Дисертації з теми "Pigment art"

This practice-based research is centred on an investigation into the use of digital technologies within the Islamic art scene in the UK. The research explores perceptions and attitudes from the public and also stakeholders (including artists, curators and scholars) closely involved in the development and dissemination of Islamic art in educational and public art spaces. The locality of the Islamic art scene in the UK presents concerns related to not only classification and curation of Islamic art, representation, and authenticity in relation to Islamic art in the contemporary context, and the use of digital technologies for art-making. The impact of local and national media and associations with the faith of Islam were also presented as strong themes both in the literature review and the findings of this research. Taken into consideration is my own artistic practice involving digital technologies alongside non-digital methods for developing artworks. I discuss the hybridised term 'digital Islamic art' and explore how conceptual themes are addressed through hybridised artistic practice from further artists both in the UK and abroad. Through studies consisting of a public survey, interviews, and post-exhibition questionnaires, results showed a willingness from the public to find out more about digital Islamic art, and an interest in viewing more of this in the UK. The discussions on these topics may be of interest to artists, practitioners, academics, and also those involved in policy relating to furthering cultural engagement, as these are people in positions of influence, able to provide access and create opportunities for the public to encounter further contemporary Islamic art in the UK.

One of the most stunning works of art on the Scripps College campus is the mural Flower Vendors(1946). The artist,Alfredo Ramos Martínez, an influential figure in Mexican Modernism, executed the work using a variety of traditional and non-traditional techniques. Prior analysis of the work indicated the use of a wax emulsion medium and established the range of pigments used. Ramos Martínez’s use of lead chromate (chrome yellow, Pb(CrO4)) was unusual in wall painting, and the pigment itself has been shown to photodegrade and darken over time in oil paintings, due to the reduction of Cr(VI) to Cr(III). The Pb(CrO4) in Flower Vendorsdoes not appear to have darkened, raising questions about the stability of lead chromate in a wax-emulsion medium relative to that of oil-based mediums. To better understand the behavior of lead chromate in wax-based mediums, a historical synthesis of lead chromate was recreated, and the pigment was suspended in four different binder matrices: a wax-water emulsion, refined linseed oil, cold-pressed linseed oil, and poppy oil. Each of these paint-binder mixtures wasaged beneath full-spectrum 6500 K LED lights. The relative darkening of the pigments was measured using UV-Vis reflectance colorimetry, and comparisons were made between the mediums.

Abstract: This research presents the first archaeometric investigation on Damirgaya and Trialeti Rock art sites and the Neolithic settlement Khramis Didi Gora, South Caucasus, Georgia. The aim is to characterize rocks and pigments, to assess painting technology, including the possible identification of organic binders and the compatibility of inorganic pigments with those locally available. In order to build up our awareness and solve scientific curiosity, the research questions are cleared up through the comparison with adjacent archaeological sites, from Armenia, Azerbaijan and Anatolia, where traces of monochromatic red pigment were recovered in settlements, barrows, on artifacts, such as grinding tools and mainly on rock art. Several analytical techniques, specifically Optical Microscopy (OM) on samples as such and thin sections, X-ray Powder Diffraction (XRPD), and Scanning Electron Microscopy with Energy Dispersive X-ray analysis (SEM-EDX) were used to obtain mineralogical and chemical composition of the samples. Moreover, with the contribution of Fourier-Transform Infrared (FTIR) and Raman Spectroscopy, inorganic compounds were better characterized in both rock paintings and grinding tools. On the contrary, it was not possible to define organic compounds such as binders, possibly due to their low amount or absence. In terms of compatibility with local supplies, with the help of thin section and cross section analysis, it was possible to deduce that the mineralogical composition of the rocks is relatively similar to pigment samples. In terms of pigments, hematite was the major pigment used for rock art and grinding tools, while in terms of rock samples, that of Trialeti is an igneous basaltic dacite, whereas that of Damirgaya is a rock mainly composed of quartz, but it is also characterized by other minerals, such as iron oxides are likely present, as well as phyllosilicates.

La présente thèse, relative aux matériaux locaux et innovation dans les métiers d’"art-isanat" en Tunisie, vise, dans un premier temps, l'étude des ambiguïtés définitionnelles liées au métiers d’art avec toutes leurs déclinaisons dans le contexte socio-économique et culturel tunisien. Ces métiers seront comparés avec ceux de la France, pays partenaire de la Tunisie,pour en tirer les points de similitudes et de différences pour faire ressortir les principaux moteurs d'expansion. Dans un second temps, notre recherche se tourne vers l’établissement d’un bilan des connaissances des matériaux locaux répartis par régions tunisiennes. La poterie/céramique artisanale et la bijouterie ont constitué les deux créneaux majeurs de notre ensemble d’études. Des argiles locales et des pigments de la Tunisie utilisés ou pas par les artisans (es) dans les métiers liés à la poterie artisanale ont fait l’objet d'une caractérisation scientifique (minéralogique, chimique et géotechnique), réalisée dans des laboratoires spécialisés. Cela a permis d’améliorer les compositions des pâtes d'argiles et de découvrir des couleurs naturelles authentiques pouvant constituer un vecteur d'innovation. D’autres matériaux locaux, comme le quartz fumé bi-pyramidé pour la bijouterie, peuvent constituer un créneau valide et important pour la promotion des métiers d’artisanat en Tunisie. Cette recherche est basée essentiellement sur des analyses scientifiques et des réflexions épistémologiques et s’intègre principalement dans le cadre de la recherche en Design
The present thesis, relating to local materials and innovation in the craft trades of “art-isanat”in Tunisia, aims, initially, at studying the definitional ambiguities related to craft trades with all their variations in the Tunisian socio-economic and cultural context. These trades will becompared with those of France, Tunisia's partner country, to draw points of similarities and differences to highlight the main drivers of expansion. In a second stage, our research isaimed at drawing up an assessment of the knowledge of local materials distributed byTunisian regions. Artisanal pottery/ceramics and jewellery were the two major niches of ourset of studies. Local clays and pigments from Tunisia used or not by craftsmen in tradesrelated to artisanal pottery have been scientific characterization (mineralogical, chemical and geotechnical), carried out in specialized laboratories. This has allowed us to improve the composition of the clay pastes and discover authentic natural colors that could be a vector ofinnovation. Other local materials, such as bi-pyramid smoked quartz for jewelers, can constitute a valid and important niche for the promotion of crafts in Tunisia. This research isessentially based on scientific analyses and epistemological reflections and is mainly part of the design research

The objectives of this project were to develop a high performance liquid chromatographic method for separating the pigment esters mixture, to determine the locations of the pigment moiety in the isolated esters using pholosiphases, and to characterize the pigment-protein complex and determine its distribution in other bacteria. Saponification of the two pigment esters 1 and 2 with aqueous KOH yielded two free pigments on TLC plates developed by two solvent systems. The fasters moving of these two free pigments co-chromatographed with the one free pigment produced from each pigment ester by phospholipase A2 treatment. This suggests that the pigment molecule is a methoxy derivative of xanthomonadin and is esterified to the 2-position of the glycerol moiety of each pigment ester. No free pigment was released from phospholipases C and D treatment of the two pigment esters, indicating that pigment is not esterified to the sorbitol or phosphate moiety of pigment esters 1 or 2.

Le fard est une composition dont l’application sur la peau donne à celle-ci plus d’éclat ou masque un défaut physique. Accusé de tromper, instrument futile ou diabolique auquel fut comparée la peinture, le fard se définit par sa fonction mais ne s’y réduit pas. L’observation de trois vidéos permet d’étudier le fard en tant qu’il est matière colorée et conduit à déterminer ses propriétés spécifiques et les possibilités plastiques qu’elles véhiculent.Cette recherche vise à établir les modalités d’une relation entre le fard, la couleur, et le corps support au travers d’expériences plastiques filmées pour le caractériser ensuite comme médium à partir d’une pratique personnelle
Makeup is a composition which when applied to the skin gives it more brightness or hides a physical defect. Accused of cheating, a futile or diabolical instrument, which paint has been compared, make-up is defined by its function but has lost nothing through this.The plastic arts experience allows study of make-up because it is colored and this helps determine its specific properties and plastic possibilities.This research aims to establish the details of a relationship between makeup, color and the body, using several videos to characterize it as a medium based on personal practice

Si bien podemos creer que el estudio de objetos arqueológicos y artísticos es de carácter netamente estilístico o histórico, en realidad, una aproximación a ellos a través de la química puede brindar información importante también.  En un país como el nuestro, con un amplio patrimonio cultural, es mucho lo que un químico puede hacer para ayudar a conocer mejor estos objetos y a saber conservarlos.
Although we may think that studies of archaeological and artistic objects are mainly historical or stylistic, a chemical approach can also provide important information about them.  In a country like ours, with a vast cultural heritage, a chemist can do a lot to further our knowledge of these objects and to help in their conservation.

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Conselho Nacional de Desenvolvimento Científico e Tecnológico
Based on the history of science, this research aimed to discover the materials used as pigment and the specificities of colonial Brazilian artistic production through literature related to decorative arts of the period. To achieve some of those materials we‟ve referred the treatises on painting of the italians Cennino Cennini‟s Trattato della Pittura (c. 1398) and Giorgio Vasari‟s Le Vite de più eccelenti architetti, pittori, et scultori italiani, da Cimabue, insino a tempi nostril (1550); of the portugueses Filipe Nunes‟s Arte da Pintura, Symetria e Perspectiva (1615); as well as the dictionary of terms of Rafael Bluteau‟s Vocabulario Portuguez e Latino (1712) and the text Segredos necessarios para os officios, artes e manufacturas, e para muitos objectos sobre a economia domestica (1794). We also observed artistic knowledge present in some of the books published by the Casa Literária do Arco do Cego and partner publishers (1799 to 1801). Several elements to the composition of this research came from contemporary studies in the areas of architecture and conservation restoration related to Jesuit constructions of art and colonial painting and scientific analyses of these materials
Com base na História da Ciência, esta pesquisa buscou conhecer os materiais usados como pigmento e as especificidades da produção artística colonial brasileira a partir da literatura referente às artes decorativas do período. Para conhecer um pouco sobre esses materiais, percorremos os tratados de pintura dos italianos Cenino Cennini, Trattato della pittura (c.1398), e Giorgio Vasari, Vida dos artistas (1550); dos portugueses Felipe Nunes, Arte da pintura, symetria e perspectiva (1615); assim como o dicionário de termos de Rafael Bluteau, Vocabulario portuguez e latino... (1712), e o texto Segredos necessarios para os officios, artes e manufacturas, e para muitos objetos sobre a economia doméstica (1794). Recorremos também aos conhecimentos artísticos presentes em alguns dos livros publicados pela Casa Literária do Arco do Cego e por editoras parceiras (1799 a 1801). Diversos elementos para a composição desta pesquisa vieram ainda dos estudos contemporâneos das áreas de arquitetura e conservação e restauração relacionados às construções jesuíticas, à arte e à pintura colonial e às análises científicas desses materiais

