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Conservation of Cultural Materials from Underwater Sites
DONNY L. HAMILTON
Nautical Archaeology Program, Texas A&M University, USA Abstract. Underwater archaeology is the only branch of ﬁeld archaeology that is dependent upon the conservation laboratory for its ultimate success. In fact, in underwater archaeology the activities of the conservation laboratory are considered to be a continuation of the ﬁeld excavations with the recording of basic data along with the stabilization, preservation, and study of the recovered material being major objectives. Commonly used procedures for conserving ceramics, glass, bone, ivory, wood, leather, and the various metals are discussed. Observation and insights are presented on the applicability of the different processes for conserving various materials.
Introduction There has been a dramatic increase in all aspects of underwater archaeology over the past decade. With this increased activity comes the responsibility to conserve the recovered materials – in other words to document, analyze, clean, and stabilize them. In order to deal with the material properly, archaeologists and conservators should know the history of the various conservation techniques frequently used. It is safe to say that relatively few procedures are utilized for the conservation of waterlogged cultural material and most are much the same as they were ten years ago. Some of the newest conservation techniques require very specialized equipment that is out of the ﬁnancial range of most laboratories; thus these techniques play a minor role in conservation. It is impossible to discuss in the limited space here all the procedures in use today for conserving waterlogged cultural material, but the core of conservation techniques and their inherent limitations need to be understood by all archaeologists. Readers interested in a more thorough introduction to the subject are referred to Plenderleith and Werner (1977), UNESCO (1968), Hamilton (1976, 1996), Pearson (1987a), and Cronyn (1990). Conservation of archaeological material is not just a set of procedures and treatments; it extends far beyond that. Often the conservator is the ﬁrst and, in the case of some very fragile items, may be the only person to see the actual artifact before it falls apart. The conservator’s responsibilities are those of archaeologist, mender, caretaker, and recorder of the artifacts that come into his or her care. Conservation, like archaeology is not just a set of techniques, it is a state of mind that holds a deep concern for the integrity of the artifacts, the context in which they are found,
DONNY L. HAMILTON
and what they represent as remnants of history. Archaeological conservation, therefore, should always include documentation, analysis, cleaning, and stabilization of an object. The objectives of cleaning and stabilization are to protect artifactual, faunal, and other archaeological materials and to prevent their reacting adversely with the environment after recovery (Hamilton, 1976: 1). The term “preservation” usually refers only to cleaning and stabilization, but it is often used interchangeably with conservation. In contrast, “restoration” refers to the repair of damaged objects and the replacement of missing parts. A specimen may undergo both conservation and restoration, but in many cases restorations are not attempted. Regardless, restoration should never be initiated without conservation. Before discussing speciﬁc conservation procedures, it is important to point out an obvious fact concerning the excavation of an underwater or waterlogged site. Proper artifact preservation is one of the most important considerations during the planning stage, before the site is excavated. Invariably, considerable material, much of it organic, will be recovered and planning for artifact conservation must start early. Current Conservation Procedures In the conservation of archaeological material, be it siliceous, organic, or metallic, from waterlogged sites, some authorities have found it convenient to separate the conservation of material from freshwater sites from the conservation of material from marine sites. Yes, there are differences in deterioration and corrosion processes, but the fact remains that any laboratory set up to handle the conservation of material from marine sites is more than capable of handling every problem that might be encountered from any other type of site. A laboratory set up exclusively for the conservation of freshwater material (Singley, 1988), however, cannot handle the multitude of problems presented by the artifacts from the saltwater site. In the interest of brevity, the conservation of the material from the two environments are discussed together, but the emphasis is placed on the conservation of material from marine sites. Where pertinent, speciﬁc differences and considerations are provided. In the majority of the cases, the two most overwhelming problems confronting the conservator responsible for conserving archaeological material from underwater sites are the conservation of iron and wood. This is especially true when dealing with shipwreck sites. For this reason, the conservation of metals and organic remains are discussed ﬁrst, followed by ceramics and glass. Much of what is presented is based on ﬁrst-hand experience and is concerned only with the time frame and material associated with historic sites in the Americas. Conservation of Metals Recovered from Marine Sites The conservation of metal artifacts from a marine site, and to a lesser degree metal artifacts from a freshwater site, is not very similar to the conservation problems
CONSERVATION OF CULTURAL MATERIALS
presented by metal artifacts from most land sites. When artifacts are recovered from the sea, especially warm areas such as the Caribbean and the Mediterranean, they are commonly encrusted with thick layers of calcium carbonate, magnesium hydroxide, metal corrosion products, sand, clay, and various forms of marine life such as shells, coral, barnacles, and plants. The term “encrustation” refers to the conglomerations that may contain one or more artifacts. Such conglomerations may range from the size of a single coin to masses weighing several thousand pounds containing hundreds of individual objects made of many different materials. In the process of dealing with encrusted metal artifacts, which are in most cases iron, one will encounter artifacts of other metals along with ceramics, glass, and various organic materials such as wood, leather, and bone. Thus, the conservation of encrustations with their concealed contents is analogous to an excavation square within a site. Any laboratory that processes these encrustations has the responsibility to preserve and stabilize the artifacts as well as conservation technology permits and to recover as much archaeological data as possible. Considerable information exists in the form of associations recoverable only by “in situ” observations made by the conservator. Extensive records have to be maintained which include notes on the encrustation; the objects it contains; and the preservation techniques used; as well as color, black and white, and X-ray photographs. Casts have to be made of disintegrated objects and of signiﬁcant impressions left in the encrustations. One must detect such things such as potsherds, cloth fragments, spikes, straps, animal bones that are inevitably encased in the encrustation. Even less obvious remains like impressions of seeds and insects, such as impressions of cockroaches found in several encrustations from the 1554 Spanish Plate Fleet, must be detected and recorded. In other words, the conservator is in a unique position to supply the archaeologist with valuable evidence and to provide the laboratory with basic conservation data for research. A typical example of an encrustation from a marine site exempliﬁes the problem. In Figure 1 is just one of several large encrustations recovered from the site of the “San Esteban”, one of the three ships of the 1554 Spanish Plate Fleet wrecked off Padre Island, Texas. This single piece contains two anchors, a wrought iron, hooped barrel gun with its wooden undercarriage, three breech blocks, and a multitude of smaller objects. It is over four meters long and weighs over two tons. A laboratory must have sufﬁcient space and equipment to take a piece like this, mechanically clean it, properly recover and conserve the encased specimens, and possibly cast a number of natural molds of disintegrated objects. It may even be necessary to prepare the encased artifacts for display. The laboratory has to have forklifts, chain hoists, large vats, specialized D.C. power supplies, hundreds of kilograms of chemicals, thousands of liters of deionized (DI) water among other resources to perform the job. The laboratory must be prepared to take an encrustation like that depicted in Figure 1, as well as hundreds of smaller encrustations and turn out an array of stabilized artifacts such as those depicted in Figure 2.
such as keeping artifacts wet after recovery. so they must be properly stored until treatment can begin. therefore. will be used to exemplify the basic requirements of metal conservation in marine archaeology. Quite often many artifacts are not conserved until months or even years after recovery. If iron is exposed to the air or placed in an uninhibited aqueous solution. hydrolyze to form ferric oxide or ferric hydroxide and hydrochloric acid. CONSERVATION OF IRON The conserved wrought iron artifacts in Figure 2 are from the 1554 Fleet wrecks off the coast of Padre Island. HAMILTON Figure 1. The hydrochloric acid in turn oxidizes the uncorroded metal to ferrous chloride and hydrogen. The wrecks from this ﬂeet are the oldest veriﬁed ships thus excavated in the Americas and serve as excellent examples for demonstrating techniques used to conserve some of the oldest iron artifacts recovered from a marine site in the New World. the corrosion process is accelerated. The greatest damage. is caused by various iron chlorides (both ferrous and ferric) found in iron recovered from marine environments. unless certain precautions are taken. Large encrustation over 3 meters long and weighing over a ton containing two anchors.294 DONNY L. the ferrous compounds can oxidize to a ferric state occupying a greater volume and causing the surface of an artifact to scale off. Iron. however. Just this process alone can disﬁgure a piece and eventually destroy it. Iron recovered from a marine environment presents the conservator with his biggest problems. . Texas. or ferric chloride and water. a bombardetta gun. on exposure to moisture and oxygen. and over a hundred additional artifacts from one of the 1554 Plate Fleet shipwrecks. Once iron has been recovered from a marine environment. Hydrated iron chlorides.
