M

Metals: Preservation and generally referred to by the year of the conference

Conservation publication, while citations from journals are
reported in standard formats. The original articles
Ian D MacLeod can be found by using Google Scholar. Many of
Western Australian Maritime Museum, the papers report on the results of practical con-
Fremantle, WA, Australia servation assessments, analyses, and treatments
that relate to the typical problems faced by those
caring for our metallic cultural heritage (Figs. 1, 2,
Introduction 3, 4, 5, 6, and 7).

The challenge of providing a summary of the most

relevant literature that relates to metal conserva- Key Issues
tion is based on exclusion rather than inclusion.
Presently there is a resurgence of energy and vigor Conservation of Iron
being found in this area of applied research. The A key paper in the quest for new understanding on
largest collection of peer-reviewed papers comes the nature of the interaction of iron with wood,
from two triennial conferences of the International bone, and other elements was recently reported
Council of Museums Committee for Conservation (ICOM-CC 2014). The study of the binding
(ICOM-CC) and a meeting of the ICOM-CC between traditional Indian swords and their hilts
Metals Working Group. The triennial conferences discovered it was the traditional use of a paste
of ICOM-CC were held in Melbourne in 2014 and made from boiled lac beetles and river sand that
in Copenhagen in 2017 (ICOM-CC 2014, 2017), formed a very stable connection between the iron
while the Metals Working Group held a meeting sword blade and the handle. The key element in
in New Delhi in 2016 at which more than this work was the thoroughness of their study of
70 papers and posters were published (Metal traditional craftspeople throughout the subconti-
2016). Other principal sources included the pub- nent and then checking the oral histories against
lications of the International Institute for Conser- contemporary experimental practice. Conserva-
vation of Historic and Artistic Works (IIC) which tion of grave goods containing a mixed collection
publishes Studies in Conservation as well as the of ferrous and nonferrous materials from the sec-
Bulletin of the Australian Institute for the Conser- ond to fourth century in Lithuania was well man-
vation of Cultural Materials (AICCM) and that of aged, and practical management advice is
the Journal of the American Institute for Conser- provided by the authors to assist archaeological
vation. Summaries of the original papers are conservators (Metal 2016).
# Springer International Publishing AG, part of Springer Nature 2018
C. Smith (ed.), Encyclopedia of Global Archaeology,
https://doi.org/10.1007/978-3-319-51726-1_539-2
2 Metals: Preservation and Conservation

Metals: Preservation and

Conservation,
Fig. 1 Active iron
corrosion from anchor
damage on a WWII Chuuk
shipwrecks

Metals: Preservation and

Conservation,
Fig. 2 Active iron
corrosion on a bogey trolley
on a WWII submarine
slipway, Fremantle

The first definitive study on the subcritical reactive nature of the iron (III) minerals within
treatment of French archaeological iron objects the matrixes. After equilibration for more than
recovered from land-based and marine sites from 30 h in the subcritical microenvironment, the
the first century CE was reported at the Metal troublesome phases had been converted into sta-
2016 conference in New Delhi. The corrosion ble Fe3O4. The effectiveness of the methodology
products were characterized with X-ray diffrac- of sectioning the samples and providing a thor-
tion and laser Raman, which confirmed the ough physical examination of the materials is
Metals: Preservation and Conservation 3

Metals: Preservation and

Conservation,
Fig. 3 Brass nail from the
wreck of the Rapid (1811)
with intergranular
corrosion, width 1.13 mm

Metals: Preservation and

Conservation,
Fig. 4 In-situ corrosion
measurements on the Gosei
Maru (1944)

enough to convince the most doubting archaeolo- testing environment in the collection stores of
gist that this “new method” has found a permanent 8 to +38  C over an annual cycle in Central
home in the conservation repertoire (Metal 2016). Anatolia, Turkey. The site has been worked for
A significant breakthrough in both first aid and more than 25 years, and it dates to the early
long-term management of archaeological iron and Bronze Age. The balance of the right amount of
bronze objects takes the form of storage/treatment RPS material and desiccants is reviewed, and tests
in Escal bags with the Mitsubishi oxygen scav- also confirmed that clips sealing the bags were as
enging RPS system. The work is based on a very effective as heat sealing which increases the
4 Metals: Preservation and Conservation

