A Drop-In Lead-Free Solder Replacement
Ning-Cheng Lee, James A. Slattery, John R. Sovinsky
Indium Corporation of America, Utica, NY
and
Iris Artaki
AT&T Bell Laboratories, Princeton, NJ
and
Paul T. Vianco
Sandia National Laboratories, Albuquerque, NM
ABSTRACT
Environmental and toxicity concerns related to the use of
lead have initiated the search for acceptable, alternate
joining materials for electronics assembly. This paper
describes a novel lead-free solder designed as a "drop in"
replacement for common tin/lead eutectic solder. The
physical and mechanical properties of this solder are
discussed in detail with comparison to tin/lead eutectic
solder. The performance of this solder when used for
electronics assembly is discussed and compared to other
common solders. Fatigue testing results are reported for
thermal cycling electronics assemblies soldered with this
lead-free composition. The paper concludes with a
discussion on indium metal availability, supply and price.
Key Words: solder, soldering, lead-free, electronic, reflow,
solder paste, SMT, surface mount, Pb-free
RATIONALE FOR LEAD-FREE SOLDER
Tin-lead solder has been used in electronics assemblies
since the earliest days of radio. Its adequate and well
documented mechanical, electrical and thermal properties,
combined with its low material cost, have made it the material
of choice for joining active and passive components.
However, well publicized environmental and toxicity
concerns have led to increased controls and legislation (in
the U.S. and other countries) which if enacted, would reduce,
tax or eliminate the use of lead in solders for electronics
assembly.
The use of lead in non-solder related materials such as
tetraethyl lead additive for gasoline, and lead naphthenate
and lead oxide for paint, have been banned for years. More
recently, lead containing solders have been banned for use
in potable water piping, food and beverage cans and
automobile bodies where they were used in repair
applications.
There are two major federal legislative initiatives on lead
currently being pursued in the U.S. Congress. The Toxic
Lead Reduction Act of 1990 (S.2637), a bill that would limit or
ban the use of lead-containing materials, including
electronics solders, was introduced four years ago, by
Senator H. Reid. After intense lobbying by the electronics
industry and the Lead Industries Association, electronics
solders were deleted from subsequent revisions to the bill.
In its present form, the bill (S.729) will probably be
reintroduced in the Senate this year, and while electronics
solders will be excluded, the bill will have a "new use and
unnecessary inventory" provision, require labeling that
would include a bar on defenses for products that require
labels, establish an "exposure concern list", and ban certain
lead-containing products.
The other legislative initiative involves taxing lead and lead
containing products. The Lead-Based Paint Hazard
Abatement Act (H.2922) was introduced in the House by
Congressman Cardin in 1991 and would place a tax of
$0.75/lb on primary refined lead and a $0.37/lb tax on
secondary refined lead, irrespective of its final use. The
revenues from these measures were targeted as funding for
the renovation of older housing units containing lead-based
paints. The revised version of this bill, (H.2479) proposes a
tax of $0.45/lb on the lead content of all lead-containing
products and is gaining support. A similar bill was
introduced in the Senate (Bradley S.1347). There is a good
chance that these bills will become law in 1994 either as
stand alone entities or attached to other legislation.
GOALS FOR DEVELOPMENT OF LEAD-FREE SOLDERS
The following goals were established for the development of
a new non-lead containing solder specifically designed for
electronics assembly use:
1. Have a melting temperature similar to 63Sn/37Pb
solder.
2. Have a narrow plastic range.
3. Have adequate wetting properties.