1976: 21–25). they can usually be stored in plain tap water for long periods. and North and MacLeod (1987: 79–80). Alkaline inhibitive solutions such as a 5% solution of sodium carbonate or 2% sodium hydroxide are most often used. If iron artifacts are left encrusted. Gilberg and Seeley (1981). the conservation can proceed in an orderly fashion with no need to rush the process. Wrought iron artifacts from the 1554 Plate Fleet conserved by electrolytic reduction. and 12 breech blocks for the gun tubes. If the encrustation is removed. . three hooped barrel gun tubes. It is important that any adhering encrustation or corrosion layers should be left intact until the objects are treated because they form a protective coating that retards corrosion. North (1982). electrolytic reduction is the only practical way of conserving iron from marine sites. For speciﬁcs of iron corrosion. the interested reader is referred to Argo (1981). but they must be checked regularly to keep the pH of the solution high (Hamilton. Because of the high chloride levels in the iron. One anchor. Storage Prior to Treatment Generally speaking. all metal objects should be kept submerged in tap water with an inhibitor added to prevent further corrosion. however. it is a safe practical way of conserving metal artifacts from most archaeological environments. If properly stored. This corrosion cycle continues until there is no metal remaining. then an alkaline solution is required to prevent the iron from corroding.CONSERVATION OF CULTURAL MATERIALS 295 Figure 2.
the more natural molds of corroded iron artifacts will be found. a door lock. It is during this phase that most of the observations on over-all associations are made. It is a critical part of conservation that is often overlooked when dealing with encrusted iron artifacts from a marine site. these natural molds have to be cast in epoxy. The older the site. It is through casting the natural molds inside encrustations that we were able to recover the complete array of small iron tools present at both sites. The X-rays also serve as a guide in extracting the artifacts from the encrustation and to determine the presence of molds. However. encrusted iron artifacts. and then using a pneumatic air scribe to remove the marine encrustation surrounding the epoxy cast. When mechanically cleaning encrusted iron artifacts. ﬁlling the void with epoxy. if it is covered with sediments to protect it against the various organisms that will attack it. especially fragile objects and ceramics. For instance. Chemicals are generally a very slow. for many objects. X-rays are used to determine the content of each encrustation and the condition of many of the encrusted objects. a cleaver. These artifacts can still be recovered by breaking into a strategic area of the encrustation. the majority of the small iron artifacts from Port Royal. All that remains of them is a void within the encapsulating encrustation. and both chemicals and electrolytic reduction will destroy any molds that might be present. Because encasing marine encrustation does not form on iron artifacts in fresh water. a hammer. Wood will outlast iron in the sea. a considerable amount of data on the full artifact assemblage will be lost. which are just a few of the hundreds of epoxy casts of iron tools from Port Royal. and the 1554 Plate Fleet ships off Padre Island have completely corroded. cleaning out the void. Well directed hammer blows on chisels are generally most effective in removing encrustations. The small pneumatic air scribes manufactured by Chicago Pneumatic. Casting The importance of casting the natural molds left by corroded iron artifacts can not be over emphasized.296 Mechanical Cleaning DONNY L. pneumatic tools are somewhat more efﬁcient and precise. Where possible. Jamaica which date from 1692. hand-held jack-hammers. casting plays a minor role in their conservation. are some of the most versatile tools for mechanically cleaning encrusted metal artifacts. Note that the handles on the hammer and the cleaver are the original wood with the hammer head and the cleaver blade are epoxy casts. In Figure 3 are two keys. HAMILTON The mechanical cleaning process is one of the most important part of conserving the large. Some have proposed using chemicals and even electrolytic reduction to remove the encrustation. natural molds of former iron artifacts are commonly encountered. ineffective process which can be damaging to any metal artifact. which in essence are miniature. Extensive casting must be done. . otherwise. If the objective is to recover the full range of artifacts at the site. and a socketed chisel.
Hamilton.CONSERVATION OF CULTURAL MATERIALS 297 Figure 3. Epoxy casts of iron tools from Port Royal. involves more than wiring up artifacts for electrolysis. 1990: 191) and are not aware of its full potential. a cleaver with the original wood handle. The sound iron artifacts that are recovered have to undergo other conservation treatments. Efﬁcient electrolytic reduction. a combination of the two. but not enough to form a natural mold. In these cases. Jamaica. Electrolytic Reduction Cleaning of Iron Iron. and how these variables relate to metal reduction. along with the versatility of electrolytic cleaning. The process can be used for most metal objects. too many conservators view electrolytic reduction as primarily a stripping process (Cronyn. The ease of set up and maintenance. as long as they have a sound metallic core. corrosion. and other parts contain metal. a ﬂexible mold has to be made of the entire object so a good cast can be made of it. and immunity (North. when it is recovered in a sound condition. a door lock. none is as widely used as electrolytic reduction but as widely misunderstood. 1976: 40–49). 1987: 223–227. In many instances some artifacts will have undergone a substantial amount of corrosion. such as electrolytic reduction. for the reduction process or. Of the techniques available for conserving iron from marine sites. however. and a socketed chisel. Unfortunately. can be conserved successfully. One must be familiar with electrode potentials and pH. See Hamilton (1976: 30–49) for a detailed discussion of this technique. passivation. It can be selected exclusively for the mechanical cleaning action produced by the evolved hydrogen. From top to bottom and left to right: a hammer with the original wood handle. and the economy of an electrolytic unit. make it one of the conservator’s most valuable tools. the voids are ﬁlled with epoxy and after extracting the piece. In other instances part of the artifact is a mold. two keys. as usually is the case. Electrolytic reduction has been the most successful way of treating iron from a marine environment. These factors are particularly crucial when dealing with chloride-contaminated metals .
As long as a low amperage rate is used during the initial stages.5 M (126 g per liter of water) of sodium sulﬁte (North and Pearson. power supply. but it can be used on wrought iron. This is not to say that satisfactory results cannot be obtained by the novice. The container. the iron object breaks up.C. but rather that a good knowledge enables the conservator better to understand and control processes in the electrolytic cell and to anticipate and correct adverse conditions.298 DONNY L.5 M (20 g per liter of water) of sodium hydroxide and 0. For artifacts from a freshwater environment. chloride monitoring. electrolyte pH. such as 2–5% sodium hydroxide. and sodium carbonate is adequate for the electrolyte. and surrounding the object with expanded steel mesh that is connected to the positive terminal of the D. which for small objects may be a glass or polyethylene jar. Bryce (1979: 21) found that the treatment is effective on iron objects that are moderately to heavily corroded. The sulﬁte solution is changed several times until the chlorides are removed from the metal. vat. is placed in an oven and kept heated to a temperature of 60 ◦ C. This may take a week or several months. the negatively charged corrosive chloride ions and other anions are eliminated from the object as they migrate toward the positively charged anode. Once the objects have been mechanically cleaned. the treatment is used to convert iron corrosion products to magnetite on iron artifacts that are too badly corroded for electrolytic reduction. the electrolyte selected.C. The solution is mixed and the object placed in it as quickly as possible to minimize contact of the solution with the air and the container should be ﬁlled as full as possible to avoid any oxidation of the solution. otherwise. they are immersed in a solution of 0. In addition. In general. electrode potentials. HAMILTON from a marine environment. and current densities. power supply. Electrolytic reduction involves connecting an artifact to the negative terminal of a D. but they must have a metallic core. Generally speaking. High current densities will strip off the corrosion layers. In the reduction process some of the positively charged metallic iron ions in the corrosion compounds are reduced. The solution does not attack any residual metal so there is no danger of too . terminal wires and clips. the corrosion layer and the original surface of the object can often be preserved. electrolytic reduction has no particular advantage other than convenience. Sodium Sulﬁte Treatment The alkaline sulﬁte treatment was developed by North and Pearson (1975) to stabilize marine recovered cast iron. maximum reduction of the ferrous corrosion compounds is achieved if sodium hydroxide is used as the electrolyte and the current density kept low. Tap water can be used for the ﬁrst one or two baths but deionized or distilled water should be used in the ﬁnal baths. and the experimental variables such as the manner in which the electrolytic cell is set up. placing it in a vat containing an electrically conductive solution called an electrolyte. anode material. 1975: 5). Other procedural factors that must be considered are the equipment. such as type of power supply.
