CHINA FOUNDRY Vol.5 No.

Analysis of precipitation in a Cu–Cr–Zr

alloy
Zhao Mei1, Lin Guobiao1, * Wang Zidong1,2, Zhang Maokui1
(1. School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China;
2. 1414, de Champigny, #4 Montreal, QC, Canada H4E1L8)

Abstract: Precipites in Cu–0.42%Cr–0.21%Zr alloy were analyzed by using scanning electron microscope
(SEM), energy dispersive X-ray spectroscopy (EDXS) and transmission electron microscope (TEM). After the
solid solution was performed at 980 ºC for 2 h, water-quenched and aged at 450 ºC for 20 h, the precipite had
a bimodal distribution of precipitate size. The coarse precipitates are pure Cr and Cu5Zr, the dispersed fine
precipitate is CrCu2(Zr,Mg) and pure Cr ranging from 1 to 50 nm. The coarse phases formed during solidification
and were left undissolved during solid solution. The fine precipitates are the hardening precipitates that form due to
decomposition of the supersaturated solid solution during aging.

Key words: Cu–Cr–Zr alloy; microstructure; precipite; energy dispersive X-ray spectroscopy
CLC number: TG 146.1+1 Document code: A Article ID: 1672-6421(2008)04-0268-04

C opper and copper alloys are widely used because of their

excellent thermal conductivity, outstanding resistance
to corrosion, ease of fabrication as well as good strength and
equilibrium at the Cu-rich corner of the phase diagram in the
ternary Cu–Cr–Zr system within the composition range up to
3.7wt.% Cr and 26wt.% Zr. They found no Cr2Zr phase in their
fatigue resistance [1]. Cu–Cr–Zr alloy has attracted considerable samples, the pseudobinary Cu–Cr2Zr system does not seem to
interest recently because of its superior combination of high exist. Thus, the Cu + Cr + Cu3Zr phase should exist. However,
electrical conductivity and high strength. It has been used different stoichiometries were suggested by various investigators
for many areas such as trolley wire, electrode for resistance for the most Cu-rich intermetallic compound in the binary
welding and lead frame materials [2-3]. Many experiments on Cu–Zr system. This causes confusing interpretations on the
the mechanical and electrical properties and microstructure microstructure observations for Cu–Cr–Zr alloys. Tang et al.[9]
have been carried out for the alloy. have identified that the precipitates in a Cu–Cr–Zr–Mg alloy
The high electrical conductivity is due to the very low are Cu4Zr and CrCu2(Zr, Mg). Zeng and Hamalainen conducted
solubility of Cr and Zr in Cu, whereas the excellent strength is theoretical and experimental investigations [10,11], showing that
attributed to precipitation and particle-dispersion strengthening three phases Cr, Cu5Zr and Cu exist in this system.
mechanisms. In order to control the microstructure, improve The above experimental investigations were however
the properties of such alloys and optimize the production performed on alloys with much higher zirconium and
techniques, identifing the composition of the phases in the chromium content. This study deals with the microstructure
Cu–Cr–Zr alloy is of great value. However, there has no and precipitation of aged Cu-0.42Cr-0.21Zr, in order to get
unanimous agreement on the precipitation of the alloy. a better understanding of the strength mechanism and the
Glazov et al.[4, 5] studied the phase equilibrium at the Cu-rich composition of the precipitates.
corner of the phase diagram in the ternary Cu–Cr–Zr system
within the composition range up to 3.5wt.% Cr and 3.5wt.% 1 Experimental procedure
Zr at temperatures between 873 K and 1,313 K. According to
A ternary alloy, Cu–Cr–Zr (Cu–0.42Cr–0.21Zr by wt.%) was
their results, at 1,213 K, the Cu phase is in equilibrium with the
prepared in a vacuum induction furnace with electrolytic copper,
Cr, Cr2Zr, Cu3Zr and liquid (L) phases, and thus Cu+Cr+Cr2Zr,
pure chromium and pure zirconium as charge materials. The
Cu+Cr2Zr+L and Cu+L+Cu3Zr three-phase triangles appear
specimens were 20 mm × 120 mm and were solution-treated
in the isothermal section. On the other hand, Kawakatsu et
at 980 ºC for 2 h, water-quenched, and then aged at 450 ºC for
al.[6], Fedorov et al.[7] and Kuznetsov et al. [8] studied the phase
20 h. The electrical resistance was determined by measuring
*Wang Zidong the resistance of a sample with 3 mm × 120 mm using the
Male, born in 1964, Ph.D, visiting scholar in Department of HEITHLEY-type standard direct-current four-probe technique.
Mathematics and Statistics, McGill University, Canada. His research The strength was measured for a sample with 5 mm standard
interests mainly focus on theory of crystal growth and nano-composite. pattern using a CMT electronic tensile testing machine.
Email: [email protected]
The specimens were ground, polished, and etched in an
Received: 2008-04-17; Accepted: 2008-07-20 aqueous solution of 10% (NH4)2S2O8. The microstructures of
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the alloy were examined using an optical microscope and a CSM 2 Results
950 scanning electron microscope (SEM) equipped with energy
dispersive X-ray spectroscopy (EDXS). Thin foils for transmission 2.1 SEM observations
electron microscope (TEM) examination were sliced from the aged The typical SEM micrography of the coarse phase in the alloy
samples and further reduced to 20-30 µm by chemical polishing after the heat treatment described above is shown in Fig. 1.
and ion beam thinning using a Gantan 600 Duo-mill. The typical EDXS qualitative analysis spectra of these phases
The microstructure of Cu-0.42Cr-0.21Zr alloy was are shown in Fig. 2. These results show the distribution of
investigated using SEM, EDXS, H-800 TEM, and JEM-2010 chromium and zirconium. The EDXS quantitative analysis
high resolution transmission electron microscope (HRTEM) results of these phases are shown in Table 1.
operating at 200 kV.

