989 resultados para thermal analyses


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This work has mainly focused on the poly (L-lactide) (PLLA) which is a material for multiple applications with performances comparable to those of petrochemical polymers (PP, PS, PET, etc. ...), readily recyclable and also compostable. However, PLLA has certain shortcomings that limit its applications. It is a brittle, hard polymer with a very low elongation at break, hydrophobic, exhibits low crystallization kinetics and takes a long time to degrade. The properties of PLLA may be modified by copolymerization (random, block, and graft) of L-lactide monomers with other co-monomers. In this thesis it has been studied the crystallization and morphology of random copolymers poly (L-lactide-ran-ε-caprolactone) with different compositions of the two monomers since the physical, mechanical, optical and chemical properties of a material depend on this behavior. Thermal analyses were performed by differential scanning calorimetry (DSC) and thermogravimetry (TGA) to observe behaviors due to the different compositions of the copolymers. The crystallization kinetics and morphology of poly (L-lactide-ran-ε-caprolactone) was investigated by polarized light optical microscopy (PLOM) and differential scanning calorimetry (DSC). Their thermal behavior was observed with crystallization from melt. It was observed that with increasing amounts of PCL in the copolymer, there is a decrease of the thermal degradation. Studies on the crystallization kinetics have shown that small quantities of PCL in the copolymer increase the overall crystallization kinetics and the crystal growth rate which decreases with higher quantities of PCL.

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Volcanic ashes are raw materials from geological deposits with a range of chemical compositions. When combined with suitable alkali activators they can be converted to geopolymers cement at ambient temperature. In this work we have investigated the possibility of use bauxite and oyster shells as mineral admixture in volcanic ashes, to enhance the properties of geopolymers synthesized. Different methods of analyses such as Fourier Transform Infrared spectroscopy (FTIR), X-ray diffractometry (XRD), and Scanning Electron Microscopy (SEM) were used to assess the variation of setting time, linear shrinkage and 28 days compressive strength of geopolymers paste. The bauxite and the oyster shells were characterized using inductively coupled plasma (ICP-AES), thermal analyses (DSC/ATG), FTIR and X-ray diffractometry. The results of these analyses has showed that bauxite and oyster shells are respectively source of Al2O3 and of CaO, and can compensate the deficiencies of these oxides in volcanic ashes. Adding mineral admixture dissolve slowly in high alkaline medium. Addition of about 20% of bauxite or 10% of oyster shells is seen to decrease the setting time respectively from 415 to 275 min and 195 min. Linear shrinkage decrease with percentage of bauxite or of oyster shells added. Efflorescence is reduced by adding 10% of bauxite. 28 days compressive strength of geopolymeric materials increase respectively for 4.77 and 7.52% for 10% of bauxite or 20% of oyster shells added. More than these percentage additive has a deleterious effect on compressive strength due to crystalized mineralogical phases of the admixture.

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To track dehydration behavior of cavansite, Ca(VO)(Si4O10)·4H2O space group Pnma, a = 9.6329(2), b = 13.6606(2), c = 9.7949(2) Å, V = 1288.92(4) Å3 single-crystal X-ray diffraction data on a crystal from Wagholi quarry, Poona district (India) were collected up to 400 °C in steps of 25 °C up to 250 °C and in steps of 50 °C between 250 and 400 °C. The structure of cavansite is characterized by layers of silicate tetrahedra connected by V4+O5 square pyramids. This way a porous framework structure is formed with Ca and H2O as extraframework occupants. At room temperature, the hydrogen bond system was analyzed. Ca is eightfold coordinated by four bonds to O of the framework structure and four bonds to H2O molecules. H2O linked to Ca is hydrogen bonded to the framework and also to adjacent H2O molecules. The dehydration in cavansite proceeds in four steps.At 75 °C, H2O at O9 was completely expelled leading to 3 H2O pfu with only minor impact on framework distortion and contraction V = 1282.73(3) Å3. The Ca coordination declined from originally eightfold to sevenfold and H2O at O7 displayed positional disorder.At 175 °C, the split O7 sites approached the former O9 position. In addition, the sum of the three split positions O7, O7a, and O7b decreased to 50% occupancy yielding 2 H2O pfu accompanied by a strong decrease in volume V = 1206.89(8) Å3. The Ca coordination was further reduced from sevenfold to sixfold.At 350 °C, H2O at O8 was released leading to a formula with 1 H2O pfu causing additional structural contraction (V = 1156(11) Å3). At this temperature, Ca adopted fivefold coordination and O7 rearranged to disordered positions closer to the original O9 H2O site.At 400 °C, cavansite lost crystallinity but the VO2+ characteristic blue color was preserved. Stepwise removal of water is discussed on the basis of literature data reporting differential thermal analyses, differential thermo-gravimetry experiments and temperature dependent IR spectra in the range of OH stretching vibrations.

