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Wear Resistance and High-Temperature Compression

Strength of Fcc CuCoNiCrAl0.5Fe Alloy with Boron Addition
CHIN-YOU HSU, JIEN-WEI YEH, SWE-KAI CHEN, and TAO-TSUNG SHUN

This study discusses the wear resistance and high-temperature compression strength of CuCoNiCrAl0.5Fe
alloy with various amounts of boron addition. Experiments show that within the atomic ratio of boron
addition from x
0 to x
1.0 in CuCoNiCrAl0.5FeBx (referred to as B-0 to B-1.0 alloys), the alloys
are of fcc structure with boride precipitation. The volume fraction of borides increases with increas-
ing boron addition. The corresponding hardness increases from HV 232 to HV 736. Wear resistance
and high-temperature compression strength are significantly enhanced by the formation of boride. The
alloys with boride are less tough. The superior wear resistance of B-1.0 alloy, which is even better
than SUJ2 wear-resistant steel, indicates that the CuCoNiCrAl0.5FeBx alloys have potential applications
as ambient- and high-temperature mold, tool, and structural materials.

I. INTRODUCTION
CONVENTIONALLY, alloys have been designed to
have a major element as their main component and other
minor element(s) as their modified alloying component(s),
such as in the cases of ferrous, aluminum, copper, titanium,
and magnesium alloys.
In an attempt to escape the conventional realm of alloy
designing, a new alloy system was proposed in 1996 by the
Alloy Research Group, National Tsing Hua University (Hsinchu,
Taiwan).[1] This alloy system (also called “high-entropy alloy”[1])
contains alloys with more than five components. Each chem-
ical constituent in the alloy system is higher than 5 at. pct and
less than 35 at. pct. The overarching design idea makes each
of the alloys in the system have many major components in a
single alloy in order to increase the degrees of freedom.
According to previous studies,[1–6] these multimajor com-
ponent alloys possess the following properties: (1) ease of
amorphization and nanoprecipitation in the alloy, (2) thermal
stability, (3) high hardness, and (4) superior corrosion resis-
tance. Among those previous studies, Reference 5 pointed
out that fcc CuCoNiCrAl0.5Fe is ductile, work hardenable,
and strong at high temperature up to 800 °C, indicating
that this alloy has potential applications in high-temperature
structures and working tools. Therefore, the purpose of this
study is to modify this alloy to further improve its high-
temperature properties. The effects of boron addition in this
alloy on the wear resistance and high-temperature strength
are also introduced in this study.
II. EXPERIMENTAL METHODS
Elemental Cu, Co, Ni, Cr, Al, and Fe with purity higher
than 99 wt pct were used in granular shape as raw materials.
CHIN-YOU HSU, Ph.D. Student, and JIEN-WEI YEH, Professor,
Department of Materials Science and Engineering, and SWE-KAI CHEN,
Researcher, Materials Science Center, are with the National Tsing Hua
University, Hsinchu 300, Taiwan, Republic of China. Contact e-mail:
jwyeh@mse.nthu.edu.tw TAO-TSUNG SHUN, Researcher, is with the
Materials Research Laboratories, Industrial Technology Research Institute,
Chutung 310, Taiwan, Republic of China.
Manuscript submitted August 6, 2003.
Fe-18.2 wt pct B master alloy was used for boron addition
in the alloy. An induction furnace was used to melt the alloy
in air. The compositions of the alloys are listed in Table I.
The size of the ingots was 8  7  14 (cm). Specimens
were cut to desired dimensions by electric arc line cutting.
JEOL-5410 scanning electron microscopy (SEM) with
JEOL-JXA-8800 M electron-probe microanalysis (EPMA)
were used to analyze the microstructure and compositions.
X-ray diffraction (XRD) patterns were obtained in a Rigaku
(Tokyo, Japan) ME510-FM2 diffractometer at 30 kV and
20 mA. Scanning angles (2), ranged from 20 to 100 deg
with a scanning rate of 2 deg/min. Vickers hardness was
measured using a Matsuzawa Seiki (Japan) MV-1 tester
with a load of 5 kg and a duration time of 15 seconds for
each measurement. Seven values were taken from each alloy.
The pin-on-disk abrasive wear resistance testing was per-
formed in a modified machine (Figure 1) where the tested
specimen was a pin with a size of 8 mm in diameter, and
the counterpart wear material was a belt of 100-mesh Al2O3.
Belt speed was 0.5 m/s. Total wearing distance was 20 m
with a loading of 3 kg on the pin. Wear resistance (m/mm3)
was measured by the inverse of the total volume loss (mm3)
after testing divided by the total traveling distance (20 m).
A Gleeble 2000 was used to measure the high-temperature
compression yield strength. In this test, the heating rate,
dwell time, and strain rate were 10 °C s1, 30 s, and
103 s1, respectively. For toughness measurement, U-notch
samples with a size of 10  10  55 mm were tested on a
Charpy impact tester, Tinius Olsen (Pennsylvania) model
84 pendulum impact tester.
III. RESULTS AND DISCUSSION
A. XRD Patterns for CuCoNiCrAl0.5FeBx as-Cast Alloys
Figure 2 shows the XRD patterns of CuCoNiCrAl0.5FeBx
as-cast alloys. As can be seen in Figure 2, CuCoNiCrAl0.5Fe
as-cast alloy is fcc. As boron content increases in the alloys,
peak intensities of Cr and Fe borides increase. However,
the matrix phase of CuCoNiCrAl0.5FeBx as-cast alloys is still
fcc, except that of B-1.0 alloy contains ordered fcc. In identi-
fying the fcc phase, sin2  ratios of the peaks indicated as
“F” in Figure 2 are found to be in accordance with the typical

