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Ancient Mercury-Based Plating Methods: Combined Use of Surface Analytical Techniques for the Study of Manufacturing Process and Degradation Phenomena

Ancient Mercury-Based Plating Methods: Combined Use of Surface Analytical Techniques for the Study of Manufacturing Process and Degradation Phenomena

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www.pubs.acs.org/accounts
Vol. XXX, No. XX 
XXXX 
000
000
ACCOUNTS OF CHEMICAL RESEARCH
A
10.1021/ar300232e
&
 XXXX American Chemical Society
Ancient Mercury-Based Plating Methods:Combined Use of Surface Analytical Techniquesfor the Study of Manufacturing Process andDegradation Phenomena
GABRIELMARIAINGO,*
,
GIUSEPPEGUIDA,
EMMAANGELINI,
§
GABRIELLA DI CARLO,
ALESSIO MEZZI,
ANDGIUSEPPINA PADELETTI
 Istituto per lo Studio dei Materiali Nanostrutturati, Consiglio Nazionale delleRicerche, Area della Ricerca RM 1-Montelibretti, via Salaria Km 29.3, 00015  Monterotondo, Rome, Italy,
 Istituto Superiore per la Conservazione ed il Restauro, via di San Michele 23, 00153 Rome, Italy, and 
§
 Dipartimento Scienzadei Materiali e Ingegneria Chimica, Politecnico di Torino, Corso Duca degli Abruzzi 24, Torino, Italy 
RECEIVED ON AUGUST 2, 2012
CONSPECTUS
F
ire gilding and silvering are age-old mercury-based processes used to coat thesurface of less precious substrates with thin layers of gold or silver. In ancienttimes, these methods were used to produce and decorate different types of artefacts,such as jewels, statues, amulets, and commonly-used objects. Gilders performedthese processes not only to decorate objects but also to simulate the appearance of gold or silver, sometimes fraudulently. From a technological point of view, the aim of theseworkmenover2000yearsagowastomakethepreciousmetalcoatingsasthinand adherent as possible. This was in order to save expensive metals and to improvethe resistance to the wear caused by continued use and circulation.Without knowledge about the chemical
À
physical processes, the ancient crafts-men systematically manipulated these metals to create functional and decorativeartistic objects. The mercury-based methods were also fraudulently used in ancienttimes to produce objects such as jewels and coins that looked like they were made of silver or gold but actually had a less precious core. These coins were minted by counterfeitersbutalsobytheofficialissuingauthorities.Thelatterwasprobablybecauseof a lack of precious metals, reflecting periods of severe economic conditions.In this Account, we discuss some representative cases of gold- and silver-coatedobjects, focusing on unique and valuable Roman and Dark Ages period works of art,such as the St. Ambrogio's altar (825 AD), and commonly used objects. We carried outthe investigations using surface analytical methods, such as selected area X-ray photoelectron spectroscopy and scanning electron microscopy combined withenergy-dispersive spectroscopy. We used these methods to investigate the surfaceand subsurface chemical features of these important examples of art and technology,interpretingsomeaspectsofthemanufacturingmethodsandofdisclosingdegradationagents and mechanisms. These findings may contribute to cultural heritage preservation, thus extending the applicability of thesurface analytical techniques.
Introduction
Sincethe18thcenturyeminentscientists,suchasBerzelius,Faraday, Berthelot, and R 
ontgen, used analytical methodsto identify the chemical composition of ancient coins,glasses, pigments, and ceramics. The pioneering approachhascontinuedthroughrecentcenturies,andmanymaterial
 