The purpose of this research was to explore two ways of the application of chitosan, a biopolymer, for ink jet printing of textiles. 1) To apply chitosan as a post-treatment on the fabric ink jet printed with pigment based inks for the fixation of pigments on the fabric. 2) To incorporate chitosan as a binder in pigment based ink jet ink formulations. The incorporation of chitosan was carried out in two ways. 1) Direct addition of chitosan into the ink formulations containing surface modified pigments. 2) Preparation of chitosan encapsulated pigment nanoparticles using complex coacervation technique and using these nanoparticles for the formulation of ink jet ink. The degree of deacetylation (DD) was determined using FTIR spectroscopy. Various protocols proposed by researchers were used to determine the DD of chitosan samples used in the present study. The protocol proposed by Raut was found to be fairly accurate in determining the DD of chitosan samples. The molecular weight of chitosan was estimated using dilute solution viscometry method. The characterisation of the film forming ability of chitosan was evaluated using scanning electron microscopy (SEM). The colour strength (K/S), colour difference, colour characteristics and colour fastness to laundering and rubbing of ink jet printed fabrics post treated with chitosan were evaluated using standard methods. Post-treatment (pad-dry-cure method) of cotton fabric ink jet printed with pigment based inks revealed that chitosan could effectively fix the pigments on cotton compared to the commercial textile binders and the water-soluble derivative of chitosan. The chemical interaction between chitosan and cotton fabric was illustrated by FTIR-ATR analysis and through determination of carboxyl group content. The ink jet printed cotton fabric post treated with 3gpl chitosan (MW 156,156) maintained almost 86% of bacterial reduction against Klebsiella Pneumoniae even after 50 launderings. Inks containing chitosan were formulated and were found to be stable in terms of mean particle size and viscosity over a period of one month and for 4 freeze/thaw cycles. A magenta ink containing chitosan was selected for ink jet printing of cotton fabric. It was found that the DF was around 97% for magenta ink containing chitosan compared to around 53% fixation for magenta ink without chitosan on cotton fabric. Surface modified carbon black pigment with carboxylated (COO-) surface functionality was selected to prepare chitosan encapsulated pigment nanoparticles by complex coacervation technique. Chitosan encapsulated pigment nanoparticles with mean particle size diameter of 876 nm and 742 nm were formed when 5 ml of 0.1% w/v pigment was mixed with 2ml and 3ml of 0.1% w/v chitosan, respectively. However, no correlation was found between the particle size of the nanoparticles formed and the concentration of chitosan. The DF with ink containing chitosan encapsulated pigment nanoparticles was found to be around 98% while the blank ink with only surface modified carbon black pigment showed 44% fixation.

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.

Since the mid 1980s, Raman and X-ray fluorescence spectroscopy have become instrumental techniques that can be easily and successfully applied to chemical analysis. In this respect, scientific studies of works of art and the materials used in their creation are one of the fields that have received great impulse.
Several reasons for the spectroscopic investigation of antiquities and art objects can be pointed out. One of them is the interest in the materials and techniques in use during a certain period or region. This knowledge may be utilized for roughly dating the art object (retrieving pigments with a known date of invention may indicate that the artifact dates from a more recent period). Another reason is that this analysis is a useful source of information during a restoration or conservation treatment, and signs of a previous restoration, retouching or even forgeries can be found.

At the beginning of this century investigation in cultural heritage became an important research field that posed great scientific interest, requiring unprecedented interdisciplinary knowledge of a wide spectrum of areas such as history, archaeology, physics, chemistry, engineering, chemometrics and many other disciplines. On the other hand, improvements in the instrumental techniques used have been the goal of many important studies. Even more, in this decade the investigation has been focalized on the development of a new generation of instruments which allows the combination of complementary analytical techniques along with the advantage of portable instrumentation. Both improvements permit a robust and non-destructive chemical analysis of works of art which are difficult or impossible to study in a laboratory (highly valuable masterpieces, large paintings, and wall paintings).
Chemometrics methods are the necessary complement to these instrumental improvements. In order to maximize the robustness of these instruments, automatic and robust data processing tools are needed to obtain the maximum possible information from a work of art.
This doctoral thesis presents a framework to perform data-fusion systems for classification analysis of pigments investigated in the field of cultural heritage. These systems were developed and evaluated within a European Community research project, the main objective of which was to develop a portable micro Raman and micro X-ray fluorescence instrument (PRAXIS).

The general aim of this doctoral thesis is to study different strategies for the implementation of Raman-XRF data-fusion systems, in order to improve classification analysis of pigments investigated in the field of cultural heritage. This study takes into account the nature of the different interferences usually encountered in these types of signals and its elimination by developing dedicated algorithms. Moreover, this study evaluates automation in classification analysis by developing inference systems.


In order to reach that global aim these particular objectives are defined:

1) To study the nature of stochastic events and signal interferences present in Raman and XRF spectroscopy in order to enable the implementation of chemometrics techniques for classification. This is done in more detail for Raman data, due to the fact that this technique is mainly used in this field for "fingerprint" analysis. The methodology used is Wavelet transform and the improvements achieved in this area are presented in a paper entitled Noise and background removal in Raman spectra of ancient pigments using wavelet transform.
2) To establish the capabilities of a fuzzy logic system for automatic pigment identification. This issue is presented in a paper entitled Fuzzy logic for identifying pigments studied by Raman spectroscopy.
3) To review the current state-of-art of data-fusion in analytical chemistry and to establish actual data-fusion methodologies onto a Raman-XRF sensor fusion system. The performance of each data-fusion architecture is discussed in a paper entitled Micro Raman and X-ray fluorescence spectroscopy data fusion for the classification of ochre pigments.
4) To improve data-fusion methodologies by dual-domain analysis achieved by Wavelet transform. The achievements are presented in two papers Data fusion and dual-domain classification analysis of pigments studied in works of art and Data fusion in the wavelet domain by means of fuzzy aggregation connectives.
5) To define the necessary parameters and propose a methodology to implement data-fusion strategies in Raman and XRF spectroscopy.

Structure

The thesis has been structured in different chapters, each one containing the following information:

Chapter 1 is a theoretical chapter; the first part gives an overview of the basic concepts and latest advances in the fields of micro-Raman spectroscopy and micro-X ray fluorescence spectrometry. The characteristics of a new instrument which combines both techniques are presented along with the improvements achieved in that area. In the second part, the background of chemometrics techniques used in this work is presented.

Chapter 2 introduces the framework for the study of ancient pigments. It describes the nature of samples analyzed and gives an overview of the different techniques used in the creation of works of art throughout the years. Finally, the instruments used in this doctoral thesis for preliminary and final validation analysis are described.

Chapter 3 deals with the data pre-treatment needed before applying chemometric techniques, both for classification and data-fusion. In that respect, the first part focuses on the principles of Wavelet transform as a tool to eliminate signal interferences. This chapter includes a paper in which the development of an innovative method to eliminate noise and background signals from Raman spectra simultaneously is presented. It has been successfully applied for Raman spectra of ancient pigments.

Chapter 4 presents a preliminary study of automatic analysis of pigments by means of soft computing solutions such as Fuzzy logic. A published paper is presented in which Fuzzy logic is used to perform an automatic system for pigment identification. This study is extended to a fusion model and X-ray fluorescence analysis data is incorporated in the developed identification system. The ability of fuzzy logic to process imprecise information is described in the last part of this chapter.

Chapter 5 deals with three data-fusion architectures and their analysis by means of hard computing solutions as Principal components analysis (PCA) and Partial least squares - discriminant analysis (PLS-DA). The models are implemented for the classification of a set of ancient pigments from Byzantine iconography. Benefits and drawbacks of each method are pointed out.

Chapter 6 incorporates a new innovative strategy for data-fusion. The fusion of data in the wavelet domain is discussed and two approaches are presented for Raman and X-ray fluorescence data-fusion: Mid-level and High level dual domain data-fusion. Both are used and successfully applied for the automatic identification of pigments in classification problems with different levels of difficulty. Two papers are included in which both methods are used for the classification of ancient pigments, which face difficult identification problems. These two methods combine the benefits described in the previous chapters of this thesis with the consequent improvement of classification results. The developed systems are suitable to perform a rapid and automatic classification of ancient pigments.

Chapter 7 presents a review of the state of the art regarding data-fusion. The different steps necessary to achieve a proper data fusion are discussed.

Finally, Chapter 8 presents the conclusions of the thesis and suggests some possible issues for future research.




Fusión de datos en espectroscopias Raman y de fluorescencia de rayos X para la identificación de pigmentos en trabajos de arte
Desde mediados de los años 80s, las espectroscopias Raman y de fluorescencia de rayos X (XRF) se pueden considerar técnicas instrumentales de fácil aplicación en el análisis químico. Uno de los ámbitos de gran aplicación de dichas técnicas se centra en el estudio científico de una obra de arte y de los materiales utilizados en su creación.
Existen varias razones para la investigación de antigüedades y objetos de arte por medio de técnicas espectroscópicas. Una de ellas es el estudio de los materiales y técnicas aplicados durante un cierto período o en una determinada región. Este conocimiento puede ser muy útil para ubicar aproximadamente un objeto de arte en una determinada época o periodo. Otra razón es que este análisis es una importante fuente de información para la restauración o el tratamiento de conservación, y permite encontrar señales de una restauración anterior, de repintado o de falsificaciones.

Desde el comienzo de este siglo, la investigación en el patrimonio cultural se sitúa como un campo de la investigación importante con un gran interés científico. Esta investigación, requiere un importante trabajo multidisciplinario que implica a especialistas en áreas como historia, arqueología, física, química, ingeniería, quimiometría y otras disciplinas. Por otro lado, el objetivo de muchos trabajos científicos y estudios importantes, ha sido el desarrollo y las mejoras en estas técnicas instrumentales de análisis. Más aun, en esta década la investigación está enfocada en el desarrollo de una nueva generación de instrumentos que permiten la combinación de técnicas analíticas complementarias junto con la ventaja de una instrumentación portátil. Ambas mejoras permiten un análisis químico robusto y no destructivo de los objetos de arte, en especial de aquellos en los que resulta difícil o casi imposible de estudiar en un laboratorio. Como por ejemplo obras de arte de gran valor y pertenecientes al patrimonio cultural del país, pinturas de grandes dimensiones y pinturas realizadas en murales.

