Variedades e estilos na obra atribuída a Frei Carlos: novas perspetivas

Este trabalho de investigação centra-se no contributo dos exames de superfície e nas análises micro-analíticas no estudo de vinte e uma pinturas atribuídas à oficina de Frei Carlos, um dos grandes Mestres Luso-Flamengos ativos em território Nacional durante a primeira metade do século XVI. A "Pintura Luso-Flamenga" é uma expressão comummente usada na história da pintura Portuguesa do primeiro terço do século XVI e no seu sentido mais básico designa o trabalho de mestres flamengos que se instalaram em Portugal durante o reinado de D. Manuel I (1495- 1521) contribuindo decisivamente para o processo de renovação da pintura Portuguesa na época. O estudo integrado combina a pesquisa histórica em fontes documentais com exames de superfície e de caracterização material das obras de arte. O estudo material das pinturas foi realizado através de microscopia ótica, microscopia de infravermelhos com transformada de Fourier, espectroscopia de micro-Raman, microscopia eletrónica de varrimento acoplada com espectrometria de energia dispersiva de raios X, micro- difração de raios-X, cromatografia líquida de alta eficiência e pirólise acoplada à cromatografia gasosa /espectrometria de massa. Esta investigação envolveu técnicas complementares de análise de superfície e de ponto no estudo técnico e material das preparações, imprimitura, desenho subjacente, camadas pictóricas e sucessões estratigráficas, dando a conhecer os materiais utilizados na execução técnica das pinturas e evidenciando especificidades técnicas da produção artística. Este estudo pretende inclusivamente evidenciar alguns detalhes técnicos do artista que possivelmente estão relacionados com a herança das práticas Flamengas. O conhecimento de algumas particularidades da técnica deste Mestre também permitiu estabelecer comparações com duas pinturas que haviam sido atribuídas, com algumas reservas, a esta oficina de pintura Luso-Flamenga. Mais recentemente, como resultado de um estudo colaborativo, foi realizada uma ampla campanha de reflectografia infravermelhos, introduzindo novos dados acerca da execução técnica do desenho subjacente, o que contribuiu para diferenciar, nestas duas pinturas, outra "mão", atribuída então a um seguidor de Frei Carlos. Esta investigação introduz um novo e profundo conhecimento sobre a Oficina de Frei Carlos, permitindo estabelecer comparações com a obra do seu seguidor e com uma pintura também atribuída a esta oficina e que incorpora o Museu da National Gallery (NG5594), evidenciando os materiais utilizados na técnica de produção artística e especificidades técnicas aliadas aos processos criativos/ construtivos que permitem estabelecer os pontos de contacto e de diferenciação entre estas obras; Varieties and styles in the works attributed to Frei Carlos - new perspectives Abstract: This investigation is focused on the contributions of surface exams and micro-analytical research in the study of twenty one paintings attributed to Frei Carlos workshop, one of the most important Portuguese-Flemish painters active in our country during the first half of sixteen Century. "Portuguese-Flemish Painting" is a common expression used in the history of Portuguese painting of the first third of the sixteenth century and in its most basic meaning designates the work of Flemish masters who settled in Portugal during the reign of King Manuel I (1495-1521) contributing decisively to the process of renewal of Portuguese painting at the time. The integrated approach combines historical research on documental sources with surface examination and material characterization of the paintings by using state-of-art analytical techniques. Microanalysis was carried out by optical microscopy, micro-Fourier-transform infrared-spectroscopy, micro-Raman spectroscopy, scanning electron microscopy coupled with energy dispersive X-ray spectrometry, micro-X-ray diffraction analysis, high performance liquid chromatography and Pyrolysis gas chromatography mass spectrometry. This complementary surface and analytical research was involved in the technical and material characterization of grounds, underdrawings, primings, paint layers and its multi-layered build-up, providing access to the painter´s materials used in the technical execution of the paintings and details of the technique of artistic production. This study also intends to expose some usual details of the artist’s technique which are possibly related to the Master´s Flemish influence. The knowledge of some particularities of the Master´s technique also allowed a new comparison with two paintings that had been attributed with some reserves to this Portuguese-Flemish workshop. More recently, as a result of a collaborative study, an extensive infrared reflectography campaign was made, giving new data concerning underdrawings technical execution and contributing to differentiate, in these two paintings, another “hand”, attributed to a follower of Frei Carlos. Complementary analytical research also added a new and deep insight into Frei Carlos workshop, his follower and a panel that still attributed to Frei Carlos workshop that integrates the National Gallery´s Museum (NG5594), evidencing the materials used in technical production, their models and sources of artistic inspiration, techniques and pictorial construction procedures that could specifically relate or distinguish between them.

