Lead Corrosion

There are three important versions of lead corrosion: Red, Brown and White.  In addition, there are other factors that can weaken the lead came.

Red lead is a corrosion product that appears as a bright red surface, is dangerous, and requires water, air and often wood, to form. Sometimes water in the manufacturing process can develop red lead.   The chemical composition of red lead (Lead (II, IV) or triplumbic tetroxide is Pb₃O₄ or 2(PbO^.PbO₂).  It is a bright red or orange crystalline or amorphous colour.

Red lead is virtually insoluble in water or in ethanol. But, it is soluble in hydrochloric acid as is present in the stomach.  When ingested, it is dissolved in the stomach’s gastric acid and absorbed, leading to lead poisoning. It also dissolves in undiluted acetic acid, as well as in a dilute mixture of nitric acid and hydrogen peroxide.

When inhaled, lead (II,IV) oxide irritates the lungs. In the case of a high exposure, the victim experiences a metallic taste, chest pain, and abdominal pain.

High concentrations can be absorbed through skin as well, and it is important to follow safety precautions when working with lead-based paint.

This means that anyone dealing with read lead needs protection against skin contact, and breathing protection.  Methods need to be implemented to ensure no dust is raised, or that the area is thoroughly cleaned after dealing with red lead. Clothing should be discarded or washed separately from all others.

White lead corrosion, Lead(II) carbonate, is the chemical compound PbCO₃. It occurs naturally as the mineral cerussite.  It is a curious compound, as it is soluble in both acid and alkali.  It is possible, but rare, for excess whiting left on the lead to give rise to this form of corrosion. Generally, it will be neutralised by the weather.

Brown lead corrosion appears as a brown to dull red colour. 

Lead(IV) oxide, commonly called lead dioxide or plumbic oxide or anhydrous plumbic acid …, is a chemical compound with the formula PbO₂. … It is of an intermediate bond type, displaying both ionic (a lattice structure) and covalent (e.g. its low melting point and insolubility in water) properties. It is an odourless dark-brown crystalline powder which is nearly insoluble in water. …. Lead dioxide is a strong oxidizing agent which is used in the manufacture of matches, pyrotechnics, dyes and other chemicals. It also has several important applications [e.g.,] in the positive plates of lead acid batteries.    Source: wikipedia

Air, water and salt are needed to form brown lead. This means coastal areas and those with driving rain are prone to this kind of oxidisation. Lead dioxide also forms on pure lead, in dilute sulfuric acid.  So, with the acid rain that we are all subject to, it can form in almost any situation, but will be more obvious on areas exposed to the prevailing wind.  The corrosion is soluble in strong acetic acid.

Tin corrosion also has a brown, almost copper appearance, very similar to brown lead.  The tin corrosion will be confined to the solder joint and surrounding area rather than all along the length of the came. 

Corrosion resistant lead

The ideal composition of lead to resist corrosion is 98.5% lead with up to 1% tin. This, combined with fractions of a percent of antimony and traces of silver, bismuth and copper provides a combination of metals and trace elements to resist corrosion of the lead as well as stiffening it.  Conservators indicate that, for whatever reason, cast lead incorporating trace elements is the most resistant to corrosion.  This is evidenced by the longevity of medieval lead cames.

Solder composition

Conservators also indicate that the higher the lead content of solder, and the better the match it is to the lead came, especially the almost pure lead came, the more resistant it is to lead came fracture at the margins of the solder joints.

Stretching the lead came, rather than simply straightening it, not only weakens the lead, it leaves very small pits in the surface of the lead.   These small pits allow the elements of the environment to penetrate the lead’s surface and act as sites for the beginning of corrosion.

Stretching also causes stress points near the solder joint.  The stretching creates stress along the length of the lead.  When the lead is heated in the soldering process the molecules of lead sort themselves into a stress-free arrangement.  As heat does not travel far or fast in lead, there is a stress point formed a short distance from the soldered lead joint where the already stressed and the stress-free lead meet.

Conclusion

Clearly there are a range of factors that relate to the resilience of lead came.  98.5% lead with trace elements including tin and antimony provides the greatest strength and resistance to corrosion.  Stretching the came can lead to general weakness and introduce pits into the surface forming sites for corrosion. Stretching can also lead to stress points near the solder joints.