Los métodos Quimiométricos de análisis son el complemento necesario a estas mejoras instrumentales. Con objeto de aumentar al máximo la robustez de estos instrumentos, es necesario proveerlos de herramientas de procesamiento automáticas y robustas para obtener el máximo de información del objeto bajo estudio.
Esta tesis doctoral, presenta un marco de referencia para realizar fusión de datos para la clasificación e identificación de pigmentos estudiados en el campo de patrimonio cultural. Estos sistemas se desarrollan y evalúan dentro de un proyecto de investigación de la comunidad europea. El objetivo principal de este proyecto ha sido desarrollar un instrumento portátil para realizar espectroscopias Raman y de fluorescencia de rayos-X (PRAXIS).

El objetivo general de esta tesis doctoral es estudiar diferentes estrategias para el desarrollo de sistemas de fusión de datos Raman y XRF para mejorar la clasificación de pigmentos. Este estudio contempla la naturaleza de las distintas interferencias que habitualmente se encuentran en estos tipos de mediciones (espectros) y su eliminación por medio del desarrollo de metodologías adecuadas. También, se evalúa la posibilidad de automatización en el proceso de clasificación.


Para alcanzar este objetivo global, se definen los siguientes objetivos particulares:

1) Estudiar la naturaleza de eventos estocásticos (ruido) e interferencias habitualmente presentes en espectroscopia Raman y XRF, con el fin de facilitar la aplicación de técnicas quimiométricas de clasificación. Este estudio se realiza más profundamente para los espectros obtenidos por espectroscopia Raman, ya que es la técnica principalmente utilizada en este campo para una identificación del tipo "huella digital." La metodología usada es la transformada Wavelet y las mejoras logradas se presentan en un artículo titulado "Ruido y eliminación de señales de fondo en espectros Raman de pigmentos antiguos por medio de la transformada Wavelet".
2) Establecer un sistema de lógica difusa para la identificación automática de pigmentos. Este estudio se presenta en un articulo titulado "Lógica difusa para identificar pigmentos estudiados por espectroscopia Raman".
3) Estudiar la situación actual de aplicaciones y desarrollos de fusión de datos en química analítica y establecer las metodologías de fusión de datos reales en un instrumento Raman-XRF. Los resultados obtenidos en distintos modelos de fusión de datos se discute en un articulo titulado "Fusión de espectros Raman y de fluorescencia de rayos X para la clasificación de pigmentos ocres".
4) Mejorar las metodologías de fusión de datos por medio del análisis en el dominio dual dado por la transformada Wavelet. Los logros obtenidos se presentan en dos artículos "Fusión de espectros y análisis de clasificación en el dominio dual de pigmentos estudiados en obras de arte" y "Fusión de datos en el dominio Wavelet por medio de conectores de agregado difuso".
5) definir los parámetros necesarios y proponer a una metodología llevar a cabo las estrategias de fusión de espectros en espectroscopias Raman y XRF.

Estructura

La tesis ha sido la estructura en capítulos diferentes, donde cada uno contiene la siguiente información:

El capítulo 1 es un capítulo teórico; donde en una primera parte se da una apreciación global de los conceptos básicos y de los últimos adelantos en espectroscopias Raman y de fluorescencia de rayos X. Las características de un nuevo instrumento que combina ambas técnicas se presentan junto con las mejoras logradas en él. En una segunda parte, se describen las técnicas quimiométricas usadas en este trabajo.

El capítulo 2 describe la naturaleza de las muestras estudiadas y de su uso en la creación de obra de arte. Finalmente, se describen instrumentos Raman y XRF usados en esta tesis doctoral.

El capítulo 3 presenta el tratamiento necesario en los datos antes de aplicar las técnicas quimiométricas, ya sea para la clasificación y/o fusión de datos. En ese sentido, se presenta un estudio de la aplicación de la transformada Wavelet como una herramienta para eliminar las interferencias señaladas. Este capítulo incluye un artículo en el que nosotros presentamos el desarrollo de un método innovador para eliminar simultáneamente las señales de ruido y fondo es espectros Raman.

El capítulo 4 presenta un estudio preliminar del análisis automático de pigmentos por medio de la lógica difusa. Se presenta artículo donde la lógica difusa es utilizada para realizar un sistema automático de identificación de pigmentos. Este estudio se extiende a un modelo de fusión y por el cuál la información obtenida por XRF es incorporada en el sistema de identificación desarrollado.

El capítulo 5 presenta tres arquitecturas de fusión de datos y el posterior análisis por medio de técnicas quimiométricas como el análisis de componentes Principal (PCA) y la regresión por mínimos cuadrados parciales para análisis discriminante (PLS-DA). Los modelos se llevan a cabo con el estudio de pigmentos antiguos referidos a la iconografía bizantina. Esta parte acaba señalando los beneficios y desventajas de cada método.

El capítulo 6 presenta una nueva estrategia para la fusión de datos, que es la fusión de datos en el dominio del wavelet. Se discuten los fundamentos y se presentan dos modelos de fusión de datos Raman y XRF en el dominio wavelet: El nivel medio y el nivel alto, ambos se aplican a la identificación automática de pigmentos. Dos artículos son incluidos, donde se describen ambos métodos y se presenta su aplicación para la clasificación de pigmentos antiguos.

El Capítulo 7 presenta un estudio sobre el estado actual en la investigación de fusión de datos y su aplicación en química analítica. Las etapas necesarias para desarrollar métodos apropiados de fusión de análisis.

Finalmente, en el capítulo 8 presenta las conclusiones de la tesis y propone posibles trabajos de investigación futura.

Includes bibliographical references.
This dissertation quantifies and compares the mass of the ochre assemblages and the surface area of rock paintings from the same sites based on colour classification from the Later Stone Age assemblages of three rock shelters, De Hangen, Andriesgrond and Diepkloof in the Western Cape, South Africa. This work begins to bridge the gap that exists between the excavated archaeology and the examination of rock paintings which has been primarily focused on the iconography. The colours present in the rock art are quantified using a standardised colour system. A preference is shown for saturated 10R hues, based on the Munsell classification, in the fine line and handprinting rock art traditions, whilst the colonial era paintings may illustrate a more ad hoc approach, an interpretation bolstered by survey analysis. The colours of the ochres from the excavated assemblages do not match the colours seen in the rock paintings, the colours of the ochres being clustered more toward 2.5YR and 5YR Munsell hues. The concept of “ghost ochre” has been proposed in order to describe those ochres, in the colours shown to be preferentially used in the rock art, that have been utilised in their entirety and are accordingly absent from the archaeology. A proposed cause for this is that the primary ochre processing strategy employed by the inhabitants may have been that of pulverisation rather than grinding. Some experimental hearths were conducted to examine possible colour changes in buried ochres, and these samples were analysed by colorimetric means and by X-ray diffraction. Ultimately it has been demonstrated that the relationship between ochre and rock paintings from the same site is more complex than has been previously assumed. The findings in this thesis have implications for future research in rock art studies and analyses of LSA and MSA ochre assemblages.

The purpose of this study was to completely characterize the protein moiety in the caroteno complex in C. poinsettae, determine if the distribution and level of protein in the pigment-protein complex in membranes of the wild type and in a colorless mutant could account for the differences in the stability of the membrane, and to determine if this protein is common to other pigmented and non-pigmented organisms. Also, electron microscopy of cell membranes of C. poinsettiae which had been exposed to gold-labelled antibody against the protein moitey of the pigment-protein complex, demonstrating that the protein is randomly distributed in the membranes of both wild type and colorless mutant.

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Science and Art are two concepts that have been greatly evolved throughout history, mainly due to cultural evolution experienced by humanity itself. Science, in its primitive stage, as synonymous of knowledge, preceded the Arts. However, according to its current concept considered as a result of the proposed method, by Francis Bacon, it is a recent phenomenon when compared to the period of human existence on Earth. Thus, Art preceded Science, because from its beginning it always configured as such, despite the different ways in which it has been presented. This is why the term Arts is used instead of Art. Among the Sciences, separated as Natural Sciences and Humanities, Physics stands out, even in the primitive stage of science, always referred to Nature as a whole, justifying its etymology Physics, the Greek Physis that means Nature and, according to available records, developed with the Arts since prehistory. In this context, this work, which presents a brief history of the evolution of perception and color reproduction by man, has as main attribute a study of the concept of color, pigment and light as taking Physics as a foundation, according to the branch of knowledge called Optics. From a literature search, the author s and other expert s experiences, both in Arts and in Science in General, an approach of Arts and Physics is presented, in terms of interdisciplinarity that exists between the color theme and concepts of physical optics, as one of the branches of this science. Records used are based on works that still exist, such as cave paintings and paintings in other processes, frescoes and sculptures, as well as the bibliography, documents preserved in museums, libraries and cultural venues, and statements from researchers, due to their own works. It was also included in this compilation the development of some technics of color reproduction, both in pictorial art, using pigments, as in architectural lightening projects, fabrication of transparent and colored glasses and at photographic, cinematographic and digital arts from light sources, in its different ways of generation and applications.
Ciência e Arte são dois conceitos que mudaram muito ao longo da história, sobretudo, em decorrência da própria evolução cultural vivida pela humanidade. A Ciência, em seu estágio primitivo, como sinônimo de conhecimento, antecedeu a Arte, todavia, segundo sua concepção atual, em razão da proposta do Método, por Francis Bacon, é algo recente em comparação ao tempo de existência do ser humano na Terra. E, nesse sentido, a Arte antecedeu a Ciência, pois desde o seu princípio ela sempre se configurou como tal, não obstante as várias formas com as quais se apresentou, por isso, por diversas vezes menciona-se Artes ao invés de Arte. No rol das Ciências, agrupadas em Ciências Naturais e Ciências Humanas, destaca-se a Física, que mesmo no estágio primitivo das ciências, referiu-se sempre à Natureza como um todo, justificando sua própria etimologia Física, do Grego, Physis que significa Natureza e, deste modo, de acordo com os registros disponíveis, acompanha as Artes desde a Pré-história. Neste contexto, o presente trabalho, que apresenta um breve histórico da evolução da percepção e da reprodução das cores pelo homem, tem como principal atributo um estudo do conceito de cor, como pigmento e como luz, tendo a Física como alicerce, de acordo com o ramo de conhecimentos denominado Óptica. A partir de uma pesquisa bibliográfica, de experiências do autor e de outros especialistas, tanto nas Artes como nas Ciências em Geral, proporcionou-se uma ampla abordagem das Artes e da Física, em termos da interdisciplinaridade que se verifica entre o tema Cor e os conceitos físicos da Óptica, como um dos ramos desta ciência. Os registros utilizados são fundamentados por obras ainda existentes, desde o tempo das pinturas rupestres até a contemporaneidade, em seus diversos processos, incluindo objetos tridimensionais, como esculturas, dentre outros. Esta fundamentação inclui também a bibliografia, documentos localizados em museus, espaços culturais e bibliotecas, bem como depoimentos de pesquisadores, em função de seus respectivos trabalhos. Contempla-se ainda a evolução de algumas técnicas de reprodução de cores, tanto na Arte Pictórica, com o uso de pigmentos, como na iluminação de ambientes, produção de vidros incolores e coloridos e a Arte Fotográfica, Cinematográfica e Digital, a partir de fontes de luz, em suas diversas formas de obtenção e de algumas aplicações.