B
ACCOUNTS OF CHEMICAL RESEARCH
000
000
XXXX 
Vol. XXX, No. XX 
 Ancient Mercury-Based Plating Methods
Ingo et al.
scientists have studied works of art or commonly usedobjects in order to determine their chemical composition,structural features, and degradation products in order tounderstand how they were manufactured or the origin of the raw materials used.
1,2
The development of new analytical methodologies, their continuous improvement, and their use in the field of culturalheritage have recently allowed us to obtain a wider range of information concerning the origin and mechanisms of materialdecay,
1
À
5
thus opening up innovative tailored approaches for thedesignandvalidationofinnovativeandreliableconservationmaterials,whichensurealongandstablelifeforancientartifacts.The commonly used techniques for these studies gener-allyprobethebulkchemicalandstructuralcharacteristicsof theobjectsandoverlooksurfacefeatures,oftenessentialfor understanding manufacturing techniques and degradationprocesses. In this field, investigators have occasionally usedsurface analytical techniques,
5
À
7
such as X-ray photoelec-tron spectroscopy (XPS), secondary ion mass spectrometry(SIMS), and glow discharge optical emission spectrometry(GDOES). They have shown that these techniques comple-ment the more commonly used analytical surface meth-odologies, such as scanning electron microscopy (SEM) and
 μ
-Ramanspectroscopyandareasignificantbreakthroughinthe study of cultural heritage.Owing to the advantages afforded by the above listedmethodologies for extracting detailed chemical and mor-phological information in a depth range from a few nano-meters to submicrometer, and the possibility of identifying the presence and chemical state of essentially the entirePeriodic Table, the combined use of XPS and SEM-EDStechniquescandisclosethecomplexmicro-andnanochem-ical surface nature of ancient artifacts; specific questionsrelated to manufacturing techniques and degradation phe-nomena are therefore answered.With these aims in mind, the above-mentioned nondes-tructive and nano- or microdestructive methods have beenusedfordetailedstudyofthinlayersofgoldorsilverdepositedviaamalgamtechniquesbyartistsandmetallurgistsfromtheseancient times. On the basis of their long-term cognitive skills,these latter perceived that the surface of metals could bemodified via empirically optimized treatments for both artistic and functional purposes. They created unique and functionalfeatures, as well as giving the deliberate impression that theobjects were made entirely of gold or silver.
8
À
10
The hereafter described results confirm the analyticalcapabilitiesofthesurfacetechniquesandevidencethehighlevelofcompetencereachedbytheartistsandcraftsmenof these ancient periods who produced objects of an artistic quality that could not be bettered in ancient times and hasnot yet been reached in modern ones.
Mercury-Based and Other SophisticatedAncient Coating Techniques
Over 2000 years ago, artists and metallurgists used variousmethods for applying a metallic layer to an object, from thesimplefoldingofaleafaroundtheartifacttomoremultistepand complex processes,
8
À
18
which were occasionally con-sidered closely guarded secrets.The following are brief descriptions of the techniquesused in ancient times that can be considered the mostinteresting from a chemical
À
physical point of view:
DepletionGilding 
.Accordingtothissubtractivemethod,a copper-based object can be surface-enriched withalayerofpreciousmetalbymeansofrepeatedcyclesof thermal treatments and selective removal of copper.Pickling solutions, such as salts and organic com-pounds, which etched away the oxidized copper leav-ing a silver or gold spongy crust on the surface wereused.
7,11,17
This latter is then burnished, leaving abrilliant and more attractive polished finish.
Macro or Inverse Segregation
. This latter phenom-enon could occur during the solidification of a copper-based alloy under specific cooling parameters; tin,arsenic,orantimonycanbeforcedtotheinterdendritic areas and to the surface of the object, thus forming species with a silver-like appearance. An example of artifactscoatedbythismethodarethe
Lybianwar 
coinsminted by Carthaginians in North Africa (241
À
238 BC)during the war between Carthage and the Libyan rebelsaftertheFirstPunicWar.
19
ThesurfaceofthesecoinswereAs
À
Sb-enriched by thermally pushing As and Sb con-tainedinthecoppercoretotheexternalregionofthecastblankviainversemacrosegregation,thuscreatingasilver-like surface. The expertise of Carthaginian metallurgistswasbasedpurelyonempiricalskills,sincetheywereableto observe phenomena and then to replicate them. It isworthnotingthatthismethodwasalsousedbyRomansto form a reflective and corrosion-resistant
δ
-Sn
31
À
Cu
8
filmonbronzemirrorsandduringtheRenaissanceinItalyfor issuing coins with a surface enriched with a silver 
À
antimony alloy.
MercurySilveringandGilding 
.Thislow-temperaturecoating method was developed in China from the4th to the 3rd century BC, and then it was likely trans-mitted to the Mediterranean basin via the silk route
 