Metals: Preservation and

Conservation,
Fig. 5 Judy dive bomber
(1944) in Chuuk Lagoon

Metals: Preservation and Conservation, Fig. 6 PVC

packing pox on a clock dial, The Bell Tower, Perth

collection management flexibility. The combined

system gave protection during excavation periods
(up to 1 week) and during the break between
annual excavation programs (Metal 2016).
Phosphoric iron has been misunderstood by
conservators and archaeologists alike, but recent
experimental archaeology has shown that despite Metals: Preservation and Conservation, Fig. 7 USS
Monitor (1862) engine in caustic treatment tank, Eric
the major impact of phosphorus impurities on Schindelholz inspection
microstructure of the cast iron alloys, they could
be effectively worked and treated to make steel for Aerobic Corrosion Products and Decay
swords. This new approach may stimulate a Mechanisms
review of the finds of archaeological iron and Scott and Eggert summarize patination of cast iron
lead to provenance studies of the ore bodies and steels in a compelling chapter in their book. Not
(Metal 2016). unexpectedly, many of the combinations of
Metals: Preservation and Conservation 5

chemicals used in the patination of iron objects are that there is hope that future resolution of the
closely related to the reagents that are currently used oxidative degradation, which follows successful
to etch iron alloys and reveal, through differential stabilization of the waterlogged wood, can be
oxidation rates, the phases that determine the effectively managed. The pyrophoric nature of
properties of the alloys. The characterization of the iron sulfide mackinawite explains why some
the physical, structural, and color properties of freshly excavated cannon balls can corrode so
goethite, lepidocrocite, akaganéite b-FeOOH rapidly that they begin to steam. A critical review
and schwertmannite Fe16O16(OH)y(SO4)z. of coating systems for reactive pyritic mineral
nH2O, feroxyhyte d-FeOOH, ferrihydrite specimens shows that storing them at a relative
Fe5O6(OH)3.3H2O, bernalite Fe(OH)3.nH2O, and humidity below 40% is the best approach (Scott
hematite a-Fe2O3 are expertly summarized. and Eggert 2009).
A major advance in understanding the distri-
bution of iron chlorides in historical Roman nails Treatment Options for Nonferrous Materials
has been developed through an X-ray tomography The chemical stratigraphy of Renaissance bronzes
study which was combined with neutron diffrac- revealed composite patinas consisting of primary
tion work. Measurements were done before and layers reflecting dezincification and secondary
after traditional treatment with alkaline sulfite layers of botryoidal copper sulfate structures
solutions. One of the real challenges of dealing using synchrotron- and neutron-aided techniques.
with significant archaeological iron objects is the These phases were topped with organic layers
inability to determine how effective a treatment which explain the apparent mystery behind the
has been without resorting to significant interven- remarkable aesthetic beauty of the bronzes
tion, such as drilling samples for wet chemical (ICOM-CC 2014). A synchrotron study of a
analysis. This new approach shows great promise 1697 Dutch pewter plate recovered in the nine-
and will be a useful additional method that can be teenth century revealed that the raw materials
applied to significant cultural objects to ensure the were English and that the complex patina of the
effectiveness of treatment programs (ICOM-CC de Vlamingh plate was due to significant amounts
2017). of copper impurities in the Cornish tin (ICOM-CC
2014).
Treatment of Iron-Organic Composites A real headache for archaeological metal con-
Desalination of composite organic and iron servators is how to manage the impact of repeti-
archaeological artifacts still presents real chal- tive treatments on the same historical object.
lenges for material conservation. This is due to Collaborative research in Spain and Portugal has
the fundamental incompatibility of chloride- demonstrated, on model systems, that electro-
infested iron, which wants a highly alkaline envi- chemical reduction of silver and lead corrosion
ronment for stability, and the desire of organic products can take place up to six times without
materials to be in a near-neutral condition. Col- loss of surface materials. Although limited to
laborative research in Switzerland and the USA standard metal tokens, the news that potentiostatic
showed that coatings of dodecane go a long way reduction retains all the metal that had corroded
to protecting the organic remains during the pro- and returns it to its metallic state is a very positive
longed immersion periods in alkaline solutions step forward in the long-term preservation of his-
that are needed to stabilize the iron components toric archaeological metal objects (ICOM-CC
(ICOM-CC 2017). 2017).
The role and significance of iron sulfides in the A 4-year project involving the Getty Conser-
fate of formerly waterlogged wooden vessels such vation Institute and French laboratories was
as the Wasa (1628) and the Batavia (1629) con- focused on a series of extraordinarily fine second-
tinue to expand, with most of the effort going into to fourth-century silver archaeological objects.
the characterization of the minerals. It is only The research discovered historical evidence
when formation mechanisms are fully understood about the nature of the hoard which demonstrated
6 Metals: Preservation and Conservation