Diagnostic research of the three mural paintings from Alcântara Maritime Station in Lisbon was conducted in order to understand the main decay phenomena and their dynamics, with respect for future conservation work. The analytical setup was composed of in-situ analyses by p-OM, spectro-colorimetry and h-EDXRF, followed by micro-sampling for a more profound analyses with OM, SEM-EDS, μ-XRD, FT-IR and py-GC-MS. Deterioration features identified include salts (salts efflorescence and sub efflorescence), flaking, lacunae, erosion and lack of cohesion of paint layers. Developed salts were classified as sulphates and their origin seems to be linked to polluted atmosphere and water infiltration into building materials. Greenish paint layer present in all three murals appears as the most deteriorated one, as it shows problems of severe flaking and lacunae; Resumo: Desvelando a arte mural de Almada Negreiros nas estações marítimas de Lisboa: Diagnóstico de pesquisa de camadas de pintura como guia para sua conservação futura Uma pesquisa diagnóstica das três pinturas murais da Estação Marítima de Alcântara, em Lisboa, foi realizada para entender os principais fenômenos de degradação e sua dinâmica com respeito a trabalhos futuros de conservação. A configuração analítica foi composta por análises in-situ com p-OM, espectro-colorimetria e h-EDXRF, seguida de micro-amostragem para análises mais profundas com OM, SEM-EDS, μ-XRD, FT-IR e py-GC-MS. As características de deterioração incluem sais (eflorescência e subflorescência), descamação, lacunas, erosão e falta de coesão. Os sais desenvolvidos foram classificados como sulfatos e sua origem parece estar ligada à atmosfera poluída e à infiltração de água em materiais de construção. A camada de tinta esverdeada presente nos três murais aparece como a mais deteriorada, pois apresenta severos problemas de descamação e lacunas.

Violacein is a purple pigment typically produced by species of Chromobacterium and Janthinobacterium. A soil isolate, identified as as Janthinobacterium, was studied. Maximal pigmentation ocurred at 25°C under aerobic conditions in the Keeble and Cross medium.

At various points in human history, tattooing has been ubiquitous on almost every continent on Earth, used for reasons of aestheticism, religious beliefs or for social purposes. To study the art of tattooing with respect to a particular culture, one must always be critical to any references to the practice (written, pictorial or artefactual) due to issues of translation and misinterpretation. Complete verification may only come with the discovery of actual tattooed human remains. In combination with artefactual and anthropological evidence, these remains not only provide physical proof of the practice in a culture's ancestry but also possess the ability to link various other forms of physical evidence, which on their own would remain speculative. By its very nature, tattooing may only exist while the bearer is alive. Once the owner dies, the skin, along with the tattoo, decomposes (under normal decomposition conditions) and is lost forever. However, tattoos may survive if the dermal layers of the skin are preserved, either by natural or artificial means. The processes of mummification in various civilisations have provided us with a rare opportunity to study the art and processes of tattooing in antiquity. Existing tattooed mummified remains have been found in: Egypt; Siberia; Eastern Central Asia; Greenland; Alaska and St. Lawrence Islands; Central Andes (Peru and Chile); Philippines; New Zealand and Italy. Existing literature regarding the analysis of tattooing inks and pigments once deposited into the skin is very limited. Comparatively, the industrial organic pigments used to colour the majority of modern tattooing inks sold today have not been officially approved by any regulating body and as such, manufacturers are not required to disclose the chemical ingredients of their products. Chemical identification of these tattoo pigments post-procedure will aid medical practitioners in the event of complications or for the purposes of tattoo removal. Forensically, tattoos are often one of the distinguishing features used in the identification of victims of crime or accidents. Experiments were carried out using an animal model (Sus scrofa) for the tattooing. Given the theoretically large but ultimately limited range of substances available to both ancient and modern tattooists, the premise of the experiment involved surveying the literature regarding possible tattooing pigments and either obtaining or reproducing a careful selection of these in the laboratory. These pigments were then tattooed onto the ii animal model and after allowing for the essential healing period, the tattooed areas were excised, with those tattooed with traditional pigments subjected to various simulated mummification environments.

Master of Science
Food Science Institute - Food, Nutrition, Dietetics and Health
Weiqun Wang
Sorghum is a staple crop consumed in certain regions of Africa and Asia, where vitamin A deficiency is prevalent. However, the correlation of sorghum intake and vitamin A deficiency is inconsistent. The objective of this study was to identify and quantify the carotenoids and pro-vitamin A in the selected sorghum accessions with various pericarp pigments by using LC-MS. Among of total five carotenoids (α-carotene, β-carotene, lutein, zeaxanthin, and β-cryptoxanthin) that were identified and quantitated, three (α-carotene, β-carotene and β-cryptoxanthin) are precursors of vitamin A. The highest content of total carotenoids was detected in the sorghum accessions with yellow pericarp (PI656096, PI585374, PI563448, PI585351), while the highest β-carotene content was found in the accessions with brown or yellow pericarp (PI655996, PI656096, PI585374, PI563448, PI585351). The lowest carotenoids were found in the accessions with white pericarp (PI533943, PI656112, PI565121, PI560493). The pro-vitamin A was 584.9 ± 38.9 ng/g DW in yellow pericarp, 250.6 ± 28.9 ng/g DW in brown pericarp, and 89.0 ± 12.3 ng/g DW in white pericarp, respectively. It appeared the phenotypic diversity of sorghum pericarp colors was strongly associated with the contents of carotenoids and pro-vitamin A, indicating a different impact of various sorghum varieties on vitamin A deficiency and suggesting a possible prevention of vitamin A deficiency by breeding certain sorghum varieties with pericarp pigments.

Cette thèse porte sur la genèse de la chimie colloïdale et étudie en particulier la trajectoire du groupe des colloïdes de la grande compagnie américaine Du Pont de Nemours pendant l’entre-deux guerres. Elle cherche à comprendre l’articulation entre les enjeux scientifiques que les substances « colloïdales » soulèvent, et les enjeux techniques, industriels et économiques des matériaux associés. Le concept de « basculement ontologique des matériaux », élaboré récemment par deux historiens de la chimie, est repris comme cadre interprétatif des bouleversements dans lesquels ces programmes de recherches qualifiés de « fondamentaux » se déploient. Le secteur industriel des peintures et vernis, matériaux en partie considérés comme colloïdaux au cours de cette période, est particulièrement étudié. Le groupe des colloïdes bouleverse l’appréhension des peintures et vernis à travers une focalisation sur les pigments minéraux qui les composent, et concoure ainsi à la domination de Du Pont sur certains pigments comme le lithopone et l’oxyde de titane. D’une manière générale, cet apport scientifique et technique s’inscrit dans une ambition globale de relier systématiquement microstructures et propriétés. Cette nouvelle appréhension des propriétés des substances sur la base de leurs constituants microscopiques devient progressivement un auxiliaire indispensable à la « rationalisation » des procédés et des propriétés des matériaux, ainsi qu’à la stratégie de brevetage de ces produits et procédés. Cette rationalisation des produits et procédés accompagne l’essor de la grande consommation - et la focalisation accrue sur la figure du « consommateur » - sur les peintures et vernis
This dissertation deals with the emergence and growth of colloid chemistry in the early twentieth century, focusing particularly on the history of the colloid group set up at Du Pont, a major American chemical company, during the interwar period. It explores the relationship between the scientific issues raised by “colloidal” substances, and the technical, industrial and economic dimensions of the associated materials. The concept of “ontological shift of materials”, recently forged by two historians of chemistry, is appropriated as an interpretative framework to account for these evolutions in colloid science and technology. The paint and varnish industry, whose materials were then largely considered as colloidal, is taken as a major case study to analyze these relationships and evolutions, and its history is explored since the beginning of the century. The group was propelled by the quantification of the microstructure of these materials, in order to better explain and master their practical properties. The dissertation details why and how this new understanding of the properties of many substances on the basis of their microscopic components became, from the interwar onwards, embedded in the “rationalization” of the properties of materials, the processes to produce them, as well as the associated patents. This rationalization of products and processes is concomitant to the emergence of mass consumption – and the new emphasis on the “consumer” figure within companies – of industrially produced goods, particularly those of the paint and varnish industry

