The impact of chloride desalination on the corrosion rate of archaeological iron

Abstract

Although desalination of archaeological iron reduces its chloride concentration and enhances object stability, the reduction in corrosion rate that this produces has never been quantified. This study measures post-treatment corrosion rates in accelerated corrosion environments to identify the impact of removing chloride ions on corrosion rate. Thirty-five archaeological iron nails, treated individually in either alkaline sulphite or nitrogen-deoxygenated sodium hydroxide, were exposed to 75°C and 75% relative humidity together with 31 untreated objects from the same archaeological sites. Object weight change and visual examination of physical change before and after the test period were used to monitor corrosion. 77% of treated objects showed no weight gain and no visible signs of corrosion, while 90% of untreated objects did corrode. The impact of chloride on corrosion of untreated objects was clearly established by a significant linear correlation between chloride content and weight gain. Treated objects with <400 ppm chloride content showed no corrosion behaviour. Corrosion of treated objects was attributed to incomplete treatment: 93% of objects treated to <5 mg/l Cl^? in the final solution bath displayed no corrosion behaviour. Based on these results, desalination of iron objects to enhance their stability offers a valuable option for reducing corrosion rates of archaeological iron, which should increase object lifespan. The results also raise the question of whether low levels of post-treatment residual chloride produce corrosion of any significance. Answering this will be an important step forward for managing the preservation of archaeological iron.     

The efficiency of chloride extraction from archaeological iron objects using deoxygenated alkaline solutions

Abstract

Chloride-contaminated archaeological iron is unstable and problematic to store and display within museum collections. Reducing its chloride ion content using aqueous desalination followed by storage in controlled relative humidity offers one treatment option. This study reports a quantitative assessment of chloride extraction by aqueous deoxygenated alkaline desalination solutions from 120 individual archaeological iron nails. The three treatment methods comprised alkaline sulphite solution (0.1 M NaOH/0.05 M Na₂SO₃) at room temperature and at 60°C and sodium hydroxide solution (0.1 M) deoxygenated using a nitrogen gas positive pressure system at room temperature. Chloride extraction was monitored using a specific ion meter. The nails were digested after treatment to measure their residual chloride content. A wide range of extraction patterns emerged, with the majority of individual treatments extracting 60–99% of the chloride present. Residual chloride levels for 87% of the objects fell below 1000 ppm and 42% were below 200 ppm. Although no treatment extracted 100% of the chloride in the object, alkaline desalination produced very significant reductions in chloride content. The impact of this on future corrosion of the objects is discussed. This quantitative and statistically viable assessment of deoxygenated desalination treatments provides evidence to support their use in conservation practice, which will impact on procedures for the preservation and management of archaeological heritage.     

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.     

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.     

Book Reviews

Abstract

The long-term stabilization of marine archaeological iron, whether cast or wrought, continues to challenge conservators responsible for treatment of this material. Results and observations obtained from past treatments highlight the daunting, prolonged, and laborious efforts required to desalinate large and complex ferrous artifacts recovered from the ocean. In general, the higher an artifact's chloride level, the less stable it is. Consequently, any stabilization treatment must involve the removal of as much Cl^?1 as possible without affecting the integrity of the corroded artifact. This problem is particularly acute with corroding cast iron objects that have formed thick, fragile, and highly unstable corrosion layers. Over the course of the twentieth century, conservators have used a variety of techniques in an attempt to mitigate the negative effects of chloride ions on iron artifacts and prevent disintegration. In spite of early promise, each of these stabilization techniques has significant disadvantages, particularly with regard to treatment efficiency, duration of treatment, and/or unacceptable risks to the artifact during treatment. For these reasons, conservators and conservation scientists at the Warren Lasch Conservation Center in Charleston, South Carolina, decided to look at the possibility of using subcritical fluids to stabilize archaeological iron. This paper compares the efficiency and effectiveness of traditional stabilization techniques (i.e. alkaline soaking and cathodic polarization) to subcritical fluids on wrought iron rivets and metal shavings from the H.L. Hunley submarine as well as Civil War era cast iron artillery shells recovered from a marine environment.     

Optimisation d'un traitement de dechloruration d'objets ferreux par plasmad'hydrogene

Abstract

The method of removing chlorides from archaeological iron objects using hydrogen plasma at low pressure has been studied and improved. To carry out the initial experiments and to limit the use of ancient material, synthetic samples were made from iron powder and corrosion products consisting mainly of akaganeite. The time and the temperature required for the complete removal of the chlorides were determined. It was also possible to demonstrate that magnetite, and iron above 400°C, are the final reaction products of the reduction of akaganeite.     

