Theodosia Stratoudaki

Pigment identification in painted artworks: a dual analytical approach employing laser-induced breakdown spectroscopy and Raman microscopy

The combined application of two laser-based analytical techniques—laser-induced breakdown spectroscopy (LIBS) and Raman microscopy—for pigment identification on painted artworks is demonstrated. Detailed spectral data are presented from analyses performed on a 19th century Byzantine icon, which was examined in order to identify the pigments used in the original painted structure, as well as in interventions carried out subsequently for restorative purposes. LIBS measurements yielded elemental analytical data which suggest the presence of certain pigments and, in addition, provide information on the stratigraphy of the paint layers. Identification of most pigments and of the materials used in the preparation layer was performed by Raman microscopy.

Analysis of pigments in polychromes by use of laser induced breakdown spectroscopy and Raman microscopy

Abstract Two laser-based analytical techniques, Laser Induced Breakdown Spectroscopy (LIBS) and Raman microscopy, have been used for the identification of pigments on a polychrome from the Rococo period. Detailed spectral data are presented from analyses performed on a fragment of a gilded altarpiece from the church of Escatron, Zaragoza, Spain. LIBS measurements yielded elemental analytical data which suggest the presence of certain pigments and, in addition, provide information on the stratigraphy of the paint layers. Identification of most pigments and of the materials used in the preparation layer was performed by Raman microscopy.

Yellowing effect and discoloration of pigments: experimental and theoretical studies

Abstract Two issues of great interest in the field of lasers in artwork conservation are the so-called yellowing effect and the discoloration of pigments. We have viewed these issues from a comprehensive point of view, considering all our present experimental results as well as ongoing modeling and theoretical calculations. The first concern to be discussed is the yellowing effect in laser cleaning of marble or stone artifacts. Although, in most cases, a yellowish layer exists underneath the black encrustation, the so-called ‘patina’, it has become clear that there are situations where yellowing cannot be attributed to an existing layer. In the present study, a light scattering model that may account for the yellowing is presented. This model considers a thin absorbent layer and the surface roughness and/or created voids and accounts for the reflectance spectra measured by (i) hyper-spectral imaging and (ii) integrating sphere. Additional experimental data, such as the absence of yellowing when the third harmonic of a Q-swihed Nd:YAG laser is used, support this model. A thorough understanding of the quantitative characteristics of pigment discoloration, on the other hand, has been attempted by means of X-ray diffraction and theoretical studies. The model developed suggests a nucleation process for cinnabar resulting in a structural modification within the volume of a pigment’s crystal or particle close to the ‘ablation front’, which extends for a few nanometers from its surface.

Comparative study of different wavelengths from IR to UV applied to clean sandstone

Abstract The dependency of ablation rate and wavelength is studied by means of an exemplary chosen sort of sandstone in order to determine the cleaning regime and the feasibility of different wavelengths for practical cleaning. Excimer laser radiation (KrF, XeCl) and Nd:YAG laser radiation (ω, 3ω) were used for the ablation of the black crust and sandstone in two independent experiments with a constant number of pulses.

LIBS-spectroscopy for monitoring and control of the laser cleaning process of stone and medieval glass

Abstract On-line monitoring or even closed-loop control is necessary to avoid over-cleaning in case the ablation process is not self-limiting. Therefore, the laser-induced breakdown spectroscopy (LIBS) was used. Basic investigations were carried out on original sandstone samples ( Elbsandstein ) with strong encrustations as well as medieval stained glass samples (13th century from Cologne Cathedral). The spectroscopic study has shown that the plasma emission can be used for determination of the elemental composition of the ablated material. The plasma was initiated by 248-nm pulses of an KrF-excimer laser (30 ns FWHM). For the spectroscopic analysis, a grating spectrograph in combination with an optical multichannel analyser was used. For the glass and stone samples we obtained a continual alteration of the LIBS spectrum (vanishing of peaks and generating of new element peaks) during the removal process. Thus, certain element peaks can be used to distinguish between encrustation layer and valuable underlying material. To show the potential of LIBS we designed an experimental laser cleaning set-up including closed-loop LIBS control and demonstrated successful automatic cleaning of an original glass fragment.