the precise manufacturing techniques. The choice spectroscopy was used to monitor the corrosive
of tarnish removal was resolved by using ultrafine attack in 3 wt.% NaCl solutions. Results show that
slurries of calcium carbonate with old organic films can be efficiently used as a transparent
coating residues being removed with a combina- bronze corrosion inhibitor coating. Some films
tion treatment of steam and alcohol. Details of the exhibited a “self-healing” behavior, allowing a
new transport and exhibition mounts are also selective release of BTA during the corrosion
reported which will ensure that the lessons learned process induced by chlorides, as well as a protec-
regarding the Berthouville silver treasure are tion barrier effect due to the organic matrix (Metal
made available to the archaeological world at 2016).
large (ICOM-CC 2017). A very useful addition to the suite of tools for
A major development for the proper interpre- conservation of archaeological metals has been
tation of the milieu of corrosion products on provided through a study of the variation of the
archaeological bronzes has shown that it is the voltage (corrosion potential) of metal objects sit-
presence of human remains, providing a rich ting in treatment or storage solutions. Increasingly
source of phosphate, that facilitates the formation positive voltages show that the patina is
of sampleite, NaCaCu5(PO4)4Cl.5H2O. In higher- interacting with the cleaning solutions to create a
sulfate soils, the hydroxy sulfate connellite passive film that lowers corrosion rates. When the
Cu19Cl4(SO4)(OH)32.3H2O is a major copper voltages become increasingly negative, it means
mineral, and recent X-ray diffraction studies that the cuprite patina is being dissolved. This
show that what was once believed to be para- monitoring process allows an archaeologist
tacamite is in fact (Cu,Zn)2(OH)3Cl, i.e., a conducting field stabilization to monitor the pro-
mixed copper-zinc hydroxychloride. The three gress of a treatment or to know when to stop
isomeric forms of Cu2(OH)3Cl are atacamite, immersion in a treatment bath (Metal 2016). Con-
paratacamite, and botallackite, and it has been servators of composite archaeological items have
determined that the old anarakite is now been happy to engage with a new device, the
herbertsmithite Cu3Zn(OH)6Cl2 (Scott 2017). Pleco, which is a free-sourced localized electrol-
Detailed analysis of a late Bronze Age object ysis piece of equipment that can be brought to
by XRF and XRD showed that bronze disease is objects in the collection and exhibition areas and
unequivocally related to the presence of nantokite the restoration work conducted in situ (Metal
(CuCl) in the subsurface pits. Scanning photoelec- 2016).
tron microspectroscopy showed that there is selec- An alternative to the hydrochloric acid-
tive corrosion on the Sn-rich phases with thiourea-based silver dip for removing tarnish
synergistic Sn and Cu attack triggered by a pecu- from archaeological metals involves using sulfu-
liar type of decuprification characterized by the ric instead of hydrochloric acid with the critically
formation of Sn(OH)Cl because of local HCl gen- important inclusion of xanthin gum. The gum
eration in the corrosion process (Bozzini appears to minimize the loss of finely attached
et al. 2017). precious metals since there was no mechanical
buffing involved (Metal 2016).
Advances in Metal Conservation and
Corrosion Inhibition Methodology Preventive Conservation
A breakthrough in the management of decay of
archaeological bronzes involves the use of smart X-Ray Fluorescence Analysis of Metals
nanostructured coatings. The method involves A guide as to how to optimize the reliability of
separation of toxic corrosion inhibitors from the portable XRF analysis of archaeological metals
coating system. For example, benzotriazole is was developed through analyses of alloy coupons
contained in halloysite nanocontainers in a before and after artificially aging them. It is criti-
hydroxypropyl cellulose matrix which is then cally important to optimize the distance from the
applied to bronze objects. X-ray photoelectron source to the artifact surface as many “weak”
Metals: Preservation and Conservation 7

