental
MoB/CoCr Powders
Three sized MoB/CoCr powders were produced by Fujimi
Incorporated as summarized in Table 1. Since HVOF coatings by
DTS-B49-45/15 (A) used in previous work (Ref. 1) were
sometimes damaged in our internal research, finer particles (B,
DTS-B46-38/10 and C, DTS-B47-30/5) were prepared to attempt
for making denser coatings.
Table 1: MoB/CoCr powders in the study
A
B
C
DTS-B49-45/15
DTS-B46-38/10
DTS-B47-30/5
Particle size
distribution (m)
-45+15
-38+10
-30+5
Clog &
spit
380
No
340
300
(c)
(b)
Slight
No
380
340
300
6
(c)
Slight
380
340
380
No
340
(d)
300
2200
2100
2000
Ch
am
be
rp
res
su
re
1900
(a) 1900, 5.1
0p
si
1800
10
0
1700
1600
1500
1400
4.5
ps
i
Product name
SD
[mm]
(c)
80
s to
ich
io
m
et
ri
Name
Barrel
length
[inches]
8
ps
i
5.0
5.5
90
6.0
ps
i
6.5
7.0
7.5
58
300 mm
50 mm
Hole: 12 mm
No rust was observed from all sealed specimens of Nos. 1s, 2s,
4s, 6s, 8s, 11s and 14s. This shows sealing is quite effective to
avoid penetration of salt water at least. However, it is unclear
this is also effective to avoid molten Zn penetration under high
temperature of around 450 C. Regardless of the effect of
sealing, it can be said that denser coating is critical for
MoB/CoCr coating to perform its intrinsic properties because
porous MoB/CoCr coating with sealant has short lifetime
under molten Zn immersion test in our previous study.
Microstructure and Hardness
Cross sectional images of typical specimens are shown in Fig.
5. Their Vickers hardness is also inserted in the figure. Both
coatings of modified No. 5 and No. 14 are quite denser with
small size pores than the No. 1 that is consistent with the salt
spray test. Dense coatings also have higher hardness of more
than 1000HV, whereas 840HV for porous coating.
59
Powder A (B49)
300
Powder B (B46)
Powder C (B47)
250
Lifetime
Life time[hrs]
[hrs]
200
150
100
50
Name
SD
Combustion
Barrel
380
a
340
c
300
380
c
340
b
300
10
11
12
380
340
380
c
340
13
14
300
d
4
Figure 4: Result of the salt spray test. Lifetime has been defined by visual observation of rust from the low carbon steel substrate.
(a) No. 1, powder A, 840HV
bottom
bottom
center
200 m
top
30 days
60 days
90 days
60 days
90 days
Analyzed by SEM/EDX
60
Fe
No. 14
60 days
Good
Good
90 days
Good
Locally NG
Mo
Mod. No. 5
90 days
Good
Good
Magnification of Zn
Zn diffusion or
adhesion
Diffused Zn
background
Zn
Mo
Magnification of Zn
Zn diffusion
Zn
Fig. 8: SEM/EDX analysis of cross section at (a) center of No.
14 after 60 days and (b) center of modified No. 5 after 90 days.
61
References
1.
Cracks
Al
Fe
Co
Zn
Cr
Mo
62
Abstract
Spray process
1940
Spray powder
1960
APS
1980
HVOF
HVAF
CS
2000
WS
Optimizing the
powder production,
powder size,
WC size,
and etc
for thermal spray
Introduction
Thermal sprayed tungsten carbide (WC) cermet coatings are
widely applied to facilities and machines to achieve the long
time maintenance-free operation because of high wear
resistance. Its trend has been accelerated by invention of high
velocity oxygen fuel (HVOF) spraying on 1980s (Ref 1),
which can produce dense coatings with high bond strength as
well as low degradation of WC cermet materials compared
with plasma spraying. However, degradation of WC cermet,
such as oxidation, decarburization and dissolution of WC to
metal binder, still occurs using HVOF that is quite different
from and inferior to sintered hard metal, which can be defined
as an ideal material. Therefore, low temperature processes,
such as cold spray, warm spray and high velocity air fuel
(HVAF) are actively researched to achieve WC cermet
coatings, similar to sintered one, where denser and harder
coatings have been prepared better than HVOF (Ref 2-6).
