Characterization of the corrosion layer on iron archaeological artefacts from K2 (825–1220 AD), an archaeological site in South Africa

Abstract

A study of the composition and phase distribution of the corrosion layers on three ferrous objects, excavated at K2 (Bambandyanalo), an archaeological site in South Africa, was conducted. The objective of the study was to obtain information that can contribute to conservation procedures to be performed on the iron artefacts from this site. Examination of cross sections by means of energy-dispersive X-ray spectroscopy coupled to a scanning electron microscope (SEM–EDX), X-ray powder diffraction (XRD), and micro-Raman spectroscopy revealed the same corrosion composition and structure for all the objects under study, namely an internal layer adjacent to the metal surface with ghost inclusions and an external layer containing quartz grains. The study also revealed that the presence of magnetite (Fe₃O₄), maghemite (γFe₂O₃), and lepidocrocite (γ-FeOOH) within the internal layer is the only difference between the chemical compositions of iron corrosion products within the two layers. The results also made it possible to retrace the corrosion history during burial and long-term storage.     

An Investigation of Deterioration of Archaeological Iron

Abstract

A small but significant proportion of the archaeological iron objects in the British Museum collection have been problematic in that some of them have required repeated treatment. The deterioration of iron objects during storage was studied using microscopy, Raman spectroscopy, X-ray diffraction, scanning electron microscopy/energy dispersive X-ray analysis, X-ray fluorescence spectroscopy and ion chromatography. A total of 125 iron objects, including 56 from two British Roman sites and 69 from three Anglo-Saxon sites, were studied. Both surface corrosion and corrosion layers on polished cross-sections were investigated. The study revealed that the present condition of the iron objects varies; some are in a stable condition and others have been deteriorating, with pitting and weeping present on the surface. No treatment method had stopped corrosion for every object, although the alkaline sulphite treatment seemed to be more effective than the other methods. The results also showed that chloride ions can be present at the interface of the metal and inner corrosion layers. It is recommended that iron objects which have been mechanically cleaned without desalination treatments are kept in a dry environment to prevent further deterioration.     

Influence of crucial parameters on the dechlorination treatments of ferrous objects from seawater

Abstract

This article compares chemical dechlorination treatments (immersion in sodium hydroxide or alkaline sulphite) and electrochemical treatments of iron bars from the Gallo-Roman period excavated from a marine environment. Some important parameters, such as storage before treatment, temperature, solution composition, and drying after treatment, were varied during the study to assess their influence on the chloride extraction process. The kinetics of these treatments depend mainly on chloride diffusion through the corrosion layers. The kinetics are promoted by high temperatures and, in the case of electrolysis, by the electric field effect. The reduction of corrosion products during electrolysis occurs only for objects previously stored in air. In fact, the manner in which the objects are stored before treatment is critical in the dechlorination processes. The sooner the objects are treated after excavation (with water storage), the better the removal of chloride ions, in both chemical immersion and electrolysis treatments. But if the object is stored in air, material losses occur, and only electrolysis results in complete extraction of the chlorides. These differences are due to modifications in the corrosion products during storage. Drying after treatment also has a significant impact on the composition of the corrosion layers. If the objects are dried too quickly, Fe(OH)₂ oxidizes into FeOOH, which thus forms a layer with low cohesion.     

THE USE OF THE AIRBRASIVE PROCESS FOR CLEANING ETHNOLOGICAL MATERIALS

Abstract

Ethnological specimens of many different materials can be dry cleaned mechanically by means of a grit-spraying unit. Plain and painted leather, corroded metal, beadwork, metallic embroidery, wood, ivory, bone, basketry, some paper, pottery, shell, some textiles and stone are items which can be cleaned with less disturbance to the surface than is often occasioned by the use of other methods. A specimen constructed of several materials may be cleaned by this one method rather than by several, thereby also avoiding the use of water, solvents or other chemicals. The powdered abrasives used are calcium magnesium carbonate, sodium bicarbonate, glass beads, and several grades of aluminium oxide. Silicone carbide powder is used occasionally for very hard corrosion products on metal.     

