133 research outputs found

    The fate of colors in the 20th - 21st centuries: preserving the organic colorants in plastic artifacts

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    Objectos modernos e contemporâneos feitos de plástico são amplamente encontrados no património cultural. Presentemente, a sua preservação levanta questões críticas aos conservadores e cientistas uma vez que estes objectos podem facilmente sofrer degradação num curto espaço de tempo. Um dos fenómenos que pode alterar significativamente a aparência de objectos em plástico é a alteração de cor (descoloração). De um modo geral, a descoloração é habitualmente associada à degradação dos polímeros, contudo, os pigmentos, que são parte integrante das formulações do plástico, também podem desvanecer devido à exposição à luz. A identificação de objetos de plástico com pigmentos sensíveis à luz é um exercício bastante exigente devido à sensibilidade dos mesmos a alterações na cor. A caracterização dos corantes nos plásticos é normalmente realizada através de amostragem, métodos de extração e testagem destrutiva. Como alternativa, esta tese apresenta uma abordagem inovadora e multi- analítica baseada em espectroscopias que foi desenvolvida para a identificação in situ dos pigmentos em plásticos históricos. Esta metodologia compreendeu a utilização de microscopia ótica (MO), microespectrometria por fluorescência de raios X dispersiva de energias (μ-EDXRF), espectroscopia UV-Vis-NIR de reflectância, fotoluminescência (PL) e micro-espectroscopia de Raman (μ-Raman) na análise de obras de arte, objetos industriais e de uso diário, datados de 1950-2000s e pertencentes a coleções Portuguesas. Deste estudo resultou a identificação dos pigmentos comumente presentes na paleta de cor dos coloristas da indústria dos plásticos portuguesa: óxido de ferro (PR 101, α-Fe2O3), molibdato de cromato de chumbo (PR 104, Pb(Cr,Mo,S)O4), vermelho de cádmio (PR 108, Cd(S,Se); PR 113, (Cd,Hg)S), amarelo de cádmio (PY 37, CdS; PY 35; (Cd,Zn)S), branco de titânio (PW 6, TiO2 ambos rutilo e anátase), oxicloreto de bismuto (PW 14, BiOCl) e lacas do pigmento orgânico β-naftol (PR 48, PR 49, PR 53). Adicionalmente, foi também identificado um pigmento fora do comum, o pigmento perlascente plumbonacrite Pb5(CO3)3O(OH)2. Para todos os casos de estudo, μ-Raman foi a ferramenta chave para a caracterização dos pigmentos nos objetos de plástico, aportando dados conclusivos para a identificação dos mesmos. A impressão digital vibracional dos pigmentos orgânicos e inorgânicos foi adquirida com sucesso recorrendo à focagem do laser na superfície das partículas. A aquisição de dados espectrais de pigmentos com concentrações muito baixas (0.1 % a 5%, aproximadamente) à escala micro foi possível através de microscopia confocal, que faz parte do sistema do equipamento de μ-Raman. Adicionalmente, foi também possível obter informação sobre o polímero base (principalmente termoplásticos) e cargas. Os métodos analíticos desenvolvidos neste estudo deverão, em trabalhos futuros, facilitar a obtenção de informação complementar sobre estes objetos de plástico e permitir uma melhor identificação e avaliação do seu estado de conservação. Esta tese foca particularmente objectos de plástico vermelhos visto que estes foram identificados como os mais severamente afetados por alterações de cor. O estado avançado de desvanecimento identificado no pigmento β-naftol PR 53 mostrou a sua fraca estabilidade à luz em formulações de plástico. Esta situação, junto com as alterações de cor descritas em literatura para o pigmento PR 48 em objetos de plástico, sugere uma sensibilidade dos pigmentos vermelhos da família dos β-naftol ao desvanecimento. O PR 53 e os pigmentos vermelhos da família dos β-naftóis são pigmentos históricos facilmente encontrados em objetos do património cultural. No entanto, o conhecimento acerca da sua estabilidade a longo prazo e resistência à foto-degradação é limitado, especialmente para os casos onde os mesmos se encontram em polímeros, sendo que este conhecimento é essencial para a sua preservação. Neste estudo, a quantificação da foto-estabilidade para uma série de pigmentos vermelhos da família dos β-naftol foi realizada pela primeira vez, através do cálculo do rendimento quântico de fotodegradação (ΦR). Os valores obtidos variaram entre 3x10-6 e 4x10-5, indicativo de uma estabilidade relativamente boa à luz por parte das moléculas. Tendo em consideração que a estabilidade dos pigmentos não se limita exclusivamente ao pigmento em si, mas também à sua interação com o meio envolvente, foram realizados ensaios de envelhecimento por exposição à luz (λ>300 nm) do pigmento em solução, em pó e incorporado em polímeros de modo a avaliar o papel do meio na estabilidade à luz dos pigmentos e as vias pelas quais estes se degradam. Verificou-se que o ligante tem um impacto significativo na estabilidade do pigmento uma vez que se foi detetada uma maior