All these indicate that resilient leaded glass windows can be produced by:

the use of lead came with 1.5% of trace elements,

the use of high lead content solders, and

the straightening (rather than stretching) of the came.

Lead Free Solders

Lead free solders have been created in response to concerns about lead, especially in the electronics industry. The following tables present a selection of available solder compositions.  The characteristics of these lead free solders can be compared to the common lead bearing solders in the last table.

Abbreviations for the metals of the compositions:

Ag=Silver; Bi=Bismuth; Cu=Copper; Ge=Germanium; In=Indium;

Sb=Antimony; Sn=Tin; Zn=Zinc

Melting Temperatures of Lead-Free Solders

Alloy  %                     Melting Temperature    Comments

Range (ºC)

Sn 65, Ag 25                         233           High strength; patented by Motorola (“Alloy J”)

Sn 99.3, Cu 0.7                     227           Eutectic

Sn 96.5, Ag 3.5                     221           Eutectic. Excellent strength and wetting

Sn 98, Ag 2                          221 – 226

Sn 77.2, Ag 2.8, In 20           175 – 186

Sn 95, Sb5                           232 – 240 Good high-temperature shear strength

Sn 42, Bi 58                         138           Well established; expensive

Sn 91, Zn 9                          199   Eutectic. Corrodes easily; high dross

Sn 95.5, Ag 0.5, Cu 4            217 – 350 Lead-free plumbing solder

Sn 97.25, Ag 2, Cu 0.75        217 – 219

Sn 91.8 Ag 3.2, Cu 0.5          217 – 218

Sn 95.5, Ag 3.8, Cu .07         217 – 220

Sn 95.5, Ag 4, Cu 0.5            217 – 225

Sn 95, Ag 4, Cu 1                 217 – 220

Sn 94.6, Ag 4.7, Cu 1.7         217 – 244

Sn 89, Zn 8, Bi 3                   192 – 197

Sn 97, Ag 0.2, Cu 2, Sb 0.8    287 – 318  High melting range; “Aquabond”

Sn 96.2, Ag 2.5, Cu 0.8, Sb 0.5      217 – 225

Sn 90.5, Ag 2, Bi 7.5             190 – 216

Sn-91.8, Ag 3.4, Bi 4.8          201 – 205

Sn 93.5, Ag 3.5, Bi 3             208 – 217

Sn 94.25, Ag 2, Bi 3, Cu 0.75   205 – 217

Sn90.7, Ag3.5, Bi 5, Cu 0.7     198 – 213

Sn 93.4, Ag 2, Bi 4, Cu 0.5, Ge 0.1         202 – 217

Sn 42.9, Bi 57, Ag 0.1           138 – 140

Sn 48, In 52                         118           Eutectic. Lowest melting point. Expensive

Source:

http://www.msed.nist.gov/solder/NIST_LeadfreeSolder_v4.pdf

Liquidus Temperatures (°C) of Candidate Lead-Free Solder Alloys for Replacing Eutectic Tin-Lead Solder

Alloy Composition%     Liquidus             Melting Range

98Sn-2Ag                                             221-226

96.5Sn-3.5Ag              221                    221

99.3Sn-0.7Cu              227                    227

96.3Sn-3.2Ag-0.5Cu     218                   217-218

95.5Sn-3.8Ag-0.7Cu     210                   217-210

95.5Sn-4.0Ag-0.5Cu                             217-219

95Sn-5Sb                                            232-240

42Sn-58Bi                   138                   138

89Sn-3Bi-8Zn                                      189-199

Where there is a single temperature in the melting range column, the solder is eutectic.

Based on:

V. Solberg, “No-Lead Solder for CSP: The Impact of Higher Temperature SMT Assembly Processing,” Proc. NEPCON West 2000 Conf. (Feb. 28 - Mar. 2, 2000) Anaheim, CA (Source: Indium Corp.) # N.-C. Lee, “Lead-Free Chip-Scale Soldering of Packages,” Chip Scale Review, March-April 2000.

