Académique Documents
Professionnel Documents
Culture Documents
Paul T. Vianco
Sandia National Laboratones
Abstract: Legislative and marketing forces both latter case was embodied in Section 1417 of tie $kife
abroad and in the US are causing the electronics Drinking Water Act Amendments enacted in 1986[1].
industry to consider the use of Pb-free solders in At the time of this enactment, the availability of
place of traditional Sn-Pb alloys. Previous case mechanical properties for soft-solder plumbing joints
studies have demonstrated the satisfactory was limited to studies on the 50Sn-50Pb (wt.%) solder
manufacturability and reliability of several Pb-free and the non-Pb containing 95 Sn-5Sb alloy that were
compositions for printed circuit board applications. performed in the late 1930s[2,3]. Recently, more
Those data, together with the results of fundamental extensive mechanical properties studies have been
studies on Pb-free solder materials, have indicated completed by the International Tin Research Institute
the general feasibility of their use- in the broader (ITRI, Ltd.) as well as by a collaborative program
range of present-day, electrical and electronic between the Copper Development Association (CDA)
components. and the National Institute of Standards and Technology
(NIST)[4,5]. These studies have greatly enhanced the
I. INTRODUCTION properties databases for the now commonly used 95Sn-
5Sb plumbing solder (ASTM “HB”) as well as the newly
Lead (Pb), either in its elemental form or when alloyed developed 95.5Sn-4.OCu-O.5Agalloy (ASTM “E)[6].
with Sn to create so-called “soft solders,” has had a role
in joining together metal structures for neariy 5000 years. The move to eiiminate Pb from electronic solders was
Those early applications included the construction of initiated in the early- 1990s. The basis for the removal of
common utensils and light-duty tools as well as their use Pb-bearing solders from electronic products was the
as a seal material to control leaks between the Pb liners contention that Pb leaching from an ever increasing
of aqueducts built by the Roman Empire (first plumbing amount of discarded electronics in landfills, would
application). contaminate nearby ground water resources. Thus, a
number of bills were introduced into the US. Congress
The Industrial Revolution in the later 19* century and, in that would’ either ban or heavily tax the use of Pb in
particular, the development of portable heat sources, manufactured products, including electronics that used
expanded the use of soft-solders in structural Pb-beming solders[7,8]. Interestingly enough, at the
applications, foremost, in the plumbing of conduit. In same time, there was very Iitde activity along these lines
the early 20¢ury, soft-solders found an entirely new occurring in European or in the Pacific rim countries.
application with the development of electronics (radios). Ultimately, these bills were defeated in their respective
The low melting temperatures of soft-solders, in governing bodies as lawmakers were made aware of the
particular, the Sn-Pb alloys, caused them to be potential consequences to the US electronics industry in
particularly well suited for the attachment of vacuum terms of lost market-share both domestic and abroad.
tubes, capacitors, etc. onto, what were then, very crude
(and extremely flammable) circuit boards. And thus, The current impetus to remove Pb-bearing solders from
from the 1920s up until the 1980s, the two principle electronic components and assemblies remains based
applications of Pb-containing soft-solders have remained upon reducing potential ground water contamination
plumbing and electronics. from discarded electronic products. Now, however, the
drivers for Pb elimination have come almost entirely
In the late 1970s and early 1980s, concerns were raised from abroad - primarily Europe and Japan. Moreover,
about the potential for Pb poisoning from solder joints while the European initiative is based largely upon
used to assemble potable water (Cu) conduit and food legislative actions, the case in Japan stems from the
containers. Mandates were subsequently issued by the initiatives of individual corporations to remove Pb-
US government, banning the use of Pb-bearing solders in containing solder from their respective electronic
the construction of food service equipment and, more products. First, the case of Europe will be examined.
importantly, the plumbing of potable water conduit. The The primary legislative action targeting the European
1Sandia is a multiprogam laboratory operated by &ndia Corporation, a ~ckh~d Mtin Company, for fie U.S. Dept. of
Energy under Contract DE-AC04-94AL85000.
DISCLAIMER
Table I. Contact Angles of Several Pb- solder[2 1]. However, the effect of gap thickness was not
Free Solders (Substrate: Cu; Flux well pronounced with the Pb-free solders, including no
RMA) significant effect had by SnSb, SnAg, and SnAgCu
solders. The overall limited capillary flow behavior
Test exhibited by the Pb-free solders was attributed directly to
the inherently high surface tension of these particular
Solder Temperature Oc alloys[22]. One method to modify (decrease) the surface
(wt.%) (“c) (0) tension of a Pb-free solder is to change the brand of flux.