sensibilidade à luz dos pigmentos PR 48 e PR 53 quando incorporados nos plásticos, comparativamente ao ensaio do pigmento em pó. Este novo conhecimento irá contribuir para o desenvolvimento de novas estratégias na conservação dos plásticos com estes pigmentos vermelhos fotossensíveis através da previsão do desvanecimento. Espectrometrias de massa (MS) por cromatografia em fase líquida e gasosa foram utilizadas na caracterização dos principais subprodutos da degradação. Observou-se uma fotodegradação significativa e a formação de compostos ftálicos e ftalatos nos pigmentos em solução e em pó.Modern and contemporary objects made of plastics are widely found in cultural heritage. Today, their preser- vation poses critical issues to conservators and scientists, as they can suffer from extensive degradation in a short time period. Color change (discoloration) is one of the alteration phenomena that can significantly affect their appearance. Discoloration is commonly associated with the degradation of polymers. However, pigments within plastics can also fade due to exposure to light. The identification of objects that contain light-sensitive pigments is demanding because of the sensitivity of plastics to color change. Normally sampling, extraction methods and destructive testing are required for the characterization of colorants in plastics. In this work, an innovative multi-analytical spectroscopic approach for the in situ identification of pigments in historical plastics was developed. Optical microscopy (MO), micro-energy dispersive X-ray fluo- rescence (μ-EDXRF), UV-Vis-NIR reflectance, photoluminescence (PL) and Raman microscopy (μ-Raman), were used for the analysis of artworks, industrial and daily objects dated from 1950s-2000s from Portuguese collections. A common colorists’ palette within the Portuguese plastics industry was identified: iron oxide (PR 101, α-Fe2O3), lead chromate molybdate (PR 104, Pb(Cr,Mo,S)O4), cadmium red (PR 108, Cd(S,Se); PR 113, (Cd,Hg)S) and cadmium yellow (PY 37, CdS; PY 35; (Cd,Zn)S) pigments, titanium whites (PW 6, TiO2 both rutile and anatase), bismuth oxychloride (PW 14, BiOCl) and organic β-naphthol lakes (PR 48, PR 49, PR 53). An exceptional pigment found was the pearlescent plumbonacrite pigment Pb5(CO3)3O(OH)2. In all the case studies, μ-Raman was the key analytical tool for pigment characterization in the plastic objects, providing conclusive data for their identification. The vibrational fingerprint of both inorganic and organic pigments was successfully recorded by focusing the laser beam on particle surfaces. The confocal microscopy system used in μ-Raman enabled the collection of spectral data from low concentrations of pigments (ap- proximately 0.1%-5%) on the micro-scale. In addition to pigments, information on the base polymer (mainly thermoplastics) and fillers was obtained. The analytical methods developed will facilitate the acquisition of complementary data from plastics allowing material identification and condition assessment in the future. This thesis focused on red pigmented plastic artifacts, as they were found to be severely faded among the studied objects. The identification of β-naphthol pigment lake PR 53 as a faded pigment highlighted its poor fastness in plastics, that together with the color change of PR 48 in plastic objects, reported in literature, suggests the particular susceptibility of β-naphthol red lakes to fading. PR 53, and the other β-naphthol reds, are historical pigments widely found in cultural heritage. However, little is known about their photodegradation and stability, especially when they are found in polymer media, and this knowledge is essential for their long- term preservation. For the first time, photodegradation quantum yields (ΦR) were calculated for a series of red pigments based on β-naphthol in order to quantify their photo-stability. ΦR values ranging from 3x10-6 to 4x10-5 were obtained, indicating relatively light-stable molecules. Bearing in mind that pigment fastness is not only related to the pigment itself, but also to its interaction with the confined environment, light-aging experiments (λ>300 nm) were conducted in solution, on powders, and in polymers to assess the role of the medium on the lightfastness of the pigments and their degradation pathways. A significant impact of the binder on their stability was found. Indeed, a higher sensitivity to light of PR 48 and PR 53 pigments, when incorporated in plastics than in powder, was observed. This new knowledge will contribute to the prediction of plastic fading and inform effective preventive conservation strategies for objects containing light- sensitive β-naphthol red pigments. Liquid- and gas-chromatography mass spectrometry (MS) were used for the characterization of the main degradation products. Extensive photodegradation was observed with the formation of phthalic compounds and phthalates in both solution and powder phases

