Materials Science and Engineering B60 (1999) 112 117

Chemical synthesis and properties of nanocrystalline CuFe Ni

alloys
J. Stolk *, A. Manthiram
Texas Materials Institute, ETC 9.104, The Uni6ersity of Texas at Austin, Austin, TX 78712, USA
Received 8 October 1998; received in revised form 25 January 1999; accepted 1 February 1999

Abstract
The chemical reduction of Cu2 + , Fe3 + , and Ni2 + ions with sodium borohydride in aqueous solution followed by heat
treatments at 300900C in a H2 atmosphere was investigated to obtain nanocrystalline Cu Fe Ni, which may have low thermal
expansion and enhanced thermal and electrical conductivities. The samples were characterized by X-ray diffraction, optical
microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, thermomechanical analysis, and electrical
conductivity measurements. Thermal conductivity was estimated using the Wiedemann Franz law. Sintering lead to the formation
of a Cu-rich phase and a g(Fe, Ni) Invar phase. The growth and stability of the Cu and g (Fe, Ni) Invar phases and the effects
of composition on the properties of CuFeNi alloys were investigated. 1999 Elsevier Science S.A. All rights reserved.
Keywords: Synthesis; Properties; Nanocrystalline CuFeNi alloys

1. Introduction
One of the greatest challenges facing the microelectronics industry is the thermal expansion mismatch
among the materials used in electronic devices and
components. Differences in the coefficients of thermal
expansion (CTE) may result in high interfacial shear
strains and premature failure of electronic assemblies.
The problem lies in the inherent difference in the CTE
of metallic versus nonmetallic materials. A particular
problem that plagues the electronics industry is the
fatigue failure of solder joints due to a CTE mismatch
between the printed wiring boards (PWB) and surfacemounted components such as leadless ceramic chip
carriers (LCCC) and high performance flip chips, which
are mounted directly to the PWB without the use of a
ceramic package.
Low CTE metals or alloys such as Invar offer one
possible solution to the CTE mismatch problem by
effectively reducing the thermal expansion mismatch
between the surface components and the printed wiring
boards during thermal cycling of the board assembly.
The disadvantage of these materials is that they typi* Corresponding author.

cally have low thermal and electrical conductivities and

cause additional problems in heat dissipation and current flow. In order to take advantage of low CTE
materials, much attention is now focused on constrained core technology (CCT), in which composites
are produced from a combination of materials with low
CTE and materials with high conductivity. The result is
a structure with balanced properties that can effectively
serve as both a core constraining material and a heat
dissipation path. Among the materials examined for use
in CCT applications are clad or roll-bonded copperInvarcopper (CIC) [13], extruded copperInvar powder composites [4], copper-infiltrated tungsten or
molybdenum powder metallurgy (PM) composites [5],
silverInvar [6], composites of copper with titanium
nickel [7], berylliumberyllia [6], and a variety of
metalceramic composites [6,8]. Many of these coreconstraining materials are currently available in commercial multilayer circuit boards.
Although many layered or PM composites offer attractive properties, their manufacturing or material
costs can often be quite high. Homogeneous alloys of
Cu, Fe, and Ni may offer an attractive alternative to
the composites currently used to lower the CTE of
printed wiring boards. The CuFeNi ternary phase

0921-5107/99/$ - see front matter 1999 Elsevier Science S.A. All rights reserved.
PII: S 0 9 2 1 - 5 1 0 7 ( 9 9 ) 0 0 0 2 2 - 7

J. Stolk, A. Manthiram / Materials Science and Engineering B60 (1999) 112117

113

diagram [9] suggests that the formation of alloys with a

Cu-rich phase and a phase of approximately Invar
composition may be possible. Extensive studies of the
CuFeNi system by X-ray diffraction [10], neutron
scattering [11,12], transmission electron microscopy and
electron diffraction [13 15], atom-probe field ion microscopy [16], and magnetic measurements [17] have
revealed that for some alloy compositions, a Cu-rich
phase and a Ni-rich Fe Ni phase form by spinodal
decomposition during aging of the cast alloys.
Metastable FeCu Cr Ni alloys that exhibit Invar
behavior have also been produced by mechanical
milling [18]. Thermodynamic calculations within the
Table 1
Nominal and actual compositions of CuInvar alloys
Sample