Source:

http://www.msed.nist.gov/solder/NIST_LeadfreeSolder_v4.pdf

Solidus and Liquidus Temperatures of Some Leadfree Alloys on Copper

Alloy  %                             Solidus (°C)        Liquidus (°C)

98Sn-1Ag-1Sb                      222                   232 

89Sn-4Ag-7Sb                      230                   230

91.2Sn-2Ag-0.8Cu-6Zn          217                   217

89.2Sn-2Ag-0.8Cu-8Zn          215                   215

89.2Sn-10Bi-0.8Cu               185                    217

85Sn-10Bi-5Sb                     193                   232

52Sn-45Bi-3Sb                     145                   178

42Sn-58Bi                            138                   138

Based on:

M.E. Loomans, S. Vaynman, G.Ghosh and M.E. Fine, “Investigation of Multi-component Lead-free Solders,” J. Elect. Matls. 23(8), 741 (1994)

Source:

http://www.msed.nist.gov/solder/NIST_LeadfreeSolder_v4.pdf

Eutectic Composition of Solders

Most solders and especially tin-lead alloys have a melting (or pasty) range between which the metal has moved from a proper solid (solidus) to a completely liquid (liquidus) state.  Wide melting ranges are ideal for plumbers, they are not for electronics, or stained glass.  It is much easier to run a nice bead with a narrow range of melting (pasty) temperatures.

Some alloys of solder have what is known as an eutectic characteristic.  This is where the liquidus and solidus states occur at the same temperature.  A composition of 61.9% tin and 38.1% lead is both eutectic and the melting occurs at a minimum temperature.

For comparison with lead free solder characteristics the following % compositions of Tin (Sn), Lead (Pb) and Silver (Ag) solders are given.

Element % of solders  Melting point        Comment

Sn 62, Pb 36, Ag 2       179                    Eutectic; traces of antimony

Sn 63, Pb 37               183                    Eutectic; traces of antimony

Sn 60, Pb 40               183-191             Traces of antimony

Sn 96.3, Ag 3.7           221                    High melting point. Eutectic

Sn 10, Pb 90               275-302

Sn 3, Pb 97                275-320

Sn 5, Pb 93.5, Ag 1.5   296-301

Source:

http://en.wikipedia.org/wiki/Solder#Lead-free_solder

Conclusions

Most of the alternative solders contain tin as it assists in the formation of bonds with a wide variety of metals.  These solders are also mechanically weaker than tin-lead solders.  Lastly, they are much more expensive than tin-lead solders.  Even within the tin-lead solders there is a variation in price, as tin is much more expensive than lead. If high temperatures were not a problem, you could use a high lead content solder.  However, that also raises the liquidus temperature and increases the pasty range.

The choice in lead free solders is between the high liquidus temperatures of the less expensive compositions and the high price of the eutectic, or nearly so, ones.  The lowest eutectic composition is the Tin-Bismuth solder, but it is also among the most expensive to buy.  You should also note that the inclusion of copper in the composition prolongs the life of the solder bit, as low lead content of the solder leads to the incorporation of small amounts of copper from the tip into the solder joint.

Lead Came with Alloys

Lead came is available in several hardnesses. One (soft) is almost pure lead, another is half hard and contains up to 5% antimony, and the third is hard, containing up to 10% antimony. The difference between these is hardness, or resistance to creep, not resistance to corrosion.

elemental lead

Lead with antimony as an alloy is subject to the same corrosion rate in atmospheric environments as chemical lead (99.9% commercial-purity lead). However the greater hardness, strength and resistance to creep of antimonial lead often makes it more desirable for use in specific chemical and architectural applications.

The ability of some antimonal leads to retain this greater mechanical strength in atmospheric environments has been demonstrated in exposure tests in which sheets containing 4% Sb [antimony] and smaller amounts of arsenic and tin were placed in semi-restricted positions for 3 years. They showed less tendency to buckle than chemical lead, indicating that their greater resistance to creep had been retained.

Handbook of Corrosion Data, by Bruce D Craig, p89ff

Antimony crystals

Thus, the use of softer leads in conservation or restoration, because they were used in earlier periods, is not indicated. It is known that lead came up to sometime in the early 19th century was melted and re-formed into came, incorporating tin from solder and other trace elements which made the lead “stiffer” than the more pure lead that began to be produced commercially and used widely at that time. This may be the reason that so many 19^th century windows contain failing leads, while many earlier ones remain sound.