Дисертація на здобуття наукового ступеня доктора технічних наук за спеціальністю 05.17.11 – технологія тугоплавких неметалічних матеріалів, Державний вищий навчальний заклад "Український державний хіміко-технологічний університет", Національний технічний університет "Харківський політехнічний інститут", Харків, 2020. Дисертацію присвячено розвитку наукових основ технології екологічно безпечних захисно-декоративних склоемалевих покриттів широкої колірної гами по сталі і кольоровим металам, а також принципів регулювання та прогнозування їх колірних характеристик. Внаслідок проведення дослідження за темою дисертаційної роботи одержані такі наукові результати: - науково обгрунтовано та експериментально доведено, що отримання на кольорових металах емалевих покриттів, які не вміщують Плюмбум, можливе на основі стекол системи Na₂O–BaO–B₂O₃–SiO₂; за комплексом визначених властивостей та здатності утворювати найбільш якісні покриття на мідній основі виділена область базової системи, мол.%: Na₂O – 24,2–40,5; ВаО – 5,0–10,0; B₂O₃ – 15,2–30,5; SiO₂ – 24,0–53,5, яка у зрівнянні з межами цих компонентів в відомих складах безплюмбатних емалей характеризується збільшеним в 2 рази вмістом B₂O₃ і відносно невеликим вмістом SiO₂; - встановлені основні тенденції зміни колірного тону стекол системи Na₂O–BaO–B₂O₃–SiO₂, які суттєво відрізняються за хімічним складом та забарвлені іонними барвниками, з огляду на розташування максимумів ІЧ-спектрів стекол та їх кислотно-основні властивості; останні оцінювались двома розрахунковими структурними параметрами: fSi – ступінь зв’язності кремнекисневого каркасу і Ψв – орієнтовний показник координаційного стану Бору в структурі скла. Доведено, що між колірним тоном λ та Ψв існує значний кореляційний зв'язок для стекол, забарвлених CuO r*=−0,83 і CoO r*=−0,87 та слабкий – для стекол, забарвлених K₂Cr₂O₇ – r*=0,5; - виявлені закономірності забарвлення одної скломатриці і емалевого покриття на її основі в системі R₂O–ВаО–ZnO–Al₂O₃–В₂О₃–TiO₂–SiO₂ рядом іонними барвників. Незалежно від вмісту барвників, вони надають однаковий колірний тон як стеклам, так і покриттям на основі цих стекол, а саме: CuO (1,0–3,0 мас.%) λ=489–494 нм (синьо-зелений), Fe₂O₃ (0,5–2 мас.%) λ=575–585 нм (жовтий), K₂Cr₂O₇ (0,5–2,0 мас.%) λ=570–576 нм (жовто-зелений), CoO (0,5–1,0 мас.%) λ=441–463 нм (синьо-фіолетовий), NiO (0,5–1,0 мас.%) λскла=559′–571′ нм, λпокриттів=598–629 нм (коричневий). Доказано, що за ступенем інтенсивності забарвлення стекол та покриттів на їх основі барвники розташовуються в наступній послідовності: CoO > NiO > CuO > K₂Cr₂O₇ > Fe₂O₃; - вперше встановлений механізм глушіння прозорого матричного емалевого скла в системі R₂O–ВаО–ZnO–TiO₂–Al₂O₃–В₂О₃–TiO₂–SiO₂ при введені МоО3, в результаті якого виникає явище опалесценції, а саме: за рахунок дифракції при розповсюдженні хвиль в мікронеоднорідному середовищі, в якому розмір часток молібден(VI) оксиду (0,05–0,15 мкм) менше довжини хвиль білого світла; - вперше встановлена залежність коефіцієнта дифузного відбиття емалевих покриттів від хімічного складу емалевих фрит, яка отримана обробкою експериментальної вибірки 471 складу покривних емалевих фрит методом множинного кореляційного аналізу і представлена у вигляді математичної моделі, що дозволяє розрахувати хімічний склад покривних емалей із заданим КДВ; коефіцієнт кореляції між експериментальними і розрахунковими значеннями – 0,98; - використовуючи ідею про введенні в будь-який матеріал (скло, пігмент, ситал, метал) певних компонентів в незначній кількості для модифікації його властивостей, вперше виявлено наступне: «малий додаток» Fe₂O₃ у кількості 0,25 мас.% в складі безплюмбатних емалевих стекол на основі базової системи Na₂O–BaO–B₂O₃–SiO₂ і 1 мас.% в складі безфлуористих склоемалей на основі базової системи Na₂O–B₂O₃–SiO₂ активізує процеси лікваційного розшарування скла, що дозволяє збільшити в 1,5–2,5 рази інтенсивність глушіння покриттів, а також покращити оптико-колірні характеристики пігментнозабарвлених склопокриттів, зокрема, червоного кольору. «Малий додаток» ZrO₂ у кількості до 1 мас.% в складі малофлуористої титанової емалі сприяє активному виділенню анатазу в покритті під час випалу та покращенню його оптичних характеристик; - за допомогою розробленої спеціальної комп’ютерної програми COLOUR GLASS, яка автоматично розраховує координати кольорності x y, колірний тон λ, чистоту кольору Р та наносить колірні характеристики матеріалів на графік МКО, вперше доказано, що за картиною розташування точок кольору, по-перше, можна робити прогнози відносно рівноваги, яка утворюється між іонними забарвлюючими комплексами під час варки скла, по-друге, про колористичні можливості суміши пігментів - вперше в області технологій, які потребують підвищених температур, встановлені залежності координат кольору емалевих покриттів від складу суміші пігментів у вигляді поліноміальних математичних моделей, що дозволило вирішити складну матеріалознавчу колористичну проблему знаходження співвідношення пігментів для відтворення кольору зразка із заданими колірними характеристиками. Практичне значення отриманих результатів: - розроблено склади емалевих стекол для кольорових металів, які не містять Плюмбуму – одного із самих шкідливих для навколишнього середовища елемента, запропоновано основи технології одержання виробів з їх використанням. Нові емалі широкої палітри кольорів, різного ступеню прозорості створено на основі матричної прозорої емалі. Вони характеризуються однаковим інтервалом випалу 780–820 °С, у зв’язку з чим спрощується технологія отримання художніх і ювелірних виробів. Емалі пройшли випробування та рекомендовані до впровадження у виробництво з виготовлення художніх виробів в майстерні, що знаходиться в структурі Музею українського живопису (м. Дніпро), а також на підприємстві з виготовлення ювелірних виробів, компанія "Diadema", м. Вінниця. Палітра емалевих покриттів та вироби з них представлені під час доповіді на 24 Міжнародному Конгресі емальєрів в м. Чикаго у 2018 р. Згідно міжнародного договору між ДВНЗ УДХТУ та компанією "Richemont International SA Varinor SA" м. Делемонт, Щвейцарія, виготовлено і передано замовнику емалеві стекла у вигляді порошку і емальовані мідні зразки; - створено каталог зразків кольорів, в якому представлено склооснови, кількість барвників, глушників, відновників та оптико-колірні характеристики емалевих покриттів, що не містять Плюмбум. Назву кольорів встановлювали у відповідності із назвою кольорів системи RAL. Палітра розроблених емалей ювелірного та художнього призначення включає 54 кольори: жовто-червоні, синьо-зелені, оливково-гірчичні, пастельні та коричнево-чорні; - розроблено склади малофлуористих білих і світлозабарвлених титанових емалей, безфлуористої склооснови для отримання яскравозабарвлених емалевих покриттів пігментним способом, які випробувані в виробничих умовах ТОВ «Новомосковський посуд» і рекомендовані до серійного впровадження на заводах з випуску емальованих виробів господарчо-побутового призначення. Технологічні особливості виробництва запропонованих емалей дозволяють здійснювати високотемпературні операції варки емалей на 100 °С, а випалу покриттів – на 30–50 °С нижче відомих, що в епоху тотальної економії топливно-енергетичних ресурсів дуже актуально. Малофлуористі світлозабарвлені кремова і сіро-блакитна емалі впроваджені на ТОВ "Новомосковський посуд"; - вперше для технології емалевих покриттів на сталі розроблено метод колірного моделювання, завдяки якому побудовано колірний трикутник-номограму для виробничої склооснови і пігментів жовтого, червоного, синього, за допомогою якого задається необхідний колір і розраховується необхідне співвідношення пігментів. Метод колірного моделювання є універсальним і може бути застосованим до широкого асортименту силікатних матеріалів: глазуровані покриття на керамічній основі, кольорові будівельні матеріали та інші. У вступі обґрунтовано актуальність теми дисертації, сформульовано головну мету та завдання роботи, представлено наукову новизну та практичну цінність одержаних результатів. В першому розділі наведено аналіз патентної та науково-технічної літератури, що стосується отримання екологічно безпечних емалей широкої колірної гами, сучасного стану виробництва кольорових емалей та контролю їх колірних показників, механізмів забарвлення скла та емалей і факторів, що впливають на формування кольору. У другому розділі надано основні поняття та визначення, які використовуються в роботі, а також методики дослідження фізико-хімічних властивостей і структури стекол, покриттів та їх колірні характеристики. В третьому розділі представлено дослідження з розробки екологічно безпечних емалей для міді та прогнозування їх колірних характеристик. В четвертому розділі представлено результати досліджень з розробки легкоплавкої титанової емалі, яка відповідала б вимогам діючих стандартів та випалювалась в ресурсо- та енергозберігаючих умовах виробництва та була максимально екологічно безпечною для навколишнього середовища. П'ятий розділ присвячений дослідженням з розробки складів емалевих фрит, що не вміщують Флуор, які використовуються для отримання яскравозабарвлених емалевих покриттів для виробів господарчо-побутового призначення. В шостому розділі представлені результати розробки методу колірного моделювання. Відтворити, а тим більше спрогнозувати колір із заданими колірними характеристиками – надзвичайно складна багатопланова матеріалознавча проблема, навіть якщо відома рецептура скла і покриття, режими їх варки та випалу. В сьомому розділі надано результати промислової апробації, реалізації та впровадження отриманих матеріалів.
Thesis for a Doctor of Science Degree in Specialty 05.17.11 – Refractory Non-Metallic Materials Technology, State Higher Educational Institution "Ukrainian State University of Chemical Technology", National Technical University "Kharkiv Polytechnic Institute", Kharkiv, 2019. The dissertation is devoted to creation of physicochemical bases of technology of ecologically safe protective and decorative glass-enamel coatings of wide color scale on steel and non-ferrous metals, development of principles of regulation and prediction of their color. As a result of the research on the topic of dissertation the following scientific results were obtained: - scientifically substantiated and experimentally proved that the production of lead-free enamel coatings on non-ferrous metals is possible on the basis of the Na₂O – BaO – B₂O₃ – SiO₂ glasses, by the complex of defined properties and the ability to form the highest quality coatings on a copper basis the selected region of the base system, mol %: Na₂O – 24,2–40,5; BaO – 5.0–10.0; B₂O₃ – 15.2–30.5; SiO₂ – 24,0–53,5, which in comparison with the limits of these components in known compositions of lead-free enamels, is characterized by a 2-fold increase in the content of B2O3 and a relatively small content of SiO₂; - the basic tendencies of color change of glasses of Na₂O–BaO–B₂O₃–SiO₂ system has been established, which differ significantly in chemical composition and has colored by ionic dyes, taking into account the structural features of glasses and their acid-basic properties. They has been evaluated by two calculated structural parameters: fSi is the degree of connectivity of the silica framework and Ψв is an indicative index of the coordination state of Boron in the structure of the glass. It had proved that there is a significant correlation between the colors λ and Ψv had proved for glasses colored CuO r * = - 0,83 and CoO r * = - 0,87 and weak – for glasses colored K₂Cr₂O₇, -r * = 0,5; - the patterns of coloring of one glass matrix and enamel coatings on its basis in the system R₂O–BaO–ZnO–Al₂O₃–B₂O₃–TiO₂–SiO₂ by a series of ionic dyes has been founded. Regardless of the content of the dyes, they give the same color tone to the glass and coatings based on these glasses, namely: CuO (1.0–3.0 wt%) λ = 489–494 nm (blue-green), Fe₂O₃ (0.5–2 wt%) λ = 575–585 nm (yellow), K₂Cr₂O₇ (0,5–2.0 wt%) λ = 570–576 nm (yellow-green), CoO (0.5–1.0 wt%) λ = 441–463 nm (blue-violet), NiO (0, 5-1.0 wt.%) λ glass = 559′ – 571 nm, λ coatings = 598–629 nm (brown). It has been proved that in the degree of color intensity of glasses and coatings based on them, the dyes has been arranged in the following sequence: CoO> NiO> CuO> K₂Cr₂O₇ > Fe₂O₃; - for the first time, the mechanism of silencing of transparent matrix enamel glass in R₂O–BaO–ZnO–TiO₂–Al₂O₃–B₂O₃–TiO₂–SiO₂ system with the introduction of MoO₃ has been established, which results in the phenomenon of opalescence, namely: due to diffraction at propagation of waves in micro inhomogeneous medium in which the particle size of molybdenum (VI) oxide is 0.05-0.15 μm less than the wavelength of white light; - for the first time, the dependence of the diffuse reflection coefficient (CDR) of enamel coatings on the chemical composition of enamel frits, obtained by processing the experimental sample 471 of the enamel frit composition by multiple correlation analysis, which is presented in the form of a mathematical model that allows you to calculate the chemical composition of the enamel coatings with a given CDR; the correlation coefficient between experimental and calculated values is 0.98; - using the idea of introducing into any material (glass, pigment, sitall, metal) certain components in a small amount to modify its properties, the following has been first discovered: "small addition" of Fe₂O₃ in the amount of 0.25 wt.% in the composition of lead-free enamel glasses based on the base system Na₂O–BaO–B₂O₃–SiO₂ and 1 wt.% in the composition of fluorless glass enamels based on the basic system Na₂O–B₂O₃–SiO₂ activates the processes of differentiation of the segregation-dropping structure of glass, which allows to increase the intensity of opaque coatings by 1.5–2.5 times, as well as to improve the optical-color characteristics of pigment-colored glass coatings, in particular, red. "Small addition" of ZrO₂ in the amount up to 1 wt.% in the composition of low-fluoride titanium enamel promotes the active release of anatase in the coating during firing and improving its optical characteristics; -with the help of a dedicated COLOR GLASS computer program that automatically calculates color coordinates x y, color tone λ, color purity P, and maps the color characteristics of materials to the СIE graph, it has been first demonstrated that the picture of the location of the color points, first, you can make predictions about the equilibrium that is formed between the ionic coloring complexes during the melting of glass, and secondly, about the color potential of the pigment mixture. - for the first time in the field of technologies requiring high temperatures, the dependences of the color coordinates of the enamel coatings on the composition of the pigment mixture in the form of polynomial mathematical models has been established, which made it possible to solve the complex material-coloristic problem of finding the ratio of pigments to reproduce the color of the sample with the specified color characteristics. The practical significance of the obtained results: - the compositions of enamel glasses for non-ferrous metals, which do not contain Plumbum - one of the most harmful for the environment element, had been developed; the basics of technology of obtaining products with their use had offered. New enamels of a wide range of colors with varying degrees of transparency had been created on the basis of matrix transparent enamel and they had characterized by the same firing interval of 780-820 °C, which makes the technology of obtaining artistic and jewelry easier. Enamels had been tested and recommended for implementation in the production of artistic products in the workshop, which locates in the structure of the Museum of Ukrainian Painting (Dnipro), as well as at the jewelry company, Diadema, Vinnytsia. The enamel coatings palette and their products had presented during a report at the 24th International Congress of Enamels in Chicago in 2018. According to an international agreement between the Ukrainian State University of Chemical Technology (Dnipro) and Richemont International SA Varinor SA, Delmont, Switzerland, enamel glass powder and enameled copper samples had been made and handed over to the customer; - a catalog of color samples, which presents the glass base, the number of dyes, opacifiers, reducing agents and the optic-color characteristics of enamel coatings which do not contain Plumbum, has been created. The color name was set in accordance with the color name of the RAL system. The palette of designed enamels of jewelry and artistic purpose includes transparent matrix enamel and 53 colors: yellow-red, blue-green, olive-mustard, pastel and brown-black; - a series of compositions of white and light-colored titanium enamels containing reduced amount of Fluorine, has been developed, also the composition of fluorless frites to obtain brightly colored enamel coatings pigmented way of color, which were fused and passed extensive testing in production conditions factories for the production of enameled household products, has been synthesized. Technological features of production of the enamels offered permits to carry out high-temperature operations of melting at 100oC below the known ones, and firing of coatings – by 30-50 °C, which is very relevant in the era of total saving of fuel and energy resources. Low-fluoride light-colored cream and gray-blue enamels has been introduced at "Novomoskovsk dishes"; - for the first time for the technology of enamel coatings on steel, a method of color modeling has been developed, through which a color triangle-nomogram has been constructed for the production glass base and pigments of yellow, red, blue, by which the required color is specified and the necessary ratio of pigments is calculated. The color modeling method is versatile and can be applied to a wide range of silicate materials: glazed ceramic coatings, colored building materials, and more. The introduction substantiates the relevance of the dissertation topic, formulates the main purpose and objectives of the work, presents the scientific novelty and practical value of the obtained results. The first section provides an analysis of the patent and scientific and technical literature concerning the production of environmentally safe enamels of a wide color range, the current state of production of colored enamels and the control of their color indices, the mechanisms of color of glass and enamels and factors affecting color formation. The second section provides the basic concepts and definitions used in the work, as well as methods for investigating the physicochemical properties and structure of glasses and coatings and their color characteristics. The third section presents studies on the development of environmentally safe enamels for copper and the prediction of their color characteristics. The fourth section presents the results of research on the development of fusible titanium enamel which would meet the requirements of current standards and be burned in resource- and energy-efficient production conditions and be the most environmentally safe for the environment. The fifth section is devoted to the research on the development of enamel frits that do not contain Fluorine and used to produce brightly colored enamel coatings for household products. The sixth section presents the results of the development the color modeling method. Reproduce, and even more so predict, color with predetermined color characteristics is an extremely complex multifaceted material science problem, even if glass and coating formulations, modes of melting and firing are known. In the seventh section the results of industrial testing, realization and implementation of the received materials has been presented.

