961 resultados para THERMAL ANALYSIS-STANDARD-CHARACTERIZATION-TRANSITION-REACTION-CHARACTERISTIC PARAMETER


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The study presented here encompasses identification, analysis and characterization of the strombine dehydrogenase (StDH) from the sponge S. domuncula, on the gene and protein level. StDH is an opine dehydrogenase which is involved in opine production pathways found mainly in marine invertebrates. These anaerobic pathways are regarded as analogues to the classical anaerobic glycolytic pathway (lactate production pathway), which is predominant in vertebrates. The StDH was previously annotated as a tauropine dehydrogenase (TaDH) on the basis of its 68% identity with the TaDH protein from Halichondria japonica. Subsequent enzymatic assays showed that S. domuncula opine dehydrogenase is in fact strombine dehydrogenase which possesses specific characteristics not found in other proteins of the same family. It is described here for the first time the StDH gene in Eukaryotes. Two allelic variants have been identified which are present in the different specimens either as a homozygotic or a heterozygotic. Phylogenetic analyses supported with enzymatic assays indicate that S. domuncula StDH is only distantly related to the opine dehydrogenases from marine invertebrates. StDH showed that the protein is highly specific to glycine and inhibited by the substrate pyruvate. Furthermore, S. domunucla StDH has a dimeric structure (~75 kDa) which is not observed in so far described OpDHs that are monomeric proteins. This enzyme showed similarities to the OCD/mu-cristallyin protein family. Results showed that a sponge StDH is unusual enzyme that belongs to the independent enzyme class. In addition, expression studies revealed that the StDH is down-regulated with aeration. Immunohistology analyses showed high expression of the protein in almost all sponge cells. A strong accumulation of the enzyme was seen around the bacteria indicating that under aerobic conditions the bacteria might metabolize strombine (end product of the reaction). In conclusion, the data documented here shed new light on the anaerobic pathways in marine invertebrates. Potential mutual influences between bacteria and sponge are discussed as well. Hopefully, these results could have a small but important contribution to the better understanding of the evolution in the animal kingdom.

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The protein silk fibroin (SF) from the silkworm Bombyx mori is a FDA-approved biomaterial used over centuries as sutures wire. Importantly, several evidences highlighted the potential of silk biomaterials obtained by using so-called regenerated silk fibroin (RSF) in biomedicine, tissue engineering and drug delivery. Indeed, by a water-based protocol, it is possible to obtain protein water-solution, by extraction and purification of fibroin from silk fibres. Notably, RSF can be processed in a variety of biomaterials forms used in biomedical and technological fields, displaying remarkable properties such as biocompatibility, controllable biodegradability, optical transparency, mechanical robustness. Moreover, RSF biomaterials can be doped and/or chemical functionalized with drugs, optically active molecules, growth factors and/or chemicals In this view, activities of my PhD research program were focused to standardize the process of extraction and purification of protein to get the best physical and chemical characteristics. The analysis of the chemo-physical properties of the fibroin involved both the RSF water-solution and the protein processed in film. Chemo-physical properties have been studied through: vibrational (FT-IR and Raman-FT) and optical (absorption and emission UV-VIS) spectroscopy, nuclear magnetic resonance (1H and 13C NMR), thermal analysis and thermo-gravimetric scan (DSC and TGA). In the last year of my PhD, activities were focused to study and define innovative methods of functionalization of the silk fibroin solution and films. Indeed, research program was the application of different methods of manufacturing approaches of the films of fibroin without the use of harsh treatments and organic solvents. New approaches to doping and chemical functionalization of the silk fibroin were studied. Two different methods have been identified: 1) biodoping that consists in the doping of fibroin with optically active molecules through the addition of fluorescent molecules in the standard diet used for the breeding of silkworms; 2) chemical functionalization via silylation.