recovered from a marine environment is sometimes used because of its potential of treating large artifacts such as cannons and a large number of artifacts quickly. It is a treatment that can be successfully used. 1953). like most conservation treatments. 1980). chemically active vapors. When iron artifacts are immersed in this hot. During the treatment. This treatment is not enthusiastically endorsed as it was for a period in the 1970s. the application of at least three coats of 20% tannic acid is recommended before applying a ﬁnal sealant. Although some use the tannic acid coating as the . a chemical reaction converts the surface of the metal to ferric tannate.. both cast and wrought. reducing solution the iron corrosion compounds are converted to magnetite and the chlorides are transferred to the solution. to form water. Hydrogen Reduction of Marine Iron Hydrogen reduction of iron. The hydrogen reduces the iron corrosion compounds to a lower oxidation state and combines with the oxygen in the corrosion products. but it is still commonly employed by some laboratories to treat numerous artifacts such as cast iron shot. Treatment Following Stabilization After iron objects have been treated by any of the techniques discussed above. The corrosive nature of the gases produced in the process have a detrimental effect on the equipment. all the moisture is driven out of the artifact and the chloride corrosion compounds are volatilized. 1977: 155–166). While this treatment has been effective for conserving iron recovered from a marine environment. where they are discarded with each bath change. or a mixture of hydrogen and nitrogen. Second. and gases. For iron artifacts. and heated to a temperature of 300 to 1. This treatment. which is more corrosion resistant than metallic iron (Farrer et al. contact with the skin should be avoided. there is the problem of the changes in the metallurgical characteristics of the metal when heated to the temperatures necessary to drive off the chlorides if care is not taken (Tylecote and Black. which is driven off by the heat. First it requires rather expensive and sophisticated equipment that is outside the ﬁnancial capabilities of most laboratoriesespecially for larger objects. In hydrogen reduction the objects are placed in a special furnace with hydrogen gas. the main drawbacks of the process are that it has to be carried out in an air-tight container. while successful. When tannic acid is applied to the surface of iron. This treatment. Because the solution is strongly alkaline. has several drawbacks. cannot be hurried. It also gives the metal an aesthetically pleasing black color. the solution must be kept heated. The iron objects come out of the treatment with a very black surface coloration.CONSERVATION OF CULTURAL MATERIALS 299 many baths.000 ◦ C (Barkman. and it is difﬁcult to determine when the chlorides have been removed from the iron and the treatment can be stopped. it is imperative that their surfaces be covered with a protective coating to insulate the metal from the effects of moisture. but caution should be exercised.
North. Immersion in molten microcrystalline wax is one of the best sealants for both wrought and cast iron. the mineral alterations in the copper alloys are more complex than those of just copper. The wax is easily removed by placing it in a vat of boiling water. With the exception of microcrystalline wax. Special care needs to be taken when treating any copper alloy that contains a high percentage of lead or tin. for it is usually treated in the same way. However. HAMILTON ﬁnal step. both of which are amphoteric metals and dissolve in alkalies. the sealant selected should be: 1) impervious to water vapor and gases. bronze. It is very important that any ﬁnal sealant or coating provides a protective moisture barrier and prevents corrosion. The conservation of chloride-contaminated cupreous objects requires that 1) the cuprous chlorides be removed. There are a number of chemical treatments for copper. In a marine environment the two most commonly encountered copper corrosion products are cuprous chloride and cuprous sulﬁde. clear. 1975: 177). 1976: 55. The hydrochloric acid then attacks the uncorroded metal to form more cuprous chloride. The processes discussed here are adequate to handle the majority of iron artifacts but there remains considerable room for improvements in the conservation of iron. If a cupreous object containing cuprous chlorides in its corrosion products is exposed to the air. 3) reversible. but most are not satisfactory for cupreous metals from marine sites. 2) the cuprous chlorides be converted to harmless cuprous oxide. CONSERVATION OF CUPROUS METALS For this paper. The following conservation treatments accomplishes one or more of these objectives. 1987: 231) as well as a clear drying zinc phosphate-based anti-corrosion primer followed by several coats of high durability. Polyurethane coatings are also used (Hamilton.300 DONNY L. in the presence of moisture and oxygen. The reaction continues until no metal remains. 2) natural-looking so that it does not detract from the appearance of the artifact. hydrolyze to form hydrochloric acid and basic cupric chloride. and 4) transparent or translucent so any corrosion of the metal surface can be quickly detected. In general. the nonspeciﬁc term “cupreous metals” is used for copper and the alloys such as brass and bronze where copper predominates. it corrodes by a process referred to as “bronze disease” where the cuprous chlorides. matt polymethyl methacrylate acrylic lacquer (North and Pearson. and brass. all present a problem if there is ever need to retreat the artifacts. In general it matters little what the speciﬁc copper alloy is. I recommend that an additional sealant be applied over it for maximum protection. Electrolytic Reduction Cleaning of Cupreous Metals Electrolytic reduction of cupreous metals is an efﬁcient method of removing the chlorides from cupreous artifact and is carried out in the same manner as described . or 3) the chemical action of the chlorides be prevented.
but a short bath in 10% formic acid. 1978). Successive changes of the alkaline solution continue until the chlorides are removed. The main disadvantage of electrolytic reduction cleaning of copper alloys is the tendency for copper to plate on the surface of the metal. He found that it dissolved out less copper from the piece being treated and there was less alteration in the coloration of the patina. 1970). it may be the only treatment required. stainless steel must be used for the anode. 1987: 43) and cannot be removed by washing in water alone. If formic acid is chosen. a fact seemingly ignored by some conservators (Patton. but everyone who has used the treatment has found that it often results in an enhancement of the color of the patina and in some instances blackened the surface. Cuprous chloride. however. Alkaline Rinses For cupreous artifacts with reasonably low chloride contamination. In contrast to iron. electrolytic cleaning of cupreous metals requires only a few hours to a few days. 2% sodium hydroxide or 5% sodium carbonate. This is especially distracting if either brass or bronze is being cleaned. otherwise. It is sometimes difﬁcult to remove the plated copper. such as alkaline rinses or electrolytic reduction. Depending on the degree of chloride contamination. The alkaline solution then neutralizes the hydrochloric acid.CONSERVATION OF CULTURAL MATERIALS 301 for iron. Sease. The purpose of the BTA is to prevent the cuprous . For artifacts from a marine environment other treatments. Weisser (1987: 106) recommends using 5% sodium carbonate instead. used on iron. Benzotriazole The use of benzotriazole (BTA) has become a standard part of any conservation treatment of copper or copper alloy. following any stabilization process and preceding any ﬁnal sealant (Green. usually have to precede the application of BTA. it is possible to rinse the chlorides out in repeated alkaline baths and in the process cause little or no alteration to any patina present. The object is then rinsed in several baths of deionized water until the pH of the last bath is unaltered. Until recently. For artifacts from a freshwater site. and polishing with baking soda is usually effective. Cuprous chloride is soluble in an alkaline solution where the hydroxyl ions of the alkaline solution react chemically with the cuprous chloride to form cuprous oxide and hydrochloric acid. it being used to prevent any future corrosion or discoloration of the patina. as well as 5% formic acid can be used. 5% sodium sesquicarbonate was used as the alkaline rinse solution (Oddy and Hughes. It is essential that the cuprous chloride present in the metal be removed to prevent any future outbreak of bronze disease. 1975. is insoluble in plain water. electrolytic reduction may not be required and satisfactory results can be obtained with alkaline rinses. The two alkaline electrolytes. mild steel is used.
it should be part of any treatment of copper or copper bearing alloys. the objects are put through a series of hot rinses in deionized water. Because BTA is a suspected carcinogen. the treatment may have to be combined with one of the other treatments described above. Pearson (1974: 302) recommends washing in several baths of denatured ethanol. the corrosion products of objects of lead or lead alloys such as pewter. Most of the .302 DONNY L. is satisfactory. Therefore. The artifacts need to be cleaned only for aesthetic reasons and to reveal surface details under the corrosion layers. contact with the skin should be avoided and the powder should not be inhaled. and copper alloys. Alternatively. CONSERVATION OF LEAD AND LEAD ALLOYS Once recovered from the sea. Precipitation of this insoluble complex over the cuprous chloride forms a barrier against any moisture that could activate the cuprous chlorides responsible for bronze disease. After drying in acetone. Old pewter. The treatment does not remove the cuprous chloride from the artifact. but ethanol can also be used. Use of this method alone is not always successful. which is an acryloid resin with BTA incorporated into it. which is Acryloid B-66 resin dissolved in toluene. See Green (1975). They may be unsightly or even disﬁguring. being an alloy of lead and tin needs to be treated as tin. 1979). complex compound with cupric ions. If a water rinse is used any tarnish that develops can be removed with 5% formic acid or by polishing with a wet paste of sodium bicarbonate (baking soda). the artifact is coated with a protective coating of clear acrylic. but they do not take part in chemical reactions that attack the remaining metal. A number of techniques are used (Lane. cupreous objects should be treated with BTA as described above. Many conservators use Incralac. it merely forms a barrier between the cuprous chloride and the moisture in the atmosphere. and Sease (1978) for additional information. and availability. Microcrystalline wax can be used. Krylon is recommended for ease of application. durability. For artifacts heavily contaminated with chloride. but in most cases has no special advantage over acrylics. no acids or sodium hydroxide should be used on it. The BTA is usually dissolved in water. I have found that Krylon Clear Acrylic Spray #1301. copper. which is the more anodic and chemically sensitive metal. HAMILTON chlorides left in the metal from reacting and to keep the cupreous metal from tarnishing. Hamilton (1976). Final Treatment and Sealant Following electrolytic or chemical cleaning. however. Because copper tarnishes in water. The benzotriazole forms an insoluble. After rinsing. are stable. as is the case with iron. The best results are obtained when the cupreous artifact is immersed in 1–3% benzotriazole solution for 24 hours. benzotriazole can be mixed with Acryloid B-72 or polyvinyl acetate and brushed on the artifact.
