Deterioration of Copper

Deterioration of Copper
Components of what may be an ancient battery. Iraq, first
century CE. At left is the clay jar in which the iron rod (center) and copper cylinder (right) would have been placed. The dark fragments are bitumen, which would have been used to hold the three components together.
Image courtesy of Department of Antiquities, Iraq.
Pourbaix diagram
showing plot of natural aqueous environments with characteristics in different regions of Eh and pH.
Image courtesy of Schweizer 1994 and David A. Scott.
Pourbaix diagram showing distribution of natural aqueous
environments, which can be seen to cover a considerable range of Eh and pH conditions. The dotted area represents the major concentration of many thousands of Eh and pH measurements, while the surrounding irregular box represents the boundary for all measurements.
Image courtesy of Baas Becking, Kaplan, and Moore 1960 and David A. Scott.
Analysis of corrosion of soils
Agency a
BNFMRA BNFMRA NBS
Soil type
5 least corrosive 4 least corrosive 9 least corrosive
Years
10 5 14
Corrosion
(m/year) 0.5 - 2.5 5.0 - 25 4.0 - 2.5
Maximum pitting
(mm/year x 104) Uniform: no pits 0.040 0.043
NBS
BNFMRA
2 next most corrosive

Acid clay/acid peat
14
10
25 130
53 66
0.033
0.046
BNFMRA NBS
2nd series: b cinders 3 most corrosive: rifle peat/ tidal marsh
5 14
66 160 355
0.32 0.115
a BNFMRA = British Non-Ferrous Metals Research Association (now defunct); NBS = National Bureau of Standards.
b 2nd series = second attempt to derive accurate results for this set of data.
Image courtesy of David A. Scott.
Typical Modern Concentrations Atmospheric Gases

Name
Ozone Hydrogen peroxide Nitrogen dioxide
Formula
O3 H2 O 2 NO2
Concentration (ppb)
50 200 10 -30 10 45
Nitric acid
Hydrogen sulphide
HNO3
H2 S
1 10
0.1 0.5
Carbonyl sulphide
Sulphur dioxide Carbon dioxide Formic acid Acetic acid Oxalic acid Formaldehyde
COS
SO2 CO2 HCOOH CH3COOH (COOH)2 HCHO
0.5 0.6
5 24 (3 6 ) x 105 0.2 1 0.2 1 Not detected 4 15
Acetaldehyde
Hydrogen chloride
CH3CHO
HCl
18
0.5 - 2
Image courtesy David A. Scott.
Conversion factors for concentrations of some pollutant gases in parts per billion (ppb) and microgram/m3 (g/m3)
Name
Acetic acid
Formic acid Acetaldehyde Formaldehyde Hydrogen sulphide Carbonyl sulphide Ammonia Sulphur dioxide Nitrogen dioxide Ozone
Conversion Factor a ppb to g/m3

2.45
1.88 1.80 1.23 1.39 2.45 0.70 2.62 1.88 1.96
g/m3 to ppb
0.41
0.53 0.56 0.82 0.72 0.41 1.44 0.38 0.53 0.51
a The general expression is microgram/m3 x conversion factor = ppb. All measurements are at standard temperature and pressure, with temperature assumed to be 25C.
Stability diagram of the
system Cu-SO4-H2O with fog and rain areas shown for urban atmospheres. Area A = atacamite stability; area B = brochantite stability. Although the diagram over-simplifies the actual situation, it does show that brochantite should form in outdoor exposure an that antlerite may form in more acidic conditions.
Image courtesy of Graedel 1987 and David A. Scott.
Concentration of air pollutants in museums and libraries
Building
National Gallery, London Victorian and Albert Museum, London Tate Gallery, London Sainsbury Center, Norwich, U.K. National Archives and Records Administration, Fort Worth, Texas National Gallery, Washington, D.C. Library of Congress, Washington, D.C. 2 25 <1 < 0.5 3 42 <4 40 (max) < 42 Low Low 10 252 7 50 4 145
SO2
(ppm)
O3
(ppm)
NOX
(ppb)
NO
(ppm)
Dates
0.25 1983 1980 83 1981
Baxter Gallery, Pasadena, California

Los Angeles County Museum of Art, Los Angeles, California Huntington Gallery, San Marino, Calif. Scott Gallery, San Marino, California
120
< 10 < 10 31 15 92 32
1982
1982 1982 1964 1974
Image courtesy of Brimblecombe 1990 and David A. Scott.
Huntington Library, San Marino, Calif.