    Image segmentation and pigment mapping of cultural heritage based on spectral imaging

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    The goal of the work reported in this dissertation is to develop methods for image segmentation and pigment mapping of paintings based on spectral imaging. To reach this goal it is necessary to achieve sufficient spectral and colorimetric accuracies of both the spectral imaging system and pigment mapping. The output is a series of spatial distributions of pigments (or pigment maps) composing a painting. With these pigment maps, the change of the color appearance of the painting can be simulated when the optical properties of one or more pigments are altered. These pigment maps will also be beneficial for enriching the historical knowledge of the painting and aiding conservators in determining the best course for retouching damaged areas of the painting when metamerism is a factor. First, a new spectral reconstruction algorithm was developed based on Wyszecki’s hypothesis and the matrix R theory developed by Cohen and Kappauf. The method achieved both high spectral and colorimetric accuracies for a certain combination of illuminant and observer. The method was successfully tested with a practical spectral imaging system that included a traditional color-filter-array camera coupled with two optimized filters, developed in the Munsell Color Science Laboratory. The spectral imaging system was used to image test paintings, and the method was used to retrieve spectral reflectance factors for these paintings. Next, pigment mapping methods were brought forth, and these methods were based on Kubelka-Munk (K-M) turbid media theory that can predict spectral reflectance factor for a specimen from the optical properties of the specimen’s constituent pigments. The K-M theory has achieved practical success for opaque materials by reduction in mathematical complexity and elimination of controlling thickness. The use of the general K-M theory for the translucent samples was extensively studied, including determination of optical properties of pigments as functions of film thickness, and prediction of spectral reflectance factor of a specimen by selecting the right pigment combination. After that, an investigation was carried out to evaluate the impact of opacity and layer configuration of a specimen on pigment mapping. The conclusions were drawn from the comparisons of prediction accuracies of pigment mapping between opaque and translucent assumption, and between single and bi-layer assumptions. Finally, spectral imaging and pigment mapping were applied to three paintings. Large images were first partitioned into several small images, and each small image was segmented into different clusters based on either an unsupervised or supervised classification method. For each cluster, pigment mapping was done pixel-wise with a limited number of pigments, or with a limited number of pixels and then extended to other pixels based on a similarity calculation. For the masterpiece The Starry Night, these pigment maps can provide historical knowledge about the painting, aid conservators for inpainting damaged areas, and digitally rejuvenate the original color appearance of the painting (e.g. when the lead white was not noticeably darkened)

    O acerto de cores na reintegração cromática: a influência dos três atributos da cor e dos fenómenos óticos de distorção visual