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Mehr als hundert Jahre archäologischer Forschung haben gezeigt, dass in Mayen in römischer und mittelalterlicher Zeit eines der wichtigsten europäischen Produktionszentren für die Herstellung qualitätsvoller Gebrauchskeramik bestand. Im Rahmen dieser Studie wurden vier Befundkomplexe aus Töpfereisiedlungen vom 4. bis in das 14. Jahrhundert untersucht. Genauer handelt es sich um Keramik aus zwei spätantiken Brennanlagen des 4. Jahrhunderts im Bereich der Flur „Auf der Eich“ an den Straßen „Am Sonnenhang“ und „Frankenstraße“. Weiterhin konnte Material aus zwei Töpferofenfüllungen des 5. bis 9. Jahrhunderts analysiert werden, das 1975 auf dem Grundstück 55 an der „Siegfriedstraße“ in Brennanlagen entdeckt wurde. Hinzu kam Brenngut aus elf Töpferöfen des späten 8. bis 14. Jahrhunderts, welches in den so genannten „Burggärten“ der Genovevaburg von Mayen in den Jahren 1986/87 durch die archäologische Denkmalpflege in Koblenz geborgen wurde. Die mineralogischen Untersuchungen zur Charakterisierung der „Mayener Keramik“ wurden systematisch an den Keramikmaterialien aus diesen Fundstellen durchgeführt. Mittelalterliche Keramik aus Bornheim-Walberberg, Brühl-Eckdorf, Höhr-Grenzhausen, Langerwehe, Frechen, Brühl-Pingsdorf, Paffrath, Raeren, Ratingen-Breitscheid, Siegburg-Seehofstraße, Siegburg-Scherbenhügel, Fredelsloh und Brühl-Badorf konnte für diese Arbeit als Referenzmaterialien ebenfalls untersucht werden. Provenienzanalysen wurden an Keramikproben aus 27 Fundorten, die makroskopisch nach Mayener Ware aussehen, mit mineralogischen Methoden durchgeführt, um sie der Fundregion Mayen eindeutig zuordnen zu können.rnPhasenanalyse, chemische Analyse und thermische Analyse wurden an Keramik sowie Ton durchgeführt. Die Phasenanalyse wurde zur Bestimmung der mineralischen Zusammensetzung von Grundmasse und Magerungsmittel (Röntgendiffraktometrie (XRD), Polarisationsmikroskop, Mikro-Raman-Spektroskopie) verwendet. Die chemische Zusammensetzung wurde durch Röntgenfluoreszenzanalyse (RFA) ermittelt. Elektronenstrahlmikroanalyse (ESMA) und Laser-Massenspektrometrie mit induktiv gekoppeltem Plasma (LA-ICP-MS) wurden bei den Proben, bei denen weniger als 2g Material zur Verfügung standen, eingesetzt. Brennexperimente wurden am originalen Rohstoff der Keramik aus den „Burggärten“ der Genovevaburg durchgeführt. Gebrannter Ton wurde durch Röntgendiffraktometrie (XRD), Infrarotspektroskopie (IR) und Differential-Thermoanalyse (DTA) analysiert. rnAnhand der Messergebnisse lässt sich die Mayener Keramik aus den vier Fundplätzen in zwei Typen zusammenzufassen: der mit Feldspat-reichem Sand gemagerte römische Typ und der mit Quarz-reichem Sand gemagerte mittelalterliche Typ. Die Änderung des Magerungsmittels von Feldspat- zu Quarzsand weist eine technische Entwicklung zu höheren Brenntemperaturen von der Römerzeit bis in das Mittelalter nach. Nach der Untersuchung und dem Vergleich mit den Referenzkeramikgruppen ist festzustellen, dass durch multivariate Statistikanalysen der chemischen Komponenten die Charakterisierung der Keramik und eine Differenzierung zwischen den Keramikgruppen gelingt. Diese Erkenntnisse bildeten die Basis für Provenienzanalysen. 16 Fundorte können durch Provenienzanalyse sicher als Exportregionen der Mayener Ware festgestellt werden. Gemäß den Brennexperimenten lassen sich die chemischen Reaktionen während des Brandprozesses nachvollziehen. Zwei Methoden wurden mittels Röntgendiffraktometrie (XRD) und Differential-Thermoanalyse (DTA) zur Bestimmung der Brenntemperaturen der Keramik modelliert. Die Töpferöfen der „Burggärten“ können nach der Brenntemperatur in zwei Typen zusammengefasst werden: solche mit einer Brenntemperatur unter 1050°C und solche mit einer Brenntemperatur über 1050°C.rn