(a) Chromium-rich (particle A) and zirconium-rich (b) SEM image of particle C in (a)
(particle B) phases, Cr primary phase embedded
in Cu5Zr matrix (particle C)

Fig. 1 SEM image of the coarse phase in the alloy

(a) (b)

Fig. 2 The typical EDXS qualitative analysis spectrum of chromium-rich phase (a) and zirconium-rich phase (b)

Table 1 EDXS analysis of second phase as shown in Fig. 1 (a)

Measured composition
Analyzed sites % Cu/Zr
Cu Cr Zr
Weight 3.26 96.45 0.29
A
Atomic 2.69 97.14 0.17
Weight 79.67 0.78 19.55
B 5.9
Atomic 84.53 1.01 14.45

There are three phases in the alloy, copper matrix, so we can suppose that the chromium-rich phase is pure
chromium-rich phase and zirconium-rich phase. The typical chromium. Most of the chromium-rich phase is distributed as
EDXS qualitative analysis spectrum of the chromium-rich little globular particles in a copper matrix, such as particle A in
phase is shown in Fig. 2(a). There are copper peaks and Fig.1(a), a few distributed as coarse particles, such as particle
zirconium peaks besides the chromium peaks in the spectrum. C in Fig.1(b). The color of the chromium-rich phase is dark in
The EDXS qualitative analysis results in Table 1 show that the backscattered electron imaging (BEI) image.
the chromium content of the particle was up to 96.45 wt.%, The typical EDXS qualitative analysis spectrum of

