A study of thermal, structural, electrical and optical characteristics of molybdenum black surface coatings on various substrates has been made. The suitability of these coatings for use as selective absorbers for solar collector applications has been assessed. Molybdenum black (Mo black) coatings were prepared by electrodeposition (on aluminium) and a chemcial conversion method (on zinc and electroplated cobalt on nickel plated copper substrates). The solar absorptancer (αs) and thermal emittances (εth) of the coatings were determined from room temperature spectral reflectance measurements in the solar (0.3 to 2.5μm) and infrared regions (2.5 to 50 μm) respectively. The effect of different preparation parameters and substrate pretreatments on the spectral selectivity has been investigated in order to optimize the thermal performance. The spectral selectivity is related to the Mo-black coating thickness and surface roughness together with the microstructure, of the substrate and the intermediate layer. Dip coatings on polished zinc have significant selectivity (αs/ εth = 8.4 when αs = 0.76). The absorptance of the dip coatings is increased to 0.87 with εth = 0.13 by chemical etching of zinc prior to coating deposition. For coatings on electroplated cobalt on nickel plated copper (cobalt (NC) substrate), an absorptance as high as 0.94 has been obtained with an emittance value 0.3. By using an addition agent in the plating solution of cobalt the high emittance can be reduced to 0.1 with αs = 0.91 giving a coating with a relatively high efficiency (82.5%) for photo-thermal energy conversion. A study of the surface composition and microstructure of the coatings has been made using scanning and transmission electron microscopy together with electron diffraction, X-ray diffraction and X-ray photoelectron spectroscopy. The structural investigations indicate that Mo-black coatings contain polycrystals of orthorhombic Mo4O11 with a small proportion of Ni(OH)2. Presence of water and also Mo4O11 in the coatings are evident from IR spectroscopy study. The bandgap of the coating has been determined from optical transmission spectra (1.66 eV) and also from reflectance spectra (0.85 eV). The discrepancy between these two values has been discussed. The refractive indices of the coatings have also been estimated. The band gaps and refractive indices are found to be related to the spectral selectivity of the coatings. The durability test of the coatings shows that the coatings on etched zinc are more resistant to heat treatment than the coatings on unetched zinc. The coatings on cobalt (NC) substrates also show good stability for relatively short periods at temperatures ~400ºC. A study of the electrical properties of Mo-black coatings suggests that at electrical field strengths (greater than 106v/m the dominant conduction process is of the Poole-Frenkel type. The activation energy of the conduction process has been estimated to be -0.56 eV at higher temperatures. The effect of heat treatment on the electrical properties of the coatings has been examined. The dielectric constant of Mo-black has been estimated from A. C. measurements. At high frequency (20 kHz) the value of the dielectric constant is about 4.0.

Orientador: Mauricio Roriz / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Civil, Arquitetura e Urbanismo / Made available in DSpace on 2018-08-11T13:02:36Z (GMT). No. of bitstreams: 1 Dornelles_KelenAlmeida_D.pdf: 6559934 bytes, checksum: 3966f1604b84180c07c07723d60bf746 (MD5) Previous issue date: 2008 / Resumo: A radiação solar é responsável por importante parcela da carga térmica dos edifícios e seu impacto sobre esta carga depende, principalmente, da absortância solar do envelope construtivo. A falta de dados precisos e atualizados de absortância solar para superfícies opacas faz com que pesquisadores e especialistas utilizem a percepção visual ou adotem tabelas baseadas em cores, consagrando-se o conceito de que a absortância seria crescente na medida em que as cores fossem mais escuras. Para comprovar que a visão humana não é instrumento adequado para indicar o quanto uma superfície absorve de energia solar, este trabalho apresenta dados de absortância solar para diferentes cores e tipos de tintas utilizadas em superfícies opacas de edificações no Brasil, a partir de medições de refletância em espectrofotômetro. Com base nesses dados, são propostos métodos de determinação da absortância solar de superfícies opacas, que podem ser utilizados por projetistas, pesquisadores e especialistas. Além do espectrofotômetro, apresenta-se um método que se baseia na digitalização de amostras em scanner comum e posterior classificação de suas cores a partir dos sistemas cromáticos digitais RGB e HSL. O segundo método utiliza dados de refletância obtidos através do espectrômetro ALTA II e o terceiro método baseia-se em medidas de temperaturas superficiais das amostras, a partir de absortâncias medidas para amostras de cores branca e preta, adotadas como referência. Os dados de absortância solar obtidos com o espectrofotômetro foram ajustados ao espectro solar padrão, considerando-se que a energia solar não é constante ao longo do espectro. Este ajuste indicou que a absortância diminui quando submetida às diferentes intensidades da radiação solar. Finalmente, analisou-se o efeito da rugosidade superficial sobre a absortância solar de amostras pintadas com diferentes cores de tintas, cujos resultados indicaram que a rugosidade aumenta linearmente a absortância das superfícies. As diversas análises e discussões apresentadas neste trabalho comprovam que apenas a cor não é fator determinante da absortância de uma superfície opaca. Além disso, os métodos propostos para sua quantificação são bastante precisos e confiáveis, cujos valores estimados através dos métodos do scanner, ALTA II e medida de temperaturas superficiais apresentaram diferenças inferiores a 10%, 6,8% e 3,7%, respectivamente, quando comparados com as absortâncias medidas em espectrofotômetro / Abstract: Solar radiation is the main responsible factor for the thermal load of buildings, and its impact over this load depends, mainly, on the solar absorptance of the building envelope. The lack of reliable and current data implies that researchers and specialists use visual perception or adopt tables based on surface colors to quantify the solar absorptance, which enhances the concept that absorptance increases as much as colors are darker. In order to show that the human eye is not reliable indicator of how much solar energy a surface absorbs, this work presents solar absorptance data for different paint colors, which are commonly used in Brazilian façades, measured with a spectrophotometer. Based on these data, determination methods of solar absorptance are proposed and can be used by designers, researchers, and specialists. Besides the spectrophotometer, it is presented a method based on samples digital images through a scanner, in which samples were classified according to the RGB and HSL digital chromatic systems. The second method uses the reflectances of samples measured with the ALTA II spectrometer, and the third method is based on the samples surface temperatures and the absorptances of black and white reference samples. Solar absorptance data measured with the spectrophotometer were adjusted to the standard solar spectrum, because the solar energy is not constant along the solar spectrum. This correction indicated solar absorptance diminishes when submitted to different solar radiation intensities. Finally, the influence of roughness on the solar absorptance was analyzed, whose results indicated roughness linearly increases surfaces solar absorptance. The several analysis and discussions presented in this work prove that only color is not a determinant factor of the solar absorptance. Furthermore, proposed methods are very reliable to identify the solar absorptance of opaque surfaces, whose estimated values with scanner, ALTA II, and surface temperature methods presented differences under 10%, 6,8%, and 3,7%, respectively, when compared to the absorptances measured with the spectrophotometer / Doutorado / Arquitetura e Construção / Doutor em Engenharia Civil

