Maney Publishing

Bronze Disease: A Review of Some Chemical Problems and the Role of Relative Humidity
Author(s): David A. Scott
Source: Journal of the American Institute for Conservation, Vol. 29, No. 2 (Autumn, 1990),
pp. 193-206
Published by: Maney Publishing on behalf of The American Institute for Conservation of Historic &
Artistic Works
Stable URL: http://www.jstor.org/stable/3179583 .
Accessed: 14/06/2014 22:30

Your use of the JSTOR archive indicates your acceptance of the Terms & Conditions of Use, available at .
http://www.jstor.org/page/info/about/policies/terms.jsp

.
JSTOR is a not-for-profit service that helps scholars, researchers, and students discover, use, and build upon a wide range of
content in a trusted digital archive. We use information technology and tools to increase productivity and facilitate new forms
of scholarship. For more information about JSTOR, please contact support@jstor.org.

Maney Publishing and The American Institute for Conservation of Historic & Artistic Works are collaborating
with JSTOR to digitize, preserve and extend access to Journal of the American Institute for Conservation.

http://www.jstor.org

This content downloaded from 195.34.78.43 on Sat, 14 Jun 2014 22:30:45 PM

All use subject to JSTOR Terms and Conditions
 BRONZE DISEASE: A REVIEW OF SOME CHEMICAL
PROBLEMS AND THE ROLE OF RELATIVE HUMIDITY

DAVIDA. Scorr

ABSTRACT--A general review of some of the theories proposed to account for the
process of "bronzedisease" is presented from both the historical and chemical
points of view. The corrosionproductof most serious concern, cuprous chloride,
and its inter-relationshipwith some of the other importantcorrosionproductsof
copperalloys, such as the coppertrihydroxychlorides,is reviewed.The criticalRH
for the transformationof cuprous chlorideis discussed and suggestions are made
concerningboth the storage conditions for bronzes and the varietyof conditions
underwhich cuprouschloridecan occurin excavatedbronze.

1. HISTORICALINTRODUCTION
THECHEMICAL examinationof the corrosionof copperand bronzeartifacts has been the
subject of study for at least 150 years. As long ago as 1826, Davy carried out an
examinationof a bronzehelmet found in the sea near Corfu. Among the incrustationshe
was able to identify the ruby-redprotoxideof copper (cuprous oxide: cuprite);the green
rust of the carbonate(basic coppercarbonate:malachite)and submuriateof copper(basic
copperchloride:probablyparatacamiteor atacamite);crystals of metallic copperthat had
been redeposited;and a dirtywhite materialidentifiedas tin oxide. On a nail froma tomb
in Ithaca that was analyzedand found to be a tin bronzewith 6%of tin, Davyagain found
the protoxide,carbonate,and submuriateof copper,as well as tin oxide, although in this
case there were no shiny crystals of redeposited copper present. The first scientific
investigationsof the aeruginous deposits on antiquities date from this periodof the early
19th century and express the same curiosity about the nature and formationof these
deposits we have today. This article summarizesthe salient informationpublished to date
on the subject of cuprous chlorideand bronzedisease.
A search of the Conservation Information Network bibliographic database (BCIN)
produces about 500 referencesfor the keywords"bronze"and "corrosion."Manypapers
do not actually deal with the process of bronze corrosionbut are concerned with other
aspects of copperalloys and their corrosionproducts.All the papers dealing broadlywith
this topic will not be reviewed here, but some specific points will be discussed that
concernthe interactionof cuprous chloridewith moisture;this reactionis the crucialpart
of the process of "bronzedisease."
Bronze disease may be defined as the process of interaction of chloride-containing
species within the bronzepatina with moisture and air, often accompaniedby corrosionof
the copperalloy itself, a process which has been more or less understoodfor the last 100
years. The products of the reaction are light green, powdery,voluminous basic chlorides
of copper, which disrupt the surface and may disfigure the object. Several corrosion
processes of copper are also enhanced by visible light. Cuprous chloride, for example, is

JAIC 29 (1990): 193-206

This content downloaded from 195.34.78.43 on Sat, 14 Jun 2014 22:30:45 PM

All use subject to JSTOR Terms and Conditions
194 David A. Scott

a light-sensitivematerialand must be kept in the dark, preferablyin a vacuum desiccator

to preventany chemical change.
One theory concerningthe origin of bronze disease attributedthe problemto bacterial
action. We now know that this is not the case, but the suggestion is not as silly as it
sounds. Bacterial action has recently been thought to be a cause of black spots on
bronzes (Madsen and Hjelm-Hansen1979), although this theory is also unlikely to be
true; a much more probablecause is the slow action of gaseous pollutants in showcases
constructed of unsuitable materialsthat evolvesulfurous contaminants(Oddyand Meeks
1982).
The best-known early attempt to deal with the problem of bronze disease is that of
Berthelot, in 1895, who reportedsome of his proposals to account for the instability of
certain bronzes. He recognizedthat there must be an importantcyclical componentto the
reaction. He also realizedthat one of the importantproducts of the reactionwas the basic
copper chloride, atacamite, which at that time was assigned the formula
3CuO,CuCl2,4H20.The formulawe know today for the copper trihydroxychloridessuch
as atacamite, Cu2(OH)s3C(one of three isomeric compounds), translates closely into
Berthelot'schemical terminology,which can be written as 3CuO,CuCI2,3H20.Berthelot's
explanation was a remarkableachievement for the chemistry of that time, especially
since these basic copperchloridesare not well known even today.
The three isomers-botallackite, atacamite and paratacamite-belong to differentcrys-
tallographic groups. Botallackite is monoclinic, atacamite is orthorhombic, and
paratacamiteis rhombohedral.Botallackiteis the least stable of the three, and its in-
stabilityaccounts for the rare instances in which it has been identifiedas a componentof
coppercorrosionproductson real objects fromburial.
Berthelot'sexplanationfor the bronze disease process suggested that a small quantity
of sodium chloride reacted with the atacamite and the metallic copper. A slow reaction
was supposed to take place, forminga double compoundof cuprous chlorideand sodium
chloride. The remainingportionof the copperwas convertedinto cuprous oxide:
+ 4Cu + 2NaC1= Cu2C2,2NaC1 + 3Cu20 + 4H20
3CuO,CuCb2,4H20 [1)