A
B
C
D
E
F
G

Nominal composition
(wt.%)

Actual composition
(wt.%)

Cu

Fe

Ni

Cu

Fe

Ni

10.0
20.0
50.0
80.0
90.0
100.0

64.0
57.6
44.8
32.0
12.8
6.4

36.0
32.4
25.2
18.0
7.2
3.6

11.9
22.4
50.3
77.0
90.1
100.0

64.2
57.2
48.5
32.4
14.8
6.0

35.8
30.9
29.1
17.3
8.2
3.9

Fig. 2. X-ray powder diffraction patterns of sample D (50 wt.%

Cu 50 wt.% Invar): (a) as-prepared, (b) after annealing in H2 at
300C, (c) after annealing in H2 at 600C, and (d) after annealing in
H2 at 900C.

low-temperature miscibility gap of the CuFeNi

ternary phase diagram and recent experimental work
suggest the possibility of forming two-phase CuInvar
alloys with reduced thermal expansion [9]. Isotropic
CuInvar alloys may offer the desired thermal and
electrical properties at manufacturing costs much lower
than those of the materials currently in use.
The present study aimed at production of nanocrystalline CuInvar powder using a novel solution-based
synthesis technique, formation of homogeneous CuInvar alloys by heat treatment, and characterization of
the resulting products.

2. Experimental procedures

Fig. 1. X-ray powder diffraction patterns of as-prepared samples with

nominal compositions of (a) 64 wt.% Fe36 wt.% Ni (Invar composition, sample A) and (b) 50 wt.% Cu32 wt.% Fe18 wt.% Ni (sample
D).

Nanocrystalline CuFeNi alloys were prepared by

reducing an aqueous solution consisting of required
amounts of 0.1 M CuCl22H2O, FeCl36H2O, and
NiCl26H2O with 0.2 M NaBH4 under constant mechanical stirring. The reaction resulted in reduction of
Cu2 + , Fe3 + , and Ni2 + ions to metallic Cu, Fe, and Ni
containing some B. Other reaction products formed

114

J. Stolk, A. Manthiram / Materials Science and Engineering B60 (1999) 112117

included sodium chloride, boric acid, and metal borates. The brownish-black precipitate that formed was
washed with warm water to remove the NaCl and boric
acid, rinsed with acetone, dried in argon, and stored in

a vacuum desiccator. X-ray powder diffraction (XRD),

transmission electron microscopy (TEM), and energy
dispersive X-ray spectroscopy (EDS) were used to characterize the as-prepared samples. X-ray reflections arising from Cu Ka2 radiation were subtracted, and the
data presented in the Figures correspond to reflections
arising only from Cu Ka1 radiation.
The as-prepared CuFeNi powders were initially
heated to 500C in H2 to cause a dissociation of any
metal borates that remained after initial washing into
B2O3 and metal particles. After heating, the powder
was washed with warm water to remove the boron
oxide, rinsed with acetone, and dried in argon. The
powders were then compacted and sintered at 900C.
The sintered pellets were characterized by XRD, EDS,
and optical microscopy. Thermal expansion behavior
was evaluated at 20300C with a Perkin-Elmer series 7
thermomechanical analyzer (TMA). The density of the
sintered pellets was measured using a gas pycnometer.
Room temperature electrical conductivity was measured by a four probe technique. Thermal conductivity
values were estimated using the WiedemannFranz
equation.

3. Results and discussion

3.1. Sample identification and characterization

Fig. 3. TEM images of sample D (50 wt.% Cu50 wt.% Invar): (a)
as-prepared, (b) after annealing in H2 at 500C.