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The aim of this work is to study the thermal behavior of geopolymers derived from kaolinite (clay). The geopolymers were characterized by various technics: Thermal analysis (DTA, TGA and dilatometer), X-ray diffractography (XRD), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). Certain physical properties of the products were equally determined: linear shrinkage of curing, percentage of water absorption and compressive strength. The results obtained after drying and thermal treatment showed that the products preserved their initial forms, but showed variable colours based on the temperatures they were treated at. The products obtained at 90, 300 and 500 °C contained hydroxysodalite. The synthesis of geopolymers is not complete at 300 °C (presence of kaolinite in the material) but the products obtained are quite consolidated. The geopolymers obtained have weak values of linear shrinkage of curing (less than 0.6 %) and the compressive strength increases from room temperature (4.9 Mpa) up to 400 °C (8.9 MPa) then becomes constant between 400 and 500 °C. The combination of results demonstrates the efficiency of the temperature parameter during the synthesis of geopolymers based on kaolinite. // L’objet de ce travail est l’étude du comportement thermique des géopolymères à base d’une argile kaolinite. Les produits obtenus ont été caractérisés au moyen de plusieurs techniques : analyses thermiques (ATD, ATG et dilatométrie), microscopie électronique à balayage (MEB), analyse par diffraction de rayons X (DRX), analyse infrarouge par transformée de Fourier (IRTF). Certaines propriétés physiques des produits obtenus ont également été déterminées : retrait linéaire de cuisson, pourcentage d’absorption d’eau et résistance à la compression. Les résultats obtenus montrent qu’après le séchage et à la fin du traitement thermique, les éprouvettes des produits conservent leur forme initiale mais présentent une variation de couleur en fonction de la température de traitement. Les produits obtenus à 90, 300 et 500 °C contiennent de l’hydroxysodalite. La réaction de synthèse géopolymère n’est pas encore terminée au moins à 300 °C (présence de kaolinite dans le matériau) mais les produits obtenus sont assez consolidés. Les géopolymères obtenus présentent de faibles valeurs de retrait linéaire de cuisson (inférieure à 0,6 %) et une résistance à la compression qui augmente de la température ambiante (4,9 MPa) jusqu’à 400 °C (8,9 MPa) puis devient constante entre 400 et 500 °C. L’ensemble de ces résultats permet de mettre en exergue l’efficacité du paramètre « température » au cours de la synthèse des géopolymères à base de kaolinite.

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Purpose Precipitation of dissolved organic matter (DOM) by multivalent cations is important for biogeochemical cycling of organic carbon. We investigated to which extent cation bridges are involved in DOM precipitation and how cross-links by cations and water molecule bridges (WaMB) stabilise the matrix of precipitated DOM. Materials and methods DOM was precipitated from the aqueous extract of a forest floor layer adding solutions of Ca(NO3)2, Al(NO3)3 and Pb(NO3)2 with different initial metal cation/C (Me/C) ratios. Precipitates were investigated by differential scanning calorimetry before and after ageing to detect cation bridges, WaMB and restructuring of supramolecular structure. Results and discussion Twenty-five to sixty-seven per cent of the dissolved organic carbon was precipitated. The precipitation efficiency of cations increased in the order Ca < Al < Pb, while the cation content of precipitates increased in the order Pb < Ca < Al. The different order and the decrease in the WaMB transition temperature (T*) for Al/C > 3 is explained by additional formation of small AlOOH particles. Thermal analysis indicated WaMB and their disruption at T* of 53–65 °C. Like cation content, T* increased with increasing Me/C ratio and in the order Ca < Pb < Al for low Me/C. This supports the general assumption that cross-linking ability increases in the order Ca < Pb < Al. The low T* for high initial Me/C suggests less stable and less cross-linked precipitates than for low Me/C ratios. Conclusions Our results suggest a very similar thermal behaviour of OM bound in precipitates compared with soil organic matter and confirms the relevance of WaMB in stabilisation of the supramolecular structure of cation-DOM precipitates. Thus, stabilisation of the supramolecular structure of the DOM precipitates is subjected to dynamics in soils.