The application of spectroscopic techniques is crucial for art historians and conservators who require knowledge of materials used in works of art (pigments, dyes, binders, additives, ...) in particular instances. In this sense, the knowledge of pigments which were in use on the ancient artists' palettes is fundamental to preserve the art works. In addition, this knowledge is important to determine correct conservation approaches, to study degradation processes or authenticity-related issues. For instance, the proper interpretation of molecular signatures from a vibrational spectroscopy gives valuable information about the materials used by the artists. In this regard, the spectral identification is one of the essential interpretations to be performed, which is generally carried out by visual comparison between the unknown spectra with an appropriate database of reference spectra. This identification approach while being simple and intuitive may turn out a complex task which usually requires an experienced analyst and inevitably introduces an element of subjectivity linked to the intervention of the investigator. Besides, these analyses can be limited due to interferences from other phenomena like noises or admixtures. This task is further complicated when the spectra are to be interpreted by a software system. Hence, the noise impact must be reduced to have an effective identification and a robust strategy for processing multi-component spectra needs to be implemented. Clearly, a fully-automated data processing system for a reliable spectral interpretation is of practical interest. Several automated methodologies were designed, developed and analysed in this Ph.D. Thesis for the purposes of art works analysis through Raman spectroscopy. In this sense, the usage of mathematical morphology together with p-spline fitting demonstrated to be a consistent combination in the application of data enhancement Raman spectra from artistic pigments. Besides, a generalised identification methodology to identify single- and multi- component spectra was developed. This identification method relies on automated spectral matching based on principal component analysis (PCA) and independent components analysis (ICA), being computationally efficient and conceptually simple. Moreover, a supervised classification methodology to automatically distinguish between Raman spectra showing small differences was developed. According to predefined reference training sets, the classification method is able to classify unknown Raman spectra relying on PCA and multiple discriminant analysis (MDA). Both the identification and classification methodologies successfully work using a single spectral observation for the unknown Raman spectra, with no user intervention or previous knowledge of the analysed sample. The designed, developed and analysed automated methodologies for noise filtering and identification and classification of artistic pigments are integrated in a global system for the automated data interpretation of spectra from art works analysis implemented in this Ph.D. Thesis, namely PigmentsLab. This software platform together with the integrated methodologies can play a good auxiliary role in the analysts' endpoint interpretation, providing insight from the raw spectral measurements into pigments. The system implementation provides an easy-to-use software platform and straightforward to update when new spectral data become available. The robust, reliable and consistent results obtained on Raman spectra demonstrated the competitiveness of the implemented data processing solutions. The system has great potential as an accurate and practical method for the automated interpretation of Raman spectra for not only pigment analysis, but essentially for any material group.
La aplicación de técnicas espectroscópicas es crucial para los conservadores de arte que requieren el conocimiento de los materiales utilizados en obras de arte (pigmentos, aglutinantes, aditivos, ...) en casos particulares. En este sentido, el conocimiento del uso de los diferentes pigmentos en las paletas de los artistas es fundamental para preservar las obras de arte. Este conocimiento es importante para determinar las estrategias de conservación correctas, para estudiar los procesos de degradación o problemas relacionados con la autenticidad de las obras de arte. Por ejemplo, la interpretación adecuada de las firmas moleculares de una espectroscopia vibracional proporciona información valiosa sobre los materiales utilizados por los artistas. La identificación espectral es una de las interpretaciones esenciales a realizar, y generalmente se lleva a cabo mediante la comparación visual entre los espectros desconocidos con una base de datos adecuada de los espectros de referencia. Esta estrategia de identificación, a pesar de ser sencilla e intuitiva, puede resultar una tarea compleja que requiere generalmente de un analista experimentado e inevitablemente introduce un elemento de subjetividad vinculado a la intervención del investigador. Además, estos análisis pueden verse limitados debido a interferencias de otros fenómenos como ruido o mezclas de pigmentos. Esta tarea se complica aún más cuando los espectros deben ser interpretados por un computador. Por tanto, el impacto del ruido debe ser reducido para tener una identificación eficaz, y se debe implementar una estrategia robusta para el procesado de espectros de múltiples componentes. El desarrollo de un sistema de procesado de datos totalmente automatizado para una interpretación espectral fiable es de evidente interés práctico. Varias metodologías automatizadas han sido diseñadas y desarrolladas en esta tesis doctoral, focalizadas en el análisis de arte mediante espectroscopia Raman. En este sentido, el uso de morfología matemática junto con el ajuste basado en p-splines demostró ser una combinación consistente en la aplicación de mejora de la calidad de espectros Raman de pigmentos artísticos. Además, se ha desarrollado una metodología de identificación generalizada para identificar los espectros Raman compuestos tanto de un solo pigmento como de múltiples pigmentos. Este método de identificación se basa en la búsqueda de coincidencia espectral automatizada basada en el análisis por componentes principales (PCA) y el análisis por componentes independientes (ICA), siendo un método computacionalmente eficiente y conceptualmente simple. Por otra parte, se ha desarrollado una metodología de clasificación supervisada para distinguir entre espectros Raman que muestran pequeñas diferencias entre ellos. A partir de conjuntos de referencia predefinidos de datos de entrenamiento, el método de clasificación es capaz de clasificar los espectros Raman desconocidos mediante PCA y el análisis discriminante múltiple (MDA). Tanto la metodología de identificación como la de clasificación funcionan correctamente utilizando una sola observación espectral para los espectros Raman desconocidos, sin intervención del usuario ni el conocimiento previo de la muestra analizada. Las metodologías automatizadas diseñadas y desarrolladas para el filtrado de ruido y la identificación y clasificación de pigmentos artísticos están integradas en un sistema global para la interpretación automatizada de datos a partir de espectros medidos en obras de arte que ha sido implementado en esta tesis doctoral, llamado PigmentsLab. Esta plataforma software puede representar un buen papel auxiliar en la interpretación de punto final de los analistas, proporcionando valor a partir de las medidas espectrales en bruto de pigmentos artísticos. Los resultados obtenidos en los espectros Raman analizados, siendo robustos y consistentes, demuestran la competitividad de las soluciones de tratamiento de señal implementadas.

