j ournal of materi als processi ng technology 2 0 4 ( 2 0 0 8 ) 111116

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Spark plasma sintering cobalt base superalloy strengthened
by YCrO compound through high-energy milling
C.F. Tang
a,
, F. Pan
a
, X.H. Qu
b
, C.C. Jia
b
, B.H. Duan
b
, X.B. He
b
a
Laboratory of Advanced Materials, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084, PR China
b
School of Materials Science and Engineering, State Key Laboratory for Advanced Metals and Materials, University of Science and
Technology Beijing, Beijing 100083, PR China
a r t i c l e i n f o
Article history:
Received 2 April 2007
Received in revised form
17 July 2007
Accepted 28 October 2007
Keywords:
Cobalt base superalloy
High-energy milling
Spark plasma sintering
Annealing
a b s t r a c t
Powder cobalt base superalloy prepared by high-energy balling and spark plasma sintering
are studied through metallography and compression test. The experimental results shows
that the powder size andcrystalline graindecrease anddistortions of crystal lattice increases
with milling time. These trends slow down after milling for 8h. Addition of 1.5% methanol
can lessen powders adherence and agglomeration. The relative density of the sintered com-
pact is 99.2% by spark plasma sintering at 1100

C and 40MPa. Its microstructure is ne

with average grain size below 5m. Its compression strength and elongation are 2506MPa
and 2.5%. Annealing heat treatment at 1300

C can improve its elongation but decrease its

strength. They are 23.0% and 1982MPa, respectively. The added nano-particles Y
2
O
3
are
changed into YCrO compounds to strengthen the cobalt base superalloy.
2007 Elsevier B.V. All rights reserved.
1. Introduction
Cobalt base superalloys have good hot-corrosion resis-
tance, antioxidation, fatigue properties and high-temperature
strength (Sung et al., 2004). They are widely used in manufac-
turing nozzle guide vanes and turbine blades and combustor
lines in gas turbine engines (Klarstrom, 1993; Kuzucu et
al., 1998). Cobalt base superalloys are usually strengthened
by carbides (such as M
6
C and M
23
C
6
) and solid-solution
atoms (such as W, Mo and Ta) (Crook, 1993). However, the
effect of solid-solution strengthening will be weak obvi-
ously when temperature is above 1000

C. At the same time,

carbides will dissolve and grow up. Therefore the creep
property and strength of cobalt base superalloys decrease
greatly at high temperature. Former research has indicated
that the dispersoids such as yttria can exist stably above
1100

C and hinder effectively the movements of dislocations

Corresponding author. Tel.: +86 10 62334311; fax: +86 10 62334311.

E-mail address: cftang@sohu.com (C.F. Tang).
(Czyrska-Filemonowicz and Dubiel, 1997). Oxide-dispersion
strengthened (ODS) nickel base superalloys (such as MA758
and MA6000) are strengthened by disperse yttria and widely
used in the aerospace engines. Comparing with nickel base
superalloys, cobalt base superalloys have higher melting tem-
perature and better weldability and hot-corrosion resistance
(Akane et al., 2007). It is necessary to develop ODS cobalt base
superalloys used at high temperature. Mincher investigated
the cobalt base superalloys strengthened by ThO
2
through
co-precipitationprocess. But mostly they were not usedindus-
trially due to toxicity of ThO
2
(Mincher, 1996).
Mechanical alloying is the main method of producing ODS
superalloys. The powders prepared by mechanical alloying are
very hard because of work-hardening during milling process.
These hard powders can be fully consolidated only by joint
operation of pressure and high temperature (such as hot iso-
static pressing and hot extrusion) (Liu et al., 2001; Bhadeshia,
0924-0136/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmatprotec.2007.10.084
112 j ournal of materi als processi ng technology 2 0 4 ( 2 0 0 8 ) 111116
Table 1 Nominal composition of the experimental
superalloy (wt.%)
Element Content
Cr 20
Ni 20
W 10
Y
2
O
3
2
Co Balance
1997). Spark plasma sintering is one rapid sintering technique,
which carries out pressing and heating simultaneously. The
materials prepared by spark plasma sintering have very high
relative density and good performance. It is now widely used
to prepare advanced alloys, ceramics, composites and func-
tional materials (Munir et al., 2006; Yoritoshi et al., 2005). There
are few literatures about ODS cobalt base superalloys. So the
presentation investigates the process to prepare ODS cobalt
base alloy by mechanical alloying and spark plasma sintering.
2. Experimental procedure
The nominal composition of the alloy is shown in Table 1. The
sizes of element powders are below 37m. The size of yttria
powder is below100nm. Their purities are over 99%. The vibra-
tion frequency of the SPEX-8000 attritor is 1000Hz. The ration
of ball to powder is 15:1. The selected process control agent
(PCA) is methanol, which addition amount is 1.5% of the pow-
ders mixture. Filling and sampling are conducted in the glove
box lled with pure Ar. SPS1050 furnace is used. The sintering
temperatures are 1000, 1050, 1100 and 1150