Rijksmuseum, Amsterdam
75
37
Concentration of air pollutants in museums and libraries
Summer measurements
Building
Rijksarchief, The Hague Rijksarchief, Arnhem Rijksarchief, Leewwarden
SO2 (ppm) O3 (ppm)

<1 1 <1 <1 2 <1
NOX
(ppb)
NO
(ppm)
Dates
1986 1986 1986
30 16 ~7
Winter measurements
Building
Rijksarchief, The Hague Rijksarchief, Arnhem Rijksarchief, Leewwarden
SO2 (ppm) O3 (ppm)

1.5 4.5 <1
NOX
(ppb)
NO
(ppm)
Dates
1986 1986 1986
49 39 ~ 46
Typical marine environments

Marine zone
Atmospheric
Environment
Small sea-salt particles carried by wind. Corrosivity varies with height above water, dew cycle, bird droppings, wind, etc. Wet, well-aerated surface, no fouling. Marine fouling present to high water. Seawater saturated with oxygen; pollution, sediment, and fouling may all be present. No plant fouling; some decrease in oxygen, especially in the Pacific, and at lower temperatures. Oxygen varies, lower here than at surface; temperature near 0C; velocity and pH both lower than at surface. Sulfate-reducing bacteria present; bottom sediments vary in origin, characteristics, and corrosion behavior.
Characteristic behavior of copper

Partially sheltered surfaces may deteriorate more rapidly than those exposed; top surfaces may be washed free of salt by rain. Most aggressive zone for may metals and for protective coatings. Copper may act cathodically at tidal zone. Corrosion may be more rapid than in exposed marine zone areas; a layer of hard shell and biofouling may restrict corrosion. Copper alloys may be well preserved.
Splash Tidal Shallow water
Continental shelf
Deep ocean
Data for copper alloys sparse, but corrosion is limited. Partially buried bronzes corroded most; submerged copper alloys may be severely attacked.
Mud
Characteristics of some copper oxide and copper hydroxide minerals
Mineral name
Cuprite Tenorite
Formula
Cu2O CuO
Crystal system
Cubic Monoclinic
Color
Submetallic red Metallic gray black
Mohs hardness
3.5 4 3.5
Spertiniite
Cu(OH)2
Often amorphous
Blue green
12?
Pourbaix diagrams for the system Cu-CO3-H2O at various
carbon dioxide concentrations
44 ppm
440 ppm
4400 ppm
44000 ppm
Images courtesy of Pourbaix and David A. Scott.
Illustration of natural
azurite and malachite crystal forms
Image courtesy of Palache, Berman, and Frondel 1951 and David A. Scott.
Characteristics of some basic carbonate minerals
Mineral name
Malachite Azurite Georgeite Chalconatronite Rosasite Aurichalcite Claraite
Formula
CuCO3 . Cu(OH)2 2CuCO3 . Cu(OH)2 CuCO3 . Cu(OH)2 Na2Cu (CO3)2 . 3 H20 (Cu, Zn)2CO3(OH)2 (Cu, Zn)5(CO3)2(OH)6 (Cu, Zn)3(CO3)(OH)4 . 4H2O
Crystal system
Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic Orthorhombic Hexagonal
Color
Pale green Vitreous blue Pale blue Greenish blue Bluish green
Mohs hardness
3.5 4 3.5 4 ? 3 -4 4.5
Pearly pale green 1 2 Translucent blue 2
Shang Dynasty ding,
bronze, shown after electrolytic stripping.
Image courtesy of Honolulu Academy of the Arts.
Shang Dynasty ding,
bronze, middle Anyang period. Detail, Shang Dynasty ding. Note black inlay.
Shang Dynasty xian
steamer vessel, bronze. Note black soot on bottom.
Western Zhou Fugeng Li
ding, bronze. 1100-1000 B.C.E.
Image courtesy of Arthur M. Sackler Gallery, Washington D.C.
Early Western Zhou
Dynasty hu, bronze, 11th to early 10th century B.C.E. Photographed before acquisition by the Freer Gallery of Art.
Image courtesy of Freer Gallery of Art, Washington, D.C.
Same Western Zhou
Dynasty hu, photographed after acquisition by the Freer Gallery of Art. Note darker area of corrosion products where lid joins vessel.
Zhou Dynasty gui, bronze, shown during treatment with
cleaned section on the right.
A. Milne Calder, bronze
statue of William Penn, cast 1889-91, City Hall Tower, Philadelphia.
Image courtesy of Andrew Lins and Tracy Power
BF x96 from the William Penn figure: a complex, multilayer
corrosion crust can develop on bronzes after long exposure to urban-industrial atmospheres in this case 97-98 years. The corrosion is approximately 200 microns thick and partly follows microstructural features, especially casting pores located near the surface.
BF x240 also from the William Penn figure, illustrates that
the delta phase is not as rapidly attacked as the alpha phase at this particular site.
BF x310 shows the irregular, porous nature of the mineral
formations within the crust.
This three-dimensional plot shows the stability of different
copper minerals in water at 25C. Below are oxidized copper species found in rain or natural waters. The x axis shows pH, the y axis shows sulfate ion activity, and the z axis shows total CO2 activity (including CO2(g), H2CO3, HCO3-, and CO3=). Zone of conditions favoring antlerite formation is shaded.
Plot emphasizing the calculated lower limit of cupric ion
activities (aant v broch) which would allow antlerite rather than brochantite to form, based on the work of Silman.
Plot showing the solubility of different copper sulphate and
oxide species in dilute sulphuric acid solutions. Data based on thermodynamic and other calculations at 25C, after Mattson and Graedel. Zones for acid rain and fog are displayed, overlaps indicating which minerals are likely at particular pH levels and sulphate concentrations. The left side shows no stable mineral forms, only Cu++ in solution.
The site of Francavilla, Southern Italy, 5th-6th C BC.
Bronze tripod legs of anthropomorphic form.

