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1.
This research evaluates the use of microblasting technique with powdered cellulose as a new tool for dry cleaning documents. Different cleaning tests were conducted on three documents with different properties following this new approach and the results were compared to those obtained with traditional dry cleaning with erasers. In order to assess changes caused to the supports, the treated documents were examined both before and after cleaning with optical and 3D stereomicroscopy, SEM-EDS and spectrophotometry. The results allow the conclusion that microblasting with powdered cellulose is a feasible technique to remove surface dirt or grime on paper documents. This research proves that the new use of the technique does not entail changes to the surface properties of the treated supports. Moreover, powdered cellulose is chemically stable and compatible with paper documents, preventing negative long-term effects derived from the presence of rubber residues that may remain in paper fibres when using erasers in dry cleaning treatments.  相似文献   

2.
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.  相似文献   

3.
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.  相似文献   

4.
The need to preserve cultural heritage on paper requires the setting up of methods and treatments that can be applied to original documents. The cellulose main degradation processes are hydrolysis and oxidation. Only the first one has been widely investigated. The Istituto Centrale per la Patologia del Libro (ICPL) focused its attention on oxidation phenomena and studied a particular class of reducing agents, namely the borane-amine complexes. During the investigation it was found that the borane tert-butylamine complex, besides being the most promising reducing agent, was also able to react with carboxylic functions. In the present study 1H and 13C NMR, Pulsed field gradient NMR spectroscopy as well as Raman spectroscopy were used as analytical tools to disclose the mechanism of the interaction between the borane tert-butylamine complex and the carboxylic functions. Given the complexity of the paper/environment interactions and the subsequent degradation phenomena, we worked on simplified models based on small carbohydrate molecules in order to reproduce the behavior of degraded paper after reductive restoration. Modified D-glucose and D-cellobiose were used in this first step in order to set up the analytical methods before approaching more complex systems such as microcrystalline cellulose and paper. Our results give the experimental evidence that borane tert-butylamine complex is also able to neutralize acidic functions. This finding has important perspectives in paper restoration.  相似文献   

5.
Xuan paper is a type of Chinese handmade paper produced for traditional calligraphy and painting in China since the Tang Dynasty (618–907 AD), and is therefore an important cultural heritage material. In this study, the fluorescence and photochemical properties of Xuan paper were investigated. Xuan paper exhibits auto-fluorescence in the blue spectral range (450–500 nm) and UVA photolysis of the paper resulted in a substantial reduction in the blue fluorescence together with the formation of chromophores absorbing in the visible spectrum, resulting in photoyellowing of the paper. A more significant yellowing of paper was observed when irradiated in the dry state than under wet conditions. The associated photogeneration of hydrogen peroxide and superoxide from three types of Xuan paper samples during irradiation showed a correlation between the yields of reactive oxygen species and their relative yellowing rates. The results are interpreted in terms of sensitised photooxidation via a mechanism of electron transfer involving the fluorophores in their excited singlet states being responsible for the photodegradation of Xuan paper. SEM/EDS analyses were performed on the Xuan paper samples to investigate their morphological and elemental characteristics. Silica-containing fibres characteristic of a special rice straw that grows in siliceous soil were observed in all types of Xuan paper. Micron-sized calcium precipitates possibly formed from the “lime-steaming” manufacture process were shown to protect against the acidification of paper during accelerated thermal ageing.  相似文献   

6.
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.  相似文献   

7.
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.  相似文献   

8.
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.  相似文献   

9.
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.  相似文献   

10.
The aging of natural triterpenoid resins used as varnishes on paintings is still insufficiently understood. Although progress has been made, questions concerning the aging pathways in light vs. darkness, or the correlation of oxidation with yellowing, remain open. The influence of aging conditions, primarily the amount of light, but also resin composition, on the aging process were investigated. The aging reactions are followed using a variety of mass spectrometric and spectroscopic techniques. Aging processes in dammar and mastic varnishes are shown to be more dynamic and extensive than had generally been believed. In unaged bulk resins, large quantities of radicals develop within weeks after application as a varnish, due to the greatly increased surface-to-volume ratio. This is true for all aging conditions, including aging in darkness, and is accompanied by considerable oxidation as well. After a few months, most of the initial triterpenoids are oxidized. Natural aging in light and darkness leads to the same main aging products. All these findings point to the conclusion that aging largely proceeds by the same pathways in both light and darkness, mainly autoxidation. Without light, enough radicals are formed to maintain extensive autoxidation, although more slowly. Thus, differences between light and dark aging mechanisms are much smaller than often believed. In mastic, the absence of the polymeric constituents is found to enhance oxidation, but reduce yellowing. It appears that the polymer acts as a natural radical stabilizer, favoring the pronounced intrinsic yellowing tendency of mastic. The manipulation of resin composition might lead to improved aging properties of triterpenoid resin varnishes.  相似文献   

11.
Within the framework of a European project, three cleaning laser devices are tested to evaluate the influence of different parameters on stone cleaning rate and efficiency. The project objective is to design a large surface-cleaning laser. One of the devices is a prototype with some technological improvements compared to the lasers used today for restoration. The tests are performed on limestone and sandstone covered with various dirt layers. The influence of fluence, water spraying, spot area, frequency, as well as particle emission rate is investigated. Results allow a comparison of the importance of each parameter and confirm the increase in cleaning speed of the new prototype. Nevertheless, it can be concluded that an automatic device will be suitable to attain a cleaning speed competitive with other traditional cleaning techniques.  相似文献   