. However.C. were conserved by electrolytic reduction. Electrolytic Reduction Cleaning of Lead This treatment is carried out in the same way as described for iron. and ferric oxide. for the general cleaning of lead. This treatment is good for lightly corroded specimens and it gives lead surfaces a pleasing appearance. If lead dioxide is present. In practice. Caley’s method has been superseded by electrolytic reduction. lead monoxide. After treating lead and pewter objects with alkaline electrolytes.CONSERVATION OF CULTURAL MATERIALS 303 pewter plates recovered from the excavations at Port Royal. Sealant Following the conservation treatment and rinsing. when there is a concern to convert lead corrosion back to a metallic state. Jamaica. the conservator should rinse them in several baths of dilute sulfuric acid (four drops of 15% sulfuric acid per liter of water) until the pH ceases rising (Plenderleith and Werner. For this reason. it remains a much used and acceptable technique provided that all residue from the HCl is removed. Chemical Treatment of Lead Because of the ease of treatment and the availability of the chemicals. lead sulﬁde. preventing further attack. Care should be taken with the ammonium acetate for it can etch the metal. However. The lead is immersed in 10% hydrochloric acid. which removes lead carbonates. an electrolyte of sodium carbonate is often used. for if the current stops. Any residual acidity from the sulfuric acid rinses is then removed by immersion in successive baths of cold deionized water until the pH remains constant with that of the water. lead and pewter objects should be dried with hot air or dehydrated in a water miscible solvent such as acetone. the ammonium acetate step is not required. calcium carbonate. 1977: 269–270). however. it is removed by soaking the object in 10% ammonium acetate. considerable care must be taken when alkaline electrolytes are used as lead will dissolve in them unless the D. the most widely used treatment for lead from any archaeological environment is the acid treatment described by Caley (1955). The power must never be turned off when lead or pewter objects are in electrolysis. a layer of lead carbonate is formed on the lead. without a lot of hands-on labor. more metal reduction is possible with sodium hydroxide. For most lead objects. as well as most of the lead pieces. electrical current is ﬂowing to the artifact. Then they should be sealed by immersion in hot microcrystalline wax or sprayed with an acrylic spray as described for copper. The surface detail that is preserved by this treatment varies with the degree of corrosion when recovered.
Mild steel is recommended over stainless steel when sodium hydroxide is used. When using a formic acid electrolyte. maximum metal reduction is achieved with an electrolyte of sodium hydroxide. humic. HAMILTON Lead is particularly susceptible to organic acids. 1979) but the main alternatives are 1) electrolytic reduction and 2) alkaline dithionite.304 Storage of Lead Objects DONNY L. differ because copper corrodes preferentially and forms cuprous chloride. Alkaline Dithionite The alkaline dithionite treatment (MacLeod and North. Possible electrolytes include 5% sodium carbonate. which continues to corrode the copper component of the silver. It is a relatively cheap.C. 2% sodium hydroxide. For marine recovered silver. 1979) is similar to that of alkaline sulﬁte described for iron. simple and rapid method . and 5% formic acid. CONSERVATION OF SILVER After iron. During the process. MacLeod and North. however. silver corrosion products need to be removed only for aesthetic reasons and to reveal detail hidden by the corrosion layers. In these cases the silver is treated as if it were copper. Both compounds are stable mineral forms and do not take part in any further corrosive action with the remaining silver. Therefore. Both electrolytes have their application depending upon the nature of the silver corrosion products. the most commonly encountered corrosion products on silver and silver alloys in a marine environment are silver sulﬁde and silver chloride. silver suffers the most damage from a saltwater environment. lead should be stored in sealed containers or polyethylene bags. power supply so that three volts are established in the cell (Pearson. Thick encrustations form around the metal and objects undergo considerable attack by sulfate reducing bacteria. Accordingly. and by reducing the silver in the corrosion compounds to a metallic state. both of which convert the silver corrosion products back to metallic silver. This can be accomplished in most instances by regulating the D. 1975). Electrolytic Reduction The electrolytic cleaning of silver takes advantage of the reduction action of electrolysis by removing chloride and sulﬁde ions from silver chloride and silver sulﬁde. the current density must be very low to achieve maximum reduction (Charlambous and Oddy. and tannic acid. such as acetic. therefore. Base silver alloys with copper. 1974: 299). Lead artifacts. Because the vapor from wood can initiate corrosion. like lead. 316 or platinized titanium should be employed. 1987. there are a number of treatments available (MacLeod. however. should not be stored in oak cabinets or drawers. only inert anodes such as stainless steel No.
The container for the solution should be completely full to eliminate any air space and capable of being sealed so that it is air tight. they are immersed in 10–12% hydrochloric acid to remove any encrustation layer consisting of sand. If necessary. shell. the silver artifacts are removed and rinsed in deionized or distilled water until the pH of the rinse water remains unchanged. the container is agitated on a regular basis to keep the solution mixed and to expose all surfaces of the specimens to the solution. The technique has been used to conserve a large number of silver coins from several Dutch East India Company ships (MacLeod and North. The silver is then sealed in a solution of alkaline dithionite that is prepared by ﬁrst mixing 40 g of sodium hydroxide per liter of water. in some cases. which may last from a day to a week. This alkaline dithionite treatment has been a very effective way of converting badly mineralized silver back to metallic silver. the rinsing should be more intensive. After approximately one week. Rinse and Sealant Following electrolysis or any chemical cleaning. During the treatment. gold and high gold alloys do not require any treatment.CONSERVATION OF CULTURAL MATERIALS 305 of consistently reducing silver corrosion products to metallic silver. In this treatment. The acid treatment. the specimens should be thoroughly rinsed in deionized water. If an alkaline electrolyte or chemical was used. 50 g of sodium hydrosulﬁte are added to the solution and the silver is then immersed quickly to eliminate the possibility of the solution oxidizing from exposure to atmospheric oxygen. The copper and/or silver corrosion . Once the sodium hydroxide dissolves. The alkaline dithionite treatment will effectively reduce the silver corrosion products to a gray. In addition to being a recommended treatment for reducing silver. The silver is dried with hot air or dehydrated in acetone and coated with clear acrylic lacquer such as Krylon Clear Acrylic 1301. the silver is rinsed thoroughly in tap water to remove all residual encrustation. and. it is also been very effective for converting badly mineralized copper buttons and brass rings back to a metallic state. After the hydrochloric acid treatment. iron corrosion compounds. therefore. continues until all evolution of gas ceases. metallic silver which can be polished with a wet baking soda paste or a ﬁberglass brush to a silvery luster. copper. any stubborn spots are removed mechanically. calcium carbonate. 1979) and I have used it to separate and consolidate a stack of ﬁve silver plates from a 1691 Spanish wreck that were encrusted together. GOLD AND GOLD ALLOYS Gold is a very noble and inert metal that does not corrode. if the silver objects are covered with marine encrustation.
Once recovered and treated. however. causing considerable shrinkage and distortion. As long as the waterlogged wood objects are kept wet they will retain their shape. and in many instances even the species because each species possesses unique characteristics. peat bogs and marine sites. After long periods in wet soil. If the wood is exposed to the air. In the process of air drying. It can. the wood shrinks and the dimensions of the wood used to make artifacts is reﬂective of the cured. HAMILTON compound of low alloy gold are treated by the same techniques described for those two metals. but the degree of shrinkage must be within acceptable bounds. The most . however. After the tree is cut. Some shrinkage is acceptable and. a particular conservation technique is often selected because it is known that the wood treated by it will shrink a desired amount (Patton. First. 1982. along with mineral salts. are broadleaf Angiosperms that have vessel pores. tanning matters and other bonding materials. Hardwoods. Waterlogged wood swells from its manufactured size. in fact desired. water soluble substances such as starch and sugar disappear from wood ﬁrst. or Gymnosperms. The remaining lignin structure of the wood cells and the absorbed water preserve the shape of the wood. for the waterlogged wood has swelled. it undergoes a complicated deterioration process (Grattan. In general. Conservation of Wood Being of organic origin. As the cellulose and lignin disintegrate. leaving a lignin network to support the wood. Proper conservation will control the amount of shrinkage. Waterlogged wood is commonly conserved by a process that involves either removing the excess water by replacing it with a material that consolidates and confers mechanical strength to the wood or the excess water is removed by a method that will prevent any shrinkage or distortion of the wood. are needle bearing trees or conifers that lack vessel pores. the wood looses moisture until it reaches an equilibrium with its local environment. cellulose in the cell walls disintegrates. the excess water evaporates and the surface tension of the evaporating water will cause the weakened cell walls to collapse. but we can generalize certain facts from the published data. Softwoods. wood normally decays under combined biological and chemical attack when buried in the ground and submerged in water. 1987). In practice. In time. Live trees contain a lot of water. through hydrolysis.306 DONNY L. 1987: 43). dried wood. survive for prolonged periods when in either a very dry or a waterlogged environment. such as pine. coloring agents. for conservation purposes. bacterial action causes a degradation of the cellulosic components of cell walls of all wood. such as oak. the treated wood will shrink to varying degrees depending upon how it was treated. When wood is deposited in an underwater site. it is very important to know whether the wood is hardwood or softwood. the wood becomes more porous and permeable to water and the cell cavities and intermolecular spaces ﬁll with water.