Image courtesy of Bolletino dArte.
The site of Francavilla
From left to right, top to bottom: Extensive working and annealing to shape, followed by cold-working of the surface. Very small crystallized grains. Copper sulfide inclusions are visible. Variable grain size with intergranular corrosion. Typical corrosive penetration along slip planes in the bronze crystals infilled with cuprite. Corrosion crust principally of malachite. Uneven intergranular attack. Overall view. Recrystallized small grain structure. Sulphide and lead inclusions and very large
Image courtesy of Bolletino dArte.
Pourbaix diagrams for the system Cu-Cl-H2O at various
carbon dioxide concentrations
35 ppm
350 ppm
3550 ppm
35500 ppm
Pourbaix diagram for
the system Cu-SO4H2O.
Pourbaix diagram for
the system Cu-S-H2O.
Image courtesy of Schweizer.
Surface corrosion
containing pustules of copper and lead salts.
Surface of the Roman
bronze statue of Roma or Virtus showing fibrous malachite occurring as curled crystals.
Images courtesy of David A. Scott.
Image courtesy of the Getty Museum.
Miniature Portrait Bust
of a Woman, Roman, 25 BC - 25 AD. Bronze with glass-paste inlays. The bust is shown before conservation, illustrating pustular corrosion with pitting created by bronze disease.
Two small penannular bronze nose ornaments from the site of La Compania, Ecuador, dated to about the tenth century CE, showing the light green, powdery eruptions typical of bronze disease.
Measures for wet metallic objects: bronze, brass, lead and
silver can generally be allowed to dry out. Iron may be better stored in oxygen-free environment, can use oxygen scavengers in sealed jar or box, silica gel, or store in water with sulphite added to mop up oxygen. Silica gel may not be enough for heavily corroded iron.
The monument of Marcus
Aurelius after restoration
Before
After
Image courtesy of The Mr. and Mrs. Lawrence Fleischman.
Elemental distribution
maps for sulfur, lead, tin and carbon, together with secondary-electron and backscattered electron images (top).
Magnesium, copper,
chlorine and oxygen with secondary-electron and backscattered electron images (bottom) for a de Vries bronze statue.
Elemental distribution maps for a bronze statue of Alexander Hamilton, New York, erected 1890: Copper (top left) Tin (top center) Chlorine (top right) Oxygen (bottom left) Zinc (bottom center)
Togati pustule
Togati pustule
Votive bronze leaf
Narrow leaf formed of thin sheet
bronze, with a prominent central rib. Bottom: view of a section of leaf showing voids that suggest selective corrosion of the alloy due to differential composition.
Magnification x100, crossed
Bronze flower rosette.
Six joining frr preserving much
of rosette. Rosette with at least eight petals, and perhaps originally as many as eleven. Hole in center; no preserved rivet
Image courtesy of Bolletino DArte: the Archaic Votive Metal Objects.
Magnification x50
Right: Overall view of rosette, unetched, showing cracking and inter-granular corrosion. Bottom right: View of etched section showing small twinned grains and intercrystalline corrosion. Bottom: etched in ammonia peroxide showing strain lines in the surface areas.
Magnification x250 Magnification x100
Bronze votive floral sprays.
Two joining flowers, plus
miniscule flower, preserving complete rod, with portions of terminals at both ends. Bent, as shown. Somewhat corroded.
Magnification x12.5
Right: View of votive floral spray
showing the corrosion crust tat displays extensive Liesegang-type phenomena in a cuprite and malachite crust.
Bottom right: Etched view
Magnification x100
showing twinned grains with corrosion through strain lines.
Preserve unique version of
Greek language. Made in pure copper Corrosion considered odd Thought to be a forgery by some German scientists Need to confirm their authenticity as very important for the history of language. One plaque in Johan von Wagner Museum: Stuttgart, another two in Norway, one lost in a private collection.
Copper plaque.
Image courtesy of West Semitic Research.
Greek Copper Plaques
Copper plaque.
Radiographic examination used
to read inscribed text on back and front without further cleaning. Chemical analysis X-ray fluorescence studies X-ray diffraction studies Metallographic studies Here the hammering marks in the x-ray image are important as same on all three plaques. Text is from 8th-9th century BC Greek evolving from Phoenician at this time. Get digamma and qoppa used.Image courtesy of West Semitic Research.
Copper plaque, X-radiograph.
Corrosion on one very
heavily chloridecontaining. This was atacamite and paratacamite, two of the copper trihydroxychlorides Cu2(OH)3Cl. German argument was that this is not acceptable. Argument based on usual predominance of malachite and carbonates in soil burial corrosion.
Copper plaque.
Detailed surface examination showed inscribed letters
preserved within corrosion, not metallic substrate.
Copper plaque, detail of inscription s.