12.
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).  相似文献   

13.
A series of tests has been conducted to evaluate the potential for using a Q-switched Nd:YAG laser (wavelengths 1 064, 532 and 266 nm) to clean both new and naturally aged cotton textiles. Tests have been carried out on i) plain weave and velvet cotton and ii) new and naturally aged cotton samples to investigate the possible roles of weave structure and ageing in the cleaning process. Cleaning trials have been carried out on artificially soiled new cotton and compared with results obtained using traditional cleaning techniques: wet cleaning and organic solvent cleaning. Cleaned surfaces were examined using optical and scanning electron microscopy.  相似文献   

14.
Papermaking has a special place in the cultural heritage of China. Papers made from different types of plant fibers were, and are still used for particular applications. Bamboo paper is a handmade paper that has been traditionally used for book printing and restoration of ancient paper objects since antiquity in China, whereas Xuan paper, the subject of recent previous study, is used for traditional Chinese calligraphy and painting. Following our previous approach on Xuan paper, four modern Bamboo papers manufactured using traditional or chemically-facilitated techniques were artificially aged by UVA radiation and changes to their optical properties were evaluated by reflectance and 3D-fluorescence spectroscopies. Paper samples produced by different methods displayed different fluorescence spectra and UVA photolysis of paper resulted in decreases in the fluorescence intensities and reflectance values, manifested as differing photoyellowing of the papers. Assays of reactive oxygen species, ROS, revealed that papers made by chemically-assisted pulping methods generally produce more hydrogen peroxide or superoxide radicals than those made by traditional methods, which correlates with their relative yellowing rates. Different spatial distributions of calcium and chlorine were also observed by SEM/EDS analysis in the chemically-manufactured papers, probably arising from the specific pulping and/or bleaching chemicals used in their manufacture.  相似文献   

15.
An innovative laser restoration tool for non-contact cleaning of painted artworks is developed. Accurate beam manipulation techniques in combination with on-line detection make the system suitable for selective cleaning of delicate surfaces. The utilisation of lasers obviates the use of various chemicals, and provides a method to remove layers that are untreatable using conventional methods. The first professional laser cleaning station for paintings is equipped with a modern mechatronic engineering tool for accurate beam manipulation (‘optical arm’). An intelligent combination of software and hardware enables accurate control, necessary to deal with the variable properties of the artworks to be treated. An on-line monitoring system is incorporated, using laser-induced breakdown spectroscopy. The user interface plays an important role in simulating the ‘hands-on’ treatment. In January 1999, the 2-year European co-operative research project ‘Advanced workstations for controlled laser cleaning of artworks’ started. The research objective is to define the boundary conditions in which laser cleaning with the present technology can be safely applied.  相似文献   

16.
Within the conservation programme of the mausoleum of Theodoric, located in Ravenna, Italy, we applied a new cleaning procedure based on the use of a recently developed Nd:YAG laser system, suitably equipped in this case with long optical fibre cables for the transmission of laser radiation to work sites on the façade. The intervention of the laser technique was required to complete the cleaning of a decoration surrounding the monolithic dome, after conventional cleaning methods had been applied with unsatisfactory results. Preliminary laboratory analyses on stone samples collected from the dome and subjected to laser treatment indicated that this technique was effective and could fully preserve the lime–Ca oxalate film existing below the thick layer of black crusts. Before starting the operative phase on the mausoleum, it was necessary to solve the practical problem of keeping free access to the monument during cleaning operations, which hindered the location of the laser in close proximity to the sites to be cleaned. This was achieved by preparing long fibre cables (up to 50 m) which permitted the successful completion of the cleaning while leaving the laser body far away from the dome.  相似文献   

17.
The aim of this study is practically to establish a chemical strategy for cleaning soiled deposits and encrustations on archaeological glasses. Investigations were performed on a series of Roman glass samples (Fragments and complete objects) coming from different excavations in northern Jordan. The chemical composition of the glass samples was determined by X-ray fluorescence spectrometer (XRF) analysis technique, whereas X-ray powder diffractometer (XRD) and Energy dispersive X-ray (EDX) methods were used to determine the mineralogical and elemental composition of the soiled deposits and encrustations on the glass surfaces. Furthermore, Scanning Electron Microscopy (SEM) examination and optical assessment were performed before and after cleaning glass. The glass samples were subjected to different cleaning protocols such as Calgon (Sodium hexametaphosphate), ethylenediaminetetraacetic acid (EDTA) at different pH values, citric and tartaric acids and piranha solution (a solution of sulphuric acid and hydrogen peroxide). Sepiolite poultices soaked by chemical agents were the most suitable methods used for applying chemical solutions on the glass surface. It can be concluded that EDTA is generally accepted as the most effective chelating agents recommended for cleaning encrustations on durable glass. It was more effective and safe at neutral pH with low concentrations around 5 to 7%. The calcareous crusts can safely be removed by using a piranha solution. Citric and tartaric acids appeared a moderate efficiency on cleaning weathered and stable glass. Calgon has a tendency to damage corroded and iridescent surfaces, and should be avoided when cleaning weathered glass.  相似文献   

18.
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.  相似文献   

19.
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.  相似文献   

20.
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.  相似文献   

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