The double salt was oxidized by air to produce cupric chloride and atacamite:
3Cu2C12,2NaC1+ 30 + 4H20 = 3Cu0,CuCI2,4H20 + 2CuCl2+ 6NaC1 [21

The cupric chloride that remained in contact with the air and copper or cuprous oxide
was also converted into oxychloride:
CuCI2+ 3Cu + 30 + 4H20= 3Cu0,CuC12,4H20 13]

This completes the series of reactions that convert copper, oxygen, and water to
cuprous oxide and atacamite in a cyclical process. Berthelot states that the constant
recurrence of the process under the influence of oxygen and moisture is the cause of
bronze disease.
Berthelot's essential conclusion-that the recurrence is due to a cyclical reaction
involving both oxygen and moisture-is indeed correct. More is known about the process
today, but we still do not know all the details of the corrosion chemistry involved. The
equations that Berthelot advanced and that are reproduced here are not, however, ac-
curate descriptions of bronze disease. Although the idea of the cyclical reaction is
accepted, the principal cause of instability in excavated bronze objects is due to the
existence of cuprous chloride formed during corrosion processes in burial. This cuprous

JAIC 29 (1990): 193-206

This content downloaded from 195.34.78.43 on Sat, 14 Jun 2014 22:30:45 PM

All use subject to JSTOR Terms and Conditions
 BronzeDisease: A Reviewof Some ChemicalProblems 195
and the Roleof RelativeHumidity

chlorideis not usually exposed to view but is present as a corrosionproduct, often close
to the surface of the residual metal.

2. TIE PRESENCEOF CUPROUSCHLORIDE

IN CORRODED
COPPER
ALLOYS
NOTALLbronzes suffer from the presence of cuprous chloride, the mineral nantokite.
The mineral form was first identified and named from the mines near Nantoko, Chile
(Palache et al. 1951). Cuprous chloride can occur as massive granular lumps or, in
laboratory-madesamples, as tetrahedralcrystals. The mineralis isotropic,with refractive
index 1.930, and under the polarizingmicroscope may show anomalous birefringence,
especially at the edges of the sample when mounted in Melt Mount (refractiveindex
1.66). The material usually occurs on copper alloys as a gray or gray-greentranslucent
waxy solid that can easily be cut with a scalpel or a fingernail,since the hardness is only
2.5 on Moh'sscale.
In the originalbronze disease model proposed by Organ (1963), the reactive cuprous
chloride, if present, is depicted as being formedat the interfacebetween the bronze and
the cuprite, which may grow over it. Other situations in which the author has observed
cuprous chlorideinclude the following:
1. adjacentto the metal surface and under a layerof cuprite
2. as isolated pits below the originalsurface of the object, often coveredin warts of
cupriteor malachiteand frequentlywith cupriteadjacent to the copperor bronze
3. above a cupritelayer. The cupritelayer is adjacentto the metal surface and the
cuprous chlorideis usually coveredby malachiteor basic copperchlorides.
4. in the central core of the object, replacingpreviousmetallicareas. In some cases
these objects may be totallymineralized. If all the cuprous chloridehas trans-
formed,these mineralizedobjectswill be chemicallystable and requirelittle conser-
vation treatmentin terms of stabilization,although they are physicallyvery fragile.
Objects studied by the author show considerable variation in the extent to which
surface disruptionoccurs with time. A numberof bronzeobjects fromPalestineare in the
Petrie Collection,Departmentof WesternAsia, Institute of Archaeology,UniversityCol-
lege, London. One of these objects, which had obviously suffered severe bronze disease
and had been stored in uncontrolledconditions for more than 20 years, was examined
and analyzed. The light green corrosion was identified as a mixture of atacamite and
paratacamite, the most commonly found mixture of isomers in many ancient bronzes
regardless of the location in which they are found. Most of the small objects in this
collection illustrate the effects of disintegrationin poor storage conditions over
many
decades. Littlechange is now evident, and many of the objects have stabilizedthemselves
by reaction of the cuprous chloride with moisture. Some of these objects could be
described as metastable, for they contain cuprous chloride at some depth and if cut or
sectioned cuprous chloridein the unreactedstate may still be found.
Objects, of course, cannot necessarily be left to stabilize themselves over long periods of
time without disintegration and loss of material, which would be unacceptable. It should
be recognized, however, that disfiguring light green corrosion excrescences on ancient
bronzes do not necessarily imply that the bronzes are still unstable, even though they
were excavated many years ago and kept in uncontrolled storage since that time. Some of
these objects are reduced to fragmented heaps of light green powder, but those that
survive may now be quite stable.

