A topographical assessment and comparison of conservation cleaning treatments

The development of laser cleaning as a conservation treatment has imposed a need for the evaluation and assessment of other cleaning techniques. The use of more traditional methods like abrasive cleaning, steam cleaning and chemical cleaning has relied so far on visual assessment, unlike much of the research applied to laser cleaning. A conscientious use of these cleaning methods requires their assessment as well as the need for a comparison based on a common methodology. A topographical assessment of laser cleaning, abrasive cleaning, steam cleaning and chemical cleaning (using hydrofluoric acid, ammonium carbonate and EDTA) is presented. Topographical variations induced on marble, oolitic limestone and architectural terracotta surfaces are assessed by means of light interferometry, showing the potential of this non-contact and non-destructive technique for surface studies in conservation. The comparison between cleaning treatments is based upon key parameters associated with cleaning surfaces. The aesthetic impact of these treatments is verified by means of optical microscopy and quantified by colour measurement. Chemical analysis of the cleaned surface (EDS) is performed to investigate the removal of surface pollutants and the presence of residues. Finally, petrographical analysis was used to investigate the removal of pollutant layers and its effect on surface texture.     

Laser cleaning of stone artefacts: a substitute or alternative method?

Laser cleaning of ancient marble and stone monuments is nowadays a well-accepted procedure in conservation. Operators and specialists are presently divided between those giving maximum confidence to this method of cleaning and others who, in contrast, are strongly critical and emphasise possible drawbacks and damages caused by laser. As any other method of cleaning, laser also offers advantages but at the same time is limited by drawbacks. Most conveniently, it should be integrated with the other methods. On the basis of the above considerations, the authors are proposing a combined procedure using laser cleaning as a first step – in this way removing the relevant part of black gypsum encrustation – followed by chemical methods as a final step. The latter, conveniently, could be accomplished by means of anion exchange resins, better than ammonium carbonate. An experimental check-up was made of four different methods applied on three different lithotypes on the façade of the Florentine Cathedral. Laser, micro-sandblasting, ammonium carbonate and sodium EDTA were the cleaning methods compared, whilst Carrara marble, green Serpentine (Verde di Prato) and a red limestone were the three lithotypes. Results are commented by showing differences in the advantages and drawbacks among the different methods on the various lithotypes.     

Laser cleaning as a part of the restoration process: removal of aged oil paints from a Renaissance sandstone portal in Dresden,Germany

Laser cleaning was applied to remove aged and soiled oil paints of the 19th century from weathered, brittle sandstone surfaces. In contrast to other tested cleaning methods, the laser technique allows the removal of the oil paint layers with a minimum of material loss in brittle zones. The cleaned test areas have been investigated by optical and scanning electron microscopy as well as by colour measurements. The investigations have shown that the dirt and the oil paint layers can be removed by laser cleaning without affecting the original sandstone surface and that the pores can be opened again. The brown shade after cleaning is not caused by laser interaction with the sandstone surface but by historic impregnation with linseed oil. Immediately after cleaning, a treatment with chemical consolidants is necessary to preserve the brittle sandstone surface. Sustainable consolidation could be problematic in some areas, because the laser cleaning also preserves heavily damaged, crumbling zones of the carvings. For economic reasons, laser cleaning should be applied only in the most endangered zones of carvings and combined with classical methods (organic solvents and scalpel).     

Low-cost sensor system for online monitoring during laser cleaning

The self-limiting effect during laser cleaning only occurs in a limited amount of specific applications in restoration (e.g. removal of black crust from white marble). In all the other cases, a control of the removal process will be necessary either by the operator himself or by the employment of sensor equipment. Various methods, mainly spectroscopic (e.g. LIBS), have been investigated and proposed by others. Despite the fact that these have been shown to be promising, they all have in common rather high investment cost close to that of the cleaning equipment. Furthermore, this highly sophisticated control equipment is not easy to handle by conservators in practice. As an alternative low-cost method, we employed a simple photodiode to detect the scattered light from the irradiation area on the artwork surface. In many cases, this signal contains several pieces of information on the layer just being removed. The scattered radiation detected by the photodiode originates from the laser-induced plasma as well as reflected laser radiation. A separation, if necessary in order to separate the information, is possible by spectral filters. First applications during laser cleaning of corroded metal, encrusted glass and stone were promising. It has turned out that there is a distinct influence on the scattered light amplitude or even the pulse-bandwidth once the laser has removed the encrustation completely. The corresponding signal can be used in a closed loop control or for online monitoring.     