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    Our visual perception is strongly influenced by the anatomical structure of the eye and bylighting conditions. While looking at the painting, we perceive existing colour attributes,using retinal photoreceptors – cones – that serve our vision at higher luminance levels. Lighting, on the other hand, affects our colour discrimination as well as our perception ofthree dimensions of colour. During the retouching process our visual system can be affected by multiple optical impressionsthat many painting conservators are not fully aware of. Colour distortion phenomena canimpact our observation stealthily, while producing simultaneous contrasts and after images that interfere with our colour discrimination as well as our decisions in pigment mixing.The aim of this paper is to analyse these optical properties and to provide practical guidelines that will minimize colour distortion. One of the proposals is the use of 18% reflective grey card to cover adjacent colours around the paint loss. This method can be adopted as a helpful implement for tuning our colour perception.Nuestra percepción visual está fuertemente influenciada por la estructura anatómica del ojo y por las condiciones de iluminación. Visualizamos los atributos de color existentes en una pintura a través de las células fotorreceptores de la retina – conos – que utilizan nuestra visión en niveles elevados de iluminación. La iluminación, por otro lado, afecta a nuestra discriminación de color, así como la percepción de las tres dimensiones de color. Durante el proceso de reintegración cromática nuestro sistema visual puede verse afectado por varios fenómenos de distorsión de los colores, de los que muchos conservadores - restauradores de pintura no son plenamente conscientes. Son fenómenos que pueden influir en nuestra observación furtivamente, como el contraste simultáneo y el contraste sucesivo, y que interfieren en nuestras decisiones durante el proceso de identificación y mezcla de pigmentos. El objetivo de este trabajo es analizar esos efectos ópticos y ofrecer algunas orientaciones prácticas para minimizar las distorsiones visuales del color. Una de las principales propuestas es el uso de un cartón gris con un 18% de reflectividad. Este método puede ayudar a la percepción de los colores circundantes de una laguna, evitando alguno de esos fenómenos.A nossa percepção visual é fortemente influenciada pela estrutura anatómica do olho e pelas condições de iluminação. Visualizamos os atributos de cor existentes na pintura através das células fotorreceptoras da retina – cones – que servem a nossa visão em níveis elevados de iluminação. A iluminação, por outro lado, afecta a nossa discriminação de cor, bem como a percepção das três dimensões da cor. Durante o processo de reintegração cromática o nosso sistema visual pode ser afectado por vários fenómenos de distorção das cores que muitos conservadores de pintura não estão totalmente conscientes. São fenómenos que podem influenciar a nossa observação furtivamente, como o contraste simultâneo e o contrate sucessivo, e que interferem nas nossas decisões durante o processo de identificação e mistura de pigmentos. O objectivo deste trabalho é analisar estes efeitos ópticos e fornecer algumas orientações práticas para minimização destas distorções visuais da cor. Uma das principais propostas é o uso de um cartão com 18% de reflectividade. Este método pode ajudar na percepção das cores circundantes de uma dada lacuna, evitando alguns destes fenómenos

    Preparation of clay-dye pigment and its dispersion in polymers

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    This thesis is concerned with an experimental study of clay intercalation by organic dye molecule which is crucial for the successful development of a stable clay-dye pigment with combined advantages of organic dye and inorganic clay. Clay-dye pigments were prepared by two different methods. Two different organic dyes were used with unmodified clay and modified clay to study the intercalation. Characteristics of clay-dye pigment have been investigated using X-Ray Diffraction, Thermo-gravimetric Analysis and Transmission Electron Microscopy. In this thesis it is shown that the absorption of cationic dye by unmodified clay in aqueous medium mainly takes place in the interlayer clay surface. More likely the dye molecules with aromatic quaternary ammonium cation intercalate the clay layer and strongly interacts with the clay interlayer oxygen plane, where solvent dye (which is hydrophobic in nature) adsorption by unmodified clay mainly takes place on outer surface of the clay. Dye molecules are weakly interacted with outer surface oxygen plane by hydrogen bonding or Vander Waals forces. Modified clay enabled the solvent dye to intercalate inside the clay interlayer surface with the suitable non-aqueous medium (because of its expanded structure). The modified clay suspension in the selected non-aqueous medium shows only partial desorption of alkyl ammonium molecule from the clay layer with the presence of both cationic dye and solvent dye. Therefore the penetrated dye molecules must have weakly interacted with the interlayer oxygen plane as well as the remaining alkyl ammonium molecule present inside the clay layer. It is believed that the thermal and UV stability of organic dye can only be facilitated by a specific interaction (Ĉ-interactions) between aromatic alkyl ammonium cation of organic dye molecule and the interlayer oxygen plane of clay minerals. This interaction possibly enables the high thermal energy or the energy of the UV radiation to transmit immediately into the clay layer. Therefore organic dye molecules are protected from high energy loading and hence thermal and UV stability are improved