JAIC 29 (1990): 193-206

This content downloaded from 195.34.78.43 on Sat, 14 Jun 2014 22:30:45 PM

All use subject to JSTOR Terms and Conditions
196 David A. Scott

The ability of cuprous chloride to lie dormant until exposed to the atmosphere is
unusual. In many other metals the presence of chloridescreates immediateinstability,as
in the case of iron, steel, and cast iron, in which the chlorides are water soluble and
undergo chemical change quite quicklyin burial environments. The relativestabilityand
insolubility of cuprous chloride in unexposed pits create problems in the mechanical
cleaning of ancient bronzes, since the exposure of such pits usually necessitates further
stabilizationmeasures or monitoringprocedures. In some cases, especially where warty
corrosionis present and it is desired to clean the warts down to the level of the rest of the
patina, the exposure of cuprous chloridecan create considerableproblemswith stability.
In such cases aesthetic and practicaldecisions have to be made concerningthe object. Is
it better to leave the objectwith unaesthetic warty corrosion,or can the warts be cleaned
and the objectbe either treatedor kept in controlledstorage and properlymonitored?

3. THEREACTIONS CHLORIDE
OF CUPROUS
Cuprous chlorideis the principalagent of bronze disease. There remains, however,some
confusion concerning both the RH values at which cuprous chloride is stable and the
reactions that may occur when cuprous chloridein a bronze artifactis exposed to air or
becomes unstable. The equations Organ proposed (1963) were the first to be generally
accepted as an explanationfor the process, but it is now generallyrecognizedthat these
equations are too simplistic. They suggested that the principalmechanism is the produc-
tion of cuprous oxide (cuprite)by hydrolysisof cuprous chloride:

2CuC1 + H20 = 2HC1+ Cu2O [4]

The hydrochloricacid generated by this reaction will then produce more cuprous
chloride:

2HC1+ 2Cu = 2CuC1 + H2 [51

The problemwith this model was that in isolation the first reaction, that of cuprous
chloridewith water, will not produce hydrochloricacid and cuprite. As MacLeod(1981)
has alreadypointed out, the AGof reactionfor equation [4] is +16.3 kcal. mole"',showing
that the reactionwill not proceedspontaneouslybecause of the positivevalue of AG.
The thermodynamicvalues used in this discussion refer to the standard free energies
of formationof the compoundsfrom the elements and are thereforein the standard state
at 25'C. As such they can only be used as a guide to the reactions that will actually
occur, for under bronze disease conditions most reactants will not be in their standard
states. Nonetheless, they are offeredhere as a model for furtherrefinementand discus-
sion. In standard conditions, the positive sign of the AGof reaction for the hydrolysisof
nantokite means that the reaction cannot proceed as such without an additional ther-
modynamic driving force. In addition, nantokite has a solubility of about 0.006 g per 100
ml of water at room temperature; this low solubility limits the extent to which hydrolysis
reactions may occur.
It is possible to provide a thermodynamic thrust to the right hand side of equation [4] if
the positive AG can be overridden by other factors. One of the factors that must be
considered is the presence of alloying elements: tin in bronze or zinc in brass for example.
If a drop of water is added to cuprous chloride spread over the surface of a piece of brass,
gas bubbles evolve from the droplet and a fim of cuprite develops on the brass surface.

JAIC 29 (1990): 193-206

This content downloaded from 195.34.78.43 on Sat, 14 Jun 2014 22:30:45 PM

All use subject to JSTOR Terms and Conditions
 BronzeDisease: A Reviewof Some ChemicalProblems 197
and the Roleof RelativeHumidity

The equation Organproposed(1963) is thereforeoperative;the drivingforce of the zinc in

the brass is sufficientto promotethe generationof hydrogen.
The same reaction on a sample of a high tin bronze (24% tin) is not sufficiently
favorableto produce cuprite as an immediateproduct, even though the AGof reaction of
tin with hydrochloricacid is -8.856 kcal. mole"'. There are, of course, electrochemical
factors and kinetic factors to be consideredhere. There is obviouslyan additionaldriving
force for the reactionif carriedout on a metal surface lowerin the electrochemicalseries
than copper,which is one reason why the reactionwith brass is so rapid.
Not only are there subtle electrochemicalfactors to be considered concerning the
differencein potentialbetween tin-rich phases and the copper-richalpha phase in bron-
zes, but there are a varietyof burial conditions to be considered.A simple examinationof
the likelihoodof the tin- or copper-richphases corrodingsuggests that tin would be the
most likely to corrode.The enthalphy of formationof cuprous oxide or cupric oxide is
some 100 kcal. mole-' less than that for stannic oxide, which should mean that loss of tin
is the preferredreaction when the bronze corrodes. But corrosion of the copper-rich
phase or the tin-rich phase is mostly dependent on the partial pressure of oxygen, as
shown by the work of MacLeod(Taylorand MacLeod1985). In seawater, MacLeodfound
that exposure to well-oxygenatedconditionsresulted in the copper-richalpha phase being
attacked, while in less oxidizing conditions the tin-rich delta phase was attacked. The
concentrationof tin compounds or coppercompounds that might form in the patina will
thereforebe stronglyaffectedby this selective corrosionphenomenon.
What happens in practicewhen cuprous chlorideis in contact with copperand a drop
of water is added? In this case there is no cuprite formation;the copper trihydroxy-
chlorides are the principalproducts. The standard way of making paratacamite,namely
the immersionof a sheet of copper in a solution of cupric chloride,produces first a thin
layerof cupriteover the copperfollowedby a layerof paratacamite.Cupritecan be formed
as a thin layer adjacent to copperif cuprous chlorideand copperare mixed togetherand
regularlymoistenedwith water, but this is not the principalreaction. On copper,cuprous
chloride slurries develop a pH of about 3.5-4.0, and the solution develops a green
precipitate;one of the copper trihydroxychloridesis formed(Tennentand Antonio 1981).
The reactionis one of oxidationand hydrolysisof the cuprous chloride,which takes place
with a negativefree energyof formation.