4. Have physical properties similar or better than
those of Sn/Pb solder.
 5. Be compatible with existing liquid flux systems.
6. Be capable of fabrication into existing physical
forms of solder i.e. wire, preforms, ribbon,
spheres, powder, paste, etc.
7. Have adequate shelf life and performance as a
solder paste.
8. Contain relatively non-toxic metals.
9. Possess low dross formation when used in a
wave soldering operation.
CURRENT LEAD-FREE ALTERNATIVES
The alternatives available today include a few lead-free
metallic solders and conductive polymers. Of the available
lead-free solders and conductive polymers, all fail to meet
one or more of the goals listed above. Table 1 lists some
common lead-free solders, their melting properties and a
brief description. More details on the solders are given
below:
52In/48Sn is considered the lowest melting point solder and
is often used as the last step in a sequential soldering
operation, and for soldering to metallizations on temperature
sensitive components.
58Bi/42Sn is relatively inexpensive and has a proven track
record where it has been used in wave soldering of printed
circuit assemblies. However the melting point is lower than
tin/lead eutectic.
91Sn/9Zn has been used to solder aluminum using
specialized fluxes. Because of its corrosion potential, zinc
poses a concern. Solder paste incorporating this alloy
would have a poor shelf life due to attack on the metal
spheres by the organic acids present in the flux vehicle.
Additionally, the alloy drosses excessively when used in a
wave soldering operation.
96.5Sn/3.5Ag and 95Sn/5Sb both exhibit good wetting
characteristics. Additionaly, 95Sn/5Sb has excellent shear
strength at 100° C. The high melting point of these alloys
may limit their application.
65Sn/25Ag/10Sb is a patented alloy developed by Motorola
and is commonly known as "Alloy J". It has good fatigue
properties but has not found widespread usage.
97Sn/2Cu/0.8Sb/0.2Ag is a lead-free plumbing solder that
was developed by Kester Solder Company and is marketed
under the trade name of Aquabond. Its performance mimics
that of Sn/Pb eutectic but at a higher melting temperature.
95.5Sn/4Cu/0.5Ag is lead-free plumbing solder developed by
Engelhard. Its wide melting range of 225°-349°C would
severely restrict its use as an electronics solder.
Conductive polymers are mixtures of organic chemical
components and a conductive metallic filler. The organic
chemical component consists of a resin system (that may be
thermoplastic or thermosetting), a solvent system and
rheological additives. To this mixture is added a metallic
filler, typically silver flake. The resultant paste can be
dispensed or screened onto the substrate, heated to drive
off the solvent and initiate a curing process. The resin
provides the mechanical attachment whereas the silver flake
provides electrical conductivity between the joined surfaces.
Conductive polymers can be isotropic, having electrical
conductivity in all planes, or anisotropic where the electrical
conductivity is only in the "Z" axis.
The major shortcomings of conductive polymers include
substantially lower conductivity compared to metallic
solders, high cost, rework difficulty, low bond strength and
absence of self alignment. These shortcomings have
inhibited their general use for component attachment.
However, there is intensive research directed to improving
the performance of these materials and they may in the
future prove to be viable replacements for metallic solders
for some applications.
HISTORICAL PERSPECTIVE OF Sn/In/Ag ALLOY
DEVELOPMENT
Although tin-lead eutectic solder has adequate physical
properties and has been used succes sfully for a long time in
electronics assembly, certain specialty solders have been
developed to meet the need for specific applications. For
example, the lead-indium system was developed to meet the
specific requirement for soldering to gold substrates. The
alloy 92.5Pb/5.0In/2.5Ag was developed to meet the need for