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Twenty-six core samples from Leg 64, Holes 474, 474A, 477, 478, 479, and 481A in the Gulf of California, were provided by the Joint Oceanographic Institutions for Deep Earth Sampling (JOIDES) Advisory Panel on Organic Geochemistry for analysis. The high heat flow characteristic of the basin provides an opportunity to study the effect of temperature on the diagenesis of organic matter. The contents and carbon isotope compositions of the organic matter and bitumen fractions of different polarity, isoprenoid and normal alkane distributions, and the nature of tetrapyrrole pigments were studied. Relative contents of hydrocarbons and bitumens depend on the thermal history of the deposits. Among other criteria, the nature and content of tetrapyrrole pigments appear to be most sensitive to thermal stress. Whereas only chlorins are present in the immature samples, porphyrins, including VO-porphyrins, appear in the thermally altered deposits, despite the shallow burial depth. Alkane distributions in thermally changed samples are characterized by low values of phytane to 2-C18 ratios and an odd/even carbon preference index close to unity. The thermally altered samples show unusual carbon isotope distributions of the bitumen fractions. The data also provide some evidence concerning the source of the organic matter and the degree of diagenesis.

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The climate during the Cenozoic era changed in several steps from ice-free poles and warm conditions to ice-covered poles and cold conditions. Since the 1950s, a body of information on ice volume and temperature changes has been built up predominantly on the basis of measurements of the oxygen isotopic composition of shells of benthic foraminifera collected from marine sediment cores. The statistical methodology of time series analysis has also evolved, allowing more information to be extracted from these records. Here we provide a comprehensive view of Cenozoic climate evolution by means of a coherent and systematic application of time series analytical tools to each record from a compilation spanning the interval from 4 to 61 Myr ago. We quantitatively describe several prominent features of the oxygen isotope record, taking into account the various sources of uncertainty (including measurement, proxy noise, and dating errors). The estimated transition times and amplitudes allow us to assess causal climatological-tectonic influences on the following known features of the Cenozoic oxygen isotopic record: Paleocene-Eocene Thermal Maximum, Eocene-Oligocene Transition, Oligocene-Miocene Boundary, and the Middle Miocene Climate Optimum. We further describe and causally interpret the following features: Paleocene-Eocene warming trend, the two-step, long-term Eocene cooling, and the changes within the most recent interval (Miocene-Pliocene). We review the scope and methods of constructing Cenozoic stacks of benthic oxygen isotope records and present two new latitudinal stacks, which capture besides global ice volume also bottom water temperatures at low (less than 30°) and high latitudes. This review concludes with an identification of future directions for data collection, statistical method development, and climate modeling.

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New heat flow observations have been made in the Iberia abyssal plain off the Galicia margin along the transeat of Ocean Drilling Program Leg 149 drill sites. in order to investigate the nature of this unusually wide and deep continet-ocean transition region. Our results indicate the presence of three separate zones. Average values of 47.5 +/- 3 mW/m in the westernmost zone III agree with predictions of standard oceanic lithospheric models for its estimated age of 126 Ma. In contrast, the heat flow within zone II is 5-15 mW/m higher than predicted. assuming that the mantle heat flow remains constant across the basin. This region of high values is coincident with the location of a major intra-crustal "S"-type reflector east of ODP Site 900. and the anomaly is consistent with the presence of 2-3 km of primarily upper continental crust above the reflector, with concentrations of radiogenic components similar to those from granodiorite samplles dredged off Galicia Bank. It is not, however, consistent with the low values of heat production measured on gabbroic sanhples from its western end at ODP Site 900. In zone I, detailed measurements across the tilted fault block south of ODP Site 901 show consistent variations which closely match predictions due to the effects of basement structure and sediment deposition. There is no evidence for variations due to vertical convective transport along the dipping basement fault block. Once corrected for these variations. measurements in zone I yield average values that agree quite well with previous measurements across Calicia Bank. indicating no systematic landward increase in heat flow with decreasing amounts of continental, extension.

