Wojciech Skrzeczanowski

Comparative Laser Spectroscopy Diagnostics for Ancient Metallic Artefacts Exposed to Environmental Pollution

Metal artworks are subjected to corrosion and oxidation processes due to reactive agents present in the air, water and in the ground that these objects have been in contact with for hundreds of years. This is the case for archaeological metals that are recovered from excavation sites, as well as artefacts exposed to polluted air. Stabilization of the conservation state of these objects needs precise diagnostics of the accrued surface layers and identification of original, historical materials before further protective treatments, including safe laser cleaning of unwanted layers. This paper presents analyses of the chemical composition and stratigraphy of corrosion products with the use of laser induced breakdown spectroscopy (LIBS) and Raman spectroscopy. The discussion of the results is supported by material studies (SEM-EDS, XRF, ion-analyses). The tests were performed on several samples taken from original objects, including copper roofing from Wilanów Palace in Warsaw and Karol Poznański Palace in ŁódŸ, bronze decorative figures from the Wilanów Palace gardens, and four archaeological examples of old jewellery (different copper alloys). Work has been performed as a part of the MATLAS project in the frames of EEA and Norway Grants (www.matlas.eu) and the results enable the comparison of the methodology and to elaborate the joint diagnostic procedures of the three project partner independent laboratories.

Characterization of Laser Cleaning of Artworks

The main tasks of conservators of artworks and monuments are the estimation and analysis of damages (present condition), object conservation (cleaning process), and the protection of an object against further degradation. One of the physical methods that is becoming more and more popular for dirt removal is the laser cleaning method. This method is non-contact, selective, local, controlled, self-limiting, gives immediate feedback and preserves even the gentlest of relief - the trace of a paintbrush. Paper presents application of different, selected physical sensing methods to characterize condition of works of art as well as laser cleaning process itself. It includes, tested in our laboratories, optical surface measurements (e.g. colorimetry, scatterometry, interferometry), infrared thermography, optical coherent tomography and acoustic measurements for “on-line” evaluation of cleaning progress. Results of laser spectrometry analyses (LIBS, Raman) will illustrate identification and dating of objects superficial layers.

Depth-Resolved Multilayer Pigment Identification in Paintings: Combined Use of Laser-Induced Breakdown Spectroscopy (LIBS) and Optical Coherence Tomography (OCT)

A detailed feasibility study on the combined use of laser-induced breakdown spectroscopy with optical coherence tomography (LIBS/OCT), aiming at a realistic depth-resolved elemental analysis of multilayer stratigraphies in paintings, is presented. Merging a high spectral resolution LIBS system with a high spatial resolution spectral OCT instrument significantly enhances the quality and accuracy of stratigraphic analysis. First, OCT mapping is employed prior to LIBS analysis in order to assist the selection of specific areas of interest on the painting surface to be examined in detail. Then, intertwined with LIBS, the OCT instrument is used as a precise profilometer for the online determination of the depth of the ablation crater formed by individual laser pulses during LIBS depth-profile analysis. This approach is novel and enables (i) the precise in-depth scaling of elemental concentration profiles, and (ii) the recognition of layer boundaries by estimating the corresponding differences in material ablation rate. Additionally, the latter is supported, within the transparency of the object, by analysis of the OCT cross-sectional views. The potential of this method is illustrated by presenting results on the detailed analysis of the structure of an historic painting on canvas performed to aid planned restoration of the artwork.

Absolute LIBS stratigraphy with optical coherence tomography

In this contribution preliminary studies on the application of Optical Coherence Tomography (OCT) to absolute depth calibration of Laser Induced Breakdown Spectroscopy (LIBS) data in application to revealing stratigraphy of easel paintings are presented. The procedure of in-situ monitoring of LIBS by means of OCT is described. Numerical method developed for precise extraction of the depth of the LIBS ablation crater is explained. Results obtained with model paintings are discussed.

Use of the LIBS method in oil paintings examination based on examples of analyses conducted at the Wilanow Palace Museum

This paper describes the preliminary results of a study of the paint layers in 17th-century paintings belonging to the collection of the Wilanow Palace Museum. The works chosen for examination are of great importance to the Museum, as they might have been painted by court artists of King John III Sobieski. The aim of the study was therefore to determine the technological structure of the paintings, to determine the scope of conservation interventions and, above all, to gather comparative material that would serve to conduct further multidisciplinary attributive research. The presentation relates to studies in which laser-induced breakdown spectroscopy (LIBS) and optical microscopy were used as diagnostic tools. LIBS is based on the evaporation of a small amount of the material under investigation, and the generation of plasma which emits continuum and line radiation. The analysis of line radiation allows us to identify the elements appearing in the sample being investigated. The microscope pictures were taken using a Bresser Digital Hand Micro 1.3Mpx and the Hirox 8700 microscopes. The results obtained have confirmed the utility of the LIBS method in the study of artworks. They have also proven that it can be used as a method to complement microchemical analysis, as well as an method to identify and examine artworks from which samples cannot be taken, as it is micro-destructive and the analysis can be conducted directly on the object, without the need to take samples.