    TECHNART 2017. Non-destructive and microanalytical techniques in art and cultural heritage. Book of abstracts

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    440 p.TECHNART2017 is the international biannual congress on the application of Analytical Techniques in Art and Cultural Heritage. The aim of this European conference is to provide a scientific forum to present and promote the use of analytical spectroscopic techniques in cultural heritage on a worldwide scale to stimulate contacts and exchange experiences, making a bridge between science and art. This conference builds on the momentum of the previous TECHNART editions of Lisbon, Athens, Berlin, Amsterdam and Catania, offering an outstanding and unique opportunity for exchanging knowledge on leading edge developments. Cultural heritage studies are interpreted in a broad sense, including pigments, stones, metal, glass, ceramics, chemometrics on artwork studies, resins, fibers, forensic applications in art, history, archaeology and conservation science. The meeting is focused in different aspects: - X-ray analysis (XRF, PIXE, XRD, SEM-EDX). - Confocal X-ray microscopy (3D Micro-XRF, 3D Micro-PIXE). - Synchrotron, ion beam and neutron based techniques/instrumentation. - FT-IR and Raman spectroscopy. - UV-Vis and NIR absorption/reflectance and fluorescence. - Laser-based analytical techniques (LIBS, etc.). - Magnetic resonance techniques. - Chromatography (GC, HPLC) and mass spectrometry. - Optical imaging and coherence techniques. - Mobile spectrometry and remote sensing

    Synthesis of ruthenium-phosphorus dyes and their incorporation in ZnO transparent conducting oxide and ZnO semi-conductor thin films for photovoltaic application

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    Cette thèse est consacrée au développement de nouveaux colorants moléculaires a base de complexes de ruthénium phosphorés, d'oxydes conducteurs transparents (TCO) et de matériaux semi-conduteurs (SC) à base de ZnO en vue de leur application dans des cellules solaires à colorants. Des voies synthétiques originales ont été développées pour la préparation de complexes symétriques et non symétriques de type ligands phosphorés fonctionnalisés. Les résultats obtenus souligne le rôle prépondérant des ligands phosphorés dans le contrôle des propriétés électroniques et optiques de ces colorants. Nous avons aussi étudié ZnO sous forme de films minces. En ciblant une interface TCO/SC homogène, des TCO à base d'oxyde de zinc dopés au Ga (ZnO:Ga) et des SC à base d'oxyde de zinc pur ont été déposés par pulvérisation cathodique radiofréquence à partir de cibles céramiques. Les microstructures et les propriétés physiques de ces matériaux ont été étudiées. Les conditions de dépôts ont été optimisées pour préparer des films minces TCO de ZnO:Ga présentant une grande transparence optique et de bonnes conductivités électroniques et des films minces SC à grande surface. La surface accessible des films minces ZnO a ensuite été améliorée par attaque chimique humide. Dans la dernière partie, nous avons associé les colorants moléculaires aux matériaux SC et TCO par greffage chimique. Des nanopoudres de ZnO ont été élaborées pour effectuer des tests de greffage avant leurs validations sur les matériaux en couche mince. Le colorant est ancré sur ZnO par les fonctions phosphorées. L'intégration de ces matériaux dans des cellules photovoltaïques à colorant sera l'objet de développements futurs.In this work, we studied the development of new molecular ruthenium-phosphorus dyes and new Transparent Conducting Oxide (TCO) and ZnO Semi-Conductor (SC) materials in view of integrating them in dye sensitized solar cells. This thesis described first the original synthetic pathways that were developed to prepare both symmetrical and non-symmetrical complexes [Ru(bpy)2LL']n+ (L, L' : functionalized phosphorus ligands). Results highlight the predominant role of the phosphorus ligands in tuning the electronic and optical properties of the corresponding dyes. Secondly, we studied the preparation of new ZnO materials. In the goal of obtaining a homogeneous TCO/SC interface, zinc oxide doped Ga (ZnO:Ga) TCO and zinc oxide SC thin films were deposited by RF magnetron sputtering using ceramic targets. The microstructure and physical properties of these materials were studied. The deposition conditions were specifically optimized to prepare dense ZnO:Ga thin films with high transparency and good electrical conductivity for the TCO layer on one hand, and porous ZnO with high accessible surface for the SC layer on the other hand. The accessible surface of relatively porous ZnO thin films were further extended by post-deposition wet chemical etching.Finally, we associated the molecular dyes to the SC and the TCO materials by chemical grafting. Preliminary grafting tests were first investigated on homemade ZnO nanopowders before being validated on thin film materials. In these new materials, the dye is anchored to the ZnO through phosphorus functionalized functions. As a continuation of this work, the integration of these new materials in DSSCs will be the focus of further studies

