Original version or not: PIXE-RBS testing of a Meissen porcelain box

Introduction: The valuation of an artistic object depends decisively on its complete originality. Regarding the 18th century snuffbox, made from Meissen Porcelain, restorers ask the following question: Are both the base body but also the hinged cover originals?

Visual discrepancies concerning especially the shade of porcelain glazing raised doubts. In addition, the onglaze decorations show slight differences in colour and flow. Assured non-destructive materials analysis was in demand to clarify the problem.
External Ion Beam Analysis: The 4-MeV proton beam used in atmosphere and PIXE (Particle Induced X-Ray Emission) simultaneously with RBS (Rutherford Backscattering Spectrometry) for analysis [1,2] proved ideal to get convincing answers. Visible marks due to the beam spot (1 mm2) on the highly sensitive porcelain were avoided by using only 200 pA beam intensity and 30 s irradiation time.
Similarities and differences:
Ornamental painting. The ancient Meissen onglaze colour palette is well-known since decades [3]. In conformity with [3] the artist used the pigment copper green for leaves of trees painted on both bottom and cover (point a). However, the green colourant of the cover contains Co and Zn, not obtained in the X-ray spectrum from the bottom. According to [3] Meissen copper green was made from Cu or brass, an alloy of Cu and Zn, which are both reduced to ashes. The addition of Co is mentioned [3] for getting special shaded green paint. Whether or not such characteristic differences are also present in the case of the crimson clothes can not be revealed. Indeed, the PIXE spec-trum taken from the pink gown on the cover (b) shows signals from Au, to be characteristic for purple [3]. Corresponding low-intensity Au-peaks cannot be identified for the pink skirt painted on the bottom. This is because of the superimposed high-intensity Pb L lines due to another type of glazing.
Porcelain glazing. The bottom comprises comparatively thick lead containing glazing, hence intense Pb-L signals are found in the PIXE spectrum.

The number of lead atoms inside the glazing of the cover (c) is much lower. The latter gets reflected also by comparing Pb-Lγ in the presented PIXE spectra taken from the green leaves painted on glazing. Moreover, RBS taken from pure glazing of the cover makes clear that the few Pb atoms are situated on the glazing surface. This is understandable when supposing Pb to originate from a surface polishing process using Pb containing polish agent. The discussed difference in glazing of cover and bottom and especially the considerable Pb-content of the latter, assumable to be bond as lead oxide, clarifies the apparent discrepancies of shades.
Unfortunately, unglazed positions had not been avail-able for getting compositions of the porcelain body.
Conclusions: Cover and base body of the porcelain box can not be related to one and the same workmanship. The cover was certainly later on replaced or it represents completely a later additive. Despite of differences regarding the green pigments of porcelain paints used on bottom and cover, the box fit the typical Meissen onglaze colour technology. Therefore, the question - original version or not - must be answered by the statement: Certainly not, but there is no doubt concerning original Meissen handcraft.
References: [1] Neelmeijer C. et al. NIMB 118 (1996) 338-345. [2] Neelmeijer C. and Mäder M. NIMB 189 (2002) 293-302. [3] Mields M., Kerami-sche Zeitschrift 8 (1963) 453-459.