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Liquid-crystalline dendrimers have been prepared from second-generation Percec-type poly(benzyl ether) dendrons or second-generation poly(aryl ester) dendrons carrying cyanobiphenyl mesogens. The Janus dendrimer, which combines the two types of dendromesogens, has also been synthesized. Those compounds have been prepared under copper-catalyzed azide–alkyne cycloaddition conditions. The mesomorphic properties have been studied by thermal analysis (POM, DSC) and small-angle X-ray scattering. Smectic A, nematic, and columnar phases have been observed depending on the dendritic building blocks. The click reaction has proven to be a powerful and elegant synthetic tool for the design of complex dendritic liquid-crystalline architectures.

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To achieve high efficiency, the intermediate band (IB) solar cell must generate photocurrent from sub-bandgap photons at a voltage higher than that of a single contributing sub-bandgap photon. To achieve the latter, it is necessary that the IB levels be properly isolated from the valence and conduction bands. We prove that this is not the case for IB cells formed with the confined levels of InAs quantum dots (QDs) in GaAs grown so far due to the strong density of internal thermal photons at the transition energies involved. To counteract this, the QD must be smaller.

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Recently, a theoretical criterion to calculate the stability of an axial-flow compressor rotor has been presented in the scientific literature. This theoretical criterion was used for determining the locus of the stability line over the rotor map and for predicting the post-stall evolution of the constant-speed line of a rotor. The main objective of this paper is to improve the predictions of such a model. To do that, the paper proposes a different characterization of the characteristic azimuthal length and a calculation of the ratio of specific heats based on a polytropic exponent. Thanks to these new values, the model predicts two bifurcation points in the behaviour of the flow: the inception point of the instability and the surge point. Experimental data from a pure axial compressor are used to validate the model showing that the prediction of the flow coefficient at the surge point has an error inferior to 5%. For the rotor studied, the paper provides a quantitative and qualitative description of the inception of the instability and of the mechanism involved in the instable region of the compressor map. The paper also discusses the role of rotor efficiency in the position of the bifurcations and gives a sensitivity analysis of its position. Finally, it presents a discussion about how the model can explain the different behaviours exhibited by the same rotor when the flow coefficient is reduced

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SUNRISE is a balloon-borne solar telescope flown with a long-duration balloon by NASA's Columbia Scientific Balloon Facility team from Esrange (Swedish Space Corporation), on 8 June 2009. SUNRISE has been a challenging mission from the thermal point of view because of its size and power dissipation. Thus, a dedicated thermal analysis has been carried out to find a solution that allows all the devices to be kept within their appropriate temperature ranges, without exceeding the allowable temperature gradients, critical for optical devices. In this article, the thermal design of SUNRISE is described. A geometrical mathematical model and a thermal mathematical model of the whole system have been set up for the different load cases in order to obtain the temperature distribution and gradients in the system. Some trade-offs have been necessary to fulfil all the thermal requirements. The thermal hardware used to achieve it is described. Finally, the temperatures obtained with the models have been compared with flight data.