PEGs of different molecular weight have different applications. It continues to be used widely. 1979: 51). Otherwise. There is a wide range of conservation treatments for wood (Grattan and McCawley. different shrinkage rates. do not penetrate as well. POLYETHYLENE GLYCOL ( PEG ) METHOD The PEG method was the ﬁrst method for treating waterlogged wood that was simple to carry out and economically efﬁcient. There are any number of variations in the treat- . depending on the species and condition of the wood undergoing the treatment. which are examples of the ﬁrst alternative above. Teredo worm infestation can be so extensive that the wood has a mushy. The higher molecular weight PEGs have large molecules. Another consideration in the treatment of marine wood is the presence of teredo worms and their calcareous tunnels. the ability to glue composite pieces together.250–6. the excess water in the wood is removed and the wood is bulked in one operation. a precipitate of crystallized white salt can form on the surface of the treated piece. The low molecular weights (300–600) are liquids. methanol. spongy consistency. Prior to any of the conservation treatments described below. Different treatments result in different colors of wood. the choice of treatment may be based on nothing more than aesthetics.500) and the higher molecular weights (3. In fact. provide differing susceptibility to ﬂuctuation of humidity. there is no difference between the conservation of wood recovered from a marine environment or a freshwater environment. the more easily it penetrates and the more hygroscopic it is. it is necessary to take the wood through a number of freshwater baths to remove the bulk of the salts. Various forms of dehydration and freeze drying are examples of the second alternative. they are distinguished from true waxes by the fact that they are freely soluble in water and alcohol (ethanol. Polyethylene glycols are synthetic materials which have the generalized formula HOCH2 ·(CH2 OCH2 )n ·CH2 OH (Pearson.000) are wax-like materials. thus every conservator has to have a range of treatments available. and the affect the treatment chemicals have on any composite wood/metal artifact. isopropanol). the smaller the size of the molecules. acetone/rosin. Depending upon the circumstances. 1987). The lower the molecular weight.CONSERVATION OF CULTURAL MATERIALS 307 commonly used of the many treatments for the conservation of waterlogged wood are polyethylene glycol. Except for the need to remove most of the soluble salts that might be present. and sugar. the calcareous burrows of the teredo may be all that is holding the wood together. The treatment accorded is based on these considerations. If the wood is from a marine environment. the intermediate members are semi-liquids or have the consistency of Vaseline (1. and are less hygroscopic. the water bulking the cells is full of soluble salts. different storage requirements. it usually contains a negligible amount of soluble salts. Although the PEGs have some of the physical properties of waxes. If the wood is recovered from a freshwater environment. During the PEG treatment. differing degrees of ﬂexibility.000–1.
Small increments of PEG are added to the heated solution to increase its concentration. and there is no need for a fungicide. however. Although some conservators have used PEG on composite pieces. and the bulk of any soluble salts should be removed. but even less expensive methods were needed. the treatment is not recommended for composite wood/metal artifacts. coarse grained unreﬁned sugar (Type A sugar) should be avoided.308 DONNY L. there has been a search for a less expensive. except that sugar is used. See the acetone/rosin treatment below. methanol. In general. lighter in weight. especially iron. over a period of time it reaches 52–60 ◦ C (125–140 ◦ F). It can be ﬂexed. James Parrent (1985). start with a . investigated the process in greater detail. the treatment time is reduced. The advantages of using sugar are that its molecules are about the same size as the lower molecular weight PEG. especially when water and lower molecular weight PEG is used. The treatment procedure is exactly the same as described for PEG. if in doubt. With highly degraded wood it is possible to start with a higher concentration of sucrose. The size of the increments depends on the species of wood and its condition. The wood is then placed in a 1– 5% solution of sugar dissolved in water. When alcohol is used as the solvent. The brownish colored. heated oven where the temperature is gradually increased until. Back in the early 1970s. but in general tend to be in the range of 1–2%. I was experimenting with sucrose treatments and one of my students. and the treatment takes less time. Because water is obviously much cheaper than any of the various alcohols (ethanol. they readily penetrate the wood. it is not recommended. When using PEG in water it is necessary to use a fungicide to prevent mold growth. but dependable way to treat it. and the sugar is much less hygroscopic than PEG of any molecular weight. Larger vats have to use circulation pumps and various means of heating the solution. but it is difﬁcult to glue treated pieces together. HAMILTON ment. alcohol/PEG treated wood is lighter in color. SUCROSE METHOD Ever since waterlogged wood has been recovered and treated. most of which involve heating the solution. white sugar. Smaller objects can be placed in a ventilated. PEG treated wood tends to be relatively heavy. In general. especially when PEG is present. for PEG is corrosive to most metal. In most instances smaller pieces of wood can be treated in an alcohol/PEG solution. the waterlogged wood is generally dehydrated and then increments of PEG are added at the rate determined for that piece. PEG provided one option. for wood treated in it is much more hygroscopic than wood treated in reﬁned. Only reﬁned white sugar (pure sucrose) should be used. isopropanol) it is generally used as the solvent when large pieces of wood are treated with PEG. Before starting the conservation. The increments can be as low as a fraction of a percent. any metal component can be adversely affected by long emersion in heated water. all the adhering dirt should be removed. In addition.
The acid treatment is said to improve the penetration of the rosin into the wood by breaking down the organic . there is the potential problem presented by having an edible artifact. Finally. The treatment starts with removing any dirt that may be present and if the piece was recovered from a marine site. This method constitutes an acceptable means of conserving waterlogged wood and is the least expensive of the methods discussed here. Jamaica. controlled drying as it adjusts to the prevailing atmospheric conditions. it is removed and allowed to undergo slow. such as canoes and structural parts of ships. and the small molecular size of the sugar shortens the treatment time. It is less expensive than PEG. Once the wood is saturated with a given x% sugar solution the concentration is increased by 1% to 10% depending upon the condition of the wood and the species of tree being treated. it has a duller. Maintaining artifacts treated by sugar in a controlled atmosphere will ensure the continued success of the conservation procedure. once the wood has reached equilibrium at a 50% solution. the results are comparable to that of the various PEG treatments. but at less expense. In general. This will maximize the success of the overall treatment. The treatment is not recommended for composite wood/metal artifacts since the metal may corrode while submerged in a heated sugar/water solution.CONSERVATION OF CULTURAL MATERIALS 309 1% weight/volume solution. The treatment consists of replacing the water in wood with pine rosin. Usually. For most specimens. matte surface. as is the case in all the wood treatment described here. The wood should be stored under conditions of less than 70% humidity. 1972). and there is a tendency for some surface checking. ACETONE / ROSIN METHOD The acetone/rosin treatment was developed to overcome the difﬁculty that the higher molecular weight PEGs had in penetrating the dense heartwood of wellpreserved oak (McKerrell and Varsanyi. Still. a 70% sugar concentration is all that is required for successful treatment. The procedure for treating waterlogged wood with acetone/rosin (McKerrel and Varsanyi. Sugar was used successfully to treat a number of door frames and sills from Port Royal. In some cases a pretreatment in dilute muriatic acid. which is the name for technical grade hydrochloric acid (HCL) may be warranted. The advantages of the treatment are that the wood is dimensionably stable with less shrinkage than comparable PEG treated wood. increments of 10% can be made. Sugar or sucrose treatments remain a viable alternative for treating as economically as possible large pieces of waterlogged wood. When the wood has reached equilibrium with the desired percentage of sugar. The disadvantages are a heavy wood that does not ﬂex. also called colophony. Artifacts thus treated require no more or no less care than those treated with other preservatives. 1972) is a simple process. the problems of insects and rodents eating the sucrose treated wood can be eliminated with proper storage conditions. it is soluble in water. the soluble salts should be rinsed out.
