Magnetita en Falcatas

7/25/2019 Magnetita en Falcatas

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L. Garca*, A. Javier Criado*, Antonio J. Criado*, J. Chamn*, F. Penco*, J. Alonso***, R. Arvalo****,J.A. Martnez* and C. Dietz**

A-,a! A metallographic study of two pre-roman Iberian arms, affected by a cremation process, revealed the presence ofan outer magnetite layer, providing highly protective properties. This layer is extraordinarily tenacious and of veryhomogeneous thickness, indicating an intentional manufacturing process rather than an accidental formationduring the severe heating/cooling cycles the artefact suffered. Up to date, the intentional production of these typesof layers has been attributed to a welding process of three different metallic sheets, here an alternative model is

proposed, allowing, as could be simulated in the laboratory, the virtually exclusive formation of a magnetitecoating.

K#+,"- Iberian armoury; Early iron; SEM; Falcate; Artificial magnetite layer; Archaeometallurgy.

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R#-/#* Se presenta un estudio metalogrficos de dos armas prerromanas afectadas por un proceso de cremacin. Las armasposeen un recubrimiento exterior de magnetita que las confieren unas altas propiedades de proteccin frente a lacorrosin. Esta capa es extraordinariamente tenaz y posee un espesor muy homogneo, indicando que son productode un proceso de fabricacin intencionado ms que una formacin accidental durante los varios ciclos de calenta-miento/enfriamiento que han sufrido los objetos. Hasta la fecha, la produccin intencional de este tipo de recubri-

mientos ha sido atribuida a un proceso de soldadura de tres lminas metlicas diferentes. En este trabajo se proponeun modelo alternativo de formacin, el cual permite una simulacin en el laboratorio en la que se forma exclusiva-mente una capa de magnetita.

Paa,a- !a# Armamento ibrico; Edad del hierro; MEB; Falcate; Capa de magnetita artificial; Arqueometalurgia.

1. INTRODUCTION

The Iberian culture basically covered the easternand southern coasts of the Iberian Peninsula, inbetween the 5th and 1st century B.C., reaching asnorthern limit the river Herault in France[1 y 2]. Theterm iberians is thus associated with people livingduring Iron Age II in Andalusia and the Mediterraneancoastal zone of Spain. The origin of their name ispossibly due to the river Iber or Iberus, today identifiedas Ebro, though first historical reference to the Iberianssettling at the coast of Huelva were already made beGreek colonists. Intense trading contacts with the

Phoenicians, Greeks, and Carthaginians could beverified. Finally, when the Roman Republicsubsequently conquered the Iberian Peninsula, theynearly completely absorbed the local culture andlanguages of the Iberian communities.

These tribes practised nearly exclusively cremationburials, where the body was burned together withpersonal belongings such as weapons or endowmentobjects. Consequently, in a warriors grave from anIberian necropolis, it is frequent to discover, remainsof the incinerated body and objects used by theindividual in life. The most characteristic Iberianweapons were defensive arms like shields, greaves

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or helmets combined with offensive ones such asfalcatas, lances, and different types of javelins, aspilum or soliferreum[3-5].

These weapons were recognised and documentedby the roman armies as quite sophisticated andpowerful due to its elevated steel quality andproperties[6-11] during the conquest of the IberianPeninsula, in turn causing reinforcement of thestandard equipment of roman legions.

For manufacturing of the steel, raw steel plateswere buried up to three years where weakened partsof the metal corroded, the remains were used forforging of the falcata. The blade was usually thenmade of three laminas of the obtained material in abloomery, which is a furnace operated at lowtemperature where carbon monoxide resulting from

incomplete combustion of charcoal reduces ironoxides to metallic iron without melting the material.The material was forged above its recrystallizationtemperature, followed by a normalised cooling at air.In case the blade used fullers, these were also hotforged. When inlets were foreseen, engraving wascarried out at room temperature using a burin, therelieves were after completion of the workpiece filledwith precious metals, silver, gold or bronze. Finally,the artificial magnetite layer was created[12-18].