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This paper presents results of investigations of unusual carbonate formations found in bottom sediments of the South China Sea shelf. These sediments were sampled from a deep fracture found by geophysical methods. According to gas-geochemical data there are high concentrations of methane, hydrogen and carbon dioxide in bottom waters of this area. The carbonate formations were defined as calcium siderite or siderodot by roentgenostructural, microprobe, atomic absorption, and thermal analyses, asawellas infrared spectroscopy. Formation of this mineral results from carbon dioxide and methane flows through bottom sediments.

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In this paper, a methodology for the integral energy performance characterization (thermal, daylighting and electrical behavior) of semi-transparent photovoltaic modules (STPV) under real operation conditions is presented. An outdoor testing facility to analyze simultaneously thermal, luminous and electrical performance of the devices has been designed, constructed and validated. The system, composed of three independent measurement subsystems, has been operated in Madrid with four prototypes of a-Si STPV modules, each one corresponding to a specific degree of transparency. The extensive experimental campaign, continued for a whole year rotating the modules under test, has validated the reliability of the testing facility under varying environmental conditions. The thermal analyses show that both the solar protection and insulating properties of the laminated prototypes are lower than those achieved by a reference glazing whose characteristics are in accordance with the Spanish Technical Building Code. Daylighting analysis shows that STPV elements have an important lighting energy saving potential that could be exploited through their integration with strategies focused to reduce illuminance values in sunny conditions. Finally, the electrical tests show that the degree of transparency is not the most determining factor that affects the conversion efficiency.

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Esta tesis propone una completa formulación termo-mecánica para la simulación no-lineal de mecanismos flexibles basada en métodos libres de malla. El enfoque se basa en tres pilares principales: la formulación de Lagrangiano total para medios continuos, la discretización de Bubnov-Galerkin, y las funciones de forma libres de malla. Los métodos sin malla se caracterizan por la definición de un conjunto de funciones de forma en dominios solapados, junto con una malla de integración de las ecuaciones discretas de balance. Dos tipos de funciones de forma se han seleccionado como representación de las familias interpolantes (Funciones de Base Radial) y aproximantes (Mínimos Cuadrados Móviles). Su formulación se ha adaptado haciendo sus parámetros compatibles, y su ausencia de conectividad predefinida se ha aprovechado para interconectar múltiples dominios de manera automática, permitiendo el uso de mallas de fondo no conformes. Se propone una formulación generalizada de restricciones, juntas y contactos, válida para sólidos rígidos y flexibles, siendo estos últimos discretizados mediante elementos finitos (MEF) o libres de malla. La mayor ventaja de este enfoque reside en que independiza completamente el dominio con respecto de las uniones y acciones externas a cada sólido, permitiendo su definición incluso fuera del contorno. Al mismo tiempo, también se minimiza el número de ecuaciones de restricción necesarias para la definición de uniones realistas. Las diversas validaciones, ejemplos y comparaciones detalladas muestran como el enfoque propuesto es genérico y extensible a un gran número de sistemas. En concreto, las comparaciones con el MEF indican una importante reducción del error para igual número de nodos, tanto en simulaciones mecánicas, como térmicas y termo-mecánicas acopladas. A igualdad de error, la eficiencia numérica de los métodos libres de malla es mayor que la del MEF cuanto más grosera es la discretización. Finalmente, la formulación se aplica a un problema de diseño real sobre el mantenimiento de estructuras masivas en el interior de un reactor de fusión, demostrando su viabilidad en análisis de problemas reales, y a su vez mostrando su potencial para su uso en simulación en tiempo real de sistemas no-lineales. A new complete formulation is proposed for the simulation of nonlinear dynamic of multibody systems with thermo-mechanical behaviour. The approach is founded in three main pillars: total Lagrangian formulation, Bubnov-Galerkin discretization, and meshfree shape functions. Meshfree methods are characterized by the definition of a set of shape functions in overlapping domains, and a background grid for integration of the Galerkin discrete equations. Two different types of shape functions have been chosen as representatives of interpolation (Radial Basis Functions), and approximation (Moving Least Squares) families. Their formulation has been adapted to use compatible parameters, and their lack of predefined connectivity is used to interconnect different domains seamlessly, allowing the use of non-conforming meshes. A generalized formulation for constraints, joints, and contacts is proposed, which is valid for rigid and flexible solids, being the later discretized using either finite elements (FEM) or meshfree methods. The greatest advantage of this approach is that makes the domain completely independent of the external links and actions, allowing to even define them outside of the boundary. At the same time, the number of constraint equations needed for defining realistic joints is minimized. Validation, examples, and benchmarks are provided for the proposed formulation, demonstrating that the approach is generic and extensible to further problems. Comparisons with FEM show a much lower error for the same number of nodes, both for mechanical and thermal analyses. The numerical efficiency is also better when coarse discretizations are used. A final demonstration to a real problem for handling massive structures inside of a fusion reactor is presented. It demonstrates that the application of meshfree methods is feasible and can provide an advantage towards the definition of nonlinear real-time simulation models.