I do not recommend pretreating the wood in hydrochloric acid. but with a little thought and ingenuity. The wood should be placed into the rosin solution when it is at room temperature. important objects. this one has a high success rate. Other advantages of the acetone/rosin treatment are that it is light in weight. McKerrel and Varsanyi (1972) suggest that objects 5–10 cm thick could be treated in 4 weeks. HCl pretreatment can be detrimental to the wood. each piece is removed from the container and the excess rosin is wiped off with a rag moistened with acetone. while objects less than 5 cm thick require 2 weeks. In the actual treatment process. therefore. This step of the treatment is very important. more independent of its storage environment. for all the water must be removed before placing it in the saturated rosin solution. for wood treated with HCl shrinks more. an excess of rosin should be placed in the container so that there is a thick viscous layer along the bottom of the container. it is dry. Because of the cost and danger of using the organic solvent. Raising the temperature of the bath after placing the wood in it creates less of a shock to the wood than if it were placed directly into a heated solution. The object being treated should be suspended or supported above this thick undissolved rosin. then the ﬁrst step following the general cleaning is dehydrating the wood completely in 3 successive baths of acetone. explosion-proof oven. it will create a barrier for the rosin which is not soluble in water. In general. Because the wood is impregnated with rosin. This step should be considered optional and is not generally recommended.310 DONNY L. it can be glued and repaired easily if it breaks. this treatment is usually used only on small. The wood and the rosin solution are then heated together to 52 ◦ C by placing them in a thermostatically controlled. HAMILTON acids in the wood and bleach the wood to a more natural or original color. For this reason. I have found that the bleaching is only temporary and rarely affects the ﬁnal color of the treated piece. If any water is present in the wood. the HCL will dissolve the calcareous tunnels and considerably weaken the wood. and is. A saturated solution of 67% rosin can be achieved in acetone at 52 ◦ C. larger objects can be safely treated. it is less susceptible to changes in the relative humidity. it is strong. Caution is warranted. However. For marine recovered wood that has any degree of teredo worm infestation. . If the acid pretreatment is not used. the acetone/rosin treatment is preferred when good storage conditions can not be assured for conserved waterlogged wood. and it can be used on compound wood and metal objects. Treatment time may last from two weeks to several months. It results in a warm-colored wood that is totally dry. each bath lasting 2–4 days depending on the thickness of the wood. the wood is placed in a sealed container containing a saturated solution of rosin dissolved in acetone. After the wood is saturated with rosin. and its other supposed purpose of lightening the color of the wood does not occur. To insure that a saturated solution is present. based on my experience. Of the conservation treatments available today. the surface often becomes checked and it is more prone to cracking after the conservation treatment is completed.
and where it may be necessary to ﬂex a piece of wood. regardless of the solvent. Colophony rosin is soluble in ethanol and isopropanol. but the treatments have been successful. This treatment is not applicable for badly degraded wood. iron and brass. acetone/rosin would not be an ideal choice because the treated wood will break if it is bent. In most cases. DEHYDRATION Treatment of waterlogged wood by dehydrating it through a series of alcohol baths and freeze-drying are often employed. Ambrose (1975) recommended using 10% PEG 400. the standard freeze-drying treatment consists of cleaning the wood thoroughly and then saturating it in 10–20% PEG 400. When room temperature treatments are used. for the rosin does not react with any of the associated metals. The early attempts at freeze-drying waterlogged wood were not too successful. For example. The saturated solution in these two solvents is less than 67% but both have been successfully used. a waterlogged Tower 1862 Enﬁeld riﬂe from North Carolina and a War of 1812 riﬂe from Lake Champlain. for the surface of the treated wood was prone to surface checking. and the over-all success is similar. only relatively small objects can be treated in the freeze-drying units commonly found in conservation laboratories. It is important that water-free alcohol or acetone be used to ensure success. . were successfully treated in ethanol/rosin at room temperature in a PVC pipe. I have always preferred the various rosin treatments when I wanted to be assured of success. I have had much better success when the treatment was increased two to three times longer than recommended. I have treated a number of odd-shaped wood objects in an acetone/rosin solution at room temperature. Its disadvantages include the high cost of the organic solvents and the rosin. The main factor that keeps conservators from relying on both much more is the cost of the solvents and the freeze drying equipment. and the ﬂammability of the acetone. Over the past 10 years. Now. to treat waterlogged wood. The use of alternative alcohol solvents makes the rosin treatment more versatile. in both heated and unheated treatments. In cases where it is necessary to reconstruct a composite piece. and can be used in polyvinyl chloride (PVC) containers.CONSERVATION OF CULTURAL MATERIALS 311 such as riﬂes. it is considered by many to be the treatment of choice for all composite wood/metal artifacts. Thus. It should also be noted here that. Both are less volatile and ﬂammable than acetone. the treatment time should be increased considerably (6– 12 months) to ensure the artifact is completely saturated with the rosin solution. At room temperature the rosin solution is less than 67%. but is it important to remember is that dehydration treatments can only be used on wood that has enough mechanical strength to support itself after conservation. while better and quicker results are achieved with a heated solution. This problem was solved by Ambrose (1975) when he pretreated the wood with PEG 400. while Watson (1987: 274) states that a 20% concentration is preferable. both composites of wood.
HAMILTON for this more concentrated solution prevents the formation of bacterial slime that forms in the soaking bath. There are others that have not been as successful. Under vacuum. First try washing in water alone. The complaints made by Jensen (1983) nearly a decade ago are still applicable today. causing minimal shrinkage. Soft brushes. The gas or water vapor that forms freezes and collects on the low temperature condenser in the freeze-drying unit. Leather Conservation To be frank. all the water is removed from the wood and the PEG is left in the wood as a humicant and stabilizer. Conservators have developed a number of variations on the freeze-drying treatment (Watson. If this is not successful. Do not use any chemicals that will damage the collagen ﬁbers of the leather and do not use any heated solutions. A good review of conserving waterlogged leather is presented in Jensen (1987) and some of the more general applicable procedures are presented here. Still. All archaeological leather conservation is preceded by washing to remove any ingrained dirt. Freeze drying is often used to conserve small pieces of waterlogged wood. 1987) which employ various combinations and concentrations of PEG 400 and PEG 3350 (4000) pretreatments. However. new. If chemical cleaning is necessary to remove ingrained dirt. there are no totally acceptable ways to treat waterlogged leather. A PEG 3350 pretreatment will bulk the wood and make freeze-drying treatment possible for wood that could not otherwise support itself after treatment. because it is a dehydration process. a small amount of non-ionic detergent (about a 1% solution) or sodium hexametaphosphate can be used. depending on the size of the wood and the capacity of the freeze-drying unit. which can disrupt the wood cells during the freezing stage. The PEG in the wood prevents the formation of large ice crystals. Rinse well after washing. After being saturated with the PEG solution. The frozen wood is then placed in the freeze-drying chamber and a low vacuum is maintained during the treatment. When conserving leather it often safer to select . The technique remains an option for select pieces. water jets. Leather may require a variety of mechanical cleaning techniques.312 DONNY L. We need new substances that are not hygroscopic that will penetrate the wood readily and will set up in the wood to prevent the cells from shrinking. Research is continuing on a number of substances that look promising. After a period of days to weeks. and ultrasonic cleaners may be required. the wood is frozen solidly in a low temperature freezer. The treatments for waterlogged wood described above are the ones most commonly used on a daily basis by many conservation laboratories. depending upon the condition of the wood. the ice crystals sublime and the ice goes directly from a solid state to a gaseous state without an intervening liquid state. it often results in excessive shrinkage. especially if the wood is badly degraded. reliable techniques need to be developed. try alternative methods. depending on the condition of the leather and the particular cleaning problem.
Slow desiccation of glutinous collagen ﬁbers allows their surfaces to become less sticky and less brittle.. monitor the process closely. a bath of 100% isopropanol. freeze drying and solvent dehydration. and that they can remove tanning. as described for wood above. Solvent solutions are much faster. For waterlogged leather. coloring agents. For stain removal. Dehydration Using Organic Solvents This treatment is identical to the process of dehydrating wood by taking it through a series of baths of water miscible organic solvent. but less expensive. leather’s main constituent. Some conservators prefer alcohol treatments. and 3350. All residue of the drying solvents is removed by air drying. Diagnostic attributes should never be removed. a bath of 100% ethanol or methanol followed by 100% methyl ethyl ketone. Soak the leather in one of these solutions for 2–3 hours or until the stains are removed. 1450. e. drying only through acetone is necessary. considerably more costly. thus more ﬂexible. Caution should be exercised when using any of these chemicals on leather. Heated solutions should not be used and PEG concentrations in excess of 30% are not necessary. One must always remember that it is often better to leave stains on the leather in order to prevent damage that may occur while attempting to remove them. it is recommended that you start with a dilute solution (1–10%) of PEG and gradually increase the concentration through evaporation of the solvent or by adding PEG up to 30%– 80%. then 100% acetone and ﬁnally 100% ether. but produce a lighter leather with more uniform shrinkage. In most cases a sequence of solvents with decreasing polarity is used. particularly iron staining. are often selected. This allows the water to evaporate as equal amounts of PEG replace the water. 600. PEG Treatments for Waterlogged Leather When treating leather with PEG 400. Check the pH of a standing bath of water containing the leather to determine complete removal of the chemicals.g. 540 Blend. 3–5% ammonium citrate and disodium ethylenediamine tretraacetate (EDTA) are used.CONSERVATION OF CULTURAL MATERIALS 313 a treatment that least affects the leather. sometimes using a vacuum. If necessary. without adding any additional lubricant. a lubricant such as PEG 400 can be added. Always keep in mind that chemicals used to clean rusts and mineral concretions may produce further hydrolysis of the proteinaceous collagen ﬁbers. then rinse the leather in running water or standing tap water until all chemical residues are removed. In most instances fewer baths are used and for some leather. Aqueous solutions of PEG are slower. a series of baths of x% H2 O–x% isopropanol. This example is a very conservative method of treatment. while others think . painted decorations and other features that are part of the diagnostic attributes of the leather object.