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ratio of fcc structure. The lattice constant is 3.59 Å.On the and interdendrite. Figure 3(b) is the microstructure of
other hand, peaks for Cr and Fe borides fit well with their CuCoNiCrAl0.5FeB0.2 as-cast alloy. Stringer-shaped pre-
JCPDS cards. cipitates can be seen in Figures 3(b) through (d). It is noted
that volume fraction and size of stringer precipitates
B. SEM Microstructure of CuCoNiCrAl0.5FeBx As-Cast increase as the amount of boron in the alloy increases. In
Alloys order to verify the composition of the stringer phase,
EPMA was used and the results are shown in Figure 4.
Figure 3(a) shows the SEM microstructure of CuCoN- According to Figure 4, stringers are rich in B, Cr, and
iCrAl0.5Fe as-cast alloy, which is composed of dendrite Fe, while they are poor in Al, Co, Ni, and Cu. It is there-
fore concluded that the stringers are borides of Cr and
Table I. Alloys Used in This Experiment Fe. Table II lists enthalpies of binary borides that might
be formed by the alloy. [7] As can be seen in Table II,
Alloy
Designation Composition (Atomic Ratio) B (At. Pct)
B-0 CuCoNiCrAl0.5Fe 0
B-0.2 CuCoNiCrAl0.5FeB0.2 3.5
B-0.6 CuCoNiCrAl0.5FeB0.6 9.8
B-1.0 CuCoNiCrAl0.5FeB 15.4

Fig. 2—XRD patterns for CuCoNiCrAl0.5FeBx alloys. Note that “F” peaks
Fig. 1—Schematic diagram of the modified pin-on-disk (or pin-on-belt) at 25 and 35 deg for the CuCoNiCrAl0.5FeB alloy indicate the existence
wear resistance tester. of an ordered fcc with the same lattice constant of the fcc phase.

Fig. 3—SEM micrographs for CuCoNiCrAl0.5FeBx alloys: (a) x
0, (b) x
0.2, (c) x
0.6, and (d) x
1.0. Stringers in (b) through (d) are boride.

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Fig. 4—EPMA of the as-cast CuCoNiCrAl0.5FeB0.6 alloy: (a) SEI image, (b) BEI image, and (c) through (i) elemental mapping for B, Al, Cr, Fe, Co, Ni,
and Cu, respectively. It shows that the stringers are rich in Cr, as can be seen in (e).

