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Buzgar N., Apopei A. I., Buzatu A. (2009) - Romanian Database of Raman Spectroscopy (http://rdrs.uaic.ro)


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Alexandru Ioan Cuza UniversityFaculty of Geography and Geology

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34 Hoiseşti L11

Sample image with white and black pigment
large image

You can move the loupe anywhere you want. Also, you can hide the magnifier loupe by clicking the 'switch' button (placed in the bottom of the image).

You have the possibility to zoom in the spectrum by selecting a spectral region you need to be increased (along axis x); to zoom keep the left mouse-click continously pressed, drag (to left or to right) and release the left button. To return to the initial size spectrum, press the right click on the spectrum -> Zoom -> Reset View.

Raman spectrum of white pigment - Raman spectrum of Anatase
Toggle Grid Toggle Coordinates Reverse Spectrum Download Raman spectrum of white pigment .spc or .txt
Legend: white pigment____, anatase____ Download Raman spectrum of anatase standard .spc or .txt
Raman spectrum of black pigment - Raman spectrum of Black Carbon (Isaiia)
Toggle Grid Toggle Coordinates Reverse Spectrum Download Raman spectrum of black pigment .spc or .txt
Legend: black pigment__ and Black Carbon (Isaiia)__ Download Raman spectrum of Black Carbon (Isaiia) standard .spc or .txt
Interpretation of the white and black pigment Raman spectra

However, the large number of spectra acquisitions on the white pigment allowed the detection of some minerals in the kaolinite clay, quartz and TiO2 (rutile and, rarely, anatase). The presence of quartz is indicated by the Raman band at ~465 cm-1, which is the most intense line of quartz. The other Raman bands are hidden by the BN&F.

Rutile gives a good Raman signal, even when it apears as very fine crystals. For this reason, the presence of rutile in the white pigment is obvious, based on the two specific Raman bands (Buzgar et al., 2009).

The presence of TiO2 in the white pigment on artefacts was indicated by Middleton et al. (2005). The analysis of a sample of white paint from a ceramic pot of Roman age, using FT-Raman spectroscopy, indicated that a component of the white paint was anatase.

An issue is the high frequency of appearance of rutile in relation to anatase. We believe that almost all artefacts made of fine ceramics from Hoiseşti were fired at ~900°C, which determined the transformation of anatase into rutile. Another argument which supports this theory is that the black raw ceramics from Hoiseşti present artificial white temper, made of small quantities of white kaolinite clay, where anatase and certainly not rutile is present. Moreover, in this case, the firing process was conducted below 700-750°C (above this temperature, black carbon is destroyed).

The presence of quartz and TiO2 in the kaolinite clay may suggest that the clay used as white pigment has a residual nature, formed by the weathering of igneous rocks. Clay deposits of this kind are very rare and generally occur near volcanic neogen sites (Parva and Cornăiţa - Bistriţa Năsăud region; Haita, Pietrosul and Stejar Valleys – Suceava county).

We believe that the anatase-rich kaolinite used as white pigment during the Roman age (Middleton et al., 2005) is of the same genetic type, many sources of kaolinite clay formed by weathering occuring on the territory of the Roman Empire.

For the raw black ceramic from Hoiseşti (and this sample from Scânteia), the paste used was a clay rich in organic substance. Through the firing process, the organic substance turned into black carbon. The Raman spectra of these samples clearly indicate the presence of black carbon, being similar to the spectrum of a black ceramic sample from Isaiia (Precucuteni culture).

References

• BUZGAR N., BODI G., AŞTEFANEI D., BUZATU A. (2010) - The Raman study of white, red and black pigments used in Cucuteni Neolithic painted ceramics. Analele Stiintifice ale Universitatii “Al. I. Cuza” - Iasi, Tome 56, issue 1 [link]

• Middleton, A.P. , Edwards, H.G.M., Middleton, P.S., Ambers, J., 2005. Identification of anatase in archaeological materials by Raman spectroscopy: implications and interpretation. Journal of Raman Spectroscopy, 36, 984-987.