From the NEPP/NASA thing: "It is widely believed (though reasons remain somewhat of a mystery) that Pb when alloyed with tin imparts whisker-inhibiting attributes to the final finish."
Not really a proof.
The main issue with lead free solder is its not so good handling of mechanical stress.
It's a combination of creep and tin whiskers. Since the time that Clech published his paper in 2004 (
http://www.jpclech.com/Clech_APEX2004_Paper.pdf ) comparing SnAgCu (SAC) to SnPb (typical tin-lead), companies like AIM and Indium have developed solders that exhibit stress characteristics that are quite good over time and temperature:
https://en.wikipedia.org/wiki/Solder_alloys
Note the mechanical characteristics of Sn77.2In20Ag2.8 are very similar to Sn63Pb37...
https://www.researchgate.net/public...ad-Free_Solder_Joints_in_Electronic_Packaging
https://aimsolder.com/technical-art...ering-properties-alternative-lead-free-alloys
But the problem for what we do in the MIL arena still lies in the worry that whisker growth can occur - esp. with the addition of alloying materials for increasing mechanical strength -
https://www.nature.com/articles/s41598-019-44758-3.pdf?origin=ppub
From :
https://www.mdpi.com/2076-3417/9/10/2044/pdf
"Currently, researchers mainly improve the performance of lead-free solders by microalloying and
nanoparticles strengthening. Microalloying is a method of improving the properties of the solder by
adding trace alloying elements to change the solder composition. The alloying elements can be mainly
divided into rare earth (RE) elements (Ce, La, Pr, Nd, etc.) [6,7] and other metal elements (Ga, In, Mg,
Ni, Ag, etc.) [8–11]. However, there are still some shortcomings in this method, which limits the widely
application of the lead-free solders containing minor alloying elements. For example, adding excessive
RE elements will result in the formation of Sn whisker on the surface of solder joints, causing premature
failure of electronic device [12,13]."
Another issue occurs due to embrittlement. (
https://en.wikipedia.org/wiki/Embrittlement) Some of the failures that were initially attributed to SAC solder mechanical failures were exacerbated - and possibly caused by - ENIG ( Electroless nickel immersion gold ) of the bare PCB's.
ENIG is one of many methods to prevent oxidation of PCB lands and pads. For years, SMOBC ( Soldermask Over Bare Copper) with HASL (Hot Air Surface Level) was used. In the early 90's some PCB fab houses started using OSP (Organic Surface Protectants). For example Rad Shacks protoboards used this. Solderability sucks as compared to other methods.
Typically, ENIG/ENEPIG (nickel electroless palladium immersion gold ) are preferred by consumer Contract Manufactures (CM) since it provides a much flatter surface for automated paste and pick and place/reflow. The gold dissolves into the solder; to prevent embrittlement., the percentage of gold in the joint should be < 2.5-3% /wt (
http://www.circuitnet.com/experts/87487.html )
The problem is that if not controlled it can build up to a point that long term reliability is affected, since embrittlement can occur months after assembly.
Although gold of a thickness under/equal to 2.54 um was and still is considered OK under 4.5 of the J-STD_001 the F revision of the specification from , section 4.5.1 added:
"Note: Gold embrittled solder connections can occur regardless of gold thickness when solder volume is low or the soldering process
dwell time is not sufficient to allow the gold to dissolve throughout the entire solder joint. "
When we were dealing with what we thought was SAC mechanical failure for some consumer gear, the lab in Oregon found that cross-sections under electron microscopy were actually embrittled with a very obvious non-metallic structure that had formed.
Some great papers here:
https://semlab.com/papers/
So another thing our MIL guys will not allow in addition to lead-free is ENIG/ENEPIG - all our fab and assembly drawings now state this.
All in all, it's difficult to ascertain, in postmortem of a failed assembly, that the cause is due to the solder or the PCB surfacing...