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Table II. Enthalpies of Binary Borides* That Might This suggests that the hardness increases due to the increase
Be Formed in the Alloy Compositions in volume fraction of boride.
Cr2B 34 kJ/mol CrB 45 kJ/mol
Fe2B 30 kJ/mol FeB 38 kJ/mol 2. Wear resistance test
Co2B 28 kJ/mol CoB 34 kJ/mol In general, wear resistance is higher for harder materials.[8]
Ni2B 27 kJ/mol NiB 33 kJ/mol As shown in Figure 6, the wear resistance is higher for harder
alloys in this experiment. The wear resistance of B-0 and
*No boride formation for Al and Cu.
B-0.2 alloys is similar to that of 316 and 17-4 stainless steels.
B-0.6 alloy has a similar wear resistance to cobalt-based
superalloy (Stellite). The higher wear resistance of B-0.6
alloy is believed to be attributed to the larger boride pre-
chromium and iron borides have the largest negative cipitates in that the worn particles are observed to be smaller
enthalpies in the alloy systems. Thus, they are likely to than the borides. For B-1.0 alloy whose hardness is HV 736,
form in the as-cast state. the wear resistance (1.76 m/mm3) is even higher than that
of SUJ2 bearing (1.52 m/mm3) and SKD61 cold-work mold
(1.39 m/mm3) steels.[9]
C. Mechanical Properties of CuCoNiCrAl0.5FeBx Alloys
1. Hardness and toughness 3. High-temperature strength
Figure 5 shows the hardness of CuCoNiCrAl0.5FeBx alloys Figure 7 shows the dependence of compressional yield
as a function of boron content. Alloy hardness increases at stress of the alloys on tested temperatures ranging from ambi-
the expense of toughness as the boron content increases. ent temperature (25 °C) to 1100 °C. Yield stress increases
gradually from 25 °C to 300 °C for B-0.6 and B-1.0 alloys,
to 500 °C for B-0.2 alloy, and to 700 °C for B-0 alloy. This
positive temperature effect for yield stress is similar to that
existing in superalloys.[10] For boron containing alloys in this
study, the yield stress is higher for higher boron content.
Boride in this experiment must play a role in affecting the
positive temperature effect since peak-strength temperature
varies with boron content. Further study on its mechanism
is needed. The influence of boride on yield stress disap-
pears at temperatures higher than 900 °C. Above 900 °C, the
alloys have the same yield stress, as can be seen in Fig-
ure 7. The yield stress of B-1.0 alloy at 700 °C reaches
1167 MPa.
It is important to mention that the mechanical properties
of the present alloys could be controlled in a large range
by the addition of boron. This is beneficial for them to fit
with requirements of more applications. In addition, the
alloys with higher boron contents could attain the hardness
Fig. 5—Variation of hardness and toughness for CuCoNiCrAl0.5Fe alloy and strength levels of Ti-based, Zr-based, and Pd-based bulk
with boron content. amorphous alloys at room temperature[11] but do not undergo

Fig. 6—Wear resistance vs hardness curve for CuCoNiCrAl0.5Fe alloy with Fig. 7—Dependence of yield stress on temperature for CuCoNiCrAl0.5Fe
different boron contents. alloy with different boron contents.

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a glass transition at glass transition temperature, Tg, and a
crystallization at crystallization temperature, Tx, as amor-
phous alloys behave. They exhibit high strength at elevated
temperatures up to 700 °C to 800 °C because of positive
temperature effect.
IV. CONCLUSIONS
Boron addition in fcc CuCoNiCrAl0.5Fe “high-entropy”
alloy precipitates borides of Cr and Fe. The volume fraction
of boride precipitates increases as the boron content increases.
Boride precipitation significantly hardens the alloy at a large
expanse of the toughness of the alloy. The alloy possesses
good wear resistance and high compression strength at high
temperature. B-1.0 alloy has higher wear resistance than
commercial SUJ2 does. The compression yield strength for
B-1.0 alloy at 700 °C is 1167 MPa.
METALLURGICAL AND MATERIALS TRANSACTIONS A
REFERENCES
1. K.H. Huang: Master’s Thesis, National Tsing Hua University, Hsinchu,
Taiwan, June 1996.
2. K.T. Lai: Master’s Thesis, National Tsing Hua University, Hsinchu,
Taiwan, June 1998.
3. Y.H. Hsu: Master’s Thesis, National Tsing Hua University, Hsinchu,
Taiwan, June 2000.
4. Y.D. Huang: Master’s Thesis, National Tsing Hua University, Hsinchu,
Taiwan, June 2001.
5. T.J. Tung: Master’s Thesis, National Tsing Hua University, Hsinchu,
Taiwan, June 2002.
6. C.Y. Chen: Master’s Thesis, National Tsing Hua University, Hsinchu,
Taiwan, June 2002.
7. F.R. de Boer and D.G. Pettifor: Cohesion in Metals, Elsevier Science
Publishers B.V., Amsterdam, Netherlands, 1988, pp. 175-336.
8. M.M. Khruschov and M.A. Babichev: Friction and Wear in Machinery,
ASME, New York, NY, 1956, vol. 11, p. 19.
9. M.R. Chen: Master’s Thesis, National Tsing Hua University, Hsinchu,
Taiwan, June 2003.
10. C.T. Sims and W.C. Hagel: The Superalloys, John Wiley & Sons, New
York, NY, 1972, pp. 5-53.
11. A. Inoue: Acta Mater., 2000, vol. 48, pp. 279-306.
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