Proprietary additions to basic flux chemicais can lessen
96.5 Sn-3.5Ag 260 36L3 the surface tension of the molten solder. Also, the use of
Au plating on the faying surfaces, with due precaution
95 Sn-5Sb 268 42*7
against excessive Au that will embrittle the joints, can
9 1.84Sn-3.33Ag 260 31*4 help to reduce the surface tension of the solder[23].
4.83Bi
58Bi-42Sn 215 3727 A second characteristic of capillary flow is the
50Sn-501n 215 63~3 propensity for voids to become entrapped in the newly
formed joint. Void formation is strongly dependent on
63Sn-37Pb 260 1724
the particular, flux type. Per a given flux brand, void
formation increases as the gap thickness decreases; a
Capillary action will often assist the wetting and smaller gap raises the difficulty with which flux volatiles
spreading action of a molten solder in the case of and air can escape during solder flow. The extent of
confined geometries such as gaps and holes. Shown in voiding, as determined by x-ray radiography of the
Figure 1 is a graph of capillary rise between two parallel, capillary flow test “samples,is summarized by the graph
Cu plates as a function of gap thickness. The solder in Fig. 2. The expected trend of more voids with smaller
alloy compositions (wt.%), abbreviations, and test gaps was observed. The behaviors of the individual
temperatures were: (1) 95 Sn-5Sb, SnSb, 280°C; (2) solders became less distinguishable when the gap was
63 Sn-37Pb, SnPb, 260”C; (3) 96.5 Sn-3.5Ag, SnAg, equal to, or greater than, 0.025 cm. Finally, the solders
260°C; (4) 91.84Sn-3.33Ag-4.83Bi, SnAgBi, 260”C; and SnAg and Sn-Pb (baseline) gave consistently more voids
(5) 95.5Sn-4.0Cu-0.5 Ag, SnCuAg, 267°C. All tests were than the other solders, particularly at the smaller gaps.
performed with an RMA flux. The SnAgBi solder
showed the highest capillary rise and sensitivity to gap
thickness amongst the Pb-free alloys. +Snsb :
-+- SnPb
-H-SnAg :
-SnAgB1 :.
—--- S. CUM ;
g
;.:
. ... .. . . . . . . . . .
g
;;;
jj :::
a
,:
..
,::
;:,
%
O.oj:ii
o
~:!m
this defect may be generalized to any similar solder joint
configuration; its occurrence will depend upon the exact
Piug joint dimensions, solder and base materials, as well as
(copper) the process techniques.
F
‘-%
6.S5mm
solder
u 21 joint
(0.791 mm)
3.18 mm
iii
..
-.:: x
.-.:-.
+
o Ring
(copper)
F
B 4;
10 mnvinh
~ 3.lJm
k 9.53 mm
N x
A list of shear strengths (25”C, 10 mrn/min displacement Figure 5. Fillet lifting of a printed
rate) for several Pb-free solders as well as that cir&it board through-~ole made with
representing the 63Sn-37Pb alloy is provided in Table II. the 91.84Sn-3.33Ag-4.83Bi solder.
Solder .’:.+<?:”
“’’””l
some phase boundary sliding and a few isolated cracks.
The resistance to thermal mechanical fatigue was further
substantiated by only a nominal decrease in the shear
strength of the chip capacitor solder joints upon
mechanical testing (10 mm/min).
III. CONCLUSION
[4] Solder AIJoyData, Publication L55(j,International Tin [23] P. Vianco and A. Claghom, “Effect of SubsWate
Research Institute, Uxbridge, Middlesex, UK. 1986 Preheating on Solderability Performance as a Guideline
[5] R. Fields, D. Shepherd, A. Cohen, and A. Kireta, Jr., for Assembly Development,” Soldering and Su@ce
“Stress Rupture of Lead-Free Soldered Joints Used to Mount Technology, No 24, October 1996, pp. 12-18.
Assemble Copper Plumbing Systems,” Proc. Inter. [24] M. Bester, “Metallurgical Aspects of Soldering
Brazing and Soldering Conference 2000, April 2-5, Gold and Gold Plating,” Proc. Inter/NEPCON Brighton,
2000, Albuquerque, NM (American Welding Society, UK, 1969, pp. 211-231.
Miami, FL), pp. 501-506. [25] R. Duckett and M. Ackroyd, “The Influence of
[6] “Solder Specification for Solder Metal,” ASTM B32- Solder Composition the Embrittlement of Soft-Soldered
96, American Society for Testing and Materials, West Gold Coatings,” Electroplate. Met. Finish, ~, 1976, pp.
Conshohoken, PA. 13-20.
[7] H. Reid, “Lead Exposure Reduction Act of 1993,” S- [26] D. Jacobson and G, Humpston, “Gold Coatings for
729. 1993 Fluxless Soldering,” Gold Bulletin 221989, pp. 9-18.
