Bismuth: Behind the Numbers

Based on a recent post I published regarding the use of bismuth in solder alloys, John writes:

If Bismuth comes from the production of Pb, and if the use of Pb is being reduced, won’t the availability of Bi be reduced…and the price would increase?”

Just thinking…

Dr. Ron responds:

Lead has been banned from many of its original uses, paints, solders, water pipes, gasoline, etc. However, its increased use in batteries has actually caused lead consumption to rise. The USGS estimates that 88% of lead produced is used for lead-acid batteries.

Many of us in electronics assembly have been focused on the 2006 RoHS lead ban. This may have caused us to believe that lead use in electronics was significant. About 9 million metric tons (MT) of lead are consumed each year, only about 20,000 metric tons were used for solders prior to July 2006, this amount is only about 0.22% of the total. Electronics lead use being so small is likely why the lead industry had little visibility in fighting RoHS. Their important customers were making batteries.

Lead is quite effectively recycled, as about 60% of the 9 million MTs/yr. are from recycling and 40% from mining.

Over 100 million lead-acid auto batteries are sold each year in the US alone. In addition, the use of lead-acid batteries in forklifts, electronic vehicles, and golf carts has increased demand for lead. So, the bottom line is that lead use is expected to grow at about 2% per year.

Considering that we calculated that bismuth use in solders would be at most 5% of total bismuth production, it is unlikely that this use, or lead production reduction, would affect bismuth supplies.

Best Wishes,

Dr. Ron

A Few Questions on Bismuth

Folks,

A few people asked some questions after a post on bismuth solders. Here they are:

1. The low melting point of these solders is encouraging. What are realistic field use conditions?

Bismuth solders tend to be brittle, so drop shock environments such as mobile phones would not be recommended. However, thermal cycle performance from 0 to 100C is good, so stationary office equipment, televisions, desktop computers, etc., may be good candidates.

2. I am working with your colleagues on an automotive application and I am curious whether you have any idea how this alloy will perform between -40 and 0°C? We have not been reviewing bismuth-containing alloys due to their lower sheer strength, but may need to look at them in the future.

We can find no information on thermal cycle performance at these low temperatures.

3. I hear that bismuth is rarer than silver. If we start using bismuth in solders, couldn’t that make it very expensive.

An old number from Prismark puts the world solder use at about 50,000 metric tons (MT) per year.  Assume bismuth solders took a 5% market share (I think this would be the highest) that is 2,500 MT of bismuth solder (Bi57Sn42Ag1) or 1,425 MT of bismuth.

Although bismuth’s occurrence in the earth’s crust is 0.009 ppm (silver is 0.075 and gold 0.004 ppm), about 22,000 MT are produced each year.  In comparison, about 2,000 MT of gold, 20,000 MT of silver, 400 MT of indium and 5 MT of rhodium are produced each year.  In comparison to more common metals, total lead production is 8,000,000 MT/year and tin a little less than 700,000 MT.

Realistically, it would seem to me to be unlikely that use of bismuth in solder, at 1,425MT/year out of 22,000 MTs,  would affect the price much, especially if the adaptation rate is more like 1-3%, instead of 5%.

For those interested in how bismuth is produced, this Wikipedia quote may be of interest:

According to the United States Geological Survey, world 2009 mine production of bismuth was 7,300 tonnes, with the major contributions from China (4,500 tonnes), Mexico (1,200 tonnes) and Peru (960 tonnes).[11] World 2008 bismuth refinery production was 15,000 tonnes, of which China produced 78%, Mexico 8% and Belgium 5%.[9]

The difference between world bismuth mine production and refinery production reflects bismuth’s status as a byproduct metal. Bismuth travels in crude lead bullion (which can contain up to 10% bismuth) through several stages of refining, until it is removed by the Kroll-Betterton process or the Betts process. The Kroll-Betterton process uses a pyrometallurgical separation from molten lead of calcium-magnesium-bismuth drosses containing associated metals (silver, gold, zinc, some lead, copper, tellurium, and arsenic), which are removed by various fluxes and treatments to give high-purity bismuth metal (over 99% Bi). The Betts process takes cast anodes of lead bullion and electrolyzes them in a lead fluorosilicate-hydrofluorosilicic acid electrolyte to yield a pure lead cathode and an anode slime containing bismuth. Bismuth will behave similarly with another of its major metals, copper. Thus world bismuth production from refineries is a more complete and reliable statistic.

So I don’t think bismuth supply and price would be affected by its use in solders.

Cheers,

Dr. Ron

By and Bi

Folks,

When the industry was preparing to transition to lead-free solders almost ten years ago (can it have been that long), tin-bismuth solders were serious candidates. Their low melting point, of about 138C, made these solders interesting candidates to replace tin-lead solder. However, if contaminated with lead, tin-bismuth solders can produce a eutectic phase that melts at 96C. In such situations the resulting solder joint exhibits poor performance in thermal cycle testing. Since early in the transition to lead-free solders it was expected that there would be numerous components and PWBs with lead-based surface finishes, this property made tin-bismuth solders unacceptable.

Another aspect of tin-bismuth solders is that they expand on cooling. This phenomenon can result in fillet lift in through-hole solder joints.

However, as we are now well into 2011, almost no components or PWBs have lead-containing finishes and many portable electronic devices have no through-hole components, so it may be time to reconsider tin-bismuth for some applications.

Some years ago, Hewlett Packard (HP) had performed work to show that adding 1% silver to tin-bismuth solder enabled this alloy to outperform eutectic tin-lead solder in 0 to 100C thermal cycle testing. Even at these low reflow temperatures, HP demonstrated solder joint strength with SAC BGA solder balls that was 65% that of tin-lead solder. Expanding on this work, Indium’s Ed Briggs and Brook Sandy performed stencil printing and reflow experiments consistent with the requirements of current miniaturized components using this 57Bi-42Sn-1Ag solder. All their results were promising. Ed presented a paper at SMTA Toronto that summarized the Hewlett Packard work and reviewed the results of this new work.

Bismuth solders tend to be brittle, so applications experiencing drop shock should be avoided.

So for applications consistent with 0-100C thermal cycling, 57Bi-42Sn-1Ag solder may be something to consider if the high temperature of SAC solder paste is an issue to components or PWBs in a product.

Cheers,

Dr. Ron