Preliminary study on the impact of relative humidity on the conservation of jades

Abstract

This paper examines the impact of relative humidity on jades by enclosing the samples under constant relative humidity (RH) of 32, 49, 61.5, and 81.7% at the same temperature of 40 ± 0.1°C for 160 days. The simulated samples were pure and dense tremolite jade and serpentine jade, impure tremolite jade and serpentine jade containing some calcite, and serpentinized calcite, which are all common materials of ancient jade found in archaeological excavations. All samples were characterized through particle-induced X-ray emission and a glossmeter. The degree of deterioration proved to be greater in impure materials than in pure ones. The best RH to conserve various kinds of materials differs: for pure tremolite and serpentine, all of the RH levels are equal; for impure tremolite with some calcite, 61.5 and 81.7% were superior; for impure serpentine with some calcite, the highest RH (81.7%) was best; and as to the serpentinized calcite, there is no clear conclusion as yet and further research is needed.     

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.     

The Surface pH Measurement and Deacidification of Prints and Drawings in Tropical Climates

Abstract

The interrelationship between the various chloride ion containing compounds associated with the corrosion of iron in a marine environment is reviewed, and their role in corrosion promotion is evaluated as a basis for the selection of conservation techniques with a high probability of success.     

Post-treatment Study of Iron/Sulfur-containing Compounds in the Wreck of Lyon Saint-Georges 4 (Second Century ACE)

ABSTRACT

A pre-restoration diagnosis revealed a high amount of pyrite in the wood of the Lyon Saint-Georges 4 shipwreck (end of the second century). The occurrence of this phase is supposed to result from the microbiologically influenced corrosion of the iron fasteners. So, all the nails and metallic elements were removed from the remains before treatment and the wreck was consolidated by polyethylene glycol impregnation coupled to a specific desalination process. Treated and non-treated samples extracted from the wreck were studied in order to identify the iron/sulfur-containing compounds present in the wood before and after treatment and figure out its effect. Sample analyses relied on an original approach combining magnetic characterization methods and more common elemental and structural analysis methods. The results showed that the treatment was effective in removing soluble salts. However, a large amount of unstable iron sulfides remained inside the wood.     

The removal of metal soaps from brass beads on a leather belt

Abstract

Severe corrosion was found covering the brass beads on several beaded belts. The corrosion was a mixture of copper soaps and zinc soaps, and was so thick in some places that it completely buried the brass beads. One of these belts was chosen as a test case for cleaning. The details of the cleaning are described, as are the effects of the corrosion process on the beads and surrounding organic materials. Two supporting studies are also reported: tests of the solubility of the corrosion in a variety of organic solvents, including mixtures of ethanol and petroleum-based solvents; and tests of leather dressings and other coatings on brass, copper, and zinc coupons in various relative humidities (RH), to determine what values of RH could be recommended for storage.     

Stability of treated archaeological iron: an assessment

Abstract

Various desalination methods had been used in the past to treat a large collection of archaeological iron objects. In order to establish whether desalination treatments had been effective, the condition of the objects was assessed and the data analyzed using statistical methods. It was found that objects which had been treated using desalination methods were less likely to re-corrode, and the conclusion was that the development of more effective techniques of chloride removal would be useful.     

Climatically Induced Degradation Processes in Conserved Archaeological Wood Studied by Time-lapse Photography

ABSTRACT

Samples of conserved archaeological wood of different ages, origins, and conservation histories were aged in a climate chamber for seven months, while the humidity alternated between 30% RH for 12 hours and 80% RH for 12 hours at a constant temperature of 30°C. Photographs were taken once every hour, which enabled the creation of a time-lapse movie. Some samples degraded visibly, whereas others were unaffected. Most of the samples were robust and would be able to survive well even in a very poor museum climate. Among the sensitive samples, three types of degradation were identified, namely disintegration, pyrite oxidation, and efflorescence of white crystals. Disintegration was ascribed to dimensional changes caused by the RH alternations in very fragile wood. The white efflorescence was interpreted as the recrystallization of an alum-associated substance, possibly mercallite (KHSO₄). The pyrite oxidation was observed as the efflorescence of a thick yellow, grey, and green powder. Characterization of selected samples was performed using X-ray fluorescence spectrometry, X-ray diffraction spectrometry, scanning electron microscopy with energy dispersive X-ray spectroscopy, inductively coupled plasma – optical emission spectroscopy, Fourier transform infrared spectroscopy, ionic conductivity – liquid chromatography, and pyrolysis-gas chromatography-mass spectrometry with in situ silylation using hexamethyldisilazane.     