Table 1 Some Common Lead-Free Solders.

Composition Melting Point Comments

52In/48Sn 118o C. (eutectic) lowest mp solder, expensive
58Bi/42Sn 138o C. (eutectic) well established history, inexpensive
91Sn/9Zn 143o C. (eutectic) corrosion concerns, high drossing alloy
96.5Sn/3.5Ag 221o C. (eutectic) excellent wetting and strength
95Sn/5Sb 232o - 240o C. good high temperature shear
65Sn/25Ag/10Sb 233o C. (mp) Motorola patented alloy, high strength
97Sn/2Cu/.8Sb/.2Ag 226o - 228o C. high melting range
95.5Sn/4Cu/.5Ag 225o - 349o C. wide and high melting range
increased fatigue resistance. 90In/10Ag solder was
developed for use in cryogenic environments. A family of
solders was developed with melting points lower than tin-
lead eutectic to allow for soldering to temperature sensitive
components and for use in a sequential temperature or
"step" soldering operations.
These solders and others were developed prior to the use of
modern analytical instrumentation and before computer
modeling existed. Today the development of unique solders
that do not contain lead benefits from the availability of
modern analytical instrumentation and computer modeling.
However, this advantage is offset by the limited number of
metals that can be incorporated in a lead-free solder due to
toxicity, physical properties, cost and availability.
It is generally agreed that tin, with its desirable physical
properties, will be alloyed with other metals to produce an
acceptable lead-free solder. The candidates for other metals
include antimony, bismuth, copper, gallium, indium, silver
and zinc. Each metal has its own specific advantages and
disadvantages for incorporation into a lead-free
composition. Additionally, the limited solubility of a specific
metal within a matrix of several other metals also complicates
the design problem. Thus the development of lead-free
solders is a formidable task, and will certainly involve a
trade-off in properties and performance. The key to a
successful alloy will be to minimize these trade-offs.
MATERIALS CHARACTERIZATION
In order to meet the target performance, a novel lead-free
1
solder, 77.2Sn/20.0In/2.8Ag, was developed . This alloy was
then evaluated against 63Sn/37Pb with respect to the
material properties, performance in SMT assembly process,
and temperature cycling behavior of the assembled devices,
as described in the following sections. In the case of material
properties, the solders were evaluated in the form of bulk
solders. As to the performance in SMT assembly processes,
the materials were examined as solder pastes comprising a
typical RMA flux and the respective solder powders (-
325/+500 mesh) at 90% metal load.
Physical Properties
Table 2 Physical Properties of Solder Alloys.
Properties
77.2Sn/20.0In/2.8Ag
Density @ 20o C (gm/cm3 )
Electrical resistivity @ 20o C (µ ohm.⋅m)
Thermal conductivity @ 30o C (W/m⋅k)
Thermal expansion coefficient @ 20o C (ppm/ o C)
Table 2 shows some of the physical properties of the solder
alloys. The density was determined with the use of a
pycnometer. The electrical resistivity was measured via a
micro-ohm meter. The thermal conductivity tests were
conducted by monitoring the temperature differential across
the sample on an axial heat flow apparatus. The thermal
expansion coefficient was determined using a
thermomechanical analyzer.
In general, the physical properties of 77.2Sn/20.0In/2.8Ag
were comparable to those of 63Sn/37Pb. The differences
observed are considered insignificant in terms of electronics
industry applications. For instance, it has been postulated2
that the electrical resistance of the solder joints should be
acceptable at a value no greater than 0.03 mΩ / joint
(approximately 5.9 x 105 µohm.m). Apparently, the electrical
resistivity of 77.2Sn/20.0In/2.8Ag is far lower than this value.
As to the density, although being lower than that of
63Sn/37Pb, it is quite comparable to that of 96.5Sn/3.5Ag.
The latter alloy exhibits a density of 7.36 gm/cm3 and has
been successfully used in hybrid industry for higher
temperature applications. Hence, it can be concluded that
the 77.2Sn/20.0In/2.8Ag solder has comparable physical
properties to the eutectic Sn-Pb alloy.
Mechanical Properties
The solders were cast into ingot form prior to the preparation
of specimens for mechanical testing. During the casting
process it was noticed that the 77.2Sn/20.0In/2.8Ag drossed
only slightly , suggesting a low dross formation rate during
wave soldering. The mechanical properties of the solder
alloys are shown in Table 3. First, this Pb-free alloy has both
a higher tensile strength and shear strength than 63Sn/37Pb.
In addition, although having a higher modulus, the tensile
elongation of 77.2Sn/20.0In/2.8Ag is still greater than that of
63Sn/37Pb. This behavior suggests that this Pb-free alloy
has adequate ductility for fabrication into various physical
forms, such as wires, ribbons, preforms, etc. The identical
value in Poisson's ratio for both solders eliminates concern
on the possible impact due to variation in the solder volume
under stress of this Pb-free alloy. Overall the data indicate
that, in bulk form, 77.2Sn/20.0In/2.8Ag exh ibits superior
mechanical properties than 63Sn/37Pb.
Alloy
63Sn/37Pb
7.25 8.36
0.170 0.146
53.5 50.9
28 25
Table 3 Mechanical Properties of Solder Alloys.