4CuCl + 02 + 4H20 = 2Cu2(0H)sC1+ 2H+ +

Cl- AGf=-360.9 kcal/mole [6]
This equation has been written using a value for the free energy of formation of
paratacamiteof -319.8 kcal. molel1.
When cuprous chloride is placed on moist
filter paper, the cuprous chloride slowly
changes to give mostly atacamite, as reportedby Tennentand Antonio(1981).
The work of Sharky and Lewin (1971) established that one of the critical factors
involved in whether one copper trihydroxychlorideisomer or another is
formed during
possible transformations leading to the formation of atacamite or paratacamite was the
concentration of complex cupric chloride ions in solution. Lewin (1973) argued incorrectly
that the concentration of the complex copper ions in solution during natural corrosion
processes in the soil would be low. With low concentrations, paratacamite is the most
favored product, and Lewin posited that the detection of a mixture of paratacamite and
atacamite in a patina implied that the corrosion was artificially induced.
Lewin's argument suffers from two serious drawbacks: first, the x-ray diffraction data
for several natural patinas examined by different laboratories has established
that, in-

JAIC 29 (1990): 193-206

This content downloaded from 195.34.78.43 on Sat, 14 Jun 2014 22:30:45 PM

All use subject to JSTOR Terms and Conditions
198 David A. Scott

deed, all three isomers may be present and not limited to paratacamite;and second, low
copper chloride ion concentrations have not been confirmed by in situ studies.
Giangrande(1987), for example, examined samples of corrosion products from several
ancient objects and, in cases where the copper trihydroxychlorideswere identified,mix-
tures of paratacamiteand atacamite were common. Pitting corrosion in both iron and
copper leads to a buildup of chloride ions beneath the pit, which functions as an
electrochemicalcell. Lucy (1972) observed the growth of crystalline cuprous chloride in
the pitting corrosion of copper. These pits were shown to function as electrochemical
cells. The cuprite that formed over the cuprous chloride not only acts as a diffusion
barrierthat reduces the loss of dissolved copper ions into the outer zone but also as a
bipolarelectrode,with an anodic reaction taking place on the inner surface of the cuprite
and a cathodic reactionoccurringon the outer surface. Cuprousions diffuse throughthe
cuprite and can become oxidizedby oxygen in water to form cupric ions. Some of these
cupric ions can be lost into the soil groundwaters,some may be precipitatedas basic
salts, and some can be reducedback to the cuprous state at the outer membranesurface.
The correspondinganodic reaction is less well understood. Lucy suggested that the
cuprous ions inside the pit are oxidized to cupric ions. This increase in cupric ion
concentration disturbs the equilibriumbetween metallic copper, cuprous, and cupric
ions. Coppercan then dissolve to maintainequilibrium.In aqueous conditionscontiguous
with a coppersurface the followingreactions must be considered:
Cu + Cu2+ = 2Cu+ [7)

2Cu+ + HzO = CuzO +2H+ [8]

4Cu + 02 + 2Hz0 = 4Cu2+ + 4(OH) [9]

Lucy proposedthat the balance between equations [7], [8], and [9] was responsible for
the precipitationof cuprous chloride. If, however,as a result of equation [7], the rate of
formationof cuprous ions exceeds conversioninto cuprite or cupric compounds, then a
layer of cuprous chloridecan form.
The four essential equations Lucyproposedwere
1. the reactionoccurringwithin the mound of corrosionabove a pit, which can vary
dependingon whether carbonateions, chlorideions, or other ionic species are
availableto interactwith the copper:

4CuCl+ Ca(HCOs)2 + CaCO3+ 2CuClz

+ 02 = CuCOsCu(OH)2 [10]

2. the cathodicelectrodereactionoccurringon the outer surface of the cuprite:

Cu2+ + e- - Cu+ [111

3. the anodic electrodereactionoccurringon the inner surface of the oxide membrane:

Cu' - e- = Cu2+ [12]

4. the reaction between the anodic product and the copper within the pit:

Cu + Cu2+ = 2Cu+ [13)

JAIC 29 (1990): 193-206

This content downloaded from 195.34.78.43 on Sat, 14 Jun 2014 22:30:45 PM

All use subject to JSTOR Terms and Conditions
 BronzeDisease: A Reviewof Some ChemicalProblems 199
and the Roleof RelativeHumidity

2.8 I I I I
-21-.,4-1- S-6 -4 2

2.\\ hydr.
2.0 - 1 Cu203

1.6-

0.8 3Cu(OH)2 CUCI2

T I CuO
0
Wu"%4 ?- rY-.1O
uN ,
Cu
HCupH
.-

-0.4

-0.8 - Cu3

-1.2%2

(b)

I
-16L I I I I I
-2 0 2 4 6 8 10 12 14 16
pH

Fig. 1: Pourbaixdiagramfor the system copper-chlorine-water at 25'C and a chlorideion concentra-

tion of 102 g-ion per liter (3550 ppm),which is approximatelya solution saturated in chlorideion
over cuprous chloride. The diagramindicates that at neutral conditions of pH and Eh cuprous
chloride should hydrolyzeto cuprous oxide. In bronze disease pits, conditions are usually acidic
(betweenpH 3 and 5) and at these pH values CuClmay change in more oxidizingconditionsto give
gamma3Cu(OH)2CuCl2.This is simplyparatacamitewrittenin a differentway.
Pourbaix'soriginal work, from which this diagram is taken (Pourbaix 1976), dealt with the
corrosionpitting of copper tubes used for the delivery of Brussels tap water. Pits filled with
cuprous chloride and covered with cuprite and malachite would form in the tubes.

