A Drop-In Lead Free Solder Replacement
A Drop-In Lead Free Solder Replacement
A Drop-In Lead Free Solder Replacement
ABSTRACT Lead Reduction Act of 1990 (S.2637), a bill that would limit or
Environmental and toxicity concerns related to the use of ban the use of lead-containing materials, including
lead have initiated the search for acceptable, alternate electronics solders, was introduced four years ago, by
joining materials for electronics assembly. This paper Senator H. Reid. After intense lobbying by the electronics
describes a novel lead-free solder designed as a "drop in" industry and the Lead Industries Association, electronics
replacement for common tin/lead eutectic solder. The solders were deleted from subsequent revisions to the bill.
physical and mechanical properties of this solder are In its present form, the bill (S.729) will probably be
discussed in detail with comparison to tin/lead eutectic reintroduced in the Senate this year, and while electronics
solder. The performance of this solder when used for solders will be excluded, the bill will have a "new use and
electronics assembly is discussed and compared to other unnecessary inventory" provision, require labeling that
common solders. Fatigue testing results are reported for would include a bar on defenses for products that require
thermal cycling electronics assemblies soldered with this labels, establish an "exposure concern list", and ban certain
lead-free composition. The paper concludes with a lead-containing products.
discussion on indium metal availability, supply and price.
The other legislative initiative involves taxing lead and lead
Key Words: solder, soldering, lead-free, electronic, reflow, containing products. The Lead-Based Paint Hazard
solder paste, SMT, surface mount, Pb-free Abatement Act (H.2922) was introduced in the House by
Congressman Cardin in 1991 and would place a tax of
RATIONALE FOR LEAD-FREE SOLDER $0.75/lb on primary refined lead and a $0.37/lb tax on
Tin-lead solder has been used in electronics assemblies secondary refined lead, irrespective of its final use. The
since the earliest days of radio. Its adequate and well revenues from these measures were targeted as funding for
documented mechanical, electrical and thermal properties, the renovation of older housing units containing lead-based
combined with its low material cost, have made it the material paints. The revised version of this bill, (H.2479) proposes a
of choice for joining active and passive components. tax of $0.45/lb on the lead content of all lead-containing
However, well publicized environmental and toxicity products and is gaining support. A similar bill was
concerns have led to increased controls and legislation (in introduced in the Senate (Bradley S.1347). There is a good
the U.S. and other countries) which if enacted, would reduce, chance that these bills will become law in 1994 either as
tax or eliminate the use of lead in solders for electronics stand alone entities or attached to other legislation.
assembly.
GOALS FOR DEVELOPMENT OF LEAD-FREE SOLDERS
The use of lead in non-solder related materials such as The following goals were established for the development of
tetraethyl lead additive for gasoline, and lead naphthenate a new non-lead containing solder specifically designed for
and lead oxide for paint, have been banned for years. More electronics assembly use:
recently, lead containing solders have been banned for use
in potable water piping, food and beverage cans and 1. Have a melting temperature similar to 63Sn/37Pb
automobile bodies where they were used in repair solder.
applications. 2. Have a narrow plastic range.
3. Have adequate wetting properties.
There are two major federal legislative initiatives on lead 4. Have physical properties similar or better than
currently being pursued in the U.S. Congress. The Toxic those of Sn/Pb solder.
5. Be compatible with existing liquid flux systems. properties but has not found widespread usage.
6. Be capable of fabrication into existing physical
forms of solder i.e. wire, preforms, ribbon, 97Sn/2Cu/0.8Sb/0.2Ag is a lead-free plumbing solder that
spheres, powder, paste, etc. was developed by Kester Solder Company and is marketed
7. Have adequate shelf life and performance as a under the trade name of Aquabond. Its performance mimics
solder paste. that of Sn/Pb eutectic but at a higher melting temperature.
8. Contain relatively non-toxic metals.
9. Possess low dross formation when used in a 95.5Sn/4Cu/0.5Ag is lead-free plumbing solder developed by
wave soldering operation. Engelhard. Its wide melting range of 225°-349°C would
severely restrict its use as an electronics solder.