In-car sound linear simulation

In recent years, vehicle acoustics have gained significant importance in new car development: increasingly advanced infotainment systems for spatial audio and sound enhancement algorithms have become the norm in modern vehicles. In the past, car manufacturers had to build numerous prototypes to study the sound behaviour inside the car cabin or the effect of new algorithms under development. Nowadays, advanced simulation techniques can reduce development costs and time. In this work, after selecting the reference test vehicle, a modern luxury sedan equipped with a high-end sound system, two independent tools were developed: a simulation tool created in the Comsol Multiphysics environment and an auralization tool developed in the Cycling ‘74 MAX environment. The simulation tool can calculate the impulse response and acoustic spectrum at a specific position inside the cockpit. Its input data are the vehicle’s geometry, acoustic absorption parameters of materials, the acoustic characteristics and position of loudspeakers, and the type and position of virtual microphones (or microphone arrays). The simulation tool can also provide binaural impulse responses thanks to Head Related Transfer Functions (HRTFs) and an innovative algorithm able to compute the HRTF at any distance and angle from the head. Impulse responses from simulations or acoustic measurements inside the car cabin are processed and fed into the auralization tool, enabling real-time interaction by applying filters, changing the channels gain or displaying the acoustic spectrum. Since the acoustic simulation of a vehicle involves multiple topics, the focus of this work has not only been the development of two tools but also the study and application of new techniques for acoustic characterization of the materials that compose the cockpit and the loudspeaker simulation. Specifically, three different methods have been applied for material characterization through the use of a pressure-velocity probe, a Laser Doppler Vibrometer (LDV), and a microphone array.

Synthesis of KOH-based geopolymers for innovative applications

This study presents an evaluation on compressive strength of metakaolin-based geopolymers synthetized by using different activators, KOH and NaOH. The influence of NaOH/KOH concentration ratio together with curing temperature and time were investigated to find the best results from the compressive strength tests of metakaolin-based geopolymers, synthesized with a commercial metakaolin. Aggregates of small grain size referred as fillers, were added to reduce brittleness, and minimize the pore size and shrinkage of the final mixture creating a stronger network. In this work, silt recovered from industrial processes of wash water used for aggregates production was used as a filler in the production of KOH-based geopolymers, examining the possible influence on the mechanical strength of the final product. The curing temperatures chosen for the synthesis were 85°C, 60°C and 40°C. The samples were tested after 7 days and 28 days, according to the UNI EN 1015-11:2019 applied on Ca-based cements, analyzing the differences in mechanical strength comparing samples with similar and different compositions. The study presented in total 72 synthetized geopolymer specimens that were analyzed with unconfined compression test (UCT). The characterization of the starting materials metakaolin and silt was carried out using X- ray diffraction analysis (XRD). Whereas, the formed geopolymers were analyzed using X- ray diffraction (XRD), and scanning electron microscopy (SEM) with energy dispersive X- ray spectroscopy (EDS).

Preparation and characterization of ethanol-treated silk fibroin dense membranes for biomaterials application using waste silk fibers as raw material

The possibility of producing valued devices from low cost natural resources is a subject of broad interest. The present study explores the preparation and characterization of silk fibroin dense membranes using waste silk fibers from textile processing. Morphology, crystallinity, thermal resistance and cytotoxicity of membranes as well as the changes on the secondary structure of silk fibroin were analyzed after undergoing treatment with ethanol. Membranes presented amorphous patterns as determined via X-ray diffraction. The secondary structure of silk fibroin on dense membranes was either random coil (silk I) or p-sheet (silk II), before and after ethanol treatment, respectively. The sterilized membranes presented no cytotoxicity to endothelial cells during in vitro assays. This fact stresses the material potential to be used in the fabrication of biomaterials, as coatings of cardiovascular devices and as membranes for wound dressing or drug delivery systems. (C) 2010 Elsevier Ltd. All rights reserved.

Characterization of the structural and surface properties of chemically modified MCM-41 material

Mesoporous Mobil catalytic materials of number 41 (MCM-41) silica was chemically modified using both inorganic and organic precursors and characterized using the techniques, XRD, XPS, MAS NMR, FTIR, W-Vis, and physical adsorption of nitrogen, hydrocarbons (hexane, benzene, acetone, and methanol) and water vapor. Modification using organic reagents was found to result in a significant loss in porosity and a shape change of surface properties (increased hydrophobicity and decreased acidity). With inorganic modifying reagents, the decrease in porosity was also observed while the surface properties were not significantly altered as reflected by the adsorption isotherms of organics and water vapors. Chemical modifications can greatly improve the hydrothermal stability of MCM-41 material because of the enhanced surface hydrophobicity (with organic modifiers) or increased pore wall thickness (with inorganic modifiers). (C) 2000 Elsevier Science B.V. All rights reserved.