REMOVAL OF SOLUBLE SALT In many ways the problems of soluble salts and stain removal in bone conservation are similar to pottery. thus they will adsorb soluble salts and stain easily. Both techniques are applicable in given situations. In some instances. as discussed under ceramics. archaeological bone and ivory can only be cleaned. Quite often. The salts are removed by going through rinses of tap water. Ivory Both bone and ivory are composed of inorganic calcium phosphate associated with carbonate and ﬂuoride and an organic tissue called ossein (Plenderleith and Werner. because of the anisotropic nature of the material. The surface of either can spall off and there is a tendency for it to split along the grain. If this is not possible. rain water. In general the insoluble salts should be removed mechanically if possible. 1977: 149). bone/ivory artifacts are damaged in the process of removing stains. Bone and ivory artifacts. STAIN REMOVAL Stains present other problems. when the decision has been made to . Drying is best accomplished by taking the object through graded baths of alcohol. ivory. Structurally unsound bone artifacts require much more careful hands-on cleaning. satisfactory restoration is often impossible. Treatment of structurally sound bone starts with the removal of any surface dirt and then the removal of any soluble salts. Bone. considerable thought should be given as to whether they should actually be removed. for in too many cases. In all cases. are not normally allowed to air dry. This is especially true for thin artifacts such as bone lice combs. removing stains. Bone. teeth. one should consider leaving the stain on the object. and the speciﬁc process is dictated by the condition of each individual artifact. After drying through acetone. The removal of insoluble salts such as calcium carbonate and various stains from bone/ivory can be a tricky process. antler. In waterlogged archaeological sites. are all porous. In some instances the bone is so delicate that it must be consolidated before the rinsing is initiated. and deionized water. the ossein is decomposed by hydrolysis and is reduced to a sponge-like consistency. The conservation of waterlogged bone from underwater sites involves removing insoluble and soluble salts. and consolidating the bone with synthetic resins. strengthened and stabilized. the bone/ivory should be consolidated by immersion in a dilute solution (5–10%) of PVA resin (V7 or V15) or in Acryloid B-72 resin dissolved in acetone.314 DONNY L. HAMILTON that alcohol treatments cause the leather to shrink more than comparable aqueous treatments. Ivory will delaminate around its circular rings.
archaeologists recover ceramics that have become encapsulated by the calcareous encrustation that forms around iron artifacts and they can be partially covered by the various corals that can grow on the surface of ceramics exposed on the ocean’s bottom. paint. In most cases the safest and most satisfactory method of removing insoluble salts from the surface of pottery is mechanically by hand. Pearson. 5–10% oxalic acid. dental tool.CONSERVATION OF CULTURAL MATERIALS 315 remove iron stains. 5–10% hydrogen peroxide is used. Unsound bone presents a multitude of problems. badly ﬁred pottery requires more care. 1975. Fragile pieces. but the procedure is the same. REMOVAL OF INSOLUBLE SALTS Quite often at marine sites. Well-ﬁred pottery can be washed in a mild detergent. 1987c). Mibach. 1987b. Earthenware. Most calcareous concretions can be removed easily when wet by scraping with a scalpel. insoluble salts can be removed chemically. In limited instances. which constitutes the bulk of the ceramics from any period. or pneumatic chisels. and soot that is left on either surface. All ceramics should be washed to remove all the adhering dirt. Care should be taken not to mar the surfaces or to remove traces of food. The latter two are ﬁred at higher temperatures and are relatively impervious to liquids. oxalic acid. or porcelain. 5% ammonium citrate by itself and 5% ammonium citrate followed by 5% oxalic acid have been successfully used. scrubbing the edges and surfaces with a soft brush. For sulﬁde stains. stoneware. but one needs to be very judicious when chemicals are used. If unsound bone is submerged in an acid solution. pottery with friable surfaces or ﬂaking surfaces may require consolidation with a synthetic resin before treatment. and . Most bone is then treated by applying a synthetic resin such as PVA or Acryloid B-72 in order to provide it with additional mechanical strength and to seal it of from the moisture of the atmosphere. Hydrochloric acid. pigments. The treatment then follows the same procedure as when rinsing soluble salts out of the artifact. One of the main things that needs to be determined ﬁrst when one conserves ceramics is whether they are earthenware. the evolution of carbon dioxide from the decomposition of the CaCO3 will break up the specimen. After cleaning any bone/ivory artifact with any chemical. thus. 1975. the conservation of ceramics recovered from archaeological sites is very straightforward and only minimal treatment is required (Olive and Pearson. earthenware pieces require more treatment. is ﬁred at much lower temperatures and will adsorb liquids along with any soluble substances that may be in the solution. In most cases it is treated with localized applications of the acid with a brush or swab. Fragile. Ceramics Generally speaking. all traces of that chemical must be removed by rinsing. disodium EDTA.
which will turn milky. In this treatment the sherds are immersed in the solution and left until the deposits are removed. The process can continue until it actually breaks up the piece through internal stresses and fractures. The salts eventually reach the surface of the pot. Care must be exercised.316 DONNY L. REMOVAL OF SOLUBLE SALTS When pottery is recovered from freshwater sites there are seldom sufﬁcient soluble salts (chlorides. then deionized water may be used for a . Simple precautions such as thoroughly wetting the sherd with water before applying the acid will concentrate the action on the surface. 1975: 64). the iron stains that are usually bound in with the calcium salts are removed along with the calcium. where they can crack and in some cases lift off the surface glaze. crystallize and expand. they should be treated in the same way as the earthenware. soluble salts will not penetrate the body of porcelain and stoneware. calcium carbonate) for the tempering material will be removed. Once the level of the salts are brought to the level of the local tap water. The soluble salts must be removed for the pottery to be stable because soluble salts are hygroscopic and they repeatedly dissolve and crystallize as the relative humidity rises and falls. Ethylene-diaminetetraacetic acid or ethylene-diaminetetraacetate (5–10% EDTA. tetra-sodium salts) is used to remove calcareous and iron deposits from the surface of ceramics without seriously affecting the iron content of the paste (Olive and Pearson. In other cases. The old conservation trick of placing sherds in the reservoir of a toilet is a very effective way of rinsing out salts with continuous changes of water and free labor. masses of needle-like crystals can cover the surface of the sherds or pot. the solution may have to be replenished. especially lead glazes. thoroughly weakening the body of the ceramic. Generally speaking. phosphates. In the process. nitrates) in the body of the sherd to present a problem and no treatment other than rinsing off dirt and possibly consolidation of the earthenware is required. but whenever in doubt. followed by rinses in either rain water or de-ionized water. for hydrochloric acid can discolor glazes. Periodically. Both porcelain and stoneware seldom require much conservation. They are then allowed to air dry. HAMILTON ethylenediamine tetraacetate are commonly employed. exfoliating off the surface and crazing the glazes. salts can be deposited below the glaze of either. Pottery excavated from brackish and marine sites is saturated with soluble salts and in some cases the surfaces become covered with insoluble salts such as calcium carbonate. Before using any acid on pottery make sure that the paste does not contain carbonate temper (shell. After using any acid the sherds should be rinsed ﬁrst in tap water. or when there is a possibility of salts penetrating the glaze. a running bath is quicker and more effective but is very wasteful. but. Soluble salts are easily removed by repeated rinsing in water. in some cases. hiding all detail. Well consolidated sherds can be immersed in the acid until all gas evolution ceases – usually less than an hour – and repeated if necessary.