C. Holding time
is 10min. The compaction pressure is 40MPa. The vacuum
of the furnace is below 10Pa. Heat treatment is performed in
the ZGS150 high-vacuumfurnace at 1300

C for 120min. Com-

pression tests at the room temperature is carried out in the
CMT4305 electronic tester. Compression tests at 850

C is car-
ried at the Gleeble-1500 hot simulationmachine. Compression
samples are 8mm12mm gauge cylinders. Density mea-
surement method is drain-off-water according to Archimedes
principle.
Philips Y-2000 diffraction instrument is used to determine
milled powder characteristics. Standard metallographic tech-
niques are used to prepare samples for observation in the
SUPRA55 eld emission scanning electron microscopy. The
etchant is a solution of 100ml ethanol and 10ml HCl 5g CuCl
2
.
The disc about 3mm in diameter and 0.4mm in thickness is
cut from the sintered compact by electrodischarge machine.
The disc is ground to a thickness below 0.05mm and then
thinned to proper thickness for TEM observation using ion-
thinning means. AJEOL2000FXTEMoperating at 160kVis used
for electron microscopy studies.
3. Results and discussions
Fig. 1 shows the XRD patterns of the powders milled for dif-
ferent time. There are not clear diffraction peaks of yttria
powders because of its very small additions. The diffraction
intensities decrease and diffraction angles move toward left
with milling time, which indicates the continuing decrease of
Fig. 1 XRD pattern of the powders prepared by MA for 0, 8,
15 and 20h.
powder grain sizes. The width of diffraction peaks increase
with milling time because of the increasing of the grain dis-
tortions. These trends slow down with continuing milling and
become stable after milled for 15h. Mechanical alloying is
the interaction of fracture and cold-welding. The powders
are hardened and fractured by ball impaction. So their sizes
decrease. On the other side, the fresh surfaces of fractured
powders have high-surface energy so that they are inclined to
weld each other. Therefore powder sizes increase. The pow-
ders have coarse size and low-surface energy at the initial
stage of high-energy milling, so fracturing action dominates.
The powders become ne with increasing milling time. Con-
tinuing milling increases powders energy. So cold-welding
action is enhanced. When fracturing and welding reaches
dynamic balance, the powder sizes change no more. Fig. 2
shows the calculated grain size and crystal lattice distortion
of elements Co and Cr with XRD data by Scherer formula and
William-Hall formula (Suryanarayana, 2001). The process of
size lessening and crystal lattice distortion is mainly com-
pleted at the rst stage. Crystal lattice distortion of Co is more
Fig. 2 Curves of Co, Cr crystalline distortion and
crystalline distortion varying with milling time.
j ournal of materi als processi ng technology 2 0 4 ( 2 0 0 8 ) 111116 113
Fig. 3 Morphologies of powders milling for (a) 0h, (b) 8h, (c) 15h and (d) 20h.
than that of Cr. Elements such as Ni and W are dissolved into
Co to exacerbate crystal lattice distortion.
The milling process can be explained by the SEM photos
of the milled powders. Fig. 3 shows the morphologies of the
powders milled for different time. The raw powder sizes are
not even(see Fig. 3a). After milling for 8h, the powders become
ner. But there are still some powders withrelatively large size
(see Fig. 3b). When milled for 15h, the powder size decreases
a little. But the uniformity of powder size is improved (see
Fig. 3c). However, the powder size showed almost no change
when milling time was over 15h (see Fig. 3d). Process control
agent (PCA) can inuence milling process. Fig. 4 shows the
effect of 1.5wt.% ethanol as PCA. Ethanol not only weakens
powders adherence to jars but also lowers cold-welding and
agglomeration of powders. Powders are ner and evener than
those without ethanol. This may be that ethanol can lower
powders surface energy.
During spark plasma sintering, powders are activated by
clearing away of absorbed gas and surface inclusions (such as
oxide lm). Simultaneously with the aid of force, sintering can
be completed in a few minutes. Fig. 5 plots the curves of sin-
tering temperature and punch displacement when sintered
at 1100