After Eighty Years: Experimental Study of Atmospheric Corrosion in the Metallic Dome of Hafez’s tomb,Shiraz, Iran

ABSTRACT

Hafez’s tomb was constructed on the grave of the well-known Iranian poet in Shiraz, in the 1930s. The dome of this monument is made of copper metal and has been exposed to the urban environment for 80 years. In this study, corrosion mechanisms and conservation conditions of the metallic dome of the Hafez’s tomb are investigated by analytical methods including optical microscopy, ICP-MS, SEM-EDX, and X-ray diffraction. The results showed that the dome is constructed from many copper sheets that are hammered to shape the dome. The corrosion products formed on the surface of copper sheets include copper oxide and copper trihydroxichlorides. In fact, the corrosion mechanism occurring in the metallic dome consists of copper oxidation and redeposition of copper II products because of reaction with air pollutants.     

CORROSION AND CONSERVATION OF A SILVER VISCERAL VESSEL FROM THE BEGINNING OF THE SEVENTEENTH CENTURY

Abstract

Two different cleaning methods were found necessary to remove silver chloride corrosion products from different areas of a silver canopic vessel containing about 6% of copper. Two possible mechanisms of silver corrosion which could have led to the differing silver chloride corrosion products are put forward.     

Problems of adhesion between support and ground layers in polychrome wooden sculptures in Guatemala

Abstract

Bibliographical research and scientific analysis of samples obtained from five polychrome wooden sculptures of the colonial tradition in Guatemala were used to study the techniques and the materials used. The methodology involved qualitative analysis of the samples and microscopic examination of cross-sections. Scanning electron microscopy (SEM) was used to identify pigments and to ascertain the composition of the gilding. It was hypothesized that the deterioration of the sculptures, particularly the separation of the ground layers from the wooden support, was due to the action of secondary products of Cedrela odorata L. The loss of adhesion of the animal glue used in the preparation may be partly related to the precipitation of the protein of the gelatin due to the action of the tannins present in the wood.     

Instability of Iron Sulfides on Recently Excavated Artifacts

Summary

The composition and nature of the different sulfides which can occur on underground iron are reviewed with reference to the literature, together with the various corrosion reactions. The type of pyrites on fossils and minerals is also included. The experimental work involved goethites and magnetites reacting with damp hydrogen sulfide gas to give mackinawite, pyrite and/or greigite. These can react exothermically and may be pyrophoric. Methods to increase stability and reduce the danger of pyrophoric oxidation are discussed.     

Metal corrosion rates in aqueous treatments for waterlogged wood-metal composites

Abstract

Corrosion rates are presented for metals in the aqueous solutions intended for treating both the wood and the metal components of a waterlogged wood-metal composite object. The metals include lead, mild steel, cast iron and the copper alloys of bronze, cast brass and wrought brass. The corrosion rates were determined using a standard weight-loss method in which clean metal surfaces were immersed in the solutions for two months at room temperature. The treatment solutions included Acrysol® G-11O for lead, Witcamine® RAD 1100 for copper alloys and Pluracol® 824 or the corrosion inhibitor Hostacor® KS 1 in PEG 400 for iron. These treatment solutions were prepared in distilled water as well as in a synthetic seawater. For reference, metal corrosion rates were also determined in distilled water, synthetic seawater and PEG 400. The results demonstrate that, in general, clean metal surfaces corrode more slowly in the treatment solutions than in PEG 400 solutions. However, before recommending these solutions for the treatment of composite objects, further testing is needed to determine how effective they are in reducing the corrosion rates of metals covered with a thick corrosion crust, and to see if Acrysol G-110 is capable of bulking and consolidating waterlogged wood.     