[8] B. Cardin and H. Waxman, “Lead-Based Paint [27] P. Vianco and C. May, “An Evaluation of Prototype
Hazard Abatement Act or 1991”, HR-2922. 1991. Surface Mount Circuit Boards Assembled with Three
[9] K. Nimmo, “Worldwide Environmental Issues in Non-Lead Bearing Solder,” Proc. Su$ace Mount Inter.
Electronics and the Transition to Lead Free,” Proc. IPC Aug. 29-31, 1995, San Jose, CA: 1995,481-494.
Works 99, October 23-28, 1999, Minneapolis, MN, (IPC, [28] P. Vianco, “An Overview of Surface Finishes and
Northbrook, IL) pp. S-01-2-1 to S-01-2-6. Their Role in Printed Circuit Board Solderability and
[10] “Alternative Solders for Electronic Assemblies,” Solder Joint Performance,” Circuit World E 1998, pp. 6-
Final Report M,!Y20073,DTI Sponsorship, 1993. 24.
[11] K. Nimmo, “Environmental Issues in Electronics [29] C. Hunt and D. Lea, “Solderability of Lead-Free
and the Transition to Lead-Free Soldering,” Proc. of Alloys,” Proc. of APEX 2000, March 12-16, 2000; Long
SMTA Inter. Sept. 14-16, 1999, San Jose, CA (SMTA, Beach, CA; pp. P-MT213-1to 3-4.
Edina, MN), pp. 377. [30] P. Vianco and J. Rejent, “Properties and
[12] K. Suganuma, “Research and Development for Performance of Sn-Ag-B i Solder for Electronics
Lead-Free Soldering in Japan,” Proc. [PC Works 99, Applications,” presentation at the TMS Fall Meeting ’99,
October 23-28, 1999, Minneapolis, MN, (IPC, November 2, 1999; Cincinnati, OH.
Northbrook, IL) pp. S-01-5-1 to S-01-5-4. [31] K. Stone, R. Duckett, S. Muckett, and M. Warwick,
[13] P. Vianco, Soldering Handbook 3“ edition, (Amer. “Mechanical Properties of Solders and Soldered Joints,”
Welding Society, Miami, FL: 2000), pp. 215-216. Brazing and Soldering No. 4 Spring 1983, pp. 20-27.
[14] P. Vianco and J. Rejent, “Properties of Ternary Sn- [32] P. Vianco, “So[id State Intermetallic Compound
Ag-Bi Solder Alloys: Pt. I, Thermal and Microstructural Layer Growth Between Cu and Selected Pb-Free
Analysis,” J. Electronic Materials 28, 1999, pp. 1120- Solders-Interface Reaction Compositions and Growth
1138. Kinetics,” Environmentally Friendly Electronics
[15]K. Feldmann and M. Reichenberger, “Assessment of Manufacturing ed. J. Hwang, to be published, 2000.
Lead-Free Solders for SMT,” Proc. APEX 2000, Mar. [33] P. Vianco, J. Rejent, and R. Grant, “Development of
12-16,2000, Long Beach, CA (IPC, Northbrook, IL) pp. Multicomponent Alloys as Pb-Free, Low-Melting
P-MT2/2-l to 12-12. ~ “ Temperature Solders,” presentation at TMF Fall Meeting
[16] P. Vianco, op. cit.p.211. ’97,Indianapolis, IN; 1997.
[17] Bina~ Alloy Phase Diagrams - Volume 2 ed. by T. [34] M. Neiisen, S. Burchett, C. Stone, and J. Stephens,
Massalski, (ASM, Inter., Materials Park, OH: 1986), p. “A Viscoplastic Theory for Braze Alloy s,” SAND94-
2086. 0984, Sandia National Laboratories, Albuquerque, NM
[18] P. Vianco, op. cit. p. 212. 1996.
[19] P. Vianco, op. cit. pp. 163-165.
[20] A. Jackson, 1. Artaki, and P. Vianco, V. ACKNOWLEDGE~NTS
“Manufacturing Feasibility of Several Lead-Free Solders The author wishes to thank Cindy Hemandez for her
for Electronic Assembly,” Proc. Th Inter. SAMPE thoughtful review of the manuscript.
Electronics Conf June 20-23, 1994, Parsipanny, NJ, pp.
381-393. Paul T. Vianco received his Ph.D. in Materials Science
[21] J. Bickerman, Swface Chemist~ for Industrial from the University of Rochester in 1986. Current work
Research (Academic Press, New York, NY: 1947), p. 19. includes solder alloy development, surface mount
[22] P. Vianco and J. Rejent, “Capillary Flow Solder assembly processing, and reliability modeling.
Nettability Test,” Soldering and Surface Mount Key words: Pb-free, solder, processing, reliability,
Technology No. 25, Februaxy 1997, pp. 4-7. intermetallic compound, thermal mechanical fatigue