C and 40MPa. Densication can be demonstrated by

the displacement of furnace punch (Song et al., 2005). The
densication of the powder compact is almost completed
during heating. During later holding, the relative density of
sintered compact almost changes no more. Fig. 6 shows the
relative density of the sintered compact at different tem-
peratures. Relative density increases with the increase of
sintering temperature. It reaches 99.2% at 1100

C. However,
Fig. 4 Morphology of powders after milling for 5h (a) without ethanol, (b) with 1.5wt.% ethanol.
114 j ournal of materi als processi ng technology 2 0 4 ( 2 0 0 8 ) 111116
Fig. 5 Temperature and displacement varying with time
sintered at 1100

C.
Fig. 6 Curves of relative density varying with sintering
temperature.
there occur some molten droplets at the rim of graphite die
when sintered at 1150

C. These droplets are mainly cobalt, so

relative density decreases some. During spark plasma sinter-
ing, discharge at particle contacts heat powder surfaces tovery
Fig. 8 TEM photo of the superalloy sintered at 1100

C.
high-temperature quickly. Sometimes local melting and atom
evaporation exist at the contacts. So atoms diffuse rapidly.
Therefore most pores are nearly spherical (see Fig. 7a). Sin-
tered compact has ne microstructure (see Fig. 7b). There are
many grains less than 1m and its average grain size was
below 5m. Fig. 8 is the TEM photo of the sintered compact
at 1100

C. The spherical particles below 100nm disperse in

the matrix. Energy analysis shows that they are YCrO com-
pound (see Fig. 9). These dispersoids can greatly strengthen
the cobalt base superalloy.
Fig. 10 shows the compression behaviors of the sintered
compact. After annealed at 1300

C for 2h, its compression

ductility increases from 2.3% to 23.0%. But its compression
strength decreases from 2506 to1982MPa, which is still higher
than that of the cobalt base superalloy L-605. The change of
the room mechanical properties is not for grain size growth.
For the oxides impediment to boundary movements, the
Fig. 7 (a and b) Porosity morphology and microstructure of the superalloy sintered at 1100

C.
j ournal of materi als processi ng technology 2 0 4 ( 2 0 0 8 ) 111116 115
Table 2 X-ray diffraction data of the sintered sample after annealing treatment at 1300

C for 2h
Condition 2 d
1 2 3 4 5 1 2 3 4 5
Sintered 43.860 51.080 75.238 91.440 96.781 2.0625 1.7866 1.2619 1.0759 1.0302
Annealed 43.879 51.088 75.340 91.600 97.020 2.0616 1.7854 1.2604 1.0744 1.0283
Fig. 9 Energy analysis result of compound.
average grain size of the annealed sample shows almost no
change (see Fig. 11). But many grains less than 1m grow
up over 3m during annealing at 1300

C. So the ductility
and strength of the annealed sample should decrease a little
after annealing. In fact, its strength decreases, but its ductil-
ity increases. It may be explained by residual internal stress
produced by lattice distortion during milling. Powders experi-
ence violent deformationand atoms depart fromtheir balance
positions during high-energy milling. Subsequently quick sin-
tering cannot eliminate the crystal lattice distortion of the
powders completely. So sintered compact has high strength
Fig. 10 Compression curves of the alloys: (A) experimental
ODS cobalt base superalloy without annealing heat
treatment, (B) experimental ODS cobalt base alloy after
annealing heat treatment at 1300