When Glass and Metal Corrode Together,VI: Chalconatronite

ABSTRACT

Chalconatronite, Na₂[Cu(CO₃)]₂·3H₂O, is formed as a corrosion product when copper alloys are exposed to sodium carbonate solutions in the air. This also happens when metals come into contact with corroding soda glass which forms alkaline surface films in reaction with humidity from clean air. More often, substantial amounts of formaldehyde are present indoors which react to formate via the Cannizzarro reaction and accumulate over time in the films. Twenty cases of chalconatronite (including two mentioned in the literature) are reported as occurring on heritage objects with glass in contact with copper alloys: Baroque reliquaries with set glass gems, enamel on metal (sixteenth century and a modern replica of intentionally unstable composition), Christmas tree glass baubles with wires, glass buttons with metal shanks, a glass figure with a wire support, miners’ lamps, and a glass framed daguerreotype. These confirmed identifications might help conservators in investigating similar cases to shed more light on the formation conditions.     

An investigation into the cause of corrosion on indoor bronze sculpture

Abstract

Corrosion noted on a number of nineteenth and twentieth century indoor bronze sculptures in the collection of the National Gallery of Canada was the cause for a major condition survey of its Canadian, American, and European bronzes. The results led to a comprehensive study, which included material analysis. This article outlines the steps undertaken to determine the extent and type of corrosion, its possible cause(s), and potential remediation. The survey included 136 bronzes, of which 40 were selected for an in-depth study. Indoor air quality tests of the current building, housing the collection since 1988, were carried out. The dossiers and database records of the selected sculptures were reviewed to investigate their condition, treatment, and storage history. The metal, patina, and corrosion products were subjected to analysis. More areas of corrosion were generally associated with predominantly green patinas and chloride-containing compounds identified in either patina or corrosion samples. The most frequently identified compounds in the patina samples were atacamite, a copper(II) chloride hydroxide, and cuprite, a copper(I) oxide. The most frequently identified compounds in the corrosion samples were atacamite and rouaite, a copper(II) hydroxide nitrate. The analysis determined that the current environment is not contributing to the surface alterations of the sculptures; however, past storage conditions, chemical residues from artificial patination, and likely casting residues are the main causes of the current condition.     

A Note on the Products of the Reaction of AMT with Bronze and with Three Corrosion Products of Bronze

Abstract

The compound 5-amino-2-mercapto-1,3,4-thiadiazole (AMT) is utilized in the conservation of archaeological and artistic bronze artifacts, for their protection and for the removal of corrosion products. Many authors have discussed the utility and efficacy of this, but few have studied the products resulting from the reaction of AMT with bronze or with the corrosion products of bronze; this leaves the restorer with many doubts concerning the acceptability of this method. This paper discusses the study of products obtained from the reaction of AMT with synthesized corrosion products of bronze (malachite, paratacamite and brochantite) and with the commercial bronze alloy TM 23 (Cu 72%, Pb 15%, Zn 8% and Sn 5%). It was found that the film obtained from the direct reaction of AMT with the bronze alloy can be AMT itself, or the metallic complex Cu(C₂H₂N₃S₂)₂·H₂O if AMT is applied in a solution of an oxidizing acid. These results are expected to be of value to conservation scientists and restorers/ conservators concerned with the use of AMT for the conservation of bronze artifacts.     

Conceptual Model for the Replacement of the Horn of a Nineteenth Century Phonograph

ABSTRACT

3D printing of missing parts of a cultural heritage artifact opens many possibilities and extends the challenges in the processes of intervention on cultural heritage assets. However, restoring these objects may not only mean the replacement of a missing element from its esthetic point of view, but restoring the function for which objects were created. In these processes, the replica of the object must be exact and of quality, but also specific. In this sense, the presented work is a multi-disciplinary attempt to reproduce the missing horn of a phonograph dated to the late nineteenth century. This phonograph belongs to the collection of the ‘Vicente Miralles Segarra’ Telecommunication Museum of the Universitat Politècnica de València. The objective was to recover its esthetic, didactic, and functional levels, i.e restoring its ability to emit sound. To this end, several models were printed with different materials, and the quality of the recorded sound with the different horns was evaluated, assessing their similarity to that obtained from an original horn.     