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O material Y2O3:Eu3+ vem sendo usado comercialmente como luminóforo vermelho desde da década de 1960, em uma grande variedade de aplicações devido ao seu elevado rendimento quântico (próximo de 100 %), elevada pureza de cor e boa estabilidade. Portanto, este trabalho propõe um novo método de síntese baseado nos complexos benzenotricarboxilatos (BTC) de terras raras trivalentes (RE3+) dopados com íons Eu3+. O objetivo principal é produzir materiais luminescente RE2O3:Eu3+ a temperatura mais baixa (500 °C) e em escala nanométrica. Os complexos precursores [RE(BTC):Eu3+] e [RE(TLA)·n(H2O):Eu3+], onde RE3+: Y, Gd e Lu; BTC: ácido trimésico (TMA) e ácido trimelítico (TLA) foram calcinados em diferentes temperaturas de 500 a 1000 °C, a fim de obter os materiais luminescentes RE2O3:Eu3+. Os complexos foram caracterizados por análise elementar de carbono e hidrogênio, analise térmica (TG), espectroscopia de absorção no infravermelho (FTIR), difração de raios-X - método do pó (XPD) e microscopia eletrônica de varredura (SEM). Todos os complexos são cristalinos e termo estáveis até 460 °C. Dados de fosforescência dos complexos de Y, Gd e Lu mostram que o nível T1 do aníon BTC3- tem energia acima do nível emissor 5D0 do íon Eu3+, indicando que os ligantes podem atuar como sensibilizadores de energia intramolecular. O estudo das propriedades fotoluminescentes dos complexos dopados foi baseado nos espectros de excitação e emissão e curvas de decaimento de luminescência. Ademais, foram determinados os parâmetros de intensidades experimentais (Ωλ), tempos de vida (τ), taxas de decaimentos radiativo (Arad) e não-radiativo (Anrad). Os materiais luminescentes RE2O3:Eu3+ foram sintetizados de forma bem sucedida por meio do método benzenotricarboxilatos calcinados a 500, 600, 700, 800, 900 e 1000 °C, apresentando alta homogeneidade química e controle de tamanho de cristalito. Os nanomateriais foram caracterizados pelas técnicas de FTIR, XPD SEM e TEM revelando a obtenção dos materiais C-RE2O3:Eu3+ mesmo a 500 °C. Os dados de XPD dos materiais confirmaram um aumento do tamanho dos cristalitos de 5 até 52 nm (equação de Scherrer) de em função da temperatura de calcinação de 500 a 1000 °C, respectivamente, corroborados pelas técnicas de SEM e TEM. Os espectros de emissão de RE2O3:Eu3+ mostram uma banda larga atribuída a transição interconfiguracional de transferência de carga ligante-metal (LMCT) em 260 nm, i.e. O2-(2p)→Eu3+(4f6). Além disso, foram observadas linhas finas de absorção devido as transições intraconfiguracionais 4f do íon európio (7F0,1𔾹LJ; J: 0, 1, 2, 3 e 4), como esperado. As propriedades fotoluminescentes dos luminóforos foram baseadas nos espectros (excitação e emissão) e curvas de decaimento luminescente. Os parâmetros de intensidade experimental, tempos de vida, assim como as taxas de decaimentos radiativos e não radiativos foram calculados. As propriedades fotônicas dos nanomateriais são consistentes com o sítio de baixa simetria C2 ocupado pelo íon Eu3+ no C-RE2O3:Eu3+, produzindo emissão vermelha dominada pela transição hipersensível 5D0𔾻F2 do íon Eu3+ no sitio C2, ao invés do sítio centrossimétrico S6. Além disso, os nanomateriais Y2O3:Eu3+ exibem características espectroscópicas semelhantes e elevados valores de eficiência quântica (η~91 %), compatível com os luminóforos comerciais disponíveis no mercado. Este novo método pode ser utilizado para o desenvolvimento de novos nanomateriais contendo íons terras raras, assim como outros íons metálicos.