Fig. 4. Optical micrograph of sample D (50 wt.% Cu50 wt.% Invar)

after sintering in H2 at 900C. NH4OH + H2O2 + (NH4)2S2O3 etch.

The nominal compositions and actual compositions

as determined by EDS of the as-prepared powders are
shown in Table 1. Close agreement between the nominal and actual compositions reveals that the three metal
ions are quantitatively reduced by NaBH4. The X-ray
diffraction patterns of the as-synthesized CuFeNi
powders are shown in Fig. 1 for samples A and D. The
X-ray pattern of sample A, which has the Invar alloy
composition, shows broad reflections that correspond
to metallic Fe and Ni or the g-(Fe, Ni) Invar phase and
iron borate Fe(BO2)2. Since the reflections are broad
and the peaks from various phases overlap, it was not
possible to establish unambiguously whether the g (Fe,
Ni) Invar phase is formed in the as-prepared samples.
The pattern of sample D, which has 50 wt.% Cu50
wt.% Invar, shows broad reflections corresponding to
metallic Cu, Fe and Ni (or the g-(Fe, Ni) Invar phase),
and Cu2O. Fig. 2 illustrates the evolution of phases
formed during annealing in a reducing atmosphere at
300900C for sample D. The reflections corresponding
to a metallic Cu phase and a face centered cubic g-(Fe,
Ni) Invar phase become separated and better defined as
the annealing temperature increases.
TEM images of sample D before and after heat
treatment are shown in Fig. 3. The as-prepared powders are 1020 nm in size and spherical in shape. The

J. Stolk, A. Manthiram / Materials Science and Engineering B60 (1999) 112117

115

Table 2
Density, electrical conductivity and estimated thermal conductivity of CuInvar alloys annealed at 900C for 8 h
Sample

Nominal composition
(wt.%)

Percent theoretical density

Electrical conductivity (S cm1)

Estimated thermal conductivity (W m1

K1)

A
B
C
D
E
F
G

100 Invar
10 Cu90
20 Cu80
50 Cu50
80 Cu20
90 Cu10
100 Cu

92.0
97.0
94.2
99.5
97.7
96.8
99.1

1.1E4
1.3E4
1.8E4
3.6E4
8.7E4
1.1E5
5.9E5

8.2
9.8
13
27
63
83
430

Invar
Invar
Invar
Invar
Invar

particle size increased to 20 200 nm after annealing at

500C for 4 h in H2. Ternary alloys that were compacted
and sintered at 900C in H2 consist of a uniform
distribution of Invar and Cu grains (Fig. 4). Samples E
and F of high Cu content have a continuous (Cu) matrix
with dispersed Invar. Samples B and C of high Fe and
Ni content show continuous Invar with a dispersed Cu
phase. The average grain size for sample D after annealing at 900C for 8 h is approximately 1.5 mm, and the
grain morphology is approximately equiaxed. The percent theoretical density of the specimens sintered at
900C for 8 h is given in Table 2.

3.2. Thermal expansion of Cu In6ar alloys

Invar and near-Invar alloys exhibit zero, negative, or
very low thermal expansion near ambient temperatures
as a result of a balance between thermal expansion and
volume magnetostriction [19]. Above room temperature,
the CTE of Invar gradually increases, with more marked
changes in CTE occurring above temperatures of approximately 225C, where the thermal expansion is no
longer balanced by the magnetostriction.
Fig. 5 compares the thermal expansion behavior of the
synthesized CuInvar alloys with that of the synthesized
Invar and pure Cu. Sample A of Invar composition
exhibits typical Invar alloy behavior, with an average
CTE of 1.2 10 6 C 1 for 25 100C. Interestingly,
similar trends in the thermal expansion behavior are
observed in the Cu Invar samples for compositions up
to 50 wt.% Cu. At temperatures around 225C, alloys B,
C, and D exhibit a change in slope of the thermal
expansion versus temperature curve.
Differences in thermal expansion of the components
in a composite or multiple phase alloy system can give
rise to thermally induced stresses that can influence the
thermal expansion behavior of a composite body. For
this reason, a simple volumetric rule of mixtures is not
typically used to predict the CTE of composite or alloy
systems. The most commonly used procedure for the
prediction of thermal expansion coefficient in two-phase
alloys is the Turner formula, which gives the thermal
expansion ac of a composite as:

