Manganese Black as an Etruscan Pigment Author(s): Franois Schweizer and Anne Rinuy Source: Studies in Conservation, Vol.

27, No. 3 (Aug., 1982), pp. 118-123 Published by: International Institute for Conservation of Historic and Artistic Works Stable URL: http://www.jstor.org/stable/1506147 . Accessed: 26/10/2011 11:24
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MANGANESE

BLACK AS AN ETRUSCAN PIGMENT

Francois Schweizer and Anne Rinuy

Abstract-Scientific examinationsof a number of black decorationson Etruscanterracottas have shownthe presence of a manganeseiron paint slip (manganeseblack). The blackcolouris mainlydue to the presenceof the spinel jacobsite (MnFe204). This pigment is formed by firing underoxidizingconditionsmanganese-and iron-richclay slips. The manganese black technique therefore differs from the classiciron-reduction significantly technique.Its main advantage is that red and black colours can be obtained in one oxidizing firing-cycle.The manganese black techniquewas first used in the Near East and the Balkans (seventh to first millenium).This contribution reports its occurrencefor the first time in the Etruscan area.

Museum, Oxford, and six objects from the British Museum, London, as indicated in Table 1. The manganese black is formed when manganese- and iron-rich clays are heated under oxidizing conditions to temperatures around 950?-1100?C. In the raw material, manganese is mostly present as pyrolusite (MnO2), a naturally occurring mineral, the iron as haematite or hydroxyoxide. In the firing process the pyrolusite is first converted to bixbyite (Mn203) and combines later with the iron oxide to form a manganese-iron compound (jacobsite MnFe204). MnO2 pyrolusite
-reu

approx. 450?C -.
->

Mn203
I

1 Introduction
In the course of a scientific examination of a decorated Etruscan terracotta head [1] we observed the presence of a black pigment containing both iron and manganese and small amounts of titanium, potassium and calcium. X-ray fluorescence analysis showed that the main constituents, iron and manganese, are present in almost equal proportions. Minute samples were removed and examined by X-ray diffraction. They revealed the presence of three distinct crystallographic phases, namely haematite (Fe203 ASTM card 13-534), bixbyite (Mn,03 ASTM card 10-69) and a manganese-iron compound of the spinel type called jacobsite (MnFe204 ASTM card 10-319). The dark colour of the pigment is due to jacobsite. This black decoration differs significantly therefore in its composition from the classic Attic black pigment, which is obtained by the reduction-firing of iron and potassium-rich clays [2]. Manganese-iron and iron-containing black slipglazes were used in antiquity for the decoration of pottery as early as the seventh millenium, first in eastern Anatolia, later in Thessaly and the southern Balkans [3]. To our knowledge, our examination of the Etruscan head reveals for the first time the presence of this so-called 'manganese black' in the Italian peninsula. We thought it worthwhile to extend our study to more Etruscan objects and so far 15 different artifacts have been examined: four decorated heads from the collection of the Musee d'art et d'histoire, Geneva, three objects from private collections, two tiles from the Ashmolean
Received 5 October 1981

bixbyite
>

MnFe,04
[ jacobsite

-2haematite haematite

t,-fx

=>950?C

The final crystallographic phases of the manganese black depend of course on the manganese-iron ratio and the firing temperature as indicated by the manganese-iron phase diagram (Figure 1).
Oc 1600 1500 1400 1300 1200 1100 1000 900
- 800 - 700

0 100

10 90

20 80

30 70

40 60

50 50

60 40

70 30

80 20

90 10

Mn203 Fe2O3

Figure I

Phase diagram of the Fe203-Mn203

system [4].