JAIC29 (1990):193-206

This content downloaded from 195.34.78.43 on Sat, 14 Jun 2014 22:30:45 PM

All use subject to JSTOR Terms and Conditions
200 David A. Scott

The work of Pourbaix (1976) suggested that similar products were formed in the
corrosionpits studied on copper that had been attacked by domestic water. The poten-
tialpH equilibriumdiagram for the ternary system Cu-Cl-H20for solutions containing
10- g-ion Clr/liter, which is about the amount of chloride ion present in a solution
saturated in CuCl, is shown in figure 1. In neutral solutions, at pH 7, the diagram
suggests that CuCl should hydrolyzeaccordingto equation [41,but such neutral condi-
tions are not encountered inside corrosion pits where copper, cuprite, and nantokite
coexist.
Examinationof the Pourbaix diagram suggests that these three components will be
stable at a pH of 3.5 and an E of +270 mVshe.Under these conditions the corrosion
reaction is reversible:the pit will grow if the electrode potential inside the pit is higher
than +270 mVshe,while the growthwill stop and metalliccoppercan be redepositedif the
electrode potential is lower than +270mVshe.The equilibriumvalues expected for the pH
in corrosioncrusts where copper, cuprite, and nantokite are present are thereforeacidic
and will contain potentiallyhigh amounts of complex copper chlorides and thereforeact
contraryto the model proposedby Sharkeyand Lewin(1971).
Sharkeyand Lewinfound that when the CuClIconcentrationreached 20%-300/% of the
copperions in solution at a pH of about 4, then atacamitewas favoredover paratacamite;
with still higher copper complexes, such as CuC12,CuCI3-,CuCl42-, paratacamiteonce
again became the favoredspecies. There is potential for greatvariationin the concentra-
tion of the complexcupric ions in solution, and it is difficultto envisage how the relative
amounts of the differentisomers can be used to obtain any useful informationon burial
conditions.
The relationshipbetween cuprous chlorideand other copperhydroxychlorides,such as
calumetite, is less clear. Calumetite--copperhydroxychloride,Cu(OH)Cl--hasbeen iden-
tified only a handful of times in the natural patina of ancient bronzes by the work of
Nielsen (1977), Meyers (1977), and Helmi and Iskander (1985). Calumetiteis at present
enigmatic: the conditions under which this mineral can form are not known and, in
addition, it is not known whether calumetite may have been formed on the bronzes in
question as a result of chemical cleaning treatment. However,since it is known as a
mineraland has been found in widelydisparateobjects it deserves serious attention.
Sharkey and Lewin(1971) found that there was no dimorphicinterconversionbetween
paratacamiteand atacamite under the conditionsthey investigated.It has been assumed
that the relative proportionsof the isomers could afford some clue to provenance or
perhaps authenticity of the patinas of differentobjects. This assumption is not really
feasible for the reasons that have been discussed above;the proportionsmay vary on one
object sampled from different locations depending on whether the object has incipient
bronze disease and fresh outbreaks of one of the copper trihydroxychlorideshave oc-
curred, or the original patina constituents are examined. Even under laboratorycondi-
tions the mode of production of the basic chlorides is very critical. If cupric chloride
solution is added to calcium carbonateand stirredthen atacamite is produced,but if left
unstirred then botallackiteis formed(Tennentand Antonio 1981). Subtle factors control
the conditions under which the differentproducts may form. Some reactions are more
repeatable than others. For example, the reaction between cuprous chloride, copper foil,
water, and air in an experiment carried out by the author gave mostly paratacamite, in
agreement with most of the previously reported results, while the same reaction, replacing
cuprous chloride with cupric chloride, gave a mixture of paratacamite and atacamite,
with more atacamite. Tennent and Antonio found that the latter reaction invariably
produced paratacamite. Unless all the parameters of the reactions, such as pH, tempera-

JAIC 29 (1990): 193-206

This content downloaded from 195.34.78.43 on Sat, 14 Jun 2014 22:30:45 PM

All use subject to JSTOR Terms and Conditions
 Bronze Disease: A Review of Some Chemical Problems 201
and the Role of Relative Humidity

ture, time, and molar concentrations,are carefullycontrolled,the end products of these