On many of those weapons recovered fromarchaeological sites up to date, a superficial magnetite

layer can be distinguished[19-23]

. As this oxide layerprovides excellent anticorrosive properties, manyiron specimens have remained in excellent conditionsof conservation. Whether these layers were producedintentionally on a large scale is currently topic ofscientific discussions, but relatively few referencescan be found in the specialised literature. This may

be partly due to that, during classical interventionsof excavation and restoration, these layers wereoften mistaken as natural oxide formed by habitualcorrosion processes in irons of archaeological origin.An incorrect interpretation of the presence ofmagnetite thus not only affects the perception wehave regarding early Iberian metallurgy, but alsocompromises the intervention strategy to be chosenfor restoration and conservation of such artefacts.Taking into account the quantity of similararchaeological findings belonging to the pre-romanperiod of the Iberian Peninsula, it seems quite likelythat most of Iberian and Celt Iberian arms may haveonce been coated with a black magnetite patina[24],upon which often inlay work was carried out in silver.Generally, these type of weapons are found in

necropolis, but numerous artefacts were also recoveredfrom a different archaeological context. Thosepresenting a worse degree of conservation are usuallysuffered cremation processes and were later on buriedin a geochemically aggressive environment.

In the present work the metallographicinvestigation on two typical Iberian arms is presented,a falcata from the Museum of Armory in lava,Spain, (Fig. 1) and a pilum from the Copper Museumin Cerro Muriano, Crdoba, Spain, (Fig. 2).

Both have, though in different grades ofconservation, the presence of a magnetite layer of

faint black colour. The chronology of the samplesoscillates between the 5th and 2nd century B.C.Up to date, the intentional production of these

types of layers has been attributed to a weldingprocess of three different metallic sheets [24], herean alternative model is proposed. The objective isto contribute to the development of an adequate

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methodology for characterisation of the morphologyof natural and artificial magnetite layers and toinvestigate which procedures and techniques couldhave been applied by Iberian craftsman in order toobtain this type of surface protection. The techniquesemployed for this purpose were Scanning ElectronMicroscopy (SEM), conventional optical microscopy

and Electron Probe Micro Analysis (EPMA).Subsequently, the production process was simulatedunder slightly oxidising conditions with the aim toobtain a uniform, tenacious and adherent magnetitelayer similar to those present on the archaeologicalsamples.

2. EXPERIMENTAL

The studied samples were taken from different,

representative zones distributed over the weaponsunder investigation (Figs. 1 and 2). With the pillumit would have been necessary to sample at the tip,the only zone where the magnetite layer was stillunaltered, but this would have caused irreversibledamage to this valuable archaeological sample andhad to be therefore discarded. For metallographicobservation they were embedded in polyester resinand conventionally grinded and polished (from a(0.3 m) to g (0.03 m, Buehler). The sample surfacewas then etched with a 4 % (m/V) ethanolic solutionof nitric acid for 15 s. For examination of the metallic

structure using SEM, the ancient steel sampleswere additionally gold sputtered because they wereembedded in resin. The SEM was coupled with anEnergy Dispersive X-ray (EDX) detector, providing

additional information on chemical composition.For EPMA analysis the embedded specimen wereused without sputtering.

In order to prove the viability of an intentionalformation of a protective magnetite layer, a laboratorysimulation of this process was carried out. Boronoxide(B2O3) was used as fluxard, applying furnace

temperatures between 800 and 1100 C at differenttimes. For the study of iron oxide formation (wstite,hematite, magnetite), a steel likewise to thoseavailable during pre-roman times in the IberianPeninsula has been used, in particular a DIN 17210material with a carbon content (mass percentage)ranging from 0.12 % to 0.18 %.

3. RESULTS AND DISCUSSION

Macroscopic surface observation by optical andscanning electron microscopy proves that bothIberian samples, the falcata and the pilum, werecovered by a magnetite layer. In the first case, thismagnetite layer can be easily distinguished andremains almost intact over the whole surface of theoriginal item (Figs. 3, 4 y 6), in the second, thislayer survived intact only in the zone round thespearhead. Possibly the cremation temperatureswere considerably different and in the case of thepilum were that high, that most of the artif icialsurface layer was braking off, with exception of a

zone close to the top point.The magnetite layer was attributed to anintentional creation rather than to the presence ofan evolution surface corrosion consisting in arbitrary

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changes in morphology and composition caused byphysical-chemical variations of the surroundingsoil. Artificial magnetite layers show strong adherenceand impermeability against compounds of atmosphericor geochemical origin, further they possess a tenacity

nearly equal to that of the base steel. These propertiesprovide a notable protection against corrosion,including during long term burial. The presence ofthese type of coatings in archaeological findingsmay be further characterised by:

A black or dark gray colour with bluish shade.It can be finished in matt colour by polishing,acquiring an intense brilliancy with metallictint.

Composed by a very homogeneous magnetite(Fe3O4) layer, though other iron oxides

directly superposed on the basis steel may bedetected. These are result of electrochemicalcorrosion due to penetration of electrolytespresent in the surrounding soil in which theitem was buried, because the outer layer,though providing efficient protection, maypresent pores to some extent.

