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Keywords
1. Introduction
Thermal sprayed coatings are not commonly used in
the field of massive forming owing to the high demands
concerning the cohesion and adhesion of tool coatings.
These requirements concerning the cohesion and adhesion
arise because of the adhesive wear induced by sticking of
the flowing material at elevated operating temperatures
and high relative velocities between the work piece and
tooling resulting in high tensile and shear stresses. In the
field of hot extrusion for example, alumina and zirconia
coatings have been deposited on extrusion tools by conventional thermal spray and exhibit a tendency to
delaminate (Ref 1).
This article is an invited paper selected from presentations at the
2011 International Thermal Spray Conference and has been
expanded from the original presentation. It is simultaneously
published in Thermal Spray 2011: Proceedings of the
International Thermal Spray Conference, Hamburg, Germany,
September 27-29, 2011, Basil R. Marple, Arvind Agarwal,
Margaret M. Hyland, Yuk-Chiu Lau, Chang-Jiu Li, Rogerio S.
Lima, and Andre McDonald, Ed., ASM International, Materials
Park, OH, 2011.
M. Erne, D. Kolar, C. Hubsch, M. Mohwald, and Fr.-W. Bach,
Institute of Materials Science, Leibniz University of Hanover, An
der Universitaet 2, 30823 Garbsen, Germany. Contact e-mail:
erne@iw.uni-hannover.de.
Peer-Reviewed
Peer-Reviewed
2. Crystallographic Aspects
Different non-stoichiometric phases are known in the
titanium-oxygen system, which exhibit the ability to be
deformed under mechanical stress due to the shearing of
crystal lattice planes. These phases show a reduction of the
frictional coefficient in dry sliding conditions at elevated
temperatures of several 100 C. The beneficial effect was
linked to the shearing processes being temperature
induced (Ref 3); the fundamental mechanisms of the
shearing processes are discussed elsewhere (Ref 4). As the
phases are not expected to be thermodynamically stable
(for a discussion of redistribution effects of titanium and
oxygen, see Ref 5), another approach was envisaged for
the present work: namely, by adding a second cation
besides Ti4+, phases can be obtained that are homologues
of the non-stoichiometric titanium oxides. These so-called
Andersson-phases were first described for the system
Ti-Cr-O (Ref 6) showing a composition of Tin 2Cr2O2n 1.
As chromium exhibits a high vapor pressure with rising
temperature and may therefore tend to evaporate out of
the lattice, the homovalent substitution of the Ti4+-cation
in the rutile base lattice was targeted. Besides Cr3+-cation,
according to the rules stated by V. M. Goldschmidt (Ref 7),
Ni3+, Co3+ and Zr4+ also appear suitable for the substitution process when considering the ionic radii and coordination given in Ref 8. The goal is, on the one hand, to
obtain phases with a similar composition compared to the
Andersson-type phases and, on the other, sufficient stability in temperature ranges up to 800 C which are
3. Experimental
3.1 Formulation and Handling of Suspensions
The spraying experiments were performed using the
Triplex-II gun (Sulzer Metco AG, Wohlen/Switzerland).
In the case of the Triplex-II gun, the control parameters
(see Table 1) were held constant during the experiments
Amperage
500 A
Plasma
gas/secondary
gas flow
40 NLPM Ar/10
NLPM He
Spraying
distance
Injection relative
angle and place
Suspension
mass flow
110 mm
against plasma
exiting at gun nozzle
60 g/min equal to
6 g/min feedstock
Injection pressures
0.1 MPa feeding gas and
0.1 MPa atomizing
gas pressure
Gun traverse
speed
1.0 m/s
Peer-Reviewed
Peer-Reviewed
Ti-oxides
Ni, Co-oxides, Cr
Ti-(Ni,Co,Cr)-oxides
Borates
Traces
55
39
13
7
0
10
26
29
75
10
33
0
2% Ni
2% Cr2O3
Alloy
AlCu4PbMgMn (3.1645)
AlZn5.6MgCu (3.4365)
CuZn39Pb3 (2.0401)
CuSn12 (2.1052)
CuCr1Zr (2.1293)
Billlet
temperature,
C (Ref 1, 2)
Container
temperature,
C (Ref 1, 2)
350-420
420-430
650-750
600-650
930-980
360
400
4. Results
4.1 Coatings Microstructure
In Fig. 4, the microstructures of one titania-chromia
(left sectional image a) and a titania-cobalt oxide coating
(right sectional image b) are shown. The cross-sectional
views were taken using a confocal scanning laser microscope. The coatings are approximately 100 lm thick and
Peer-Reviewed
Fig. 4 Microstructures of a titania-chromia (left sectional image a) and a titania-cobalt oxide coating (right sectional image b)
Peer-Reviewed
Fig. 6 Top views of the resulting scar tracks and the corresponding friction surfaces of the counterparts from RT (top) to
800 C (bottom)
example, the COF of 3.1645 at temperatures of approximately 400 C is the highest of all pairings, demonstrating
intense stick-slip; in the case of the TBC, the coefficient of
friction is considerably lower with values of 0.4 or less. For
the high tendency towards adhesion of the aluminum
based alloy compared to the rutile coating, two mechanisms can be considered. As stated in Ref 16, temperature
induced reactions of the counterpart material with the
oxide ceramic can lead to a change of the wetting behavior
of the oxide ceramic by metal melts. Besides estimating
that this effect should be negligible in temperature ranges
below the alloys melting range, the absolute value of
titanias Gibbs free energy is significantly higher in comparison to that of alumina or copper oxide under standard
conditions, and reactions between the alloys and the titania coating probably do not occur. However, remembering
that the rutile lattice tends to release oxygen from its
surface at elevated temperatures which results in the formation of non-stoichiometric oxides (Ref 3), the adhesion
is possibly the result of an interaction of the alloying base
metal with titanium cations on the surface of the coating.
The good intermiscibility of titanium with both aluminum
and copper would then result in a high tendency towards
adhesion effects making rutile coatings unsuitable for the
targeted operation.
After these preliminary tests, three SPS sprayed Andersson type coating systems were tested against the alloys
2.1052, 3.1645, and 3.4365 (see Fig. 9). In the case of the
aluminum based alloys, the COF is higher when running
the specimens at high temperature but a significantly different behavior exists. In the case of the Cu4PbMgMn
Fig. 10 Laser optical image micrograph of debris from the copper alloy 2.1052 on an Andersson type coating
Peer-Reviewed
Peer-Reviewed
5. Conclusion
Using x-ray diffraction analyses it was possible to prove
that mixing of titania and other oxide ceramic feedstock
could be realized in the SPS process. The obtained
Andersson type coating systems sprayed with suspensions
containing titania and chromia showed a different
behavior during tribological testing on aluminum and
copper based extrudable alloys. Significantly different
results were measured regarding the pairing of the different alloys with the coatings. Further experiments will
be conducted to better understand both the parameters
controlling the feedstocks mixing process in the suspension plasma spraying process on one hand and the influence of temperature induced material separation and
adhesion effects.
Acknowledgments
The work carried out for this contribution was funded
by the German Research Foundation (DFG) within the
scope of the priority program 1299 Adaptive Surfaces for
High Temperature ApplicationsThe Skin Concept
(reference number SPP 1299 BA 851/94-1). This support is
gratefully acknowledged by the authors.
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