63
Particle size
distribution
Benchmark
2.0m
High speed
Fine WC
Fine CoCr
WC size
WC-10mass%Co
-4mass%Cr
-30+5m
Particle
porosity
Spray condition
A
2.5m
0.2m
12%
1.0m
2.0m
Porous particle
Fine particle
CoCr size
-15+3m
2.5m
26%
15%
Experimental
Spray condition
HVAF Coatings
HVAF coating specimens are summarized in Table 1. Benchmark
coating was fabricated by using WC-10mass%Co-4mass%Cr
powder with spray condition A which is listed in Table 2. WC size
and nominal particle size distribution were 2m and -30+5m,
respectively. The coating named high speed was fabricated by
using same powder in benchmark with spray condition B which is
predicted to be higher gas speed condition compared with spray
condition A. Figure 2 shows the SEM images of the powder used
in this study. The coatings named Fine WC, Fine CoCr,
Porous particle and Fine particle were fabricated by using
powder in Table 1 and Figure 2 with spray condition A.
Chamber type
52mm (#2)
74mm (#3P)
Nozzle type
Coating Evaluations
Coating structure was investigated using SEM. Porosity was
measured by image analysis with optical micrographs of cross
section of coatings. Micro Vickers hardness at cross section of
coatings were measured under the load conditions of 1.96 N
(200 gf) and 10 s. Abrasive wear properties were studied using
Suga-abrasion tester (ASTM D6037) where abrasive paper of
SiC F180 as a counter material was selected under the load of
30.9 N (3.15 kgf). Volume loss of carbon steel (JIS SS400)
was set to reference to estimate volume wear ratio. X-ray
diffraction (XRD) was conducted for the powders and asfabricated coatings with the Cu K radiation.
Propane ( C3H8 )
Air pressure
0.59MPa
0.62MPa
0.45MPa
0.51MPa
1000mm/s
Spray distance
200mm
Substrate
Preheat substrate
temperature
140
Benchmark
Fine WC
Fine CoCr
Porous particle
Fine particle
64
HVOF
Benchmark
Fine WC
Fine CoCr
High speed
Porous particle
Fine particle
2.0%
HVOF
Porosity
1.5%
1.0%
0.5%
0.0%
Benchmark
High speed
Fine WC
Fine CoCr
Porous particle
Fine particle
0.09
0.08
0.07
0.06
0.05
0.04
0.03
0.02
HVOF
0.01
0.00
Benchmark
High speed
Fine WC
Fine CoCr
Porous particle
Fine particle
65
1600
WC
W2C
Co
1400
1200
HVOF
1000
Fine particle
800
Porous particle
Fine CoCr
600
Fine WC
400
High speed
Benchmark
200
WC-CoCr powder
(Benchmark)
Benchmark
High speed
Fine WC
Fine CoCr
20
Porous particle
Fine particle
30
40
50
Diffraction angle, 2(Cu K)
60
70
References
1. Browning, J.A., U.S. patent 4416421, 1983
2. Chivavibul P., et al., Development of WC-Co Coatings
Deposited by Warm Spray Process, Journal of Thermal
Spray Technology, Vol.17, No.5, (2008), pp.750/56
3. Lima, R.S. et al., Microstructural Characteristics of ColdSprayed Nanostructured WCCo Coatings, Thin Solid
Films, Vol.416, Issues 1-2, (2002), pp. 129/35
4. Kim, H-J., et al., Fabrication of WCCo Coatings by Cold
Spray Deposition, Surf. Coat. Technol., Vol. 191 (2005),
pp.335/340
5. Kim, H-J., et al., Superhard Nano WC12%Co Coating by
Cold Spray Deposition, Mater. Sci. Eng., Vol. A391
(2005), pp.243/248
6. Li, C-J., et al., Characterization of Nanostructured WC-Co
Deposited by Cold Spraying, J. Thermal Spray Technol.,
16 (2007), Issue 5-6, pp. 1011/1020
7. A. Verstak., et al., Activated Combustion HVAF Coatings
for Protection Against Wear and High Temperature
Corrosion, Thermal Spray 2003, pp. 559/565
8. A. Verstak., et al., Deposition of Carbides by Activated
Combustion HVAF Spraying, Thermal Solution: Advances
in Technology and Application, DVS-German Welding
Society (2004), pp. 551/555
9. K. Sakaki., et al., Improvement of Mechanical Properties
of WC-Cermet Coatings Prepared by High Velocity Air
Fuel Spraying, CD-R of proceedings of the JSME/ASME
2011 International Conference on Materials and
Processing (2011).