Frontiers of Preventive Conservation

ABSTRACT

This work considers areas where our present lack of knowledge curtails the effectiveness or efficiency of preventive conservation practice. Mixed media, especially archaeological metals and organics have incompatible requirements for relative humidity (RH). An approach based on understanding the risk versus RH for both materials and considering the showcase performance is elucidated as a solution. Pollution, both the mixed atmospheres around most cultural heritage and the complex, variable nature of deposited particles, are further areas in need of more research. Damage functions and measurement of object deterioration rates are investigated as a path forward, and examples are given.     

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.     

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.     

The application of vapour-permeable synthetic membranes to the climatic stabilization of museum showcases

Abstract

This paper describes a novel technique to stabilize the relative humidity (RH) of the air inside museum showcases by using a synthetic hydrophobic membrane coupled with a hygroscopic solution in a membrane contactor. RH-monitoring data for two identical test cases, one of them controlled by a set-up with a plane-plate membrane contactor crossed by forced air and lithium chloride (LiCl) solution flows, show a significant stabilizing effect on RH fluctuations. A theoretical model permits forecasts in close agreement with the experimental RH data. Further calculations carried out over a one-year period show that notable damping of external RH variations can be obtained by using a low air circulation rate, small membrane surface area and low solution mass per unit case volume. A more general analytical solution in harmonic conditions is derived and discussed.     

ABSTRACTS

Abstract

The deterioration of Bronze Age objects from the archaeological site at Fort-Harrouard (France) has been studied, firstly, in relation to their external appearance and the elemental composition of the sound metal. A relationship between the composition of the corroded surface and the underlying sound metal was deduced. In addition, examination of metallographic sections of one of the bronzes allowed the differentiation of corrosion processes which are related to the shape of the object: the stratification of the corrosion products and the intergranular and transgranular corrosion processes. The existence of a pseudomorphic microstructure suggests that the mechanism of deterioration may be stratigraphic, which may be explained by the growth of the corrosion products in fissures which do not involve periodic precipitation.     

Study of Fe(II) sulphides in waterlogged archaeological wood

Abstract

Wet organic archaeological materials extracted from seawater may suffer damage as a result of degradation influenced by micro-organisms. One of the most common phenomena is indirectly induced by sulphate-reducing bacteria (SRB). Due to their metabolic activity in anoxic conditions, SRB generate hydrogen sulphide from sulphate ions present in seawater. When steel items are in contact with organic matter in presence of sulphides, corrosion of the metal leads to the precipitation of Fe(II) sulphides. These phases are responsible for dramatic post-excavation damage: their oxidation during storage or exhibition in museums leads to the formation of voluminous crystals, which may cause cracking and crumbling, and lead to the production of sulphuric acid. In order to characterize Fe(II) sulphides and their by-products, 13 waterlogged samples were analysed by environmental scanning electron microscopy, micro-Raman spectroscopy, and X-ray diffraction. Experiments were performed on untreated wood fragments, on a fragment of rope, and on mineral concretions scratched from the surface of wood remains, all extracted from different shipwrecks. Mackinawite was detected inside the fragments and between the fibres of the rope. Greigite was detected in scattered locations. Pyrite and sulphated phases, like gypsum and iron sulphates, were identified at the surface of the wood fragments and in the mineral concretions.     

Hydrogen plasma reactions in a d.c. mode for the conservation of iron meteorites and antiquities

Abstract

Four iron meteorite fragments and 13 archaeological iron objects were exposed to a lowpressure hydrogen plasma for up to two weeks in a pilot apparatus. In the experiment the objects acted as cathodes in a 600–1600V d.c. electrical field. While the chlorine-containing β-FeOOH, akaganeite, was present in all objects before the test, no akaganeite and no chlorides were present afterwards. The objects, including one meteorite which had been exposed for more than 5000 years to seawater, were found to be stable after the glow discharge treatment. The major mineral after treatment was identified as magnetite, and the objects generally assumed an iron-grey surface colour. No sputtering and no reduction to free iron took place under the test conditions, operating at or below 120°C and at pressures of O·4–1mb hydrogen.