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Grewia gum is a naturally occurring polysaccharide which has potential as a pharmaceutical excipient. Differential scanning calorimetry and Fourier transform infrared (FT-IR) spectroscopy techniques were used to examine the thermal and molecular behaviours, respectively, of mixtures of grewia gum with cimetidine, ibuprofen or standard excipients, to assess potential interactions. No disappearance or broadening of the melting endotherm was seen with cimetidine or ibuprofen. Similarly, there was no interaction between grewia gum and the standard excipients tested. The results obtained using thermal analyses were supported by FT-IR analysis of the material mixtures. Grewia gum is an inert natural polymer which can be used alone or in combination with other excipients in the formulation of pharmaceutical dosage forms. © 2011 Akadémiai Kiadó, Budapest, Hungary.

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The reduction in energy consumption is the main requirement to be satisfied in refrigeration and air conditioning by mechanical vapor compression system. In automotive system isn´t different. Thermal analyses in these systems are crucial for a better performance in automotive air conditioner. This work aims to evaluate the conditions of use of R134A refrigerant (used in vehicles) and compare with R437A (alternative refrigerant), varying the speed of the electric fan in the evaporator. All tests were performed in automotive air conditioning unit ATR600, simulating the thermal conditions of the system. The equipment is instrumented for data acquisition temperature, condensation and evaporation pressures and electrical power consumed to determine the coefficient of performance of the cycle. The system was tested under rotations of 800, 1600 and 2400 rpm with constant load of R- 134a. It occurred with the same conditions with R437A. Both recommended by the manufacturer. The results show that the best system performance occurs in the rotation of 800 RPM for both refrigerants.

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The ongoing depletion of fossil fuels and the severe consequences of the greenhouse effect make the development of alternative energy systems crucially important. While hydrogen is, in principle, a promising alternative, releasing nothing but energy and pure water. Hydrogen storage is complicated and no completely viable technique has been proposed so far. This work is concerned with the study of one potential alternative to pure hydrogen: ammonia, and more specifically its storage in solids. Ammonia, NH3, can be regarded as a chemical hydrogen carrier with the advantages of strongly reduced flammability and explosiveness as compared to hydrogen. Furthermore, ammine metal salts presented here as promising ammonia stores easily store up to 50 wt.-% ammonia, giving them a volumetric energy density comparable to natural gas. The model system NiX2–NH3 ( X = Cl, Br, I) is studied thoroughly with respect to ammine salt formation, thermal decomposition, air stability and structural effects. The system CuX2–NH3 ( X = Cl, Br) has an adverse thermal decomposition behaviour, making it impractical for use as an ammonia store. This system is, however, most interesting from a structural point of view and some work concerning the study of the structural behaviour of this system is presented. Finally, close chemical relatives to the metal ammine halides, the metal ammine nitrates are studied. They exhibit interesting anion arrangements, which is an impressive showcase for the combination of diffraction and spectroscopic information. The characterisation techniques in this thesis range from powder diffraction over single crystal diffraction, spectroscopy, computational modelling, thermal analyses to gravimetric uptake experiments. Further highlights are the structure solutions and refinements from powder data of (NH4)2[NiCl4(H2O)(NH3)] and Ni(NH3)2(NO3)2, the combination of crystallographic and chemical information for the elucidation of the (NH4)2[NiCl4(H2O)(NH3)] formation reaction and the growth of single crystals under ammonia flow, a technique allowing the first documented successful growth and single crystal diffraction measurement for [Cu(NH3)6]Cl2.