Formaldehyde Oxidation and Lead Corrosion

Abstract

Carbonyl compounds are of concern in museums because of their potential to damage artifacts. The mode of damage for aldehydes is far from clear and seems to require oxidation. Lead coupons were exposed to gaseous formaldehyde (methanal) and formic acid (methanoic acid) in various humid oxidizing atmospheres. The resulting corrosion products were weighed and identified using X-ray diffraction analysis after as much as 56 days exposure. When fomaldehyde was in more oxidizing environments (atmospheres containing hydrogen peroxide) it caused heavy corrosion but in the dark, with no oxidant, there was only very slight tarnish, even at high humidities. This suggests that oxidation is an important control on corrosion by formaldehyde. Thermodynamic calculations indicate that at low formic acid concentrations (below about 1 ppb) the corrosion products should be carbonates (plumbonacrite and hydrocerussite) while at higher concentrations lead formate would be expected. The mineralogical complexity and the importance of oxidants make it very difficult to set standards for formaldehyde in the museum environment.     

Technical Analysis of an Early Painting by Botticelli

Abstract

A study is presented of the growth of sulphidecontaining corrosion products on antiquities in museums. Analysis of the corrosion products suggests that they are dependent on the mode of formation. Techniques for conservation have also been investigated and l-amido-l-cyanoethylene, 2,2-di(sodium thiolate) is recommended for dissolving the sulphide layers, while a treatment with benzotriazole followed by lacquering is recommended for long-term protection.     

Decay and treatment of Macael white marble

Abstract

This paper reports the process of deterioration of the white marble used in the Alhambra of Granada, and its consequences. Variations in mineralogical composition, microscopic topology, hardness, compressive strength, propagation of ultrasonic waves, absorptIon and diffusion of water and properties related to the pore structure were studied. The relationships between these factors, the visible deterioration and possible mechanisms are discussed. A preliminary evaluation of some protective treatments was carried out. The results can also be applied to white Macael marble used in other monuments in an environment with wide fluctuations in temperature and relative humidity.     

Models for Chloride Ion Diffusion in Archaeological Iron

Summary

The rate at which chloride ions diffuse from archaeological iron into a treatment solution depends on how the chloride ions are initially distributed in the corrosion layer. This paper compares solutions of the diffusion equation for two limiting cases: (1) where the chloride ions are initially spread uniformly through the corrosion layer; and (2) where the chloride ions are initially concentrated at the interface between the iron and the corrosion layer. Although the first model has been used in the past to describe chloride ions diffusing from marine iron, the second is more appropriate in cases where corrosion has drawn chloride ions toward the iron surface. Because diffusion processes in archaeological iron are complicated, the limitations of both these models are discussed.     

The occurrence of brochantite on archaeological bronzes: a case study from Lofkënd,Albania

A technical study was conducted on a group of copper alloy artifacts excavated from the burial tumulus of Lofkënd (fourteenth–ninth century BCE) to identify the alloy compositions and methods of manufacture. The surface corrosion was also examined in order to understand the diagenetic processes affecting the preservation of the finds and their condition. Portable X-ray fluorescence spectroscopy, metallographic examination, and X-ray powder diffraction (XRD) analysis were used to characterize the alloy composition and identify the corrosion products present. XRD analysis showed the presence of brochantite (Cu₄SO₄(OH)₆) on five of the metallic artifacts. Brochantite is not commonly reported on archaeological bronzes from terrestrial sites, but is more readily found on copper alloy objects exposed to sulfur pollutants in the air or soil. The possible conditions that could have led to the formation of this corrosion on the bronzes from Lofkënd are discussed in the context of the particular burial environment found at the tumulus.     

ON THE OCCURRENCE OF BROMINE IN CORRODED SILVER

Abstract

Attention is drawn to the finding of silver bromide as a regular corrosion product on buried ancient silver. The chemical processes leading to this, and their relation to the burial environment, are discussed.     

Pollutants in the Museum Environment - Practical Strategies for Problem Solving in Design,Exhibition and Storage

Abstract

The Oddy test is an 'accelerated' corrosion test employed by museums to evaluate the suitability of materials proposed for use in display and storage cases, The standard Oddy test requires a 28-day test period, and the results are assessed by visual observation. This paper describes an improved test method, which could reduce the length of the test period by half The improved method uses metal films as substitutes for the traditional metal coupons posing as 'surrogate art object', The new test results are then evaluated by computer with digital image processing for more objective selection of less corrosive materials.