The mechanism of protection by carotenoids against photodynamic killing in Curtobacterium flaccumfaciens pathover poinsettiae (C. poinsettiae) was studied using pigment mutants isolated by treatment with nitrosoguanidine and DNA gyrase inhibitors. Growth rates, pigment composition, pigment levels and the ultrastructure of the wild-type streptomycin resistant strain of G. poinsettiae (wt-str) and all mutants were compared. One mutant, NTG-1, lacked colored carotenoids, and another, NTG-2, was a slow growing mutant containing low levels (14%) of wild-type carotenoid pigments. Except for NTG-1, the other pigment mutants had different proportions of the same pigments found in the wild type as determined by high performance liquid chromatography (HPLC). Only NTG-2 was morphologically distinct at the ultrastructural level.

Дисертація на здобуття наукового ступеня доктора технічних наук за спеціальністю 05.17.11 – технологія тугоплавких неметалічних матеріалів, Державний вищий навчальний заклад "Український державний хіміко-технологічний університет", Національний технічний університет "Харківський політехнічний інститут". Дисертацію присвячено науковим основам технології екологічно безпечних склоемалевих покриттів широкої колірної гами для сталі і кольорових металів, розробці принципів регулювання та прогнозування їх кольору. Розроблена спеціальна комп’ютерна програма COLOUR GLASS, яка за визначеними координатами кольору XYZ автоматично розташовує точки кольору на графіку МКО. Отримані емалі ювелірного та художнього призначення на основі стекол системи Na₂O–BaO–B₂O₃–SiO₂. Розроблені малофлуористі білі і світлозабарвлені титанові емалі, безфлуориста основа для пігментного способу забарвлення. Створено метод колірного моделювання, за допомогою якого можна розрахувати співвідношення пігментів для відтворення кольору зразка за заданими колірними характеристиками.
Thesis for a Doctor of Science Degree in Specialty 05.17.11 Refractory Non-Metallic Materials Technology, State Higher Educational Institution "Ukrainian State University of Chemical Technology", National Technical University "Kharkiv Polytechnic Institute". The dissertation is devoted to development of scientific bases of technology of ecologically safe protective and decorative glass-enamel coatings of wide color scale on steel and non-ferrous metals, making of principles of regulation and prediction of their color. The introduction substantiates the relevance of the dissertation topic, formulates the main purpose and objectives of the work. The first section provides an analysis of the patent and scientific and technical literature. The second section provides the basic concepts and definitions used in the work, methods for investigating the physicochemical properties and structure of glasses and coatings and their color characteristics. The third section presents studies on the development of environmentally safe enamels for copper and the prediction of their color characteristics. The fourth section presents the results of studies on the development of small fluoride titanium enamel with a firing temperature of 830 °C. The fifth section had devoted to scientific bases of technology of fluorless enamel frits for pigment method of coloring. The sixth section has devoted to the development of the color modeling method for reproducing the color of a sample with specified color characteristics. In the seventh section the results of industrial testing, implementation and implementation of the received materials has presented. As a result of the research on the topic of dissertation the following scientific results has obtained: - scientifically substantiated and experimentally proved that the production of lead-free enamel coatings on non-ferrous metals is possible on the basis of the Na₂O–BaO–B₂O₃–SiO₂ glasses, the regions of glass formation has been determined, and the regularities of changes in the properties of glasses depending on their chemical composition has been established; - the main tendencies of change of glasses color tone has established in the Na₂O–BaO–B₂O₃–SiO₂ system, which has colored by ionic dyes given the structural features of the glasses and their acid-base properties; - it has been proved that the degree of color intensity of glasses in the system R₂O –BaO – ZnO – Al₂O₃ – B₂O₃ – TiO₂ – SiO₂ and coatings based on them has been arranged in the following sequence: CoO> NiO> CuO> K₂Cr₂O₇> Fe₂O₃; - for the first time the mechanism of opacifying of transparent matrix enamel glass in the R₂O – BaO – ZnO – TiO₂ – Al₂O₃ – B₂O₃ – TiO₂ – SiO₂ system was introduced when MoO₃ has been established, namely: due to diffraction, which results in the phenomenon of opalescence; - for the first time the dependence of the diffuse reflection coefficient of enamel coatings on the chemical composition of enamel frits has been established, which is presented in the form of a mathematical model; the correlation coefficient between experimental and calculated values is 0.98; - for the first time the mechanism of opacifying of transparent matrix enamel glass in the R₂O – BaO – ZnO – TiO₂ – Al₂O₃ – B₂O₃ – TiO₂ – SiO₂ system was introduced when MoO3 has been established, namely: due to diffraction, which results in the phenomenon of opalescence; - for the first time it has been discovered that Fe₂O₃ "small additive" in the amount of 0.25 wt.% in the composition of lead-free enamel glasses on the basis of the Na₂O – BaO – B₂O₃ – SiO₂ base system and 1 wt. Fe₂O₃ in the composition of fluor-free enamel glasses on the basis of the Na₂O – B₂O₃ – SiO₂ base system activates the processes of glass removal stratification, which allows to increase 1.5-2.5 times the intensity of coating damping; - with the help of a special computer program COLOR GLASS, which automatically calculates the coordinates of the color x, y, the color tone λ, the purity of the color P and applies the color characteristics of the materials to the CIE graph, it has been proved for the first time that the chart of the location of color points can make forecasts about the equilibrium, which formed between ionic coloring complexes during glass melting; - for the first time in the field of technologies requiring high temperatures, the dependences of the color coordinates of enamel coatings on the composition of the pigment mixture in the form of polynomial mathematical models has been established, which allowed to solve the complex material-coloristic problem of finding the ratio of pigments to reproduce the color of the sample with the specified color characteristics. The practical significance of the obtained results: - the compositions of enamel art and jewelry glasses for non-ferrous metals, which do not contain Plumbum, has been developed. They are characterized by the same firing interval of 780-820 °C. A catalog of color samples has created. The palette includes fondon and 53 colors: yellow-red, blue-green, olive-mustard, pastel and brown-black; - a series of compositions of white and light-colored titanium enamels containing reduced amount of Fluorine (up to 2.5 wt.%), has been developed, also the composition of fluorless frites to obtain brightly colored enamel coatings pigmented way of color. Temperature operations of the enamel melting is 100 °C and firing of coatings is 30-50oC below the known ones.

Ce travail de thèse concerne la caractérisation et la compréhension de la réactivité du système sépiolite-indigo. Il vise, d’une part, à l’approfondissement de la connaissance physicochimique du célèbre pigment mésoaméricain « bleu Maya », et d’autre part, à proposer le système sépiolite-indigo comme modèle d’un procédé de fabrication de couleurs à base d’argiles fibreuses et de colorants. Par l’élaboration de nanocomposites hybrides colorés, cette étude s’inscrit dans le domaine, en plein essor, de la « chimie verte » et des matériaux nanocomposites d’origine naturelle. Cette recherche s’inscrit également au cœur d’une polémique entre deux écoles scientifiques étudiant le bleu maya, ‘lune « théorique », l’autre » expérimentale », autour de la localisation de l’indigo « in » dans ou « out » hors des tunnels de l’argile. Aujourd’hui les auteurs s’accordent à dire que les molécules d’indigo ne sont pas situées dans les tunnels de l’argile, mais dans les canaux, après une caractérisation approfondie des matériaux de départ choisis par souci de simplification, à savoir la sépiolite et l’indigo, la mise au point du procédé de fabrication (équilibre-température-durée-concentration) et l’élaboration des échantillons ont été réalisées. L’analyse de ces derniers via différentes techniques (FTIR, ATG, RMN, DRX, MEB/EDS, TOF-SIMS) a permis d’apporter au moins quatre preuves expérimentales de la présence, dans certains cas, profonde de l’indigo dans les tunnels de la sépiolite. Deux types de complexes réversibles ont été mis en évidence. L’un, à température ambiante via l’établissement de liaisons hydrogène et de liaisons de Van Der Waals avec les deux molécules d’eau coordinée de la sépiolite, l’autre à chaud, suite au départ d’une molécule d’eau coordinée. Pour la première fois la réversibilité du système est observée et caractérisée. A ce résultat très original s’ajoute l’ypothèse de l’obtention des verts maya via la photodégradation d’un mélange palygorskites-indigo non cuit. Le savoir-faire acquis lors de ce travail, c’est-à-dire l’encapsulation (introduction, stabilisation et protection) de molécules organiques dans une matrice de sépiolite ou d’attapulgite, nous a permis d’obtenir une large gamme de composites bleus, verts, violets, jaunes et noirs, qui sont le point de départ vers l’élaboration de nouveaux pigments inspirés des matériaux anciens
This work reports on the characterization and understanding of the reactivity of the sepiolite-indigo system. The aim is first, increasing chemical knowledge of the famous maya blue, second proposing the sepiolite-indigo system as a model of color fabrication process based on palygorskites clays and dyes hybrid nanocomposites elaboration is part of the full expansion fields of both green chemical and natural materials research. This work is taking part in a wild polemic debate about the location on indigo molecules, oppositions exist between the theoretical and experimental points of view are the indigo molecules are not in tunnels of the clays ? It is generally agreed today that the indigo molecules are not in tunnels but in the channels of palygorskites clays. So, in this work, after r=the thorough characterization of the raw materials, sepiolite and indigo, the process and sample elaboration have been realized. The process is a slight equilibrium between temperature, time and concentration. The results obtained from various analytical methods (FTIR, ATG, RMN, DRX, MEB/EDS, TOF-SIMS) permit us to bring out at least four experimental proofs concerning the presence of indigo molecules deeply introduced in the tunnels of sepiolite. Two types of temperature dependent complexes were observed. The first were characterized at room temperature, the second were obtained after high temperature treatments when the coordinated water molecule are leaving both are reversible. Hydrogen and Van Der Waals bonds are supposed to be the main complete interactions. These results are quite new and original. It is the first time that the reversibility is observed. Concerning archaeological topic this work propose hypothesis concerning the elaboration of green pigments by the Mayan painters. The photodégradation of an indigo-sepiolite blend is the key point. The experience of introduction, stabilization and protection of organic molecules palygorskites clay matrices allow us to obtain a large range of blue, green, purple, yellow, and black shades. This is the beginning of new color processing made from ancient pigments