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The WTP produce many kinds of residue on your treatment stages, but the sludge is the more problematic from the final disposition point view. The actual rate of residue production deriving from technological evolution and the crescent population needs prevents the subtle equilibrium generation between consumption and recycling/reuse, creating problems of pollution resulting from inappropriate management of residues. Thus, is necessary achieve a new equilibrium between the grow from raw materials and energy and the residue generation. This equilibrium should be achieved by technical and economic feasibility of environmental supported models through recycling and reuse. The red ceramic industry stand out in residue absorption question as raw material due their clay mass heterogeneity, constituted by clay minerals and non-clay minerals with wide mineralogical variation, allowing residue inclusion which act like plastic or non-plastic materials, contributing to retain heavy metals contained in residues in the vitreous mass formed during the burning of the ceramic bodies. This work propose the study of the influence of incorporation of 25 wt.% sludge from wastewater treatment plant, according preliminary results, in the mass to produce ceramic bodies. The raw materials was characterized through chemical composition analyses by XRF, mineralogical analyses by XRD, thermal analyses by TG and DTA, Atterberg limits and thermodilatometry. Subsequently was composed the mass with 75 wt.% of clay and 25 wt.% of dried wastewater sludge from UFRN WWTP. Samples with 6,0 x 2,0 x 0,5 cm was produced with unidirectional compacting under pressure of 20MPa and burned in temperatures between 950 and 1,200ºC. After fired, the ceramic bodies have been submitted to physical and mechanical analyses through the measure of firing shrinkage, water absorption, density, apparent porosity and flexural strength; crystallographic analyses through XRD and microstructure analyses by SEM. The technological properties obtained was satisfactory to production of roof tiles with 25 wt.% at 1,200 ºC, but the production of others products at lower temperatures was not feasible

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Ye’elimite based cements have been studied since 70’s years in China, due to the irrelevant characteristics from a hydraulic and environmental point of view. One of them is the reduced fuel consumption, related to the lower temperature reaction required for this kind of cement production as compared to Ordinary Portland Cement (OPC), another characteristic is the reduced requirement of carbonates as a typical raw material, compared to OPC, with the consequent reduction in CO2 releases (~22%)from combustion. Thus, Belite-Ye’elimite-Ferrite (BYF) cements have been developed as potential OPC substitutes. BYF cements contain belite as main phase (>50 wt%) and ye´elimite as the second content phase (~30 wt%). However, an important technological problem is associated to them, related to the low mechanical strengths developed at intermediate hydration ages (3, 7 and 28 days). One of the proposed solutions to this problem is the activation of BYF clinkers by preparing clinkers with high percentage of coexisting alite and ye'elimite. These clinkers are known Belite-Alite-Ye’elimite (BAY) cements. Their manufacture would produce ~15% less CO2 than OPC. Alite is the main component of OPC and is responsible for early mechanical strengths. The reaction of alite and ye´elimite with water will develop cements with high mechanical strengths at early ages, while belite will contribute to later curing times. Moreover, the high alkalinity of BAY cement pastes/mortars/concretes may facilitate the use of supplementary cementitious materials with pozzolanic activity which also contributes to decrease the CO2 footprint of these ecocements. The main objective of this work was the design and optimization of all the parameters evolved in the preparation of a BAY eco-cement that develop higher mechanical strengths than BYF cements. These parameters include the selection of the raw materials (lime, gypsum, kaolin and sand), milling, clinkering conditions (temperature, and holding time), and clinker characterization The addition of fly ash has also been studied. All BAY clinker and pastes (at different hydration ages) were mineralogically characterized through laboratory X-ray powder diffraction (LXRPD) in combination with the Rietveld methodology to obtain the full phase assemblage including Amorphous and Crystalline non-quantified, ACn, contents. The pastes were also characterized through rheological measurements, thermal analyses (TA), scanning electronic microscopy (SEM) and nuclear magnetic resonance (NMR). The compressive strengths were also measured at different hydration times and compared to BYF.