 Vol. XXX, No. XX 
XXXX 
000
000
ACCOUNTS OF CHEMICAL RESEARCH
C
 Ancient Mercury-Based Plating Methods
Ingo et al.
in the 1st century BC. It was used as a less expensivealternativemethodtodepositthinneradherentfilmsof gold or silver on works of art, jewels, decorative items,andforgeries.
8
À
11,14
Themethodwas usedwidely andsuccessfully due to its unique decorative effects, theconsistent saving of precious metals, and the conse-quent increase of profit. By the 2nd and 3rd centuryAD, the use of mercury-based methods was rapidlyexpanded in Europe. It was the predominant goldcoating technique until the invention of electroplating in the mid-19th century when mercury-gilding fell intodisusebecauseitwasmoreexpensive,andthethreatof mercury toxicity became known. There are two differ-entmethodsformercurygildingandsilvering.
8
À
13
Thefirst one is based on the use of mercury as a
glue
toapply a gold leaf by forming an amalgam at the sub-strate
À
leaf interface, that is, cold mercury gilding. Thesecond method is a solid-state reaction based on theuse of an amalgam of gold or silver and mercury,produced by grinding Au or Ag dust with mercury andgently brushing the amalgam paste on a clean andoxide-free metal substrate to be coated. A thermaltreatment was then carried out at about 250
À
350
°
C,below the boiling point of mercury (357
°
C); this wasdone for a few minutes in air in order to volatilize themercury and leave a gold or silver film with a residualpresence of mercury.
8
À
10
Because of its unevenness andporosity, the final finishing was carried out mechanicallyby means of a metal, bone, or stone burnisher to gentlycompresstheporousstructureinordertocreateasmooth,shiny surface, similar to that of gold or silver.
11
À
13
This Account illustrates the chemical and structural fea-tures of a thin metal layer produced by using the mercury-basedtechnique.Forthispurpose,wehavefirstinvestigatedagoldlayer,whichwaspreparedappositelybymercurygilding.Themicro-andnanostructureandthechemicalcompositionof agoldamalgamareshowninFigure1bySEMimagesandEDSspectra; they are shown both after a partial evaporation of mercury and after the overall treatment. These latter resultsrevealthatthesurfaceisporousandcomposedofsmallroundgrains whose size ranges from 200 nm to about 1
μ
m. It isworth noting that the nanoporosity of the gold layer couldhave a detrimental effect during burial because it could act asnanochannels along which the anions coming from the soilcould corrode the less noble substrate.EDS results reveal that the thermal treatment does notremove the mercury entirely; it is retained in the preciousmetal in noticeable amounts ranging from a few weightpercent for gold-coated objects, to about 25
À
30 wt % for silver-coatedones.Theamountofresidualmercurydependson the nature of the precious metal, and the adoptedtechnologicalparameters,suchastemperatureanddurationofheat treatment, aswellas ontheAg orAu/Hg ratio in theamalgam.Theexperimentaldetailsdependedontheartist'sskill, the size of the object, and the desired thickness of thegold or silver layer.For the above-mentioned reasons, fire gilding is easy todetectbecausemercuryisneverremovedcompletelybytheheatingprocess,andtheHgresidualcontentcanbedetectedby surface analytical techniques, which allow the identifica-tion of the manufacturing method.
Surface Studies of Coated Objects
ThisAccountprovidessomerepresentativeexamplesofthechemical nature and micro- and nanostructure of thin goldor silver layers produced via the mercury-based coating techniquebyartistsandcraftsmeninancientperiods.Thesetechniques manipulated and combined metals to create
FIGURE 1.
The morphology and surface chemical composition of theAu
À
Hgamalgamaftermildthermaltreatmentcarriedoutat250
°
Cfo2 and 15 min (images 1 and 2, respectively). High-resolution SEMimages for the gold layer after the overall thermal treatment (images 3and 4) show that the surface is porous due to Hg evaporation andcomposedofsmallroundgoldgrainscontaininganoticeableamountof Hg (about 12 wt %), whose diameter ranges from 200 nm to 1
μ
m.

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