Electronic paramagnetic resonance as a tool for studying the blackening of Carrara marble due to irradiation by a Q-switched YAG laser

Several authors or practitioners have remarked that Q-switched lasers have an immediate blackening effect on mineral pigments such as vermilion (HgS), minium (Pb₃O₄), white lead [2PbCO₃. Pb(OH)₂], malachite [Cu₂CO₃.(OH)₂] and yellow ochre (FeOH₂). A similar blackening effect can also be obtained on veined Carrara marble. This stone contains several trace elements, particularly iron and manganese. The latter is responsible for a particular response in electronic paramagnetic resonance spectroscopy (EPRS). We investigated the effect of a Q-switched Nd:YAG laser irradiation on the EPRS trace of Carrara marble. Further experiments were performed with the same analytical tool on synthetic calcite powders that had been doped with iron or manganese. It appeared that no significant change of EPRS trace could be put into evidence after laser irradiation of both bulk Carrara marble or doped calcite powders, although some samples had actually blackened. It is concluded that the blackening effect is not due to an oxidation of manganese ions. Colour measurements were also performed within the framework of this investigation. They showed that the colour shift to black is proportional to the fluence applied to the stone surface     

A spectral imaging methodology for determining on-line the optimum cleaning level of stonework

This study aims to introduce a new spectral imaging methodology that can be used to monitor on-line, non-destructively and in situ the cleaning level of pollution encrustation on stonework. The suggested technique is based on the optical properties of monochromatic light penetration in matter. The calculated differences of images, obtained at two different spectral bands, could reliably map the depth of cleaning. This novel approach was tested in the laboratory during laser cleaning trials on polluted stonework enabling high accuracy measurements (such as the detection of thin crust layers remaining on the under-cleaned marble surfaces). However, it may also apply for the monitoring of any other cleaning technique (micro air-abrasive, etc). A detailed presentation of the results will be demonstrated while the potential of its wide application on everyday conservation practice on stonework will be discussed.     

Near-UV laser interaction with contaminants and pigments on parchment: laser cleaning diagnostics by SE-microscopy,VIS-, and IR-spectroscopy

Potentials and limitations of the near-UV pulsed laser cleaning of parchment (wavelength 308 nm, pulse duration 17 ns) are demonstrated by the application of scanning electron microscopy (SEM), colour metrics and diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) at model contamination/pigment/parchment systems. Pigment-binder systems stable and unstable against near-UV laser treatment could be identified. A chemical degradation threshold fluence of a goat parchment model substrate was determined which practically coincided with its ablation threshold fluence. This indicates that the fluence range of destructionless laser cleaning at 308 nm is almost not impaired by chemical modfications below the ablation limit. Nevertheless, spectroscopic diagnostics are necessary to guarantee destructionless cleaning for practical cases where the chemical conversion threshold fluence deviates from the ablation threshold to lower values.     

The effect of Nd:YAG laser radiation on medieval pigments

Very often traces of paint and pigment have been found on medieval sculpture. Presently, little is known about the effects of laser radiation on polychromy. It is important to protect and preserve these traces during any cleaning or restoration process. The absorption properties of polychrome materials are likely to be different from those of the underlying stone or substrate and as a result special care must be taken to avoid any damaging or discolouring phenomena associated with laser cleaning. Spectroscopic methods (XPS, AES, reflectance spectroscopy) together with optical microscopy, digital photography and X-ray diffraction analysis have been used in a series of experiments on simulated samples of common medieval pigments (vermilion, red and white lead and ochres in linseed oil) on limestone plates, in order to study the reaction of these materials to infrared laser radiation.     

Assessment of the state of conservation of stone artworks after laser cleaning: comparison with conventional cleaning results on a two-decade follow up

The utilization of laser light to produce fine and selective cleaning of superficial deposits and encrustation from stones was originally proposed more than 20 years ago by John Asmus who performed pioneering trials of laser cleaning on stone façades in Venice, Cremona and Padua. The opportunity to collect stone samples from these sites allowed us to carry out an original study aimed at evaluating the conservation state of stone surfaces cleaned 10–20 years ago by means of three different techniques: Nd:YAG laser radiation, micron sandblasting and chemical pads. Samples of various stone types, as Istria limestone, Botticino limestone and Nanto sandstone were collected and examined by means of optical and SEM microscopy, FT/IR, and EDAX analyses. The results provided preliminary indications that the state of conservation of stone surfaces previously subjected to laser cleaning is generally better in comparison with those which concurrently underwent mechanical and chemical cleaning.     