X-rays, such as tin, are attenuated by the air different patinas was determined by X-ray fluo-
(ICOM-CC 2014). An exciting breakthrough for rescence spectroscopy, X-ray diffraction, and
restorers of gilded artifacts involves the incorpo- cross-sectional metallography. The large varia-
ration of small amounts of indium and palladium tions in the lead and tin content brought about a
into gold leaf. The additive elements do not alter dynamic visual range of colors on the patina that
the properties of gold leaf but instantly allow varied from greenish-white via blue-green to
discrimination of “new” and “old” gold through black. The metal was mechanically cleaned
routine measurements using X-ray fluorescence using urea formaldehyde powdered resin with
(Metal 2016). some corundum media. Re-patination with a cop-
per nitrate solution was necessary to restore the
Responses to Traditional and Modern Coating color of the patina (Metal 2016).
Systems
The Getty Conservation Institute applied full Experimental Archaeology
forensic skills to the deconstruction of commer- Characterization of four bronze shields dating to
cial Incralac and developed laboratory versions of c.1300–800 BC from the British Museum collec-
the traditional commercial coating. This work was tion and one experimental replica showed them to
promoted by the increasingly severe regulations have 9–14% tin in the bronzes with trace impuri-
regarding emissions of volatile organic com- ties. Cold working of some of the shields brought
pounds and import restrictions. For archaeologi- up to a 60% reduction in the as-cast thickness. The
cal conservators facing such challenges, the work high microhardness values of the original shields
provides new hope for both field and laboratory and the survival of the replica shield in a combat
conservation of copper alloys (ICOM-CC 2017). test suggest that the Bronze Age shields could
Prohibitive costs and customs regulations on have been used in combat rather than being
imported conservation chemicals mean that merely ceremonial. This data provides the oppor-
important archaeological conservation can be tunity for reinterpretation of historical archaeolog-
extremely challenging; this is where the use of ical analyses (Metal 2016).
natural chemicals from fruit extracts provides
ways of overcoming these issues. Indian conser- Air Borne Pollution
vators found that extracts from crushed fruit of the In the last few years, the impact of particulate
plant Emblica officinalis reacted with all the pollution on the corrosion of metals in heritage
chloride-containing iron corrosion products asso- locations has diminished simply because of
ciated with problematic archaeological iron improvements in collection management of
objects. The extract converted reactive minerals museum metallic objects. The impact of dust on
into stable magnetite (Fe3O4) and left surfaces metallic corrosion and how important the orienta-
with a pleasing dark lustrous patina. If a matte tion of the surfaces can be, particularly inside a
finish is required, the treated objects can be coated showcase, has been the subject of a recent expert
with an appropriate matting agent (Metal 2016). research project (ICOM-CC 2014). Special care
and attention to the early seventeenth-century
Conservation of Large Objects ebony- and silver-decorated Walbaum Cabinet at
Although not formally archaeological, the treat- the Kunstgewerbemuseum (Museum of Decora-
ment of the massive Column of the Grande tive Arts) in Berlin demonstrates the extraordinary
Armée, or “Vendôme Column,” is pertinent to care needed for rare and precious objects. To
very large metal objects from a buried context. prevent the re-tarnishing by acetic acid off-
The 260-m-high frieze comprises 425 bas-relief gassing from the timber on more than 3400 indi-
panels cast from the bronze cannon captured dur- vidually cleaned and reassembled silver parts, the
ing the Napoleonic campaign of 1805. The col- object was stabilized through the introduction of a
umn was rebuilt in 1875 with no treatment for custom-made air filtration system that prevents
130 years. The elemental composition of the buildup of vapors (ICOM-CC 2014). Chinese
8 Metals: Preservation and Conservation