ac =

a1x1E1 + a2x2E2
x1E1 + x2E2

(1)

where a1 and a2, x1 and x2, and E1 and E2 are,

respectively, the thermal expansion coefficients, volume
fractions, and elastic moduli of phases 1 and 2 in a
composite [20]. Eq. (1) assumes only hydrostatic stresses
in the two phases and uses the elastic modulus of each
component to account for changes in the expansion due
to thermally induced stresses.
Average CuInvar CTE values for the temperature
range 25100C are shown in Fig. 6. The TMA data
show a reduction in the average CTE with increasing
Invar content, but the CTE values do not match those
predicted by Turners formula. The experimental values
are higher than that predicted by Turners formula,
which may be due to variation in the Invar phase
composition. The extraordinarily low CTE of Invar is
only maintained if the Fe:Ni ratio is very close to 64:36
in weight percent. Deviations of the Fe:Ni ratio from this
ideal value and incorporation of Cu into the Invar phase

Fig. 5. Thermal expansion of Cu Invar alloys after sintering at

900C for 8 h.

116

J. Stolk, A. Manthiram / Materials Science and Engineering B60 (1999) 112117

Fig. 6. Average 25 100C CTE values for CuInvar alloys after

sintering at 900C for 8 h. The data points correspond to experimental values and the dotted line corresponds to the prediction by
Turners formula.

tent are significantly lower than one might anticipate.

The low alloy conductivities may be due to Fe and
Ni contained in the Curich solid solution. Fig. 8
shows both the calculated and experimentally determined boundaries of the miscibility gap in the Cu
FeNi system at room temperature [10,21]. The
calculated ternary phase diagram indicates a solubility
limit of about 8 at.% Cu in the (Fe, Ni) phase and
close to zero solubility of Fe in the (Cu, Ni) phase
under equilibrium conditions. Early experimental
work, however, showed much higher solubility of Fe
in Cu-rich solid solutions for slowly cooled alloys.
Dissolved Fe is deleterious to the conductivity of Cu,
with as little as 0.05 wt.% Fe in solution reducing the
conductivity of Cu by over 20% [22]. Ni contained in
Cu solid solution can have a similar but less dramatic
effect on the electrical conductivity of Cu [22].
If the calculated ternary phase diagram correctly
represents the location of the miscibility gap
boundaries for equilibrium conditions, improved conductivity may be achieved by further atomic segregation achieved through aging heat treatments. Fe may
be driven out of the Cu phase by heating the CuInvar alloys to temperatures around 0.5 TM and holding for some time. Such experiments are currently in
progress in our laboratory.
Thermal conductivity values calculated using the
WiedemannFranz law [23] are shown in Table 2.
The thermal conductivity decreases with increasing Invar content similar to the electrical conductivity.

Fig. 7. Electrical conductivity of CuInvar alloys after sintering in H2

at 900C for 8 h.

or Fe and Ni into the Cu phase will cause a dramatic

increase in the CTE of the composite.

3.3. Conducti6ity of Cu In6ar alloys

The electrical conductivity of the Cu Invar alloys
decreases exponentially with increasing Invar content,
as shown in Fig. 7 and Table 2. The electrical conductivity values for Cu Invar alloys of high Cu con-

Fig. 8. Partial ternary Cu Fe Ni phase diagram showing calculated

and experimental boundaries of the miscibility gap at approximately
25C. Solid lines represent calculated boundaries for equilibrium
conditions, while dashed lines show experimentally determined
boundaries for slowly-cooled alloys.