    Photonic Hydrogel Sensors

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    Analyte-sensitive hydrogels that incorporate optical structures have emerged as sensing platforms for point-of-care diagnostics. The optical properties of the hydrogel sensors can be rationally designed and fabricated through self-assembly, microfabrication or laser writing. The advantages of photonic hydrogel sensors over conventional assay formats include label-free, quantitative, reusable, and continuous measurement capability that can be integrated with equipment-free text or image display. This Review explains the operation principles of photonic hydrogel sensors, presents syntheses of stimuli-responsive polymers, and provides an overview of qualitative and quantitative readout technologies. Applications in clinical samples are discussed, and potential future directions are identified

    Photonic hydrogel sensors

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    Analyte-sensitive hydrogels that incorporate optical structures have emerged as sensing platforms for point-of-care diagnostics. The optical properties of the hydrogel sensors can be rationally designed and fabricated through self-assembly, microfabrication or laser writing. The advantages of photonic hydrogel sensors over conventional assay formats include label-free, quantitative, reusable, and continuous measurement capability that can be integrated with equipment-free text or image display. This Review explains the operation principles of photonic hydrogel sensors, presents syntheses of stimuli-responsive polymers, and provides an overview of qualitative and quantitative readout technologies. Applications in clinical samples are discussed, and potential future directions are identified

    Modeling and Halftoning for Multichannel Printers: A Spectral Approach

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    Printing has been has been the major communication medium for many centuries. In the last twenty years, multichannel printing has brought new opportunities and challenges. Beside of extended colour gamut of the multichannel printer, the opportunity was presented to use a multichannel printer for ‘spectral printing’. The aim of spectral printing is typically the same as for colour printing; that is, to match input signal with printing specific ink combinations. In order to control printers so that the combination or mixture of inks results in specific colour or spectra requires a spectral reflectance printer model that estimates reflectance spectra from nominal dot coverage. The printer models have one of the key roles in accurate communication of colour to the printed media. Accordingly, this has been one of the most active research areas in printing. The research direction was toward improvement of the model accuracy, model simplicity and toward minimal resources used by the model in terms of computational power and usage of material. The contribution of the work included in the thesis is also directed toward improvement of the printer models but for the multichannel printing. The thesis is focused primarily on improving existing spectral printer models and developing a new model. In addition, the aim was to develop and implement a multichannel halftoning method which should provide with high image quality. Therefore, the research goals of the thesis were: maximal accuracy of printer models, optimal resource usage and maximal image quality of halftoning and whole spectral reproduction system. Maximal colour accuracy of a model but with the least resources used is achieved by optimizing printer model calibration process. First, estimation of the physical and optical dot gain is performed with newly proposed method and model. Second, a custom training target is estimated using the proposed new method. These two proposed methods and one proposed model were at the same time the means of optimal resource usage, both in computational time and material. The third goal was satisfied with newly proposed halftoning method for multichannel printing. This method also satisfies the goal of optimal computational time but with maintaining high image quality. When applied in spectral reproduction workflow, this halftoning reduces noise induced in an inversion of the printer model. Finally, a case study was conducted on the practical use of multichannel printers and spectral reproduction workflow. In addition to a gamut comparison in colour space, it is shown that otherwise limited reach of spectral printing could potentially be used to simulate spectra and colour of textile fabrics
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