<p>The optical efficiency of a commercially available sputter deposited spectrally selective solar absorber was improved. The main purposes were to decrease the thermal emittance, increase the solar absorbtance of the absorber and to protect the substrate from degradation due to environmental influence. The adhesion properties between the corrosion-protecting barrier and the substrate were also studied. This project was focused on process improvements that are realistic to implement in industrial production.</p><p>The thermal emittance of the absorber was decreased from 0.12 to 0.06 by changing the material of the corrosion-protecting layer from nickel-chromium to copper-nickel. Copper-nickel was less sensitive to variations in the sputter parameters than nickel-chromium. A novel method that could simplify the search for alternative corrosion resistant materials with a low thermal emittance has been purposed. Since resistivity data usually exist or can easily be measured and infrared measurements require more sophisticated measurements, the Hagen-Rubens relation was investigated for copper-nickel and nickel-chromium alloys. The dc-resistivity was found to be related to the infrared emittance or the integrated thermal emittance for alloys in their solid soluble fcc phase.</p><p>The solar absorbtance was increased when a graded index absorbing coating was tailored for a crossover of the reflectance from low to high reflectance at about 2.5 µm. The solar absorber graded index coating was optimized for nickel metal content in nickel oxide and a solar absorptance of 0.89-0.91 was achieved. The solar absorptance was further increased to 0.97 when an antireflection coating was added on top of the absorbing layer.</p><p>Finally, extrapolation algorithms were developed to assure correct determination of the thermal emittance for coatings on glass since modern spectrometers that do not cover the complete wavelength interval required to calculate the thermal emittance of surfaces at room temperatures accurately. The error arising from the extrapolation algorithms were smaller than the noise from the optical measurements. Similar strategies can be used for other surfaces.</p>

The optical efficiency of a commercially available sputter deposited spectrally selective solar absorber was improved. The main purposes were to decrease the thermal emittance, increase the solar absorbtance of the absorber and to protect the substrate from degradation due to environmental influence. The adhesion properties between the corrosion-protecting barrier and the substrate were also studied. This project was focused on process improvements that are realistic to implement in industrial production. The thermal emittance of the absorber was decreased from 0.12 to 0.06 by changing the material of the corrosion-protecting layer from nickel-chromium to copper-nickel. Copper-nickel was less sensitive to variations in the sputter parameters than nickel-chromium. A novel method that could simplify the search for alternative corrosion resistant materials with a low thermal emittance has been purposed. Since resistivity data usually exist or can easily be measured and infrared measurements require more sophisticated measurements, the Hagen-Rubens relation was investigated for copper-nickel and nickel-chromium alloys. The dc-resistivity was found to be related to the infrared emittance or the integrated thermal emittance for alloys in their solid soluble fcc phase. The solar absorbtance was increased when a graded index absorbing coating was tailored for a crossover of the reflectance from low to high reflectance at about 2.5 µm. The solar absorber graded index coating was optimized for nickel metal content in nickel oxide and a solar absorptance of 0.89-0.91 was achieved. The solar absorptance was further increased to 0.97 when an antireflection coating was added on top of the absorbing layer. Finally, extrapolation algorithms were developed to assure correct determination of the thermal emittance for coatings on glass since modern spectrometers that do not cover the complete wavelength interval required to calculate the thermal emittance of surfaces at room temperatures accurately. The error arising from the extrapolation algorithms were smaller than the noise from the optical measurements. Similar strategies can be used for other surfaces.