J. Stolk, A. Manthiram / Materials Science and Engineering B60 (1999) 112117

4. Conclusions
Alloys consisting of Cu, Fe, and Ni have been synthesized at ambient temperatures using NaBH4 as a reducing
agent. An isotropic two-phase composite of Cu and Invar
was formed upon sintering of the powders in a H2
atmosphere at 900C. The coefficient of thermal expansion and electrical conductivity of the Cu Invar alloys
decreased with increasing Invar content, and specific
values of CTE and conductivity ranging from pure Cu
to Invar were easily obtainable by this procedure. Further aging heat treatments based on the calculated
ternary phase diagram are expected to lower the thermal
expansion of Cu Invar and improve electrical and
thermal conductivities. The simple synthesis and processing methods outlined here may prove to be an effective
method for producing Cu Invar alloys for use as core
constraining materials in printed wiring boards or as low
CTE-high conductivity materials in other applications.

Acknowledgements
Financial support by the National Science Foundation
Grant DMR-9401999 is acknowledged. The authors wish
to thank Tad Armstrong for his assistance with the
conductivity measurements.

References
[1] R.A. Reynolds, Electric. Design News 29 (17) (1984) 211.

117

[2] L.J. Boccia, Printed Circuitboard Fabr. 9 (7) (1986)

34.
[3] W.R. Johannes, W. Johnson, Int. J. Microcircuits Elec.
Packag. 17 (2) (1994) 135.
[4] S. Jha, Proc. 45th Electronic Component and Technology
Conf. Las Vegas, NV, USA, 1995, p. 542.
[5] C. Zweben, JOM 44 (7) (1992) 15.
[6] D.E. Jech, J.L. Sepulveda, Int. Sym. Microelectron. SPIE
Proc. Ser. 3235 (1997) 90.
[7] H. Mavoori, S. Jin, JOM 50 (6) (1998) 70.
[8] K.W. Hang, A.N. Prabhu, J. Andrus, S.M. Boardman, L.S.
Onyshkevych, RCA Rev. 45 (1984) 33.
[9] R.D. Cottle, X. Chen, R.K. Jain, Z. Eliezer, L. Rabenberg,
M.E. Fine, JOM 50 (6) (1998) 67.
[10] A.J. Bradley, W.F. Cox, H.J. Goldschmidt, J. Inst. Met. 67 (1)
(1941) 189.
[11] R. Poerschke, W. Wagner, H. Wollenberger, J. Phys. F: Met.
Phys. 16 (1986) 421.
[12] J. Aalders, C. van Dijk, Phys. Rev. B40 (1984) 1646.
[13] R.J. Livak, G. Thomas, Acta Metall. 19 (1971) 497.
[14] R.J. Livak, G. Thomas, Acta Metall. 22 (1974) 589.
[15] R. Gronsky, G. Thomas, Acta Metall. 23 (1975) 1163.
[16] V.M. Lopez, H.N. Sano, T. Sakurai, K. Hirano, Acta Metall.
Mater. 41 (1993) 265.
[17] E.P. Butler, G. Thomas, Acta Metall. 18 (1970) 347.
[18] K. ODonnell, Q. Qi, A.S. Ilyushin, J.M.D. Coey, J. Magn.
Magn. Mater. 123 (1993) 243.
[19] R.M. Bozorth, Ferromagnetism, Van Nostrand, Princeton, NJ,
1978, p. 641.
[20] A.A. Fahmy, A.N. Ragai, J. Appl. Phys. 41 (1970) 5108.
[21] P. Villars, A. Prince, H. Okamoto (Eds.), Handbook of
Ternary Alloy Phase Diagrams, ASM International, Materials
Park, OH, 1995, p. 9380.
[22] E. Klar, Metals Handbook, vol. 7, 9th ed., American Society
for Metals, Metals Park, OH, 1984, p. 106.
[23] F.J. Blatt, Physics of Electronic Conduction in Solids, McGraw-Hill, New York, 1968, p. 127.

.
.