From the technological point of view, this black manganese glaze is of importance as it enables the potter to obtain in one oxidizing firing-cycle both black and red colours. The quality of the glaze surStudies in Conservation 27 (1982) 118-123

118

blackas an Etruscan pigment Manganese Table1 Iron: manganese ratiosand phases of manganese black Collection Musee d'artet d'histoire,Geneva Object Head -beard of figureon diadem -hair of figureon diadem -bird on diadem -right eyebrow -right iris -left iris -left ear Antefix -right iris -decoration on diadem Antefix -decoration on diadem Head -right eyebrow -rim of diadem Fragments of architectural tiles Inv. no. 22009 0-42:0-52 SP, B, HE 0-72:0-28 nd 0-48:0-52 nd 0-54:0-46 SP, B, HE 0-72:0-28 nd 0-67:0-33 nd 0-63:0-37 nd MF 794 0-72:0-28 nd 0-50:0-50 nd MF 782
0-70:0-30

Fe:Mn Phases weightratio

Colour

Lab. no. LMAHG 78-57

black black black black brown-black brown-black black 77-5 black black 79-111 black 79-110 black black black black black black black darkbrown RLBML 14105X 14104Z 14101U 14100W 14102S 14103Q LMAHG 80-633-1 80-633-2

nd

MF 402 0-63:0-37 0*59:0-41 SP, HE, (B) B 610-7 0*66:0-34 B 610-4 0*34:0-66 B 626.20 0*76:0-24 B 626-22 0-38:0-62 B 626-11, 12, 13 0.57:0-43 B 594 0-8 :0-2 1920-255 1876-61
0-52:0-48

BritishMuseum, London

Antefix AshmoleanMuseum, Antefix Oxford Tile

SP, HE SP SP, HE SP SP, B HE

SP black 0-69:0-31 HE, d values slightly Y higherdue to of incorporation Mn in HE lattice

Privatecollections, Head Geneva -eye -hair -ear Fragmentof a tile Brick

0-68:0-32 nd
0-57:0-43 0-42:0-58

SP, HE, B 0-40:0-60 SP, B 0-30:0-70 B

black black black black

black

LMAHG 80-290 80-739 80-291

Key: SP = spineljacobsite,B = bixbyite,HE = haematite,nd = not determined.

face is, however, inferior to that of the classical iron-reduction technique. This may well explain why the Etruscans used the latter for the decoration of larger areas, such as statues or vases, and the manganese black technique for the decoration of small areas (eyebrows, iris on heads or decorative elements on tiles and bricks). 2 Analysis of the black decoration of Etruscan terracottas 2.1 Experimental The iron-manganese ratios of the black pigment 27 Studiesin Conservation (1982) 118-123

were analyzed by X-ray fluorescence spectrometry, using an energy dispersive system, at 25kV and 0.6mA [5]. The observed peak height ratios for Fe ka and Mn ka were converted into Fe:Mn weight ratios using a specially prepared calibration graph (mixtures of Fe2O3 and Mn203 powders). The crystallographic phases were examined by removing a very small sample, which had previously been analyzed by X-ray fluorescence. This sample was mounted on a fine glass rod and a powder pattern was obtained in a Gandolfi Camera of 114-5mm 0 at 30kV and 14mA, using unfiltered Fe radiation. As the same pigment grain was examined by both tech119

and FrancoisSchweizer Anne Rinuy lines of manganese black (sampletakenfrom the left eyebrowof an Etruscan head.Inv. No. Table2 X-ray diffraction camera114-5mm0, 30kV, 14mA,10 hours,Fe Museed'artet d'histoire 22009, Laboratory sample78-57 004). Gandolfi radiation. Pigment d (A) 5-65 4-92 4-27 3-70 3.43 3-36 3-00 2-70 2-55 2-12 1-64 1-54 1-49 1-38 1-29 I 5 3 2 1 5 10 3 2 8 3 3 3 3 2 2 Jacobsite MnFe204 ASTM 10-319 I d (A) 4.91 (20) 3-84? 3-01 2-56 2-12 1-64 1-49 1-29 (35) (100) (25) (35) (40) (29) (25) 3-34 2-72 1-66 (100) (30) 2-69 1-69 (100) (60) (100) Bixbyite Mn203 ASTM 10-69 d (A) Haematite Fe203 ASTM 13-534 I d ) Quartz SiO ASTM 5-490 I d( d(A)