reactions cannot be predictedwith certainty.
A series of experimentswas conductedby Scott and O'Hanlon(1987) using a varietyof
cuprous chloride powders;some were freshly made in the laboratoryand stored under
nitrogen, while others were commercialproducts. The chemicals used in this series of
experimentswere all analytical grade reagents with very low levels of impuritiespresent
(less than 0.1%). The reaction products were sampled after a period of 5 days, and the
temperatureemployed was room temperature(20'C). The experimentalwork was con-
ducted to determinewhat the most common productswould be when differentcombina-
tions of the followingreactants were employed:copperfoil, cuprous chloride,and sodium
chloride, cuprous oxide. Analysis was carried out by x-ray powder diffractionusing a
Debye-Scherrercameraand by Fouriertransforminfraredspectroscopy.
The cuprous chloridepowderswere preparedby the followingmethods:
1. Cuprouschloridewas laid out on filterpaperand exposed to 70%/RH. The most
commonproductof this reactionis atacamite (Frondel1954), but mixturesof
paratacamiteand atacamitehave also been noted.
2. Copperfoil was suspended in a solution of 0.02M cupricchlorideand stirredfor 48
hours. The productof this reactionis paratacamite(Feitknechtand Maget1949).
3. Calciumcarbonatepowderwas reactedwith 0. 13Mcupric chloride.The product
has usually been identifiedas botallackite.
4. Copperfoil was sprinkledwith cuprous chloridecrystals and exposed to 70%RHfor
5 days. The productis mostly paratacamite(Tennentand Antonio 1981).
5. Copperpowderwas sprinkledwith cupric chloridedihydrateand exposed to 70%
RHfor five days. The productis a mixtureof paratacamiteand atacamite.
6. Copperfoilwas sprinkledwith sodium chlorideand exposed to 70%RHfor 5 days.
The productis mostly paratacamite.
7. Cuprouschloridepowderwas mixed 50:50 by weightwith sodium chlorideand ex-
posed to 70%RHfor 5 days. The productis a mixtureof paratacamiteand
atacamite.
8. Cuprouschloridepowderwas mixed 50:50 by weightwith cuprous oxide and ex-
posed to 70%RHfor 5 days. The productsare a mixtureof atacamiteand
paratacamite.
The same series of reactions was also attempted under nitrogen. If oxidation and
hydrolysisof cuprous chlorideis the principalreaction, then placing the reactants in an
inert atmosphereshould result in very little or no reaction. This was indeed found to be
the case, and in most of the reaction mixtures only slight alterationcould be found after
analysis by x-ray powderdiffraction.
The experimentsabove illustrate the comparativedifficultyof synthesis of botallackite
under ordinarylaboratoryconditions, a fact borne out by the analysis of the products of
bronze disease on antiquities: botallackite is rarely reported, while paratacamite and
atacamite predominate.
Some of the experiments were designed to see what products might be expected from
the reaction between copper metal and sodium chloride to simulate events that may occur
in highly saline environments, as well as to determine the reactions between cuprous
chloride and copper foil in the presence of moist air or with added
water. It is interesting
that the cuprite in experiment 8 is attacked during the reaction with cuprous chloride
and the red color of cuprite gradually changes, the whole mass becoming pale green. It is

JAIC 29 (1990): 193-206

This content downloaded from 195.34.78.43 on Sat, 14 Jun 2014 22:30:45 PM

All use subject to JSTOR Terms and Conditions
202 David A. Scott

clear that cupriteis vulnerableto attack under extremeconditionsThis characteristichas

potentialimportance,for the originalsurface detail of some objects, which is preservedin
cuprite, could be disrupted and suffer alteration as a consequence of reaction with
cuprous chlorideand moisture.
No change was observed in a similar experiment where the cuprous chloride was
replaced by sodium chloride. Reaction did ensue between copper powder and sodium
chloride with the formationof atacamite. Although more complex reactions may some-
times occur in highly saline environments, leading to complex copper salts, such a
reaction was not observedhere. As a result of the increase in chlorideion concentration
that is a necessary consequence of equation [6], a whole series of copper chloridespecies
becomes possible in the burial environment,where furtherreactionwith copperor copper
corrosionproducts could lead to the formationof complexspecies such as CuCl2,CuCl',
CuC42-. Indeed, Fabrizi and Scott (1987) found crystalline eriochalcite, CuCl2.2H20,
occurringas a corrosionproducton a copperalloy object fromMemphis,Egypt.This is a
noteworthyoccurrence,since high chlorideion contents of Egyptiansoils can lead to the
formation of unusual products. Eriochalcite may also be formed as a result of the
alterationof nantokite in the laboratory. It could not, of course, survive in moist condi-
tions since eriochalcite is soluble in water, but the site was a dry one and showed
unusual corrosionproducts, such as sampleite,which is discussed in detail by Fabriziet
al. (1989).
There is still much to be understood about the chemistry and pH conditions that
prevailin copperobjects and lead to an accumulationof cuprous chloridein the corrosion
products. The cupric complexes must play an importantrole in the continued reactions
giving rise to bronze disease before either all of the cuprous chlorideis consumed or the
humidity levels in pits or in zones contiguous with the surface dropbelow levels required
for continuous reaction.

4, BRONZEDISEASE AND RELATIVEHUMIDITY

SOMEOF the aspects of water layers formedon copper surfaces exposed to the atmos-
phere have been reviewedby Graedel (1987). Several monolayers of water can be ad-
sorbed onto the surface of pure copperat moderateor high humidities. At an RH of 60%
and a temperatureof 20'C, for example, the number of water monolayers on a metal
surface is estimated to be 15, while at 90%RHthe numberof layers is about 27. Current
views in surface chemistry suggest that when the number of monolayers rises above
three, the layerpossesses the chemicalpropertiesof bulk water.
The kinds of surface interaction phenomena discussed here are quite different than
those found on a pure metal, and they involve corrosion products of copper and tin as
well as impuritiesthat may exist within the alloy. Structuraldefects in crystallinephases
and grain boundaryeffects may well play a role, too. Clearly,the potentialexists for some
reactions to continue independent of the critical RH for the transformationof cuprous
chlorideand forvariationsin stabilityto be apparentwith differentobjects.
What is the best model for the RH values for storage that we currently have? It has
been proposed as a result of empirical observations in museum collections that unstable
bronze artifacts must be stored at an RH of less than 39% if the reactions of cuprous
chloride are to be stifled. The situation is complex for a variety of reasons. First, the
critical RH value for cuprous chloride in air in isolation from a metallic substrate is higher
than 46% RH. An experiment was conducted by the author for two years in which
compressed tablets of cuprous chloride (which becomes waxy when consolidated by
compression in an IR press), powdered cuprous chloride, and copper powder mixtures