Properties Alloy
77.2Sn/20.0In/2.8Ag 63Sn/37Pb

Tensile strength @ 20o C (psi) 6800 3900

Tensile elongation @ 20o C (%) 47 35
Shear strength @ 20o C (psi) 4800 3450
Poisson's ratio @ 20o C 0.40 0.40
Young's modulus @ 20o C (x106 psi) 5.6 4.5

Creep Behavior
The creep behavior is also relevant to solder joint fatigue
reliability performance. Materials being more creep resistant
usually exhibit a better fatigue resistance. In this study, the
creep test was conducted on the bulk solders per ASTM
E139-83 at 20°C. As shown in Figure 1, the data indicate that
the steady creep rate of 77.2Sn/20.0In/2.8Ag is about two
and half orders of magnitude lower than that of 63Sn/37Pb.
This superior creep resistance behavior suggests an
improved solder joint reliability with the 77.2Sn/20.0In/2.8Ag
alloy.
Melting and Softening Behavior
The melting properties of the Sn/In/Ag solder were
determined by Differential Scanning Calorimetry. (DSC). The
procedure was to initially run the sample at a heating/cooling
rate of 20°C/minute past the liquidus temperature in order to:
(1) allow it to conform to the sample pan, thereby minimizing
thermal lag in the peak positions, and (2) homogenize the
microstructure. Then, the sample was scanned at 1°C/minute
1E-4
Creep at 20C
1E-5
Steady Creep Rate (s-1)
from which the melting point was determined from the onset
temperature of the peak (s). The first run (20°C/min) shows
an endotherm with an onset of 165.3°C and a peak
temperature of 185.5°C. The second run of the sample (1°
C/min), and from which the thermal properties were obtained
(Fig. 2), showed that there is a small low temperature peak at
113.5°C. As to the main peak, although a slight sign of
melting may be noticed at 150°C, significant melting really
occurs between 174.7°C and 186.5°C, with the latter as the
peak temperature. The source of the small low temperature
peak is likely a depression of the 118°C eutectic point
accompanying the formation of 52In-48Sn caused by the
high indium content in the material. Of course, without
metallographic data, the formation of a low temperature
ternary phase cannot be ruled out.
The higher temperature (or main) peak will allow to define the
processing temperature of the solder during product
manufacturing (which is typically 30-50°C above the liquidus
point). On the other hand, the low temperature peak may
define the maximum service temperature of the solder. The
close proximity in the main peak temperature of
77.2Sn/20.0In/2.8Ag and 63Sn/37Pb suggests that the
processing temperature required for the two alloys should be
very comparable. Hence, this solder has utility as a "lead-

free alternative" if a processing temperature similar to that of

tin-lead solders is acceptable and the service requirements
1E-6
are not jeopardized by the presence of structural changes to
the alloy responsible for the low temperature peak.
1E-7
63Sn/37Pb
In order to further understand the relation between the
melting range and the softening behavior, both solders were
1E-8
77.2Sn/20.0In/2.8Ag examined on a thermo mechanical analyzer (TMA). Again,
the measurement was conducted at 1°C/min heating rate.
1E-9 Also, the load on the sample was set at 14.2 psi. As shown
1E-1 1E+0 1E+1 1E+2 in Figure 3, regardless of the temperature difference at the
onset of melting process, the softening point of
Apparent Stress (MPa)
77.2Sn/20.0In/2.8Ag was found to be almost identical to