ESEM studies showed pseudomorphic preservation of wood
cellular structure within copper corrosion products of malachite. Note spiral thickening of cell wall and some pits.
Copper plaque. Copper corrosion has replaced the wood
Minute wood and some charcoal fragments preserved within
corrosion crust.
Copper plaque with attached
More examples of pseudomorphic preservation of cellular
wood structure.
Metallographic examination reveals coherent cuprite layer
beneath thick green corrosion crust contiguous with metal
Copper plaque microstructure.
Mineralogical complexity to this corrosion crust
Copper plaque microstructure.
Argument for authenticity too
strong: Surface preserved within corrosion. Coherent cuprite layer Pseudomorphic replacement of wood Hammering marks of the plaques Knowledge that pure copper was used for other artefacts Corrosion acceptable Conclusion: previous view that plaques are fake is totally incorrect. Based on a superficial view that patinas primarily of copper chlorides do not exist, which is incorrect.

Deterioration of Copper

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Deterioration of Copper

Components of what may be an ancient battery. Iraq, first

Image courtesy of Department of Antiquities, Iraq.

Image courtesy of Schweizer 1994 and David A. Scott.

2 next most corrosive

2nd series: b cinders 3 most corrosive: rifle peat/ tidal marsh

Typical Modern Concentrations Atmospheric Gases

Conversion Factor a ppb to g/m3

Image courtesy of David A. Scott.

Image courtesy of Graedel 1987 and David A. Scott.

0.25 1983 1980 83 1981

Baxter Gallery, Pasadena, California

Huntington Library, San Marino, Calif.

SO2 (ppm) O3 (ppm)

SO2 (ppm) O3 (ppm)

Image courtesy of Brimblecombe 1990 and David A. Scott.

Typical marine environments

Characteristic behavior of copper

Splash Tidal Shallow water

Image courtesy of David A. Scott.

Image courtesy of Brimblecombe 1990 and David A. Scott.

carbon dioxide concentrations

azurite and malachite crystal forms

Pearly pale green 1 2 Translucent blue 2

Image courtesy of Brimblecombe 1990 and David A. Scott.

bronze, shown after electrolytic stripping.

Image courtesy of Honolulu Academy of the Arts.

Image courtesy of Honolulu Academy of the Arts.

steamer vessel, bronze. Note black soot on bottom.

Image courtesy of Honolulu Academy of the Arts.

ding, bronze. 1100-1000 B.C.E.

Image courtesy of Arthur M. Sackler Gallery, Washington D.C.

Image courtesy of Freer Gallery of Art, Washington, D.C.

Image courtesy of Freer Gallery of Art, Washington, D.C.

cleaned section on the right.

Image courtesy of Freer Gallery of Art, Washington, D.C.

statue of William Penn, cast 1889-91, City Hall Tower, Philadelphia.

Image courtesy of Andrew Lins and Tracy Power

Image courtesy of Andrew Lins and Tracy Power

Image courtesy of Andrew Lins and Tracy Power

formations within the crust.

Image courtesy of Andrew Lins and Tracy Power

Image courtesy of Andrew Lins and Tracy Power

Bronze tripod legs of anthropomorphic form.

Image courtesy of Bolletino dArte.

carbon dioxide concentrations

the system Cu-SO4H2O.

Images courtesy of Pourbaix and David A. Scott.

the system Cu-S-H2O.

Image courtesy of Schweizer.

containing pustules of copper and lead salts.

Surface of the Roman

Miniature Portrait Bust

Aurelius after restoration

Narrow leaf formed of thin sheet

Magnification x100, crossed

Image courtesy of David A. Scott.

Six joining frr preserving much

Image courtesy of Bolletino DArte: the Archaic Votive Metal Objects.

Magnification x250 Magnification x100

Image courtesy of Bolletino DArte: the Archaic Votive Metal Objects.

Two joining flowers, plus

Image courtesy of Bolletino DArte: the Archaic Votive Metal Objects.