workers from heavily polluted cities found that ▶ Pacific Islands, World Heritage in the
high levels of ozone in moderately humid condi- ▶ Shipwreck Archaeology: Cultures in Crisis
tions have a significant impact on the corrosion ▶ Submerged Landscapes, Environmental
behavior of bronzes in museums. A surprising Archaeology of
discovery is that bagging objects has turned out ▶ Underwater Archaeology: Site Survey and
to be beneficial since bagged objects demon- Excavation
strated greater RH stability than theory would
suggest. It appears that, in storage, without tem-
perature or humidity control, the benefits of bag-
References
ging objects to reduce the risk of pollution and
insects and to buffer against short-term fluctua- Bozzini, B.A., M. Amati, M. Boniardi, V. Caramia,
tions in RH may outweigh the risk of mold growth G. Giovannelli, L. Gregoratti, and M.K. Abyaneh.
within the bag (ICOM-CC 2014). 2017. Novel insight into bronze disease gained by
synchrotron-based photoelectron spectro-microscopy
in support of electrochemical treatment strategies. Stud-
ies in Conservation 62 (8): 465–473.
Cross-References ICOM-CC 2014. 17th Triennial Conference Preprints,
Melbourne, 15–19 September 2014, ed. J. Bridgland.
▶ Archaeological Conservation and Preservation: Paris: International Council of Museums.
ICOM-CC 2017. 18th triennial conference preprints,
Introduction Copenhagen, 4–8 September 2017, ed. J. Bridgland.
▶ Archaeological Heritage Management Paris: International Council of Museums.
▶ Archaeology and the Emergence of Fields: Metal 2016, Proceedings of the interim meeting of the
Maritime ICOM-CC metals working group, Sept 26–30, New
Delhi, India, ed. R. Menon, C. Chemello, and
▶ Archaeology Museums and the Public A. Pandya, New Delhi, India.
▶ Archaeometry and Archaeology Scott, D. 2017. New insights on the corrosion of ancient
▶ Atlantic Ocean Maritime Archaeology bronzes using X-ray powder diffraction: The impor-
▶ Australia, Maritime Archaeology in tance of paratacamite, sampleite and connellite. Studies
in Conservation 62 (7–8): 410–418.
▶ Authenticity in Archaeological Conservation Scott, D.A., and G. Eggert. 2009. Iron and steel in art,
and Preservation corrosion, colourants conservation. London: Arche-
▶ Caribbean Sea Maritime Archaeology type Books.
▶ Charter for the Protection and Management of
the Underwater Cultural Heritage (1996) Further Reading
▶ Conservation and Management of Archaeolog- McCarthy, M. 2005. Ships’ fastenings, from sewn boat to
ical Sites steamship, 1–229. College Station: Texas A&M Uni-
▶ Conservation in Museums versity Press.
North, N.A., and Pearson, C., 1975, Alkaline sulphite
▶ Cultural Heritage Management and Submerged reduction treatment of marine iron. ICOM Committee
Sites for Conservation Preprints, 4th triennial meeting, Ven-
▶ Experimental Maritime Archaeology ice 75/13/3, 1–14.
▶ In-Situ Preservation in Underwater and Mari- Selwyn, L., 2004 Metals and corrosion, A handbook for the
conservation professional, Canadian Conservation
time Archaeology Institute, Ottawa, 1–224.
▶ Maritime Archaeology and Museums