JAIC 29 (1990): 193-206

This content downloaded from 195.34.78.43 on Sat, 14 Jun 2014 22:30:45 PM

All use subject to JSTOR Terms and Conditions
 Bronze Disease: A Review of Some Chemical Problems 203
and the Role of Relative Humidity

were kept in a humidity cabinet over a saturated salt solution providinga humidity that
only fluctuated between 42% and 46% RH during the period of the experiment. No
observable change in either the pure cuprous chlorideor the powdermixture occurred.
Samples of the copper powderwere mounted in resin for microscopicexamination and
polished for metallographicstudy. No change could be observedat the interfacebetween
the cuprous chlorideparticlesand the coppersubstrate, showing that if any reaction had
occurredit was quite negligible:the coppersurvivedmore or less intact.
Whenthe same experimentwas conductedat an RHof 70%,reactionwas rapid;within
a day the compressedcuprous chloridetablet exfoliatedand burst as it changed to one of
the copper trihydroxychlorides.Samples of polished copper sessile beads covered with
crystals of cuprous chlorideto which droplets of water are added periodicallydevelop a
waxy crust of cuprous chlorideadjacent to the metal surface, with a coveringprincipally
composedof paratacamite. If the waxy layer that adheres to the copperis removedwith a
scalpel, clear indications are found that the copper surface has been attacked. The
surface is dull and etched by the reactionwith cuprous chlorideunder these conditionsof
wetting and drying. In relation to copper, cuprous chloridehas a relative molar volume
(RMV)of about 3.36, while the copper trlhydroxychlorideshave RMVsof about 3.99. A
considerable force for expansion exists as a result of this transformation;the relative
molarvolume increase is even more markedcomparedwith cuprite,which has an RMVof
1.67.
An unknown factorin coming to a conclusion concerningcriticalRHs for objects is the
potential role that could be played by the existence of chloro-complexesof copperwithin
the corrosion crust. Their effect, coupled with the uncertainty as to the presence of
adsorbed water or internally trapped water due to microcapillarity,will be to produce
continued activityuntil the object has either reactedwith the availablewater or has dried
out beforethe availablecuprous chlorideis exhausted.
It is clear, however,that there is no reason per se to reduce the RH of stored bronzes
that are not showing signs of active corrosion to levels below 39%. Storage at an RH
between 42% and 46% should provide adequate conditions for most objects. The
humidity should not be allowed to rise above 55% because the reactions of cuprous
chloridebecome very rapid as the RH rises and will not necessarily stop as soon as the
RHis loweredagain.
Although the reactions reviewed here suggest a cyclical process in the absence of
further contaminationthe process will stop or will slow to low rates of reactionwhen the
cuprous chloride has been transformed.The sound metal remnants comprisingpart of
the object (if any metallic component was extant upon excavation) can suffer attack
during the process, but attack of the remaining metal itself will not be appreciable,
especially if the RH is kept below 46%;the primaryproblemis the cuprous chloridethat
is transforming,togetherwith the potential effects of the alterationof cuprite within the
patina.

5. CONCLUSIONS

THIS ARTICLEhas attempted to review some of the relevant information concerning

bronze disease and to suggest that more work is required to understand precisely all the
variables involved in the process. Some of the more important points are summarized
here.
The presence of paratacamite or atacamite on the surface of a bronze object does not
necessarily mean that the object is undergoing active corrosion. Further research is

JAIC 29 (1990): 193-206

This content downloaded from 195.34.78.43 on Sat, 14 Jun 2014 22:30:45 PM

All use subject to JSTOR Terms and Conditions
204 David A. Scott

requiredon the basic copper chlorides to understand in more detail their chemistryand
their interrelationships with cupric complex species, particularly in the case of
calumetite.
The location of cuprous chloridewithin the patina constituents can vary. In some cases
it is adjacent to the metal surface, but in other examples it may overlie cuprite or be
sandwichedbetween cuprite layers.
The problemsof the appropriateRHfor the storageof bronzes has been examined,and,
for the majorityof bronzes, an RH between 42% and 46% was found to be sufficient;
cuprous chloridewill not undergo chemical reactionat this humiditylevel, which already
incorporates a margin of safety. More problematic objects may require lower levels.
Testing this hypothesis is not easy, since bronzes are often treated and stored at low
humidity in the conservation laboratoryand then returned to display or storage after
treatment;there the RH levels may be much higher, making continuous assessment of
the situation difficult.
Since the cost of maintaining an RH of 39% is high, further museum work will be
required to ascertain if the recommendationof 42% to 46% RH can be confirmed as
soundly based.
REFERENCES

Berthelot, M.P.E. 1895. Etude sur les metaux qui composent les objets de cuivre de
bronze, d'6tain,d'or, et d'argent,d6couvertsdans les fouilles de Dahchour, on provenant
du Muste de Gizeh. In Fouilles d Dahchour,ed. J. de Morgan. Vienna:A. Holzhausen.
131-46.

Davy, J. 1826. Observationson the changes which have taken place in some ancient
alloys of copper. Philosophical Transactions of the Royal Society of London 116(2):55-59.

Fabrizi,M., H. Ganiaris,S. Tarling,and D. A. Scott. 1989. The occurrenceof Sampleite,a

complex copper phosphate, as the principal corrosion product on ancient Egyptian
bronzes fromMemphis,Egypt. Studies in Conservation34:45-51.