4.26

(35)

1-54

(15)

niques, Fe:Mn ratios and crystallographic phases are directly comparable. From different objects, small fragments of the manganese paint could be removed and studied as cross-sections first by optical microscopy and later with the scanning electron microscope (this work was kindly carried out by Mr R. Wessicken of the Laboratorium fur Festkorperphysik of the Eidig. Technische Hochschule in Zurich). 2.2 Iron:manganese ratios and crystallographic phases In Table 1 we listed the Fe:Mn weight ratios and the phases of the objects which have so far been examined. As can be seen, the Fe:Mn ratios vary sometimes up to 30% on different areas of the same object, due to the inhomogeneity of the raw material. In general, the ratios are between 0-72 Fe:0-38 Mn and 0*30 Fe:0.70 Mn. We observed the presence of the following phases: haematite (Fe203), bixbyite (Mn203) and the spinel jacobsite (MnFe204). Further, we noted the presence of quartz (SiO2) and sometimes calcite (CaCO3). A typical example of the observed X-ray diffraction lines is listed in Table 2. Manganese black samples, which contain a low proportion of manganese, show only the pattern of haematite, as it can absorb up to 10% of manganese without changing its structure. The introduction of the larger manganese ion results in an extension of the haematite lattice and, therefore, slightly higher d-values in the powder diffraction pattern [5]. 120

In order to estimate the firing temperature range of the manganese black we compared, as suggested by Noll [2], the Fe:Mn ratios and the corresponding crystallographic phases of the samples with the phase diagram (Figure 1). The firing temperature range can be estimated by seeing at which temperature the observed Fe:Mn ratios and phases agree with the 'theoretical' phases of the diagram. Results indicate that the firing temperature must have been between 950?C and 1100?C. 2.3 Morphology The Etruscan manganese black paint appears under the binocular microscope as a slightly sintered, porous layer. Examination with the scanning electron microscope confirmed this observation. The paint slip has been applied directly to the unfired clay surface (Figures 2-4). Cross-sections of the paint layer show that the thickness of the layer varies between 40/, and 80,S. These values are considerably higher than those reported by Noll [2] for Near Eastern material. Underneath the slightly sintered surface layer of approximately 2-4Ac there are larger dark grains. This inhomogeneity of the paint layer composition was confirmed by X-ray fluorescence analyses. It therefore seems likely that the paint layer was prepared with a naturally occurring earth mineral of variable composition and not with an 'artificially' produced pigment. Deposits of manganese-rich minerals are still exploited in the small town of Gambatesa, close to La Spezia [6]. 27 Studiesin Conservation (1982) 118-123

Manganese black as an Etruscan pigment

Figure 2 Manganese black and iron oxide red decorations on an Etruscan brick (private collection, Geneva, LMAHG No. 80-291).

ferent mixtures of Fe203 and Mn203 powders, to which 10% of clay powder had been added. These mixtures were applied to leather-hard unfired clay slabs and heated to temperatures between 700? and 1100?C. The resulting paint layers were examined for their colour, and X-ray diffraction patterns were taken. Simultaneously, we fired pure Fe203 and Mn203 paint slips. Up to 900?C there was no apparent change in the colour of the grey-red iron-manganese oxide mixture. At 1000?C this sample was black and the intensity of the black increased only very slightly by heating it up to 1100?C. X-ray diffraction analysis of the different samples showed that the appearance of the black colour is linked with the formation of the iron-manganese spinel jacobsite. Figure 5 shows the X-ray diffraction patterns of four samples, heated for one hour to 800?, 900?, 1000? and 1100?C. Up to 900?, we observed the lines of haematite and bixbyite.