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The oily sludge is a complex mix of hydrocarbons, organic impurities, inorganic and water. One of the major problems currently found in petroleum industry is management (packaging, storage, transport and fate) of waste. The nanomaterials (catalysts) mesoporous and microporous are considered promising for refining and adsorbents process for environment protection. The aim of this work was to study the oily sludge from primary processing (raw and treated) and vacuum residue, with application of thermal analyses technique (pyrolysis), thermal and catalytic pyrolysis with nanomaterials, aiming at production petroleum derived. The sludge and vacuum residue were analyzed using a soxhlet extraction system, elemental analysis, thin layer chromatography, thermogravimetry and pyrolysis coupled in gas chromatography/mass spectrometry (Py GC MS). The catalysts AlMCM-41, AlSBA-15.1 e AlSBA-15.2 were synthesized with molar ratio silicon aluminum of 50 (Si/Al = 50), using tetraethylorthosilicante as source of silicon and pseudobuhemita (AlOOH) as source of aluminum. The analyzes of the catalysts indicate that materials showed hexagonal structure and surface area (783,6 m2/g for AlMCM-41, 600 m2/g for AlSBA-15.1, 377 m2/g for AlSBA-15.2). The extracted oily sludge showed a range 65 to 95% for organic components (oil), 5 to 35% for inorganic components (salts and oxides) and compositions different of derivatives. The AlSBA-15 catalysts showed better performance in analyzes for production petroleum derived, 20% increase in production of kerosene and light gas oil. The energy potential of sludge was high and it can be used as fuel in other cargo processed in refinery

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Research funded by the Army Research Laboratory (ARL), the Metallurgical and Materials Engineering Department at Montana Tech investigated various methods of extracting and refining rare earth elements (REEs) from mineral ores and concentrates. Extensive thermodynamic, thermogravimetric and differential thermal analyses were performed to evaluate the relative stabilities of various REE compounds in order to assess potential methods for selective separation and recovery of specific REEs. Conversion of rare earth oxides (REO) to rare earth chlorides or bromides is a possible initial step in pyrometallurgical and hydrometallurgical processing of REEs. REO can be converted to chlorides or bromides by roasting in the presence of a chloridizing or bromidizing reactant. (e.g. NH4Cl and NH4Br).

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Ultrasonic welding process is a rapid manufacturing process used to weld thin layers of metal at low temperatures and low energy consumption. Experimental results have shown that ultrasonic welding is a combination of both surface (friction) and volume (plasticity) softening effects. In the presented work, a very first attempt has been made to simulate the ultrasonic welding of metals by taking into account both of these effects (surface and volume). A phenomenological material model has been proposed which incorporates these two effects (i.e. surface and volume). The thermal softening due to friction and ultrasonic (acoustic) softening has been included in the proposed material model. For surface effects a friction law with variable coefficient of friction dependent upon contact pressure, slip, temperature and number of cycles has been derived from experimental friction tests. Thermomechanical analyses of ultrasonic welding of aluminium alloy have been performed. The effects of ultrasonic welding process parameters, such as applied load, amplitude of ultrasonic vibration, and velocity of welding sonotrode on the friction work at the weld interface are being analyzed. The change in the friction work at the weld interface has been explained on the basis of softening (thermal and acoustic) of the specimen during the ultrasonic welding process. In the end, a comparison between experimental and simulated results has been presented showing a good agreement. © 2008 Elsevier Ltd. All rights reserved.