Figure 1 Relation Between Steady Creep Rate and Apparent

Stress.
that of 63Sn/37Pb. This result strongly suggests that the
upper limit of the service temperature of both solders should
be very comparable.
Wetting
The wetting property is one of the most important
characteristics of solders. The wetting tests were determined
with the use of a wetting balance at 200°C and 240°C. The
temperatures chosen here represent the lower temperature
limits for reflow and wave soldering, respectively. Copper
coupons were used and preconditioned at 100°C for 3 hours
prior to testing in order to mimic the "difficult to solder"
condition. The geometric mean of the wetting data, as shown
in Table 4 and Table 5, of four fluxes with different flux
chemistries were used to determine the overall wetting
capability of the solders.
Overall, 77.2Sn/20.0In/2.8Ag wets somewhat slower than the
conventional 63Sn/37Pb. However, the difference in the
wetting time is fairly insignificant when compared with the
soldering time typically employed by the assembly process.
For example, the typical reflow profile demands a total
heating time of 4 to 6 minutes, with 30 to 90 seconds above
the liquidus temperature. In the case of a wave soldering
process, a 1 to 2 minutes preheat step followed by 4 seconds
in-contact with a 250°C wave solder is very common. In both
cases, the soldering process time well exceeds the wetting
time needed for the "difficult to solder" situation.
The wetting force of 77.2Sn/20.0In/2.8Ag appears to be
slightly lower than that of 63Sn/37Pb. The small difference
observed suggests that any effect should be negligible.
Therefore, it can be concluded that, in a practical sense, the
wetting behavior of 77.2Sn/20.0In/2.8Ag is comparable to
that of 63Sn/37Pb solder.
SURFACE MOUNT ASSEMBLY EVALUATIONS
The manufacturing assembly performance of the Sn/In/Ag
solder was assessed relative to that of the Sn/Pb and Sn/Bi
solders, for which extensive processing information already
exists in the literature. The surface mount assembly
evaluations were conducted on test vehicles consisting of
0.4 mm, 0.5 mm, 0.6 mm (25 mil) and 1.2 mm (50 mil) pitch
leaded surface mount IC packages (PQFPs, PLCCs and
TSOPs) and 0803 discrete capacitors.
To avoid the metallurgical effects caused by lead
contamination in lead-free solders, the conventional Sn/Pb
surface finishes on printed wiring boards and component
leads were replaced with lead-free alternative finishes. The
two printed wiring board surface finishes evaluated in this
study were immersion tin and organic azole (imidazole) on
copper. The components were hot dipped in 100% tin after
chemical removal of the Sn/Pb layer.
Each of the three solder paste materials was printed on 2
imidazole and 2 immersion tin coated test vehicles. For the
Sn/In/Ag and the Sn/Pb solders, the boards were fully
populated and reflowed under the optimum condition
established for 63Sn/37Pb solder. In the case of the Sn/Bi
solder, the boards were reflowed under its own optimum
reflow condition. The solder reflow was performed in a
nitrogen atmosphere with oxygen levels not exceeding 20
ppm.
The defect analysis was based on a visual inspection under

Table 4 Wetting Time (seconds) of Solders.

Fluxes 77.2Sn/20.0In/2.8Ag 63Sn/37Pb

200o C 240o C 200o C 240o C
Flux A 10.60 4.60 2.87 1.48
Flux B 1.53 0.42 1.03 0.50
Flux C 5.08 2.40 1.65 1.00
Flux D 5.73 2.09 2.50 1.44
Geometric Mean 4.66 1.76 1.87 1.02

Table 5 Wetting Force (mN/mm) of Solders.

Fluxes 77.2Sn/20.0In/2.8Ag 63Sn/37Pb

200o C 240o C 200o C 240o C
Flux A 0.70 0.71 0.73 0.72
Flux B 0.72 0.56 0.71 0.61
Flux C 0.72 0.64 0.75 0.72
Flux D 0.67 0.67 0.73 0.73
Geometric Mean 0.70 0.64 0.73 0.69
Table 6 Defect Analysis.

