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Silver Cleaning and Conservation

Silver Cleaning and Conservation

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Published by AFLAC ............
Silver Cleaning and Conservation
Silver Cleaning and Conservation

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Published by: AFLAC ............ on Jun 24, 2012
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Silver Conservation
IN THIS FILE
:Silver CorrosionGalvanic CleaningElectrolytic Reduction CleaningElectrolyteCurrent Density  Anode MaterialCathode ContactProcedureReduction in Formic AcidReduction in Sodium HydroxideConsolidative Reduction Alkaline DithioniteRinse and SealantChemical Cleaning
SILVER CORROSION
Silver is a very noble metal and is often found in a native state combined withgold, tin, copper, and platinum. It is completely stablein aqueous solutions of any pH as long as oxidizing agents or complexingsubstances are not present. In addition, silver is notappreciably affected by dry or moist air that is free from ozone, halogens,ammonia, and sulfur compounds (Pourbaix 1966:393;Plenderleith and Werner 1971:239). Silver is particularly susceptible to theeffects of the sulfide radical. This is best demonstrated by the formation of tarnish on silver objects that are exposed to sulfur in any form,particularly hydrogen sulfide and sulfur dioxide, which can convert to sulfuric acid.In a marine environment, with its abundance of soluble sulfates and oxygen-consuming, decaying organic matter, sulfatereducing bacteria utilizes available sulfates under anaerobic conditions to form hydrogensulfides as a metabolic product. Thehydrogen sulfide reacts with the silver to form silver sulfide. The overall reactionproceeds in the same process as described earlier foriron:2Ag + H2S >> Ag2S + H2In anaerobic marine environments, silver sulfide (Ag2S) is the most commonmineral alteration compound of silver (North andMacLeod 1987:94). It is commonly reported from shipwrecks in the Caribbeanand Australia and constitutes the most prevalentcorrosion compound on silver objects from marine sites. Most marine-recoveredsilver artifacts have a thin sulfide surface layer, which has removed some surface detail, such as inscriptions, marks, and stamps. A large percentage of the artifacts, however, arecompletely converted to sulfide; others have only minimal metal remaining.
 
In aerobic seawater, the most commonly encountered corrosion product onsilver and silver alloys is silver bromide (AgBr). Varying amounts of silver chloride (AgCl) and silver sulfide (Ag2S) may also bepresent (North and MacLeod 1987:94). Silver chlorideis generally not extensive on silver recovered from salt water. Gettens (1964:563)notes that silver coins recovered from salt water aresometimes superficially altered to this mineral. In sites where the conditions vary between aerobic and anaerobic, combinations of allthe major silver corrosion products are likely to be present (North and MacLeod1987:94-95). In the case of relatively pure silverobjects, silver sulfide (Ag2S) and silver chloride (AgCl) will predominate. In thecase of base silver alloys with significant amounts of copper, the copper will corrode preferentially and form cuprous oxide, cupriccarbonate, and cuprous chloride. In such cases, the silveralloy object should be treated as if it were copper.Regardless of what silver corrosion products are formed, all are stable and donot take part in any further corrosive reaction withthe remaining silver. In fact, the corrosion layers impart some degree of protection against further corrosion to the metal. They alsooften provide an aesthetically pleasing patina, which is often desirable anddeliberately preserved. The only reason to treat silver is toremove disfiguring corrosion layers to reveal detail, for aesthetic reasons, toreduce mineral products back to a metallic state, and toremove the chlorides from the copper component part of base silver alloys.Prior to conservation treatment, marine encrustation should be removedmechanically or, in some cases, by immersion in 10-30percent formic acid solution. The conservation alternatives for cleaning silverand silver alloys are:1. galvanic cleaning2. electrolytic reduction3. alkaline dithionite treatment4. chemical cleaning5.stabilization and consolidation.
 
GALVANIC CLEANING
Treating silver galvanically can be accomplished by using mossy zinc oraluminum in caustic soda, asdescribed earlier for iron. Variations include using mossy zinc or aluminum granules with heated 30percent formic acid (Plenderleith and Torraca 1968:241-246; Plenderleith and Werner 1971:197, 221). After treatment, the metal is rinsedthoroughly and then dehydrated in a water-misciblesolvent and sealed with clear acrylic lacquer. Galvanic cleaning is effective, butthere is no reason to recommend it over electrolyticreduction or alkaline dithionite treatments.
ELECTROLYTIC REDUCTION CLEANING
The electrolytic cleaning of silver takes advantage of the reduction action of electrolysis by removing the chloride and sulfide ions fromsilver chloride and silver sulfide. When a direct current is applied, the negatively charged chloride and sulfide ions migrate toward thepositively charged anode. The chlorides may form as chlorine in the solution,and the sulfides oxidize to sulfates. Since the anions donot react with the inert anodes, they accumulate in the electrolyte and arediscarded with it. During the process, the silver in thecorrosion compounds is left in a metallic state.Two methods of electrolytic reduction cleaning have been described in theconservation literature; the methods are referred to by Organ (1956) as normal reduction and consolidative reduction. Normalelectrolytic reduction uses a fully rectified direct current (DC)power supply. Consolidative reduction employs a partially rectified(asymmetrical) alternating current (AC) power supply. Bothtechniques require that a metal core be present in the object. The ConservationResearch Laboratory at Texas A&M University dealsprimarily with the normal reduction process in 5 percent formic acid, essentially as it is described in Plenderleith and Werner(1971:222). Both techniques are discussed below.
ELECTROLYTE
Two electrolytes, formic acid (HCOOH) and sodium hydroxide (NaOH), are usedto clean silver. Although electrolyte concentrationsof 5-30 percent HCOOH and 2-15 percent NaOH in de-ionized water have beenproposed (Organ 1956:129; Plenderleith and Werner1971:222; Pearson 1974:299), 5 percent HCOOH or 2 percent NaOH solutionsare generally used as electrolytes for cleaning silver.

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