Corynebacterium poinsettiae mutant strains blocked in carotenoid biosynthesis were obtained by treatment with the mutagen N-methyl-N1-nitro-N-nitrosoguanidine. Additional carotenoid (Crt) mutant strains were obtained from a previous study conducted in our laboratory. Fifty-nine Crt mutants affected in carotenoid biosynthesis were examined by a normal phase high performance liquid chromatography (HPLC) system. Pigment extracts of Crt mutants and C. poinsettiae wild type strains were resolved by an isocratic system with hexane:acetone:dicholoromethane, 11.35:1.73:1.00 (by vol.) as the eluting solvent. In addition to the five major peaks, twelve minor peaks were observed in the wild type C. poinsettiae strain used in this study. Crt mutant and wild type strain peak heights were measured from the individual chromatograms and the peak height data set created was analyzed using the Statistical Analysis System program to perform a cluster analysis. The cluster analysis revealed five carotenoid mutant groups. Carotenoid pigments which accumulated or were absent in each of the cluster groups are reported. Cluster group 1 mutants (CrtA) are blocked in the dehydrogenase(s) which is(are) responsible for the dehydrogenations between phytoene and lycopene. Cluster group 2 mutants (CrtB) appear to be blocked at a second dehydrogenase specific for the dehydrogenation from C.p. 470 to C.p. 496. Cluster group 3 mutants (CrtC) are blocked at a cyclization step in the pathway which involves cyclization of C.p. 496 to C.p. 470 and which may cyclize C.p. 473 to C.p. 450. The genes CrtA and CrtB map only 0.5 map units from each other while CrtA and CrtC map 2.1 map units from one another. Mutants which accumulate end products but which lack certain precursors indicate a branched pathway for pigment biosynthesis exists in this organism. Media for the formation, fusion and regeneration of C. poinsettiae protoplasts are reported and a protocol for the use of these media in genetic crosses of strains blocked in carotenoid biosynthesis is described. While isolating antibiotic resistant mutants useful in genetic analyses, novobiocin resistant mutants were observed to have a distinctly different colony pigment phenotype as compared to the wild type strain. HPLC chromatograms of a novobiocin resistant strain showed a distinctly different carotenoid pigment profile. The results provide evidence for differential gene expression in the carotenoid biosynthetic pathway when these mutants are grown in the presence of novobiocin.

The purpose of this study was (1) to determine whether a correlation exists among the protein profiles, extracted from cell membranes of mutants belonging to five pigment cluster groups, (2) to locate the protein moiety and cartenoprotein complex in the membranes of wild type and colorless mutant (designated W-19) of C. poinsettae and to show whether there are any structural differences between cell membranes of the wild type and a colorless mutant, (3) to determine the effect of six antibiotics on cartenoid gene expression.

A travers l’étude par fluorescence X et diffraction de rayons X de trois grottes ornées Paléolithiques en rapport avec les questionnements des archéologues, c’est un travail de recherche physico-chimique autant que méthodologique qui est présenté au lecteur. La complexité analytique qu’il y a derrière l’étude in situ et non-invasive d’un art rupestre, a guidé notre réflexion sur le développement de procédures de traitement quantitatif des données, adaptées au site étudié (nature des pigments analysés, condition de conservation des œuvres). Cette complexité vient du fait qu’une couche picturale, tracée sur un support rocheux, est discontinue et ne recouvre pas uniformément la roche. Elle est de plus généralement peu épaisse. Pour ces raisons, une forte contribution de la paroi se retrouve dans l’information physico-chimique propre au pigment.Trois approches différentes ont ainsi été proposées pour approcher la matière picturale des grottes de Rouffignac et de Font-de-Gaume, situées en Périgord dans le sud-ouest de la France, et de la grotte de La Garma, localisée dans la région Cantabrique dans le nord de l’Espagne. L’une consiste en la semi-quantification d’oxydes discriminant le pigment de la paroi, bouclés à cent pourcent, permettant de s’affranchir de paramètres propres aux conditions expériences ; une deuxième est une semi-quantification par rapport à l’élément calcium, de sorte que la contribution de la paroi à travers la couche picturale reste la même d’un point de mesure à l’autre ; la dernière adopte une approche par simulation Monte Carlo afin de séparer clairement les informations de la paroi de celles du pigment. L’application de ces approches quantitatives a permis d’enrichir la connaissance stylistique que les archéologues en avaient, en apportant une vision physico-chimique à l’organisation des œuvres au sein de la grotte et des relations qu’elles entretiennent les unes avec les autres. Ce travail s’ouvre également au milieu karstique lui-même en intégrant à l’étude de l’art pariétal, un travail sur la genèse des faciès des parois. Le but étant d’acquérir le recul nécessaire pour mieux évaluer les interactions entre support et œuvres, et l’évolution des supports ornés, resituées dans leur contexte karstique général
The present study is a physicochemical research as well as a methodological work, carried out through the study of three Palaeolithic caves by X-ray fluorescence and X-ray diffraction. The analytical complexity behind in situ and non-invasive study of rock art, has guided our reflexion about the development of quantitative procedures of data processing, in order to adjust them appropriately to the specificity of the site and its rock art (specific constitution of the analysed pigment and conservation condition of the ornamented wall). This complexity is due to the fact that pigment layers don’t cover uniformly the rock surface. Also, the layers are generally very thin. For this reason, in the pigment signal, the proportion of the physicochemical information specific to the substrate is very high.Three approaches have been tested in the caves of Rouffignac, Font-de-Gaume and La Garma to characterise their Palaeolithic rock art. The two first are located in the Périgord region in the south-west of France, the last one in the Cantabrian region of Spain. One is related to the semi-quantification of oxides which discriminate the pigment from the substrate, allowing to not taking account experimental condition parameters; the second is a semi-quantification related to Ca, in order that the contribution in the concentration of the substrate detected through the paint layer remains the same for each measurement point; the last one is based on a Monte Carlo simulations method to separate distinctly the pigment information to those from the wall. These quantitative approaches enhanced the stylistic knowledge of archaeologists, bringing new physicochemical insights into the organisation of the representations and their relationship with the others inside the cave. Also, this work is concerned by the karstic environment; incorporating a research on wall taphonomy to the pigment study. The aim is to access to a better appreciation of the pigment-wall interactions and their evolution during time, given their global environmental context

The Ghost Water exhibition of artworks by Michael Sharp was comprised of four main works titled: 30 x 60 Minute Grid Series, Suspension, History/Prehistory, and Lake Bonneville Remnants. The artwork was created as a reaction to the land that once held the prehistoric Lake Bonneville and to its current remnant Great Salt Lake. The work explores the dialogue between absence and presence.

Les recherches archéologiques, en cours depuis une dizaine d'années, sur l'art rupestre du bassin du Salado (du désert d'Atacama au nord du Chili) signifient l'existence de plusieurs styles de représentations pour l'Horizon Formatif (1500 av. J-C. - 850 apr. J. -C. ) et l'Horizon Tardif ou Inca (1450-1550 apr. J. -C. ). Notre recherche porte sur 14 sites d'art rupestre dont les contextes archéologiques associés sont datés de la période Intermédiaire Tardive (850- 1450 apr. J. -C. ). L'étude a pour but de caractériser et de définir les styles en présence: les manifestations rupestres correspondant à cette période de l'histoire préhispanique de la région n'ayant. Jusqu'à présent. Fait l'objet d'aucune étude spécifique. Pour cela, nous abordons plusieurs perspectiyes d'analyse : - une approximation iconographique et stylistique afin de caractériser formellement les images et d'identifier les compositions des panneaux. - une approche contextuelle à partir de l'étude des vestiges archéologiques datés associés et une étude technologique des types de pigments employés dans les peintures rupestres. Cette triple démarche, qui couvre plusieurs approches du panorama méthodologique d'étude de l'art rupestre, vise à caractériser de façon globale les manifestations pariétales du bassin du Salado. Enfin, les résultats obtenus sont discutés en relation aux processus socioculturels de la période Intermédiaire Tardive de l'histoire préhispanique de désert d'Atacama

The detennination of trade routes and social interactions has previously been undertaken using cultural records and archaeological trends. In many regions this infonnation is sparse or inconclusive. By provenancing materials such as the pigments used by Aboriginal artists the movement of materials in the past can be directly investigated. This study is an attempt to characterise and provenance the excavated pigments from Fem Cave, Chillagoe, Southeast Cape York Peninsula. Two techniques, Fourier transform infrared -photoacoustic spectroscopy and proton induced X-ray and gamma-ray emission spectroscopy, have been used to examine the mineralogy and elemental composition of earth pigments. Both these techniques are suited to the examination of solid samples, requiring only very small samples (