An external coating, similar to a coveringskin or membrane, perfectly reproducingdesigns or relieves worked onto the basissteel surface.

Very uniform thickness in cross sections,

though found values may vary from 50 - 100micrometers. Nevertheless, a post depositionalprocess of fluid accumulation beneath thesurface, or in one or more cavities is likely

to take place, causing higher thickness. Thisin turn may cause descaling of the material.

Its crystallographic microstructure is regularand uniform, developing a growth from thenucleus in radial or column shaped structuralcomponents.

Shows good adherence, tenacity and thermaldilatation coefficients similar to those ofiron (Pilling-Bedworth ratio between 1 and2 value) figure 5. During magnetite formationits volume is virtually equal to that of thesubstrate. This prevents fissures and

detachment of the outer layer. A direct relation in between the degree ofcorrosion of the basis steel and the fractureand/or deformation of the outer magnetitelayer (and the accumulation of externalcorrosion products) can be observed.

The material is hard and tenacious, not easyto graze or to chafe and capable to supportmoderately intense impacts.

Unintentional magnetite formation during thecremation process could also been excluded, first

because temperature and chemical conditions duringthe process do not favour the formation of a compactand homogeneous magnetite layer formation andsecond, because the conditions during cooling

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would have produced a quite different grain sizedistribution in the outer layer.

Assuming the before mentioned points, we believethat it is possible to establish a sequential typology

of variations in topography by characterisingmorphostructural changes in the evolution surface.This in turn could provide a powerful tool in orderto identify the presence of artificial magnetite layers,including at rather corroded metallic remains.

In spite of being rather continuous, homogeneousand compact, the magnetite layer possesses certainporosity, as can be seen in figure 6 a). Through thesepores electrolytes may penetrate from the soil inwhich the burial was carried out, producing corrosionof the metallic nucleus underneath the protectivelayer[25 and 26]. This effect can be observed in figure1A-

6 d), where the oxidation occurred over millennia,though not severe due to the protective properties ofthe magnetite layer, in some areas has producedcorrosion which in turn caused detaching of the

magnetite layer from the nucleus. Here, the tenacityof the artificial magnetite successfully preventedfracture of the layer in spite of suffering enhancedinterstitial pressure caused by the higher volume of

oxidation products. Nevertheless, a cremation processmay cause partial or complete detachment of thislayer.

The metallic nucleus of both pieces have, withslight differences, rather similar structures. Theyexhibit an idiomorphic needles of iron carbidestructure type Widmansttten, which is typical aftercremation, though with higher quantity in the pilumthan in the falcata (Figs. 7 y 8). Upper temperaturelimits achieved during a cremation process can bevery high, reaching about 950-1000 C, as provenby investigations on incinerated bones, melted

bronze, etc.[27-32] found in cremation burials. Thestructure type indicates that the cooling of theweapons occurred using severe temperature gradients,leaving at room temperature carbon saturated

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quenched ferrite. The solubility of carbon in steel atambient temperature is only 0.008 % in weight, thisfact provokes, over thousands of years, precipitationin these typical structures[33]. The nature of these

precipitates was subject of discussion over the lastdecades, being the most accepted hypotheses aniron carbide or nitride. Some researches, e.g.Piaskowski and Broker et al postulated iron nitride

compounds, due to either the nitrogen content ofthe proteins forming part of the incinerated body orto that the object has been heated in contact withcombustion material containing ammonia, such as

animal dung. In 1984, a team from Lehigh andPennsylvania University[33], making use ofTransmission Electron Microscopy (TEM), establishedthat in fact these precipitates are iron carbide. This

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finding is in-line with the results of EPMA analysis

carried out within the present study (Fig. 9).Another interesting fact which could be detectedis related to the process of artificial magnetiteformation, as mentioned above abundant in Iberian

armoury, though only in the case of the metallic

structure belonging to the falcate sample.Observing the SEM images shown in figures 10and 11 at low magnification, it can be clearly seenthat the grain size of the ferrite crystals is much greater

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at the outer than in the inner zone. The areas sufferingmore intense deformation after the process of hotforging of the blade were the external ones, which isgenerally happening in plastic deformation of steelsand metals[34]. If a metal is exposed to elevatedtemperatures, recrystalisation accompanied by excessivegrain growth occurs in those areas which are moreintensively deformed. This is the case of the Iberianfalcate, where recrystalisation and intense graingrowth are due to heat exposure subsequent to theforging process, applying high temperatures andelevated time with the objective of obtaining a highly

tenacious, temperature stable magnetite layer ofappropriate thickness. In order to obtain a suchprotective and adherent layer, the work piece has tobe covered with a fluxard based on refractory clay,

thus preventing an excessive oxygen content whichwould bias the reaction towards Fe2O3 formation, aporous and less adherent material[35 and 36].