Solder/Flux Bridges Opens # Components Wettability Solder Balls PWB Cond.

ppm ppm misplaced 1 poor, 5 good 1 poor, 5 good 1 poor, 5 good
Sn/In/Ag
imidazole 0 0 0 3.9 5.0 5.0
immersion 0 0 1 4.6 5.0 5.0
tin
Sn/Bi
imidazole 2300 180 1 4.1 5.0 5.0
immersion 0 180 0 4.8 5.0 5.0
tin
Sn/Pb
imidazole 0 0 0 5.0 5.0 5.0
immersion 0 0 0 5.0 5.0 5.0
tin

a stereo microscope. The defects were categorized as THERMAL CYCLING PERFORMANCE

bridges, opens or misaligned devices. Also, the wettability
of the pads, the quality of the solder joint fillets, formation of
solder balls and any thermal damage suffered by the board
were assessed.
A few random bridged and open joints (5-10 total) were
observed on the Sn/Bi solder test vehicle, and were due to
printing and placement inaccuracy.
Due to the large number of pads associated with the test
vehicle, the extent of pad wetting was judged on a relative
scale of 1 to 5, 5 indicating that the pad is 100% wetted by
the solder, 3 indicating that it is ∼ 75% wetted and 1 that it is
less than 50% wetted. Wetting figures of merit were
individually assigned to each device and then averaged over
the entire test vehicle. The defect analysis is summarized in
Table 6 .
After analysis of the results in Table 6 above, the following
conclusions can be drawn:
Overall, 0.4 mm pitch assembly is feasible with the
Sn/In/Ag alloy. The processing windows, as for any
other lead-free solder, are narrower than for Sn/Pb, and
further process improvements (fine-tuning the thermal
profiles and solder paste composition) should further
improve the performance level. All solder fillets look
good. Solder balls are minimal.
The immersion tin surface finish enhances the wetting of
both the Sn/In/Ag and Sn/Bi solders by providing a more
favorable metallurgical substrate for solder spreading.
Lastly, it is not possible to clearly establish the
performance of the new alloy composition based on
manufacturing assembly evaluation alone. The validation
will need to be based on the results of long term
reliability assessment studies.
Preliminary reliability data was obtained for the Sn/In/Ag
solder by an evaluation of thermally cycled solder joints on
prototype circuit boards. The test vehicles were constructed
of FR-4 laminate and contained 50 mil pitch 68 I/O plastic
leaded chip carrier (PLCC) and 24 I/O small outline integrated
circuit (SOIC) package solder joints. Discrete 1206 chip
capacitors were also assembled on the circuit boards. The
device packages and circuit board layout were daisy-chain
connected for monitoring the electrical conductivity of the
solder joints.
The test vehicles were exposed to the following thermal
cycling conditions under a laboratory atmosphere: (1) lower
temperature limit of 0°C; (2) upper temperature limit of 100°
C; (3) 5 min soak time at each of the temperature limits; and
(4) 10°C/min ramp rate between temperature limits. The
testing apparatus did not permit the continuous electrical
monitoring of the solder joints in the test vehicle. Therefore,
the first test vehicle was initially subjected to 1052 cycles.
Then, it was monitored electrically for open solder joints
over a subsequent 54 cycles (for a total of 1106 thermal
cycles). The electrical monitor was then removed and the
prototype was exposed to an additional 1296 cycles followed
by 59 cycles under electrical monitoring. The particular test
vehicle was subjected to a grand total of 2461 thermal cycles,
after which the solder joints on selected PLCC, SOIC, and
chip capacitor units were cross sectioned and prepared for
metallographic observations. A second test vehicle was
introduced into the thermal cycling chamber for exposure to
5000 thermal cycles; that test sequence is currently in
progress.
The metallographic cross sections were used to evaluate the
evolution solder joint microstructure. It was noted that the
solder joints contained some void formation. The pattern of
the voids suggested that they were not due to the thermal
cycling exposure but rather, were a result of the soldering
process used to fabricate the prototype units. The location
of the voids was at the interfaces of the substrate and the
solder and the solder and the leads, and suggested that their
probable source was a wettability problem with the copper
lands on the circuit boards or with the device leads or
teminations. Similar voiding phenomena, maybe to a less
extent, were observed on the Sn/Pb solder joints. The
voiding phenomena appeared to have been the result of
either poor solder paste performance (the flux utilized was
formulated for 63Sn/37Pb solder) or an inappropriate furnace
schedule (although the latter was optimized for 63Sn/37Pb
solder, the alloy to be replaced by the present lead-free
candidate). Plastic deformation and excessive interfacial
intermetallic compound layer growth were not observed in
any of the solder joints.
The electrical monitoring at either of the interrupted cycle
sequences showed no opens in the Sn/In/Ag solder joints,
suggesting that t he voids observed may not be a concern.