C for 2h and (C) the

superalloy L-605 after deformation and aging treatment.
Fig. 11 Microstructure of the experimental superalloy
annealed at 1300

C for 2h.
and low ductility. During high-temperature annealing, atoms
have enough time and energy to diffuse to the balance posi-
tions. Internal stress induced by remnant strain disappears.
Therefore the dislocation movements become easy. It can be
veried by movements of diffraction peaks towards left and
decrement of crystal plane distance (see Table 2). Therefore,
the annealed compact has higher compression ductility but
lower compression strength.
4. Conclusion
Powder cobalt base superalloy strengthened by YCrO com-
pound can be prepared by high-energy milling and spark
plasma sintering. The superalloy with relative density over
99% has ne microstructure. Decreasing of powders size and
increasing of crystal distortion are mainly completed at the
rst stage during milling. Addition of ethanol as process con-
trol agent can lessen powders adherence and agglomeration.
Annealing treatment can greatly improve the ductility of the
sintered compact. Roomcompression strength of the superal-
loy preparedby the process is better thanthat of the superalloy
L-605.
Acknowledgement
The study was nancially supported by Major State Basic
Research Development Program of China (973 Program), No.
2006CB605207.
116 j ournal of materi als processi ng technology 2 0 4 ( 2 0 0 8 ) 111116
r e f e r e nce s
Akane, S., Garret, C.D., Tresa, M.P., 2007. Flow stress anomalies in
/

two-phase CoAlW-base alloys. Scripta Mater. 56,

385388.
Bhadeshia, H.K., 1997. Recrystallisation of practical mechanically
alloyed iron-base and nickel-base superalloys. Mater. Sci. Eng.
A 223, 6477.
Crook, P., 1993. Properties and Selection: Non-ferrous Alloys and
Special-Purpose Materials, vol. 2., 10th ed. Metals Handbook,
ASM Int., USA, p. 446.
Czyrska-Filemonowicz, A., Dubiel, B., 1997. Mechanically
alloyed, ferritic oxide dispersion strengthened alloys:
structure and properties. J. Mater. Process. Technol. 64,
5364.
Klarstrom, D.L., 1993. Wrought cobalt-base superalloy. J. Mater.
Eng. Perform. 2, 523530.
Kuzucu, V., Ceylan, M., Celik, H., et al., 1998. Phase investigation
of a cobalt base alloy containing Cr, Ni, W and C. J. Mater.
Process. Technol. 74, 137141.
Liu, G.Z., Tian, Y., Shan, B.-Q., 2001. Superalloys strengthened by
dispersed oxides. Powder Metall. Technol. 19, 2023.
Mincher, A.L., 1996. Dispersion-strengthened cobalt alloys. Cobalt
32, 119123.
Munir, Z.A., Anselmi-Tamburini, U., Ohyanagi, M., 2006. The
effect of electric eld and pressure on the synthesis and
consolidication of materials: a review of the spark plasma
sintering method. J. Mater. Sci. 41, 763777.
Song, X.-Y., Liu, X.-M., Zhang, J.-X., 2005. Mechanism of
conductive powder microstructure evolution in the process of
sps. Sci. China Ser. E 35, 459469.
Sung, J.-K., Hong, G.-S., Kim, W.-Y., et al., 2004. Mechanical
property of single phase CoNiCrMo based superalloy
produced by cold working and recrystallization heat
treatment. Mater. Sci. Forum 449452, 573576.
Suryanarayana, C., 2001. Mechanical alloying and milling. Prog.
Mater. Sci. 46, 1184.
Yoritoshi, M., Yuichiro, K., Nobuhiro, T., et al., 2005.
Microstructures and mechanical properties of bulk
nanocrystalline FeAlC alloys made by mechanically alloying
with subsequent spark plasma sintering. Sci. Technol. Adv.
Mater. 5, 133143.