Synthesis and characterization of ternary hybrid material based on poly-o-methoxyaniline and poly(ethylene oxide) in mesostructured V(2)O(5)

New hybrid composites based on mesostructured V(2)O(5) containing intercalated poly(ethylene oxide), poly-o-methoxyaniline and poly(ethylene oxide)/poly-o-methoxyaniline were prepared. The results suggest that the polymers were intercalated into the layers of the mesostructured V(2)O(5). Electrochemical studies showed that the presence of both polymers in the mesostructured V(2)O(5) (ternary hybrid) leads to an increase in total charge and stability after several cycles compared with binary hybrid composites. This fact makes this material a potential component as cathode for lithium ion intercalation and further, a promising candidate for applications in batteries.

Synthesis, characterization and electrochemical behavior of the vanadium pentoxide/cetyl pyridinium chloride hybrid material

In situ and ex situ studies concerning the new hybrid material vanadium pentoxide xerogel in the presence of the cationic surfactant cetyl pyridinium chloride (V(2)O(5)/CPC) are presented. The in situ characterization studies revealed the presence of a lamellar structure for the V(2)O(5)/CPC hybrid material. The intercalation reaction was evidenced on the basis of the increase in the d-spacing as well as the displacement of the infrared bands toward lower energy levels. Electrochemical studies comprising the cyclic voltammetry and the electrochemical impedance spectroscopy techniques showed that the behavior of the hybrid material is considerably influenced by the electrolyte composition. The ion insertion/de-insertion into the V(2)O(5) xerogel structure accompanying the charge transfer process is influenced by the solid-state diffusion process modeled by using the finite-space Warburg element.

Unstabilized rammed Earth: characterization of material collected from old constructions in South Portugal and comparison to normative requirements

Unstabilized rammed earth is a recyclable, economical, and eco-friendly building material, used in the past and still applied today. Traditionally, its use was based on a long empirical knowledge of the local materials. Because this knowledge was mostly lost or is no longer sufficient, in many countries normative documents have been produced to allow the assessment of rammed earth soils. With the aim of contributing for a refining of these normative requirements, this article presents a research work that included: (i) collection of Unstabilized rammed earth samples from six constructions in Portugal; (ii) a literature survey of normative and complementary documents to identify the most mentioned key-properties, the test procedures and the corresponding threshold limits; and (iii) a discussion of the test procedures and of the thresholds limits in the light of the experimental results. The analyzed properties are the particle size distribution, maximum particle size, plasticity, compaction, linear shrinkage, organic content, and salt content. The work highlights the advantages of taking into account the characteristics of existing constructions as a basis for the establishment and further refining of consistent threshold values. In particular, it shows that it is essential to adjust the requirements to the specificities of local materials.

Unstabilised rammed earth: characterization of material collected from old constructions in South Portugal and comparison to normative requirements

International Journal of Architectural Heritage, 8: 185–212, 2014

Manufacturing and characterization of a recombinant adeno-associated virus type 8 reference standard material.

Gene therapy approaches using recombinant adeno-associated virus serotype 2 (rAAV2) and serotype 8 (rAAV8) have achieved significant clinical benefits. The generation of rAAV Reference Standard Materials (RSM) is key to providing points of reference for particle titer, vector genome titer, and infectious titer for gene transfer vectors. Following the example of the rAAV2RSM, here we have generated and characterized a novel RSM based on rAAV serotype 8. The rAAV8RSM was produced using transient transfection, and the purification was based on density gradient ultracentrifugation. The rAAV8RSM was distributed for characterization along with standard assay protocols to 16 laboratories worldwide. Mean titers and 95% confidence intervals were determined for capsid particles (mean, 5.50×10(11) pt/ml; CI, 4.26×10(11) to 6.75×10(11) pt/ml), vector genomes (mean, 5.75×10(11) vg/ml; CI, 3.05×10(11) to 1.09×10(12) vg/ml), and infectious units (mean, 1.26×10(9) IU/ml; CI, 6.46×10(8) to 2.51×10(9) IU/ml). Notably, there was a significant degree of variation between institutions for each assay despite the relatively tight correlation of assay results within an institution. This outcome emphasizes the need to use RSMs to calibrate the titers of rAAV vectors in preclinical and clinical studies at a time when the field is maturing rapidly. The rAAV8RSM has been deposited at the American Type Culture Collection (VR-1816) and is available to the scientific community.