Effect of low and high fluence on experimentally laser-cleaned sandstone and marlstone tablets in dry and wet conditions

The eligibility of laser cleaning is tested on regionally specific sculptural stones. Marlstone and sandstone represent the most common building, architectural and sculptural stones employed in the Czech Republic since the Romanesque period. These stone types differ greatly from the marbles on which positive results have been obtained using laser cleaning. Experimental samples were prepared by sawing rock cores. Artificial blackening of samples’ surfaces simulates natural black patinas. The experimental laser cleaning was conducted using Nd:YAG commercial laser (Laserblast 50) at two different fluences—the low one corresponds to the minimum operating capability of the equipment, and the high fluence represents the maximum operating mode of the equipment (i.e. in the ordinary operating range of the equipment). The samples were cleaned under dry and wet conditions. Use of a high fluence resulted in cratering/spalling that is discussed in terms of rock mineralogical composition (presence of clay minerals), adsorption of moisture on clay minerals and physical properties (porosity). Tensional fracturing (evidenced by scanning electron microscopy) along the cleaned surface is the main mechanism of sample destruction due to the vaporization of adsorbed moisture and due to the different elasticity of present rock-forming minerals. Observed discoloration due to high fluence and insufficient cleaning effect of low fluence present other problems encountered.     

Chromatic modulation technique for in-line surface monitoring and diagnostic

A fast and reliable surface monitoring and diagnostic technique is essential to develop a real-time automatic control system for laser cleaning of artworks. In this paper, an in-line surface monitoring and diagnostic system based on chromatic modulation using tristimulus detectors and fibre optics is presented. The system produces measurements that are dependent on the spectral signature of the incident light but are independent of intensity. In order to demonstrate its usefulness and versatility, the technique was applied to surface monitoring in the laser cleaning of metal and stone. Results show that the spectral parameters derived from chromatic detection not only provide a clear indication of the surface cleanliness and surface damage but also much surface chromatic information from its versatility. It is also shown in this paper how a chromatic modulation technique may be utilised as a robust method for monitoring and diagnosing the surface during laser cleaning.     

Yellowing effect and discoloration of pigments: experimental and theoretical studies

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.     

Laser cleaning of stained glass windows. Overview on an interdisciplinary project

The German Federal Foundation for the Environment (Deutsche Bundesstiftung Umwelt) is one of Europe's largest organizations of its kind. It supports innovative, exemplary projects for the protection of the environment and of national historic monuments and cultural landscapes. All projects are set up to provide a platform for researchers, craftsmen and restorers to find a common solution to difficult problems in conservation practice. More than 360 projects have been funded since 1990. Two recent projects deal with laser cleaning, one for stone and the other one for stained glass windows, the latter being presented here. This publication gives an overview on cleaning problems on stained glass windows and the project methodology. The interdisciplinary approach of the project provides the possibility of including experts in different fields to examine perspectives and limits of laser cleaning for stained glass windows. Two other publications in this issue (LACONA III) give selected results on cleaning experiments achieved within this project.     

Laser cleaning of terracotta decorations of the portal of Palos of the Cathedral of Seville

Laser cleaning has been used to restore the soiled terracotta statues and decorations of the tympanum of the portal of Palos of the Cathedral of Seville in Spain. A simultaneous laboratory study performed on a representative sample helped to identify the optimum laser conditions to remove the dark soiling layer produced by air pollution. It was found that irradiation at 1064 nm with a Q-switched Nd:YAG laser was more effective than the harmonic wavelengths of 532 or 266 nm. LIBS and Raman microscopy gave information on the composition of terracotta and identified the presence of a protective layer made of gypsum and calcite. As detected by Raman spectroscopy, laser irradiation caused the elimination of the carbon component of the soiling layer and the appearance of an anhydrite component in the laser irradiated gypsum layer applied over the terracotta substrate for protective purposes. Local heating of the surface caused by laser irradiation at 1064 nm, the laser wavelength used for restoration of the portal, might be responsible for a process of partial dehydration of gypsum into anhydrite.     

Femtosecond laser cleaning of historical paper with sizing

Lasers have served as cleaning tools for historical objects and artworks for about 40 years. In many cases, superior results of laser cleaning were achieved with respect to traditional methods. In this technique, contaminations on the surface of the object are ablated by laser irradiation. In order to apply laser cleaning method to fragile materials such as paper made of cellulose or parchment, heat deposition to the bulk should be minimal, to prevent damage. In this work, it is demonstrated that laser pulses with femtosecond (fs) duration can exhibit non-thermal ablation of contaminants on paper samples. In particular, laser cleaning studies are concentrated on paper samples with sizing. Fs laser cleaning is performed on artificially soiled and aged samples, as well as on historical ones. The laser used in the experiments has pulse duration of 550 fs and 1030 nm center wavelength. The fluence of the laser is varied and the post-cleaning statuses of samples are investigated. The analyses are color changes, fiber integrity, chemical composition changes and mechanical strengths. These results show that fs lasers can be very efficient in cleaning paper samples, yielding minimal discoloration and no damage to fibers distinguishable on microscopic examination. The presence of sizing also provides further protection against possible side effects.     