Measurement of material nonlinearity using surface acoustic wave parametric interaction and laser ultrasonics

A dual frequency mixing technique has been developed for measuring velocity changes caused by material nonlinearity. The technique is based on the parametric interaction between two surface acoustic waves (SAWs): The low frequency pump SAW generated by a transducer and the high frequency probe SAW generated and detected using laser ultrasonics. The pump SAW stresses the material under the probe SAW. The stress (typically <5 MPa) is controlled by varying the timing between the pump and probe waves. The nonlinear interaction is measured as a phase modulation of the probe SAW and equated to a velocity change. The velocity-stress relationship is used as a measure of material nonlinearity. Experiments were conducted to observe the pump-probe interaction by changing the pump frequency and compare the nonlinear response of aluminum and fused silica. Experiments showed these two materials had opposite nonlinear responses, consistent with previously published data. The technique could be applied to life-time predictions of engineered components by measuring changes in nonlinear response caused by fatigue.

Cheap optical transducers (CHOTs) for narrowband ultrasonic applications

We have developed an innovative ultrasonic transducer system (CHOT) which is optically excited by means of lasers. It can be used both for generation and detection of narrowband ultrasound and provides non-contact (or even remote), couplant-free generation and/or detection. It has also the advantage of being inexpensive to manufacture and the simplicity of its concept makes it ideal for industrial applications. In this study we present results where CHOTs have been used both for excitation and detection of surface acoustic waves. An initial theoretical model is also presented which describes the principle of operation.

Measurement of elastic nonlinearity using remote laser ultrasonics and CHeap Optical Transducers and dual frequency surface acoustic waves

A nonlinear ultrasonic technique for evaluating material elastic nonlinearity has been developed. It measures the phase modulation of a high frequency (82MHz) surface acoustic wave interacting with a low frequency (1MHz) high amplitude stress inducing surface acoustic wave. A new breed of optical transducers has been developed and used for the generation and detection of the high frequency wave. The CHeap Optical Transducer (CHOT) is an ultrasonic transducer system, optically activated and read by a laser. We show that CHOTs offer advantages over alternative transducers. CHOTs and nonlinear ultrasonics have great potential for aerospace applications. Results measuring changes in ultrasonic velocity corresponding to different stress states of the sample are presented on fused silica and aluminium.

Laser-induced breakdown spectroscopy and Raman microscopy for analysis of pigments in polychromes

Abstract A polychrome from the Rococo period was analysed by use of two laser-based analytical techniques, laser-induced breakdown spectroscopy (LIBS) and Raman microscopy. The analysis, performed on a fragment of a gilded altarpiece from the church of Escatron, Zaragoza, Spain, provided detailed spectral data that have been used for the identification of pigments. LIBS measurements yielded elemental analytical data that suggest the presence of certain pigments and, in addition, provide information on the stratigraphy of the paint layers. Identification of most pigments and of the materials used in the preparation layer was performed by Raman microscopy.

Discoloration of pigments induced by laser irradiation

Abstract Laser irradiation may alter the colour of certain pigments used in artwork. Owing to the increasing use of lasers in artwork conservation this problem becomes extremely crucial, especially in the case of a polychromy covered by environmental encrustation. X-ray diffraction analysis and optical microscopy were used to study the crystalline structure of selected irradiated pigments in order to identify the changes that take place upon laser irradiation. Two representative pigments were studied, cinnabar (HgS) and lead white (Pb(OH)2 .2PbCO3 ). The results revealed a change in the crystalline phase or chemical composition, respectively, which can be barely detected owing to its superficial character, which is of a nanometre scale.