INDIUM METAL AVAILABILITY, SUPPLY AND PRICE
Historically there has always been an ample supply of lead
to meet the need for electronics solders. In fact, electronics
solder accounts for only 0.6% of the total consumption of
lead, in contrast to the 80% of the metal used to manufacture
lead-acid storage batteries. Besides the advantage of
supply, the low cost of lead at well under $0.50/lb makes it
the least expensive metal that can be used in solder
(excluding disposal, safety and potential future liability
costs). Lower toxicity substitute metals for lead in solder
certainly will be more expensive and will require a careful
examination of the present and future availability.
It is estimated that 4500 metric tons of lead are consumed per
year in the U.S.3 to manufacture electronic solder; the world
wide consumption is probably three times this figure. If
indium were to replace lead at this usage (40% lead in
solder), an adjustment to account for the different densities
of lead and indium would need to be applied, in order to
maintain the volume of solder. Since the density of indium is
7.3 and the density of lead is 11.35, the required U.S.
consumption of indium would be 2894 metric tons per year.
(7.3/11.35 times 4500). However, if the solder contained 20%
indium (which is more realistic), the U.S consumption would
be one-half that amount or 1,447 metric tons, and world wide
consumption would be 4,341 metric tons. While it is true that
today's indium metal production of 160 metric tons per year
could not meet this demand, indium does in fact have a
future as an alloying metal in lead-free solders. Consider the
following:
Conversion from Sn/Pb Solder to Lead-Free Solder
At the present moment, it is very unlikely that lead
containing electronic solder "will be banned". The more
likely scenario will be that leaded solder will be taxed, which
will make lead-free solders more viable from an economic
perspective. An orderly conversion to lead-free solders will
allow time for expansion of other metal production capacity.
It is also very likely that a family of lead free solders will be
utilized, each possessing characteristic advantages and
disadvantages, and which may or may not contain indium.
The characteristic advantages of the 77.2Sn/20.0In/2.8Ag
solder are fatigue resistance, high reliability and a melting
point similar to 63Sn/37Pb.
Indium Supply/Price History
Producers have been expanding availability to meet the
increasing demand on supply . Figure 4 shows that the
indium availability has increased some 300% from the 50 to
53 metric tons per year requirement of the early 1980's to the
160 metric tons today. Indium producers have responded to
what the market has required over this period, in increased
production of indium for both growth in current uses for the
metal and meeting the demands for new applications
developed during the mid 1980's. Figure 5 shows the
historical price trend for the metal. As consumption of the
metal increased, its price decreased, evidence that supply is
ahead of demand. To increase future capacity, indium
producers will need to add new facilities and/or improve on
extraction technology. We believe that the favorable long
term outlook for the metal will provide the impetus to
accomplish these tasks.
Present and Future Indium Supply
Indium was discovered in sphalerite ores at the Freiburg
School of Mines in Germany in 1863. It is found as a trace
element in many minerals, particularly the sulfides of zinc but
also in copper, tin and lead. Indium is currently recovered
principally as a by- product of zinc processing.
The primary sources of indium in recent times have been and
likely will continue to be Canada, South America and Japan.
The former Soviet Union, (the CIS) which is the largest zinc
producer in the world has also been a significant producer of
indium. While their plants may need to be modernized, the
CIS potential from a resource and reserve point of view can
not be discounted. Indium currently is recovered in lead/zinc
metallurgical complexes, which extract but a small portion of
the available indium. CIS total production of indium is
thought to be 1/4 to 1/3 of what it could be if indium was
extracted from all of the ores that contain indium.
Additionally, substantial known, but undeveloped, deposits
exist in China and Australia and there are potential new
indium sources in Bolivia, China, Czechoslovakia, France,
Hungary, Japan, Peru, and Sweden, as well as here in the
U.S.
It is important to realize that the figures on indium metal
production often cited are from the U.S. Bureau of Mines
Statistics which are estimates derived from zinc reserves
only. They do not take into consideration the indium
content of copper, lead or tin ores. A further complication is
the fact that indium production is a by-product of other
metal recovery operations and often smelters do not report
values. In the face of steadily increasing indium production,
which should lower available resources, the USBM reserve
METRIC TONS DOLLARS PER TROY OUNCE
160
11