10. J.Kitamura., et al., Mechanical Properties of WC/Co
Coatings Prepared by Cold Spraying, CD-R of Proc. of
International Thermal Spray Conference (2008),
pp.1246/1250
11. C. Verdon., et al., A Study of High Velocity Oxy-Fuel
Thermally Sprayed Tungsten Carbide Based Coatings, Part
66
67
Abstract
Frictionally engaged joints are widely used in mechanical
engineering and require a high static friction. Thermally
sprayed hardmetal coatings have a high potential to fulfil this
requirement. However, almost all research activities are
traditionally focused on the decrease of the dynamic
coefficient of friction. In this paper the static coefficient of
friction of as-sprayed Cr3C2-NiCr coatings in torsion
experiments with different contact pressures was studied. The
form, orientation and the geometric characteristics of the
friction surface have been investigated. The slipping curves
have been determined and a static coefficient of friction max
up to 0.80 was measured. The results show a standard
deviation depending on the nominal contact pressure.
Introduction
Hardmetal coatings sprayed by high velocity oxy-fuel (HVOF)
spraying are intensively studied for wear applications, in
particular for lubricated and dry sliding applications, where
usually a low coefficient of friction is required (Ref 1-3).
However, these coatings have also a high potential for static
friction applications requiring an opposite property profile
an increase of friction to a maximum value (Ref 4). It is
supposed that for these applications an excellent bonding to
the substrate, as typical for HVOF-sprayed coatings, and a
high coating roughness is required. Coating roughness is
depending on the carbide grain size. However, current
feedstock materials for HVOF processes are optimized to
small carbide grain sizes. Thus, such a development is
challenging.
Thermally sprayed WC-based hardmetal coatings are reported
to be used as friction pads in large joint flanges (Ref 4). A
calculated static coefficient of friction is given with 0.65. In
the current development, the general focus is to further
increase of the static coefficient of friction and decrease of its
68
Geometric Characterization
The interaction of two surfaces in a tribological system
requires a holistic approach that includes the characterization
of all geometrical properties such as form, waviness and
roughness with a 3D evaluation method. The friction surface
of the specimen has been extracted holistically to derive
parameters for the complete friction surface in the same
reference system. The form, waviness and roughness are
extracted by a precision form measuring instrument Mahr
MFU 100 with a roughness stylus (Fig. 2a).
hydraulic normal
force actuator
force transducer
stamp
a)
b)
flexible coupling
hydraulic torque
actuator
a)
2 TR
.......................................................(1)
FN Dm
2 d 3 di3
.......................................................... (2)
Dm a2
3 d a di2
b)
69
a)
b)
Figure 6: Principle of the evaluation for a static torsion load
and determination of the slipping moment (slipping curve).
m
110
100
90
80
70
60
50
40
30
20
10
0
From the data recorded and the resulting twisting angle torsion
moment diagrams (so called "slipping curves"), the slipping
torque TR can be derived as shown in Fig. 6. Most notably,
elastic deformation of the test bench (linear increase) and
partial micro movements in the joint (alignment of surface
asperities) were recorded during global adhesion of the joint.
Since it might be difficult to distinguish between the sticking
and slipping range, the evaluation method according to (Ref 8)
was applied. This method specifies the static friction
coefficient according to a specific twisting angle. The
maximum coefficient of friction value can be calculated from
the known friction area geometry and preload force, using eq.
(1).
a)
b)
70
27.90 m
Anzahl vonNumber
Inseln
of islands
1262
1138m
VolumederofInseln
material (m/m) 0.9554
Durchschnittshhe
1262
1138 m
Mean surface
of islands
Durchschnittsvolumen
der Inseln
6849 m
4.238 m
b)
Durchschnittliches
Verhltnis Hhe
/ Flche
m/m
Figure
9: Geometrical
parameters
of the coating0.003726
surface
c)
71
pressure
nominal
[MPa]
B 04 06
B 04 05
30
slipping
torque TR0.1
[Nm]
friction
coefficient
0.1
friction
coefficient
max
29.6
93
0.51
0.65
30.0
100
0.54
0.64
axial load FN
[kN]
contact
pressure P
[MPa]
15.7
15.9
B 04 01
15.9
30.0
124
0.67
0.71
B 04 15
53.0
100.0
351
0.57
0.70
52.9
99.8
439
0.71
0.77
B 04 11
53.0
100.0
389
0.63
0.74
B 04 03
158.8
299.5
1270
0.69
0.79
159.2
300.3
1280
0.69
0.80
159.2
300.3
1214
0.65
0.79
B 04 09
B 04 08
B 04 12
100
300
Figure 13: SEM micrographs of the coating surface in the assprayed state (a) and after the friction experimen: (b) at 30
MPa, (c) 100 MPa and (d) 300 MPa nominal contact
pressure.
200 m
Conclusion
Measurements of the static coefficient of friction of as-sprayed
Cr3C2-NiCr coatings has shown their high potential for use in
frictionally engaged joints. The coatings were deposited on the
72