Figure 3 Polished cross-section of a manganese black paint layer. Note the dark grains. (Head, LMAHG No. 78-57.)

tigure 5 X-ray diffraction patterns of iron- and manganese-oxide mixtures (1:1) heated to different temperatures. (a) 1 hour at 800?C (haematite and bixbyite); (b) 1 hour at 900?C (haematite and bixbyite); (c) 1 hour at 1000?C (jacobsite, haematite and traces of bixbyite); (d) 1 hour at 1100?C (jacobsite and traces of bixbyite).

Figure 4 Surface structure of manganese black paint (scanning electron microscope). Left: edge of fractured paint chip. Note the very thin 'sintered' surface layer. Right: surface of paint layer. (Head, LMAHG No. 78-57.)

The powder pattern changes completely at 1000?C. There are only traces of haematite and bixbyite and strong lines of the spinel jacobsite. The iron oxide develops a full red colour in the firing process. 4 Identification of manganese black

Reproduction of manganese black

We reproduced the manganese black decoration technique by firing under oxidizing conditions difStudies in Conservation 27 (1982) 118-123

Manganese black decorations can easily be identified by X-ray fluorescence analysis. The Fe ka and Mn ka peaks are well separated and their relative intensity ratios vary between 1:1 and 1:0-2. Apart from this non-destructive test, the presence of 121

FranCois Schweizer and Anne Rinuy

manganese may be shown by optical emission spectroscopy (strong lines at 4034-49A, 4033.07A, 4030-75A and 2576-10A). Most of the manganese black pigments show in their X-ray diffraction pattern the lines of jacobsite (ASTM card 10-319). At low Mn-contents, only the lines of haematite are present (see 2.2). At high Mn-contents, bixbyite and hausmannite (ASTM card 16-154) may be present as well. Optically, it is difficult to distinguish a good manganese black paint layer from a poor iron reduction glaze. 5 Discussion

Laboratory of the British Museum by kind permission of Dr M. S. Tite, Keeper. Mrs A. Brown was very helpful in showing us the collection of the Ashmolean Museum in Oxford and giving us permission to sample two objects. Mrs F. Cottier-Angeli kindly lent us one Etruscan brick. We thank Prof. Dr Noll for his interest in our work and Dr C. Lapaire, Director of the Musee d'art et d'histoire, for his encouragement. References
1 SCHWEIZER, and RINUY, A., 'De l'authenticit6 F. d'une tete etrusque', Revue d'Archeometrie,

The present contribution shows that manganese black was used in Etruscan times as a painting pigment on terracottas. It seems, so far, that its use was restricted to small areas, larger ones being decorated with the traditional iron-reduction technique. The paint slip was applied to the unfired dried ware, and fired under oxidizing conditions. By combining it with iron oxide paint slips, red and black colours were obtained simultaneously. Noll has shown that the manganese black technique was first applied in the Near East and later on in Cyprus, the Balkans and eastern Greece [2]. It would be interesting to study why this technique turns up suddenly in the Etruscan area. So far, no examples have been reported from the Peloponnese and southern Italy. As Noll correctly points out [2], the application of this technique may well be linked to the occurrence of manganese-rich deposits. The use of natural earth minerals rather than refined artificially prepared pigments is corroborated by the heterogeneity of the paint layer. The firing temperature of the pottery decorated with the manganese black can be estimated by the iron-to-manganese ratio and the phases with the Fe203-Mn203-FeMn204 phase diagram. Practical experiments have shown that the evaluated firing temperature must have been higher than 900?C. The phase diagram is of limited validity only, due to the presence of earth and clay minerals in the paint layer [7]. Further, it must be kept in mind that we are dealing with heterogenous raw material, and that the firing time may well be too short to establish an equilibrium by diffusion. In the cross-sections, the presence of manganese-rich inclusions was observed. Acknowledgements We are grateful to Mr B. F. Cook, Keeper, Department of Greek and Roman Antiquities, British Museum, for giving us permission to have six objects analyzed. The analyses were carried out by Miss M. Bimson and Mr M. R. Cowell of the Research
122