10
140

9
120
8

100 7

6
80

60
4

40 3
1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1988 1989 1990 1991 1992 1993 1994
YEAR YEAR
Figure 4 Estimated Indium Consumption. Figure 5 Average Annual Indium Price.

Table 7 Reserves of Select Metals (metric tons).

Metal Annual Production Reserves Years of Supply

indium 140 2300* 16
lead 3,200,000 63,000,000 20
silver 13,700 280,000 20
zinc 7,365,000 140,000,000 19
*zinc ores only.

Table 8 Silver vs. Indium.

To summarize, the current 160 metric tons per year
Metal Concentration in Current production of indium is insufficient to fully substitute for
Earth's Crust Market lead in all electronic solder used today. However, for the
indium ∼0.1 ppm 160 MT high-fatigue-reliability-required applications, indium does
silver ∼0.1 ppm 15,000 MT have a future as an alloying metal in lead-free solders for the
following reasons:

figures have actually increased 54% from their 1987
tabulation. Another indicator of potential availability is
years of reserves left based on production levels. Using
USBM conservative data, Table 7 shows that indium is
presently about the same position as lead, silver and zinc in
terms of years of reserves at their respective production
levels. Reserves are only a confirmation that adequate ore
exists to assure a 15 - 20 year supply and not a scientific
evaluation of the total amount of the metal that is
recoverable in the earth's crust.
Finally, an interesting comparison can be made between
indium and silver. Table 8 shows that while the abundance
of indium and silver in the earth's crust is about the same,
today's market for indium is only 160 metric tons compared
to the 15,000 metric tons of silver. Silver, like indium is
typically recovered as a secondary metal. The production of
silver over time, increased to meet marketplace demand. The
same scenario has always and will continue to apply to
indium.
Availability of the metal should not be a concern.
Published indium reserves and resources are
substantially understated and based on indium-
containing zinc ore only. Substantial indium deposits
exist worldwide in other ore types.
Extraction efficiency of producing indium from ore is very
low. Improvements in extraction technology can provide
a substantial increase to indium production without the
need for geological exploration.
SUMMARY
A novel lead-free solder, 77.2Sn/20.0In/2.8Ag solder alloy,
has been developed and evaluated as a replacement for
63Sn/37Pb. In general, this Sn/In/Ag alloy exhibits
comparable physical and wetting properties, but superior
mechanical and creep properties than Sn/Pb solder. Test
results from the surface mount assembly process and
temperature cycling study indicate that this alloy is indeed a
viable candidate as an electronic soldering material. The
availability and price of indium have been reviewed, with the
conclusion that the potential supply is very promising in
terms of meeting the demand.

REFERENCES
1. J.A. Slattery and C.E.T. White, "Lead-Free Alloy
Containing Tin, Silver and Indium, " U.S. Patent 5,256,370
(Oct. 26, 1993).
2. R.N. Wild, "Some Fatigue Properties of Solders and Solder
Joints", INTERNEPCON, Brighton, England (Oct., 1975).
3. Annual Report on Lead, U.S. Bureau of Mines, 1991.