CURRENT LEAD-FREE ALTERNATIVES
The alternatives available today include a few lead-free Conductive polymers are mixtures of organic chemical
metallic solders and conductive polymers. Of the available components and a conductive metallic filler. The organic
lead-free solders and conductive polymers, all fail to meet chemical component consists of a resin system (that may be
one or more of the goals listed above. Table 1 lists some thermoplastic or thermosetting), a solvent system and
common lead-free solders, their melting properties and a rheological additives. To this mixture is added a metallic
brief description. More details on the solders are given filler, typically silver flake. The resultant paste can be
below: dispensed or screened onto the substrate, heated to drive
off the solvent and initiate a curing process. The resin
52In/48Sn is considered the lowest melting point solder and provides the mechanical attachment whereas the silver flake
is often used as the last step in a sequential soldering provides electrical conductivity between the joined surfaces.
operation, and for soldering to metallizations on temperature Conductive polymers can be isotropic, having electrical
sensitive components. conductivity in all planes, or anisotropic where the electrical
conductivity is only in the "Z" axis.
58Bi/42Sn is relatively inexpensive and has a proven track
record where it has been used in wave soldering of printed The major shortcomings of conductive polymers include
circuit assemblies. However the melting point is lower than substantially lower conductivity compared to metallic
tin/lead eutectic. solders, high cost, rework difficulty, low bond strength and
absence of self alignment. These shortcomings have
91Sn/9Zn has been used to solder aluminum using inhibited their general use for component attachment.
specialized fluxes. Because of its corrosion potential, zinc However, there is intensive research directed to improving
poses a concern. Solder paste incorporating this alloy the performance of these materials and they may in the
would have a poor shelf life due to attack on the metal future prove to be viable replacements for metallic solders
spheres by the organic acids present in the flux vehicle. for some applications.
Additionally, the alloy drosses excessively when used in a
wave soldering operation. HISTORICAL PERSPECTIVE OF Sn/In/Ag ALLOY
DEVELOPMENT
96.5Sn/3.5Ag and 95Sn/5Sb both exhibit good wetting Although tin-lead eutectic solder has adequate physical
characteristics. Additionaly, 95Sn/5Sb has excellent shear properties and has been used succes sfully for a long time in
strength at 100° C. The high melting point of these alloys electronics assembly, certain specialty solders have been
may limit their application. developed to meet the need for specific applications. For
example, the lead-indium system was developed to meet the
65Sn/25Ag/10Sb is a patented alloy developed by Motorola specific requirement for soldering to gold substrates. The
and is commonly known as "Alloy J". It has good fatigue alloy 92.5Pb/5.0In/2.5Ag was developed to meet the need for
Properties Alloy
77.2Sn/20.0In/2.8Ag 63Sn/37Pb
Properties Alloy
77.2Sn/20.0In/2.8Ag 63Sn/37Pb
Creep Behavior from which the melting point was determined from the onset
The creep behavior is also relevant to solder joint fatigue temperature of the peak (s). The first run (20°C/min) shows
reliability performance. Materials being more creep resistant an endotherm with an onset of 165.3°C and a peak
usually exhibit a better fatigue resistance. In this study, the temperature of 185.5°C. The second run of the sample (1°
creep test was conducted on the bulk solders per ASTM C/min), and from which the thermal properties were obtained
E139-83 at 20°C. As shown in Figure 1, the data indicate that (Fig. 2), showed that there is a small low temperature peak at
the steady creep rate of 77.2Sn/20.0In/2.8Ag is about two 113.5°C. As to the main peak, although a slight sign of
and half orders of magnitude lower than that of 63Sn/37Pb. melting may be noticed at 150°C, significant melting really
This superior creep resistance behavior suggests an occurs between 174.7°C and 186.5°C, with the latter as the
improved solder joint reliability with the 77.2Sn/20.0In/2.8Ag peak temperature. The source of the small low temperature
alloy. peak is likely a depression of the 118°C eutectic point
accompanying the formation of 52In-48Sn caused by the
Melting and Softening Behavior high indium content in the material. Of course, without
The melting properties of the Sn/In/Ag solder were metallographic data, the formation of a low temperature
determined by Differential Scanning Calorimetry. (DSC). The ternary phase cannot be ruled out.