Excimer laser removal of beeswax from galician granite monuments

The paper presents the use of laser radiation for cleaning of beeswax treated granite stone. In the early sixties, prestigious restorers decided to apply molten beeswax on the granite surface of valuable monuments with the aim of preventing the erosive action of atmospheric agents. An interesting example of this treatment is the Renaissance Frieze in the Cloister of the Cathedral of Santiago de Compostela in Galicia (Northwest Spain). With time, salt accumulation beneath the beeswax layer has caused an intense surface disintegration of granite. Conventional cleaning methods can destroy sculptured details of these emblematic monuments. For this reason, excimer laser cleaning has been chosen as a promising non contact, selective and environmentally friendly cleaning technique to be studied.The cleaning tests have been carried out using an excimer laser (ArF, 193 nm), with fluences between 0.5 and 2 J cm⁻² pulse⁻¹ and a spot area of 0.025 cm². Samples representing beeswax films over Roan granite have been irradiated and their degree of cleaning has been studied as a function of the number of pulses and the laser fluence.Cleaning efficiency has been evaluated by FT-Raman Spectroscopy, allowing to establish the beeswax ablation threshold and the ablation rate.Excimer laser cleaning allows a progressive and controlled removal of a few tenths of micrometers of beeswax per pulse without damaging the underlying granite stone.     

Experimental investigations of stained paper documents cleaned by the Nd:YAG laser pulses

The historical paper samples from XIII–XIX c. are characterised by means of techniques of the optical spectroscopy. The influence of pulsed laser cleaning by means of the Q-switched Nd:YAG laser at 532 nm on the spectra and also cleaning results of stained paper documents are reported and considered. In the absorption spectra, the minima around 280 and 370 nm are identified and luminescence reveals a characteristic band centred around 430 nm. The laser cleaning diagnosed by the recording of the LIF spectra with 266 nm excitation shows a profile of increasing intensity and preserved structure. The LIPS spectra reveal sharp emission lines recorded at 612.5, 644.2, 646.5, 671, 714.9, 720.2 nm (Ca I), 589.4, 616.4, 780 nm (Na I), and 766.5: 769.9 nm (Mg I) which are ascribed to the surface contaminations. The intensity decrease of these peaks is in accordance with successive laser pulses and monitors the cleaning progress of the stained paper.     

Efflorescence on thin sections of calcareous stones

Limestone and marble, still frequently used as building materials are especially vulnerable to the destructive effects of efflorescence. The effect of interaction between five different calcareous stones and corrosive atmospheres has been investigated. A novel technique of stone degradation analysis has been used where thin sections of fresh stone materials were exposed in a corrosion chamber under controlled conditions (temperature, relative humidity (RH), SO₂ and NO₂ concentration). Following 1-week’s exposure; observations of the initial crystallisation were studied by light microscopy, scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX) and X-ray diffraction (XRD). The results obtained from the surface analysis clearly showed sulphation of the samples and formation of gypsum. Observations of the initial corrosion indicated differences in the location of efflorescence and its shape among and within the samples. The mineralogy, grain shape and size, mineral defects and existence of cracks and pores, all influenced the substrate’s reactivity. The most vulnerable areas and the places where the corrosion started on the calcitic stones were the triple grain junctions followed by grain boundaries, and on the dolomitic marble cracks and pores.     

Laser cleaning applied in the restoration of a medieval wooden panel chamber at Pirna

A medieval wooden panel chamber was rediscovered during reconstruction of the Tetzelhouse in the Saxon town of Pirna. Ceiling and walls are made from 600-year-old fire wood panels fitted together. The complete removal of layers (limewash, plaster, glue and dirt) from the wall panels was the precondition for conservation of the wood panels and for the restoration of the wooden panel chamber. The cleaning was carried out with a pulsed Nd:YAG laser after basic investigation of ablation mechanisms of the layers on the old wood. All layers of the different materials were removed both from the normal surface and out of depressions and woodworm holes with a special range of laser parameters, without damaging the wood. Within this range of parameters the laser cleaning is a self-limiting process. The health hazard from emitted waste products were determined and checked with work place measurements. The laser cleaning of the wooden wall panels was completed in March 1999. A uniform visual impression of all panels was obtained with a warm wooden colour tone.     

The history of the “Virgin with Child” sculpture (Ottaviano,Naples, southern Italy): Hypotheses from archaeometric multi-technique investigations

A life-size whitish marble statue of a “Virgin with Child” has been recently rediscovered in the St. Rosario church located in Ottaviano, a small town near Naples (southern Italy). This artwork shows stylistic features of the Tuscan-Roman school of the 16th century, and is framed in an intriguing historical context. Historical documents testify that the sculpture was a property of the cadet branch of noble Tuscan family of the Medici, the Medici of Ottaviano. A multianalytical approach has been used to try to indicate the supply area of the white marble of the studied sculpture. Considering the whole mineralogical, petrographic and geochemical data, the source rock can be possibly limited to the main classical white marbles of the Mediterranean district, as the classical marble of Aphrodisias. A reuse practice of a former artwork can be also hypothesized.