The influence of environment on corrosion of cast iron and carbon steel representing samples of outdoor metal technical heritage

This paper presents the results of annual measurements of the corrosion progress at test samples of cast iron and carbon steel placed in different natural environments. Comparative tests were performed in two outdoor stations, one at the Railway Museum in central Warsaw and one at the location of a Railway Museum in the small town of Sochaczew, 50 km west of Warsaw. The influence of surface roughness on the development of corrosion was determined by two kinds of treatment of all sample surfaces − metal brush or grinding. Stratigraphy and composition of corrosion products in quarterly periods were analyzed with laser-induced breakdown spectroscopy (LIBS) and Raman laser spectroscopy. Comparative tests were performed using a scanning electron microscopy (SEM) system equipped with energy dispersive spectrometer (EDS) and micro-chemical analytical methods. The corrosion layers on carbon steel have proven to be thicker on average than on cast iron, and thicker on the brushed parts of both materials. Furthermore, a thicker corrosion layer was found on the cast iron test samples exposed in Sochaczew than in Warsaw. Different iron oxides, namely lepidocrocite, goethite, hematite and magnetite were identified in the surface Raman spectra of corrosion layers, the last compound only in the sample from Sochaczew. SEM EDS measurements of surface elemental concentrations showed a higher concentration of sulfur in all samples from Sochaczew. Registered LIBS spectra have been additionally analyzed with statistical approach, using Factorial Analysis (FA). Results generally confirmed conclusions drawn from SEM/Raman/LIBS results.

Simple CCD-based wavemeter

A construction and results of basic parameters of laser wavelength meter with digital processing of data are presented. The instrument designed for measurements in the 400 - 1100 nm range of spectrum consists of the optical head including quartz or glass Fabry-Perot resonator, a system of filters and lenses and detection and data processing blocks. The last two blocks include linear CCD camera, buffer memory, 8-bit A/D converter, an interface and PC/12 MHz 80286. The meter allows one to measure the wavelengths and spectral line widths of both cw and pulsed laser. The preliminary results of the investigations are presented.

LIBS spectra of multi-component Al, Fe, Cu alloys and composite materials used for selected elements of armament and munition

Spectral investigations in the UV-VIS range of selected Al, Cu, and Fe alloys and composite materials were performed using LIBS technique. The investigated objects were typical rifle cartridges, mortars, rocket launchers and samples of different type steel, Cu and Al alloys, as well as composite materials of special chemical composition. Two Nd:YAG lasers were applied: a short 4 ns, 60 mJ Brio Quantel/BigSky laser (1064 nm) and a long pulse 200/400 (up to 1000) µs (~ 2/4 up to 10 J) laser (1064 nm) constructed at the Institute of Optoelectronics MUT. This spectrochemical analysis was possible for Al, Cu, and Fe alloys objects for both lasers, and in case of composites only if the samples were irradiated by short laser pulse since in the experiment with the long pulse, all composite materials spectra, in general, were very similar to each other – they imitated a grey/black body spectra. For metal alloys in experiments with a short laser pulse only atomic spectra were observed while for long microsecond laser pulses molecular transitions have been registered for Al alloys. Electron temperatures of plasma created on different materials for short and long laser pulses were found on the base of Boltzmann plots. Temperatures are clearly higher for plasmas generated with a short laser pulse which results from much higher laser power density on the sample surface for short pulse and not from fluence which is 20-40 times larger for long pulse.

LIBS, optical and multivariate analyses of selected 17 th-century oil paintings from the Museum of King Jan III’s palace at Wilanów

The paper presents measurement results of LIBS and optical microscopy investigations applied to five 17th-century oil paintings, belonging to the collection of the Museum of King Jan III’s Palace at Wilanów. The analysis devoted to ground layers at depths of about 200 – 300 μm (40 – 60 laser pulses) allowed to find stratigraphy distributions of elements characteristic for ground layers. During the latest investigations, the researchers concentrated mainly on the comparison of some specific elements like Li, Ba, Ti which could indicate the origin of the pigment and help in the process of classification of the paintings. LIBS spectra analyses were supported by statistical factorial analyses which visibly confirmed conclusions drawn from spectral and optical microscopy research.

Modeling of remelting processes of metal targets using pulses of continuous laser with pre-impulses

The study presents preliminary results of theoretical analyses concerning interaction of quasi-cw laser radiation with an aluminium target. The range of laser power the authors were interested in was from 1 to 10 kW, and target thicknesses from 0.1 to 1 cm. It was also assumed that a laser beam diameter on the target (Al) was around 0.5 cm. A mathematicalphysical model of the phenomenon was based on the equation of conservation of energy (spatially one-dimensional model – (z,t)) taking into account: radiation absorption and transport inside the target, heat conduction, reflection of part of radiation from the target’s surface, and heat losses in the processes of melting and evaporation. Coefficients of light absorption and reflection from the target’s surface were described with semi-empirical expressions, which took into account their dependence on the temperature and density. Initially, a case of target static during heating was considered. Subsequently, the problem of enhancement of radiation interaction with the target (decrease of reflection coefficient) by the use of short (< 20 ns), high power pre-impulse was analyzed. The last case needed expansion of a set of equations with the continuity equation and the equation of motion, to take into account evaporation of target’s surface under influence of the pre-impulse. It was shown that thermal effect of the pre-impulse is practically not influencing final depths of target remelting. On the other hand, damage (matting) of the target’s surface by the pre-impulse, causing the decrease of reflection coefficient can have a substantial influence on the remelting depth.