Fabrizi,M., and D. A. Scott. 1987. Unusual copper corrosionproducts and problems of

identity. In Recent advances in the conservation and analysis of artifacts, comp. J. Black.
London:Summer School Press. 131-33.

Feitknecht, W., and K. Maget. 1949. Zur Chemie und Morphologieder basischen Salze
zweiwertiger Metalle. XIV Die Hydroxychloridedes Kupfers. Helvetica Chimica Acta
32:1639-53.
Frondel, C. 1954. Paratacamite and some related copper chlorides. Mineralogical
Magazine 29:34-45.

Giangrande,C. 1987. Identificationof bronze corrosionproducts by infraredabsorption

spectroscopy. In Recent advances in the conservation and analysis of artifacts, comp. J.
Black. London:Summer School Press. 135-48.

Graedel,T. E. 1987. Copperpatinas formedin the atmosphere, II:A qualitativeassess-

ment of mechanisms. CorrosionScience27:721-40.

JAIC 29 (1990): 193-206

This content downloaded from 195.34.78.43 on Sat, 14 Jun 2014 22:30:45 PM

All use subject to JSTOR Terms and Conditions
 BronzeDisease: A Reviewof Some ChemicalProblems 205
and the Roleof RelativeHumidity

Helml, F. M., and N. Y. Iskander. 1985. X-ray study, treatment and conservation of
Rameses II's stove from the Egyptian Museum, Cairo. Studies in Conservation 30:23-30.

Lewin, S. Z. 1973. A new approach to establishing the authenticity of patinas on copper-

base artifacts. In Applicationof science in examinationof works of art, ed. W. J. Young.
Boston: Museum of Fine Arts. 62-66.

Lucy, V. F. 1972. Developments leading to the present understanding of the mechanism

of pitting corrosion in copper. British CorrosionJournal 7:36-41.

MacLeod, I. D. 1981. Bronze disease: An electrochemical explanation. Institute for the

Conservationof CulturalMaterialsBulletin 7:16-26.

Madsen, H. B., and N. Hjelm-Hansen. 1979. Black spots on bronzes: A microbiological or

chemical attack. In The conservation and restoration of metals, Proceedings of the sym-
posium, Edinburgh. Glasgow: Scottish Society for Conservation and Restoration. 33-39.

Meyers, P. 1977. Technical examination of an Achaemenid bronze mirror, from the

collection of Norbert Schimmel. In Bibliotheca Mesopotamia, ed. Giorgio Buccellati.
Malibu, Calif.: Undena Publications. 7:196-98.

Nielsen, N. A. 1977. Corrosion product characterization. In Corrosion and metal artifacts,

ed. B. Floyd Brown et al. NBS Special Publication 479. Washington, D.C.: U.S. Depart-
ment of Commerce. 17-37.

Oddy, W. A., and N. D. Meeks. 1982. Unusual phenomena in the corrosion of ancient
bronzes. In Science and technologyin the service of conservation,ed. N. S. Brommelleand
G. Thomson. London: International Institute for Conservation of Historic and Artistic
Works. 119-24.

Organ, R. M. 1963. Aspects of bronze patina and its treatment. Studies in Conservation
8:1-9.

Palache, C., H. Berman, and C. Frondel. 1951. Dana's system of mineralogy. 7th ed. New
York: John Wiley and Sons. 2:18-19.

Pourbaix, M. 1976. Some applications of potential-pH diagrams to the study of localized

corrosion. Journal of the Electrochemical Society 123(2):25c-35c.

Scott, D. A., and J. O'Hanlon. 1987. The analysis of copper trihydroxy-chlorides and their
occurrence as corrosion products on bronze antiquities. Unpublished internal
report.
London: Department of Chemistry, University College.

Sharkey, J. B., and S. Z. Lewin. 1971. Conditions governing the formation of atacamite
and paratacamite. American Mineralogist 56:179-92.

Taylor, R. J., and I. D. MacLeod. 1985. Corrosion of bronzes on shipwrecks: A comparison

of corrosion rates deduced from shipwreck material and from electrochemical methods.
Corrosion (National Association of Corrosion Engineers) 41:100-104.

JAIC29 (1990): 193-206

This content downloaded from 195.34.78.43 on Sat, 14 Jun 2014 22:30:45 PM

All use subject to JSTOR Terms and Conditions
206 David A. Scott

Tennent, N. H., and K. M.Antonio. 1981. Bronzedisease: Synthesis and characterisation

of botallackite, paratacamiteand atacamite by infra-red spectroscopy. ICOMCommittee
for Conservationpreprints,6th TriennialMeeting,Ottawa.81/23/3-1-81/23/3-11.

DAVIDA. SCOTT
DAVIDA. SCOTT,B.Sc., B.A., Ph.D., C.Chem. MRSC,FIIC,has been head of Museum
Services of the Scientific Programat the Getty ConservationInstitute since 1987. He has
been a lecturer in conservation at the Institute of Archaeology,University of London,
Departmentof ArchaeologicalConservationand MaterialsScience, and, since 1984, an
editor of Studies in Conservation.He was named a fellowof the InternationalInstitute for
Conservationin 1989. His principal research interests are the analysis and technical
study of ancient metallic objects and their corrosionproducts, the conservationof metal-
lic artifacts, the study of Chumash Indian rock art and the archaeometallurgyof ancient
South America,particularlyColombiaand Ecuador.Address:The J. Paul GettyMuseum,
P.O. Box 2112, Santa Monica,Calif.90406.

JAIC 29 (1990): 193-206

This content downloaded from 195.34.78.43 on Sat, 14 Jun 2014 22:30:45 PM

All use subject to JSTOR Terms and Conditions