In the past celluloid glues such as Duco have been used. and even many wet land sites. In marine sites. local application of 10% oxalic acid with cotton swabs on the surface of wet pottery is generally successful in removing iron stains from stoneware and earthenware ceramics which contain iron oxide in the paste or glaze. The process should be carefully monitored. nearly all of the tin enamel ceramics such as delft and majolica excavated from the submerged town of Port Royal. This type of staining is easily removed by immersing in 10–25% by volume hydrogen peroxide solution for a short period of time – minutes to hours – until the stains disappear (Olive and Pearson. STAIN REMOVAL Iron oxide stains are one of the more common stains encountered.CONSERVATION OF CULTURAL MATERIALS 317 ﬁnal bath or two. majolica. In fact. Hydrogen peroxide is also useful for removing organic stains. and loose. faience). 1988). acetone/toluene or acetone and amyl acetate can be used. In other cases the ceramics are submerged in the EDTA solution until the iron stains are removed. 1986). Alternatively. black sulﬁde staining of ceramic glazes is very common. Intensive rinsing after cleaning is required. the hydrogen peroxide should be applied with a cotton swab and observed closely. A thick PVA solution in acetone. By blotting and reapplying the hydrogen peroxide. a good reversible glue. 1975: 65). especially on tin enamel wares (delft. but they have too short a serviceable life to be used in conservation (Selwitz. for it will burn skin very badly. the progress can be monitored with a conductivity meter to determine when to change the baths and when the treatment is completed. If the decision is made to remove them. should be used (Koob. such as Acryloid B-72 or PVA. the stains can be removed. RECONSTRUCTION When it is necessary to glue sherds together. In all treatments. Stains should be left unless there is an overriding reason to remove them. . Five percent EDTA. When pottery is being rinsed in separate baths. Jamaica were badly stained with sulﬁdes. caution must be exercised to avoid overcleaning. If the glaze is friable. silver nitrate can be used to test for the presence of sodium chloride in a sample of the rinse water. One note of caution: concentrated hydrogen peroxide is potentially one of the most dangerous chemicals used in conservation. disodium salt is recommended for use on pottery containing iron oxide in the glaze or paste because it dissolves less iron out into solution. Very friable and fragile sherds may have to be consolidated in a dilute solution of the glue before they are glued or repaired. because the glaze on these ceramics is often crazed and the hydrogen peroxide solution can ﬂow under it and the bubbles generated during treatment can lift off the poorly attached glaze. Wear gloves at all times and use caution if concentrated solutions are used to make the dilute working solutions.
Whether or not there are problems depends more upon the original composition of the glass than upon anything else. The other problem often encountered with lead glass is its tendency to develop a black lead sulﬁde ﬁlm over its entire surface. HAMILTON Glass is usually the most stable of archaeological materials. There are considerable differences of opinion on what to do with unstable glass. Conservation problems are most often encountered with the early lead crystal. commonly called “Onion” bottles. especially saltwater. Historically. In my own experience. Other glass conservators try to remove the alkalinity from the glass to halt the deterioration. it took a while to formulate a stable lead glass. but it can go through some complex disintegration processes (Brill. Problems arise when there is an excess of alkali and too little ﬂux in the glass mixture. simple sulﬁde staining of leaded glass. usually lime (calcium oxide). the sodium and potassium carbonates can leach out leaving only a fragile. The weeping or sweaty condition is sometimes made worse by the application of a surface lacquer or sealant. Some advise that the only treatment should be to keep the glass in low relative humidities so the glass does not react with any excess atmospheric moisture. I have found glass to be either no problem at all. 1975). In some cases there is an actual separation of layers of glass from the body. Then hours are spent reconstructing the angular. Ideally.318 Glass Conservation DONNY L. In water. crack. and the cheap liquor bottles of the late 17th and early 18th centuries. fractured pieces. When examples of early lead glass were encountered in the Port Royal excavations. 16–22% alkali or soda ash (sodium carbonate) or potash (potassium carbonate. ﬂake and pit giving the surface of the glass a frosty appearance. porous hydrated silica (SiO2) network. 1962. and the disintegration continues under the sealant until the glass falls apart. glass is stable. Jamaica I have found that the majority of the glass that we excavated has been stable and required little attention. Unfortunately there are few in between cases. While a RH range of 40% to 55% is usually recommended. with dilute PVA or Acryloid B-72. GLASS TREATMENT From my underwater excavations of Port Royal. for resin sealants are not impervious to water vapor. Conservation consists of rinsing the pieces thoroughly with de-ionized water and then controlled drying through graded alcohol baths. Moncrieff. This causes the glass to craze. they were badly fractured. in the same way as described for . glass should consist of 70–73% silica. followed by consolidation under vacuum. As long as the mixture is kept in balance. or a complete disaster. The early formulations were unstable and were very subject to crazing. for then it will be especially susceptible to attack by moisture. it varies in relationship to the stability of the glass. The alkali lowers the melting point of the sand and the ﬂux facilitates the mixture of the components. usually derived from wood ash) and 5– 10% ﬂux.
a clear epoxy formulated for glass.CONSERVATION OF CULTURAL MATERIALS 319 the various tin enamel ceramics. therefore. During the deterioration process. The bottle is then thoroughly rinsed in de-ionized water. lead stem ware and various cut. In other cases. The bottles are then dried in several baths of ethanol or acetone and either a PVA or an Acryloid B-72 resin is applied under a vacuum to secure the layers of glass in place. as described for ceramics. Various requirements and procedures have been discussed. In marine sites. but clear epoxy resins are generally used because they adhere to the smooth. They dry clearer and shrink less than the solvent resins and are. there is a residual layer of sound glass under the deteriorated glass and the pieces can be preserved by keeping then stored in freshwater until conservation can be started. . Then place the bottle in a bath of 2% sulfuric acid to remove any remaining calcareous deposits and to neutralize the alkalinity of the glass. Conclusion This chapter has attempted to present the current state of conservation of archaeological material from waterlogged environments as evidenced by the procedures in common use. opaque glass that forms layers like an onion skin. individuals interested in archaeological conservation should consult the referenced sources and a trained conservator before attempting the procedures described herein. In many cases the deterioration goes completely through the glass and the bottle literally falls apart in a matter of minutes upon exposure to air. The bottle should then be stored in relative humidity of 40% or below to ward off any future breakdown of the glass. It is exceptionally difﬁcult and time consuming to ﬁll the gaps left by missing pieces and it is also difﬁcult to match transparent glass colors. non-porous glass more readily. All treatments should be reversible in the event that the object should require additional preservation. mechanically clean the bottle of adhering encrustation. Time and space did not allow a thorough discussion of each technique. Glass reconstruction should be left to a glass specialist. If required. it develops a layer of dead. A 10–15% hydrogen peroxide solution. lead crystal pieces are solid black when recovered. Do as much mechanical cleaning as possible without damaging the bottle. usually irreversible. however. therefore. but many more were not. GLASS RECONSTRUCTION Glass can be repaired and reconstructed with the same glues as described for pottery. is used to remove the sulﬁde stain. The epoxy resins are. The ubiquitous liquor bottles of the 17th century are made of a very cheaply made green soda glass that is unstable in sea water. Fragments can then be glued together with a good glue or when deemed necessary. The preservation of antiquities should produce objects that are chemically stable with an aesthetically acceptable appearance. less noticeable and develop stronger bonds.
it becomes necessary to improvise continually. and other faunal material identiﬁed. The archaeological perspective brings to the ﬁeld of conservation an outlook and an appreciation of the archaeological record and material culture that otherwise might not be considered. has wood samples. Their presence is just as important as the artifacts that survive intact. and labor. Factors such as budget. HAMILTON Successfully conserved objects may still deteriorate in the future. Much more is contributed by the conservation laboratory than simply an array of stabilized artifacts. a welder. makes preliminary identiﬁcations. must also include the qualities of an administrator. that has often been ignored. The costs of conservation force some hard decisions. detailed information can be lost if an attempt is made to process archaeological material in inadequate facilities or in the ﬁeld because many of the artifacts are completely converted to corrosion products or deteriorated. and processes artifacts. the only possible documentation is in the form of in situ photographs and measurements from which reconstructions can be made. Conserving the recovered artifacts is just one of the responsibilities. as well as possible retreatment. photographs. their provenances can be recorded and measurements taken in situ can be shown in scaled drawings. a mechanic. Occasionally the most appropriate equipment or facilities are not available and it is up to the conservator to manipulate what is at hand to fulﬁll the necessary requirements. an electrician. bones. an archaeologist. reads the textbook descriptions. the skills of a conservator.320 DONNY L. and time are important considerations. and even a carpenter. In lieu of total conservation. . The decision as to what to treat or not to treat must be worked out with the investigating archaeologist. and particularly. Additional information is recovered by casting the natural molds and impressions found of disintegrated objects. conducts preliminary research on the items. facilities. photographs the artifacts. Occasionally. equipment. chemicals. perhaps it is most realistic to say that the objective of archaeological conservation is to delay reprocessing as long as possible by proper storage and to make any necessary retreatment simple and brief. As one learns the various conservation techniques. as normally deﬁned. At time. Metal artifacts. as well as those made of organic or siliceous material can become chemically unstable from myriad causes and require periodic inspection and evaluation. it is not economically feasible to treat every artifact from a site. that of the archaeologist. a chemist. recorded observations have to sufﬁce. It is this last role. In the process. arranges or conducts various analytical tests. and scaled drawings will have to sufﬁce for the more common specimens and even for some of the less ordinary pieces. Although these specimens are not recoverable. Large objects pose special problems because of the equipment required to process them and the great expense inevitably involved. The conservation laboratory documents the associations. and makes casts of artifacts. At our present stage of knowledge. Only if stored or displayed under optimum conditions can stability be assured. Clearly. in addition to cleaning and stabilizing the material. With the continuing increases in the cost of utilities.
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