procedure was to initially run the sample at a heating/cooling
rate of 20°C/minute past the liquidus temperature in order to: The higher temperature (or main) peak will allow to define the
(1) allow it to conform to the sample pan, thereby minimizing processing temperature of the solder during product
thermal lag in the peak positions, and (2) homogenize the manufacturing (which is typically 30-50°C above the liquidus
microstructure. Then, the sample was scanned at 1°C/minute 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
1E-4
Creep at 20C 77.2Sn/20.0In/2.8Ag and 63Sn/37Pb suggests that the
processing temperature required for the two alloys should be
1E-5 very comparable. Hence, this solder has utility as a "lead-
Steady Creep Rate (s-1)
It is estimated that 4500 metric tons of lead are consumed per The primary sources of indium in recent times have been and
year in the U.S.3 to manufacture electronic solder; the world likely will continue to be Canada, South America and Japan.
wide consumption is probably three times this figure. If The former Soviet Union, (the CIS) which is the largest zinc
indium were to replace lead at this usage (40% lead in producer in the world has also been a significant producer of
solder), an adjustment to account for the different densities indium. While their plants may need to be modernized, the
of lead and indium would need to be applied, in order to CIS potential from a resource and reserve point of view can
maintain the volume of solder. Since the density of indium is not be discounted. Indium currently is recovered in lead/zinc
7.3 and the density of lead is 11.35, the required U.S. metallurgical complexes, which extract but a small portion of
consumption of indium would be 2894 metric tons per year. the available indium. CIS total production of indium is
(7.3/11.35 times 4500). However, if the solder contained 20% thought to be 1/4 to 1/3 of what it could be if indium was
indium (which is more realistic), the U.S consumption would extracted from all of the ores that contain indium.
be one-half that amount or 1,447 metric tons, and world wide Additionally, substantial known, but undeveloped, deposits
consumption would be 4,341 metric tons. While it is true that exist in China and Australia and there are potential new
today's indium metal production of 160 metric tons per year indium sources in Bolivia, China, Czechoslovakia, France,
could not meet this demand, indium does in fact have a Hungary, Japan, Peru, and Sweden, as well as here in the
future as an alloying metal in lead-free solders. Consider the U.S.
following:
It is important to realize that the figures on indium metal
Conversion from Sn/Pb Solder to Lead-Free Solder production often cited are from the U.S. Bureau of Mines
At the present moment, it is very unlikely that lead Statistics which are estimates derived from zinc reserves
containing electronic solder "will be banned". The more only. They do not take into consideration the indium
likely scenario will be that leaded solder will be taxed, which content of copper, lead or tin ores. A further complication is
will make lead-free solders more viable from an economic the fact that indium production is a by-product of other
perspective. An orderly conversion to lead-free solders will metal recovery operations and often smelters do not report
allow time for expansion of other metal production capacity. values. In the face of steadily increasing indium production,
It is also very likely that a family of lead free solders will be 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.
figures have actually increased 54% from their 1987 Availability of the metal should not be a concern.
tabulation. Another indicator of potential availability is
years of reserves left based on production levels. Using Published indium reserves and resources are
USBM conservative data, Table 7 shows that indium is substantially understated and based on indium-
presently about the same position as lead, silver and zinc in containing zinc ore only. Substantial indium deposits
terms of years of reserves at their respective production exist worldwide in other ore types.
levels. Reserves are only a confirmation that adequate ore
exists to assure a 15 - 20 year supply and not a scientific Extraction efficiency of producing indium from ore is very
evaluation of the total amount of the metal that is low. Improvements in extraction technology can provide
recoverable in the earth's crust. a substantial increase to indium production without the
need for geological exploration.
Finally, an interesting comparison can be made between
indium and silver. Table 8 shows that while the abundance SUMMARY
of indium and silver in the earth's crust is about the same, A novel lead-free solder, 77.2Sn/20.0In/2.8Ag solder alloy,
today's market for indium is only 160 metric tons compared has been developed and evaluated as a replacement for
to the 15,000 metric tons of silver. Silver, like indium is 63Sn/37Pb. In general, this Sn/In/Ag alloy exhibits
typically recovered as a secondary metal. The production of comparable physical and wetting properties, but superior
silver over time, increased to meet marketplace demand. The mechanical and creep properties than Sn/Pb solder. Test
same scenario has always and will continue to apply to results from the surface mount assembly process and
indium.
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.