As Criado, Juez-Lorenzo and Kolarik say inprevious works not only oxidation of i ron to itscorresponding oxides takes place, but also reductionprocesses due to partial decarburation of the basissteel[36-39]. At high temperatures, the equilibriumbetween Fe2O3 and Fe3O4 within the Fe-FeO-Fe3O4-Fe2O3, system, is shifted towards the latter, due toreduction of Fe2O3 by means of CO, which is formingwhen carbon dissolved in the basis steel diffuses to

the surface during the decarburation process.Results of experiments carried out in a temperaturechamber X-ray diffractometer to understand theformation of oxides in steels[36-39] can be summed up

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in these terms: Low oxygen pressures enhance theformation of Fe3O4 and prevent the formation ofFe2O3. At normal oxygen condition, does not start

the formation of Fe2O3 during the evolution of Fe3O4since 570 C but only appears in minimal quantities.It is only from 800 C when Fe2O3 when starts itsformation in significative manner.

The analysis of archaeological samples detectmagnetite, as well as in the laboratory simulationusing boronoxide as a fluxard, therefore it ispresumable that a sort of clay was used to preventthe massive diffusivity of oxygen when the magnetitecoating was manufactured in the archaeologicalobjects.

Nearly exclusive magnetite formation in thesimulation was obtained at retention times between15 and 30 min, exceeding this period, growth of aFe2O3 occurred. Optimum conditions for magnetiteformation were found to be a temperature of 950

C and a retention time of 15 min. After polishing,the outer layer presented a matt black colour withmetallic lustre. Once cooled down, its adherenceto the basis steel was strong enough to sustainmoderate strokes with a forging hammer.

As shown in figure 12, highly adherent andtenacious magnetite layers of different thicknesseswere obtained. Magnetite possesses a dilatationcoefficient similar to that of iron, this facilitates goodadherence properties. In spite of having suffered acremation, the magnetite layer of the falcata is basicallyintact and has lost adherence only in a small

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proportion, the latter most possibly not by impact ofheat but by subsequent corrosion processes duringthe 2.000 years the artefact was buried.

When observing the falcate sample the

decarburation of the surface suffered is clearly shown.It is distinguish because appears different quantitiesof iron carbide between the core and the externalzone. This is due to the gradual diffusion of theprocess.

4. CONCLUSIONS

Macroscopic observation of the artefactsdetermines that both falcata and pilum, werecovered by an artificial magnetite layer.

This finding suggests the hypothesis that themajority of similar pre-roman Iberian weaponsmay have been treated in the same manner,producing a protective superficial layer. Casesin which the presence of this layer could not beconfirmed may be due to that their degree ofconservation was not adequate or that remainsof the layer were removed during previousrestoration campaigns, when the presence of anintentional magnetite layer was still not understudy. This hypothesis will need further researchand systematic study of more Iberian armoursto be confirmed.

The recrystalisation behaviour of the falcatasuggests that the artificial magnetite layer hasbeen formed by heating at high temperatures,applying a fluxard based on refractory clay inorder to control oxygen uptake and to assure atenacious and thoroughly attached magnetitelayer upon the metallic substrate. Both samplesshow needle-like precipitations of iron carbidewith Widmansttten structure inside ferriticgrains, typical for steel specimen exposed to

cremation processes. EPMA analysis furthermoresupports the theory that the nature of theseprecipitates is iron carbide instead of iron nitride.

Natural corrosion did not significantly affect theareas of the arms where the magnetite layer keptmore or less intact after the cremation. The pilumis in worse conditions of conservation due to thefact that this layer remained only in a zone closeto the tip of the, meanwhile over the rest of theartefact the layer detached during cremation.

Future investigation will be focussed on trying toclarify whether this technique can be classified

as genuine Iberian or whether it was adopted bypreroman tribes in contact with the Celts. Ongoingstudies are as well centred on a more detailedinvestigation of the magnetite production process

itself, e.g. which clays were originally used asfluxard and at which temperatures. In this contextareas in the Spanish Peninsula where thistechnique is still in use will be studied. As example,

Sierra Morena in Andalusia may be mentioned,where herdsmen still fabricate bells for cattleand goats in that manner.

A!'*+#"%##*-

The authors want to thank to Alfonso Rodrguezand Alfredo Fernndez, from the Centre for ElectronMicroscopy Luis Bru of the Complutense Universityfor providing help and advice concerning SEM/EDXand EPMA data.

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