1981 IHI(1980) 273-284. Supplement 2 NOLL, W., 'AnorganischePigmente in der Vorgeschichte und Antike', FortschrMiner. 57 (1979) 203-263. 3 NOLL, W., HOLM, R., and BORN, L., 'Manganschwarz-Malerei eine Technik der Omamentierungantiker Keramik',Ber. Deutsch 4 MUAN,A., and SOMIYA, SH., 'The system iron oxide',Amer.J. Sci. 260 (1962) oxide-manganese 230-240. 5 MCANDREW, 'The cell-edge of jacobsite',Amer. J., Min. 37 (1952) 453-460. 6 UsoNI, L., Installations preparation minerais de des en Italie, Centro di Studi per la preparazionedei minerali,Roma (1963) 53-54. 7 BIMSON, privatecommunication. M., engineeringin 1965 in Zurich.From 1965-67, Research Chemist with Sandoz Ltd, Basle; 1967-69, Research Chemistat the Institutefor InorganicChemistry,Zurich University;1969-73, ResearchAssistantat the Research Laboratoryfor Archaeology, Oxford University. From 1974, Head of the Laboratory and Keeper of Geneva.Fellowof Museed'artet d'histoire, Conservation, IIC. Author's address: Musee d'art et d'histoire, 9-11 rue du Clos, 1207 Geneve,Switzerland. Laboratoire, in 1971 fromthe University Geneva.From1971-74 she of servedas ResearchAssistantat the Instituteof Pathology doing researchin immunology.In 1976 she joined the ResearchLaboratoryof the Musee d'art et d'histoirein Author's Geneva, where she is a ResearchCollaborator. address:as for Schweizer. la des Resume-A l'analyse, peinturenoireddcorant terres
ANNERINUYreceived her degree in chemical engineering SCHWEIZER received his degree in chemical FRANCOIS Keram. Gesell. 50 (1973) 328-333.

cuites etrusques s'est revelee etre composee d'une argile h

base de fer et de manganese(noir de manganese).La couleur noire est due au spinelle jacobsite (MnFe2O4), pigmentforme au cours de la cuisson oxydante d'argile richeen oxydes de manganese(Mn203)et de fer (Fe,03). La techniquede peinture au noir de manganesediffere doncnettementde la techniqueclassiqueconsistant une en reductiond'oxydes de fer. Le principalavantage reside
Studies in Conservation 27 (1982) 118-123

Manganese black as an Etruscan pigment

dans le fait que les couleursrouge et noire peuvent etre au obtenuessimultanement cours de la cuissonoxydante. La techniquede peintureau noir de manganese6taitconnue au Proche Orient et dans les Balkans oi elle a et6 av. utilis6edu 7e au ler mill6naire J.-C. Cette etude mentionne pour la premierefois son utilisationegalementpar les Etrusques. Zusammenfassung-Eine Untersuchung von einigen schwarzen Malschichten auf etruskischen Terrakotten ergab, dass diese aus Manganund Eisen enthaltendem Tonschlickerbestehen (Mangan-Schwarz). schwarze Die

Malschicht enthalt meistens das Pigment Jacobsit (MnFe204)neben Bixbyit(Mn203)und Hamatit(Fe203). Die schwarzeMalschicht wird beim oxydierendenBrand von Tonschlicker gebildet,die Manganund Eisen enthalten. Die Mangan-Schwarz Technik unterscheidet sich deshalb deutlich von der klassischen Eisenreduktions Technik. Sie bietet den Vorteil, dass rote und schwarze Farbtonesimultanin einem oxydierenden Branderhalten werdenkonnen.Die Mangan-Schwarz Techniktrittzuerst im Nahen Osten und dem Balkan auf (7.-1. Jahrtausend v.Chr.). Diese Mitteilungberichtet zum estenmale von ihremGebrauchim etruskischen Raume.

Studies in Conservation 27 (1982) 118-123

123