Generation and Characterization of Knockout Mice and Analysis of Patient Material Demonstrates a Role for Tissue Inhibitor of Metalloproteinases 4 (Timp4) in the Cardiovascular System and Tumor Metastasis

This thesis focuses on tissue inhibitor of metalloproteinases 4 (TIMP4) which is the newest member of a small gene and protein family of four closely related endogenous inhibitors of extracellular matrix (ECM) degrading enzymes. Existing data on TIMP4 suggested that it exhibits a more restricted expression pattern than the other TIMPs with high expression levels in heart, brain, ovary and skeletal muscle. These observations and the fact that the ECM is of special importance to provide the cardiovascular system with structural strength combined with elasticity and distensibility, prompted the present molecular biologic investigation on TIMP4. In the first part of the study the murine Timp4 gene was cloned and characterized in detail. The structure of murine Timp4 genomic locus resembles that in other species and of the other Timps. The highest Timp4 expression was detected in heart, ovary and brain. As the expression pattern of Timp4 gives only limited information about its role in physiology and pathology, Timp4 knockout mice were generated next. The analysis of Timp4 knockout mice revealed that Timp4 deficiency has no obvious effect on the development, growth or fertility of mice. Therefore, Timp4 deficient mice were challenged using available cardiovascular models, i.e. experimental cardiac pressure overload and myocardial infarction. In the former model, Timp4 deficiency was found to be compensated by Timp2 overexpression, whereas in the myocardial infarct model, Timp4 deficiency resulted in increased mortality due to increased susceptibility for cardiac rupture. In the wound healing model, Timp4 deficiency was shown to result in transient retardation of re-epithelialization of cutaneous wounds. Melanoma tumor growth was similar in Timp4 deficient and control mice. Despite of this, lung metastasis of melanoma cells was significantly increased in Timp4 null mice. In an attempt to translate the current findings to patient material, TIMP4 expression was studied in human specimens representing different inflammatory cardiovascular pathologies, i.e. giant cell arteritis, atherosclerotic coronary arteries and heart allografts exhibiting signs of chronic rejection. The results showed that cardiovascular expression of TIMP4 is elevated particularly in areas exhibiting inflammation. The results of the present studies suggest that TIMP4 has a special role in the regulation of tissue repair processes in the heart, and also in healing wounds and metastases. Furthermore, evidence is provided suggesting the usefulness of TIMP4 as a novel systemic marker for vascular inflammation.

Characterization and Investigation on Material Compatibilities of Building Integrated Photovoltaic Module Components

Building Integrated Photovoltaics (BIPV) are considered as the future of photovoltaic (PV) technology. The advantage of BIPV system is its multi-functionality; they fulfil the functions of a building envelope with the added benefit of generating power by replacing the traditional roofing and façade materials with PV that generate power. In this thesis, different types of PV cells and modules have been described in detail with their efficiencies and usage trends in the last decade. The different BIPV products for roof and façade are discussed in detail giving several examples. The electricity generation potential of BIPV in selected countries is compared with their actual electricity consumption. Further, the avoided greenhouse gas (GHG) emissions associated with electricity generation from traditional sources and transportation and distribution (T&D) losses are calculated. The results illustrate huge savings in GHGs. In BIPV different types of façade and backsheets are used. In this thesis, selected backsheets and façade were characterized in terms of their surface structure identification using infrared spectroscopy (FTIR-ATR), scanning electron microscopy with energy dispersive X-ray (SEM-EDX) and physical characterization using surface energy measurements. By using FTIR-ATR, surface polymeric materials were identified and with SEM-EDX, identification of the surface elements was possible. Surface energy measurements were useful in finding the adhesives and knowing the surface energies of the various backsheets and façade. The strength of adhesion between the facade and backsheets was studied using peel test. Four different types of adhesives were used to study the fracture pattern and peel tests values to identify the most suitable adhesive. It was found out that pretreatment increased the adhesive strength significantly.

Characterization of Hydrothermally Annealed Low Temperature Bioactive Thin Film Coatings of Hydroxyapatite on TiAl6V4 Implant material

This thesis summarizes the results on the growth and characterisation of thin films of HA grown on TiAl6V4 (Ti) implant material at a lower substrate temperature by a combination of Pulsed laser deposition and a hydrothermal treatment to get sufficiently strong crystalline films suitable for orthopaedic applications. The comparison of the properties of the coated substrate has been made with other surface modification techniques like anodization and chemical etching. The in-vitro study has been conducted on the surface modified implants to assess its cell viability. A molecular level study has been conducted to analyze the adhesion mechanism of protein adhesion molecules on to HA coated implants.

Synthesis and characterization of γ-Fe2O3—a magnetic tape material

Acicular FeC~O4-2H20 was precipitated from glycerol and starch media. Thermal decomposition of this oxalate in dry and moist nitrogen yielded primarily FeO and Fe 3Oa respectively. Characterization was attempted through DTA, TG, x-ray diffraction, TEM and magnetization studies. It was found that the oxalate can be completely decomposed to FeaO~ in moist nitrogen (PH~o ,"-" 35 torr) at 775 K and then oxidised by dry air to acicular "/-Fe~Oa at 575 K. The resulting material has saturation magnetization (,-,., 70 emu/g), coercive field (N300 Oe) and squareness ratio ( ,~, 0-60-0-65), which values art comparable with those of the commercial samples