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zirconium-rich phase is shown in Fig. 2(b). There are only analyzed by means of TEM.
copper and zirconium peaks. The zirconium content of the Figure 3(a) shows a typical TEM bright field micrograpy
particle was up to 19.55 wt.%. The Cu:Zr atomic ratio is and SADP image of an aged specimen. and Fig. 3(b) shows the
5.9:1, as shown in Table 1. Considering the contribution of dark field. Fine precipitate particles dispersed within the grains
the matrix, we supposed that the zirconium-rich phase could in the Cu matrix, having a sizes ranging from 5 – 20 nm. It
be Cu5Zr. Almost all of the zirconium-rich phase is distributed was found that the electron-diffraction evidence is consistent
as coarse particles, as particle B in Fig. 1(a). The color of the with the crystal structure of the phase belonging to the space
zirconium-rich phase is white in the BEI image. group Fm3m, which is common to the group of inter-metallic
Some chromium is the primary phase embedded in a Cu5Zr compounds known as Hesuler alloys [13]. The composition
matrix, such as particle C in Fig. 1(b). This phenomenon of the precipitate is likely to be CrCu 2(Zr, Mg) which has
agrees well with experimental examinations of the copper- a similar lattice to Fe 3Al. The Hesuler alloys have an fcc
rich corner of the ternary system Cu-Cr-Zr [12]. From the Zr- crystal structure with a large unit cell that can be thought of
rich white particles at the border of many pits and the presence as containing 8Cu, 4Cr and 4Zr or Mg atoms. This unit cell
can be thought of as containing eight bcc sub-cells with each
of Zr detected in large Cr-rich pits, we assume that white
sub-cell having a Cu atom at its center, and the corner-sites
precipitates and pits are two aspects of the same feature. If the
alternately occupied by Cr and either Zr or Mg atoms. It is the
pits, in which pure chromium was detected, once surrounded
sub-lattice that obeys the Nishyama-Wasserman orientation
by the Zr-rich phase, their composition corresponds best to
relationship with the matrix [12]:
Cu5Zr; Stamm postulated that chromium precipitates around a
(111)fcc ∥(110)bcc
core of Cu5Zr embedded in a pure copper matrix.
[0 1]fcc ∥[001]bcc
[ 11]fcc ∥[ 10]bcc
2.2 TEM observations In this orientation relationship, the closed-packed planes in
To clarify the fine precipitates, the microstructure was the two phases, viz. {111}fcc and {110}bcc are parallel.

(a) (b)

Fig.3 TEM micrography of the alloy: bright field micrograph and SADP image (a); dark field micrograph (b)

2.3 HRTEM observations further resolve their morphological features, HRTEM was carried
From the TEM observations, it can be seen that the out. Figure 4(a) depicts an HRTEM micrograph exhibiting lattice
decomposition product appears to exist in different states of fringes associated with (220)Cu. The fringe spacing measured
evolution with different structure; namely, solute segregation, from the micrograph was seen to be approximately 0.13 nm,
nano-domains of precursor and fine ordered bcc precipitates. To which agrees well with d220 of Cu (0.1278 nm).

Cu
(a) (b)

Cu
Cu
Cr Cr Cr
O

0 2 4 6 8 10 12 14 16 18 20
keV
Fig. 4 HRTEM micrographs of the alloy (a) and the typical EDXS qualitative analysis spectrum of phases (b)

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Fine precipitates of the ordered bcc phase, as shown in of chromium and zirconium exists. The coarse phases formed
Fig. 3(b), with a lobe-shape contrast can also be seen in during solidification and were left undissolved during solution.
the HRTEM micrography in Fig. 4(a). The typical EDXS (2) The TEM and HRTEM results showed that the dispersed
qualitative analysis spectrum of the chromium-rich phase fine precipitate is CrCu 2(Zr,Mg) and pure Cr, with sizes
is shown in Fig. 4(b). There are copper spectrum peaks and ranging from 1 to 50 nm, The fine precipitates are the ones that
chromium peaks, so we can suppose that the lobe-shape form due to decomposition of the supersaturated solid solution
contrast is pure chromium. during aging.
(3) The key factor in improvement of the mechanical
3 Discussions properties of the alloy is avoiding coarse precipitation during
solidification or fragmenting the coarse precipitates and
As described above, there are three phases in the alloy,
redistributing the alloying content.
copper matrix, chromium-rich and zirconium-rich phases.
No intermetallic phase of chromium or zirconium exists.
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