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Los materiales base cemento (pastas, morteros, hormigones y otros tipos de mezclas) son materiales ampliamente utilizados en la sociedad actual y son uno de los pilares de la ingeniería civil debido a sus buenas propiedades estructurales, facilidad de fabricación y bajo coste. Sus propiedades permiten su uso en ambientes industriales y naturales, siendo materiales muy versátiles siempre y cuando, se tenga en cuenta que sus propiedades durables son limitadas en ambientes donde se producen fenómenos de lixiviación y ataque por diversos iones agresivos. El presente proyecto de investigación se desarrolló motivado por la necesidad de profundizar en el conocimiento del comportamiento de los materiales base cemento en situaciones concretas de exposición a cierto tipo de degradaciones que se producen frecuentemente en explotaciones agropecuarias ubicadas en ambientes naturales. Se diseñó un procedimiento experimental que nos permitiese evaluar el efecto que tienen los ácidos orgánicos sobre la matriz cementicia, así como la acción que presentan los sulfatos y las aguas naturales en los mismos. Teniendo muy presente siempre las características de las disoluciones a las cuales se ha expuesto el material. En último término, se trata de conocer los mecanismos de los procesos de ataque para poder definir el comportamiento del material en estos medios. Los procedimientos de ensayo, así como las técnicas de caracterización son las herramientas fundamentales con las que profundizar en el conocimiento del material, por lo que resulta de vital importancia conocer a fondo las posibilidades que su empleo nos ofrece. En el presente trabajo se ha desarrollado un profundo estudio del uso del termoanálisis en la caracterización de pastas de cemento. Además se han optimizado los procedimientos de caracterización de las muestras con otro tipo de técnicas. La caracterización de las probetas nos ha permitido comprobar el comportamiento del material en situaciones de exposición en ensayos acelerados de laboratorio. Los resultados obtenidos han permitido determinar que el pH del medio agresivo es una variable fundamental cuando se trata de evaluar la agresividad del mismo. La presencia de ciertos iones desarrollaría efectos de sinergia con respecto al pH y condicionaría los valores de las constantes termodinámicas que rigen los equilibrios. La posibilidad de formación de sales de ácidos orgánicos y la diferente solubilidad de las mismas derivaría en cambios en los comportamientos mecánicos. La proporción de compuestos de aluminio o la presencia de puzolanas capaces de fijar el calcio son también factores evidenciados como determinantes en el comportamiento del material. Además se podría afirmar que la disolución de la portlandita es un efecto determinante en el proceso de degradación. Nowadays, cement based materials (pastes, mortars, concrete and other mixtures) are widely used. These kinds of material are one of the pillars of Civil Engineering due to their structural properties, easy manufacturing and low cost. Their properties allow the use in industrial and natural environments. They are very versatile materials for use in this type of environment. But it is necessary to to keep in mind that they have a durability limited when they are exposed to aggressives environments where leaching process occur and various aggressive ions can damage the materials. This research work was developed motivated by the need to go in dept in the knoledge of the behavior of cement based materials. These kinds of materials frecuently are exposed to some types of damage that occur on farms located in natural environments. An experimental procedure that would allow us to evaluate the effect of organic acids on the cement matrix and the action presented by sulfates and natural waters in the same was designed. Always bearing in mind the characteristics of the solutions to which the material is exposed. Ultimately it comes to understanding the mechanisms of the processes leading to define the material behavior in this type of environment. Test procedures and characterization techniques are fundamental tools which to deepen the knowledge of the material, so it is important to know in its potential uses. In this work we have developed a deep study of the use of thermal analysis in the characterization of cement pastes. Furthermore, we have optimized characterization procedures of samples with other techniques. The characterization of the samples has allowed us to check the behavior of the material on exposure to accelerated laboratory tests. The results have established that the pH of the corrosive media is a fundamental variable when it comes to assessing the aggressiveness of it. The presences of certain ions develop synergies with respect to pH and would determine the values of the constants governing thermodynamic equilibria. The possible formation of salts of organic acids and the different solubility of the same would lead to changes in mechanical behavior. The proportion of aluminum compounds or the presence of pozzolans capable of binding calcium is also evidenced as determining factors in the material behavior. Besides we could assert that the dissolution of the portlandite is a determining effect on the degradation process.

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SUNRISE is a balloon-borne solar telescope flown with a long-duration balloon by NASA's Columbia Scientific Balloon Facility team from Esrange (Swedish Space Corporation), on 8 June 2009. SUNRISE has been a challenging mission from the thermal point of view because of its size and power dissipation. Thus, a dedicated thermal analysis has been carried out to find a solution that allows all the devices to be kept within their appropriate temperature ranges, without exceeding the allowable temperature gradients, critical for optical devices. In this article, the thermal design of SUNRISE is described. A geometrical mathematical model and a thermal mathematical model of the whole system have been set up for the different load cases in order to obtain the temperature distribution and gradients in the system. Some trade-offs have been necessary to fulfil all the thermal requirements. The thermal hardware used to achieve it is described. Finally, the temperatures obtained with the models have been compared with flight data.

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In this work the thermal analysis of a small satellite orbiting around the Earth has been approached by direct integration of the heat balance equations of a two-node reduced model, obtaining a linearized second order ODE problem, similar in form to the classical case of the forced vibration of a damped system. As the thermal loads (solar radiation, albedo, etc.) are harmonic, the problem is solved by means of Fourier analysis methods. Research on that field can be directly applied to the analysis of thermal problems and the results obtained are satisfactory. Working on the frequency domain streamlines the analysis, simplifies the study and facilitates the experimental testing. The transfer functions are obtained for the two-node case but the study can be extended to an n-node model.