L’éco-innovation : une opportunité du développement durable ? Quelques éléments de bilan et de prospective niveaux européen et international.

Ce texte se focalise sur le rôle que les éco-innovations peuvent jouer en matière de compétitivité,notamment pour l’économie et les entreprises européennes.Une première partie fait ressortir les grandes tendances internationales en émergence quant aux caractères des éco-innovations, afin d’identifier les leviers permettant d’accroître leur performance.Ensuite,une vision prospective de ce que seront les écoinnovations les plus probables à moyen et long terme permet de comprendre la place des différents pays dans leur développement ainsi que leurs principaux marchés et enjeux. Enfin, nous identifions les écueils à éviter et les précautions à prendre afin de s’assurer que l’éco-innovation ne soit pas guidée que par des considérations économiques et qu’elle obéisse également aux principes d’équité et d’acceptabilité sociétale, à la base du développement durable.

Homo- and Heteronuclear Transition Metal Complexes Supported by Multinucleating Ligands

This dissertation is mainly divided into two sub-parts: organometallic and bioinorganic/materials projects. The approach for the projects involves the use of two different multinucleating ligands to synthesize mono- and multinuclear complexes. Chapter 2 describes the synthesis of a multinucleating tris(phosphinoaryl)benzene ligand used to support mono-nickel and palladium complexes. The isolated mononuclear complexes were observed to undergo intramolecular arene C¬–H to C–P functionalization. The transformation was studied by nuclear magnetic resonance spectroscopy and X-ray crystallography, and represents a rare type of C–H functionalization mechanism, facilitated by the interactions of the group 10 metal with the arene π–system.

Chapter 3 describes the construction of multinickel complexes supported by the same triphosphine ligand from Chapter 2. This chapter shows how the central arene in the ligand’s triarylbenzene framework can interact with dinickel and trinickel moieties in various binding modes. X-ray diffraction studies indicated that all compounds display strong metal–arene interactions. A cofacial triangulo nickel(0) complex supported by this ligand scaffold was also isolated and characterized. This chapter demonstrates the use of an arene as versatile ligand design element for small molecular clusters.

Chapter 4 presents the syntheses of a series of discrete mixed transition metal Mn oxido clusters and their characterization. The synthesis of these oxide clusters displaying two types of transition metals were targeted for systematic metal composition-property studies relevant to mixed transition metal oxides employed in electrocatalysis. A series of heterometallic trimanganese tetraoxido cubanes capped with a redox-active metal [MMn₃O₄] (M = Fe, Co, Ni, Cu) was synthesized starting from a [CaMn₃O₄] precursor and structurally characterized by X-ray crystallography and anomalous diffraction to conclusively determine that M is incorporated at a single position in the cluster. The electrochemical properties of these complexes were studied via cyclic voltammetry. The redox chemistry of the series of complexes was investigated by the addition of a reductant and oxidant. X-ray absorption and electron paramagnetic resonance spectroscopies were also employed to evaluate the product of the oxidation/reduction reaction to determine the site of electron transfer given the presence of two types of redox-active metals. Additional studies on oxygen atom transfer reactivities of [MMn₃O₄] and [MMn₃O₂] series were performed to investigate the effect of the heterometal M in the reaction rates.

Chapter 5 focuses on the use of [CoMn₃O₄] and [NiMn₃O₄] cubane complexes discussed in Chapter 4 as precursors to heterogeneous oxygen evolution reaction (OER) electrocatalysts. These well-defined complexes were dropcasted on electrodes with/without heat treatment, and the OER activities of the resulting films were evaluated. Multiple spectroscopic techniques were performed on the surface of the electrocatalysts to gain insight into the structure-function relationships based on the heterometallic composition. Depending on film preparation, the Co-Mn-oxide was found to change metal composition during catalysis, while the Ni-Mn oxide maintained the NiMn3 ratio. These studies represent the use of discrete heterometallic-oxide clusters as precursors for heterogeneous water oxidation catalysts.

Appendix A describes the ongoing effort to synthesize a series of heteromultimetallic [MMn₃X] clusters (X = O, S, F). Complexes such as [ZnMn₃O], [CoMn₃O], [Mn₃S], and [Mn₄F] have been synthesized and structurally characterized. An amino-bis-oxime ligand (PRABO) has been installed on the [ZnMn₃O] cluster. Upon the addition of O₂, the desymmetrized [ZnMn₃O] cluster only underwent an outer-sphere, one-electron oxidation. Efforts to build and manipulate other heterometallic [MMn₃X] clusters are still ongoing, targeting O₂ binding and reduction. Appendix B summarizes the multiple synthetic approaches to build a [Co₄O₄]-cubane complex relevant to heterogeneous OER electrocatalysis. Starting with the tricobalt cluster [LCo₃(O₂CR)₃] and treatment various strong oxidants that can serve as oxygen atom source in the presence Co²⁺ salt only yielded tricobalt mono–oxo complexes. Appendix C presents the efforts to model the H-cluster framework of [FeFe]-hydrogenase by incorporating a synthetic diiron complex onto a protein-supported or a synthetic ligand-supported [Fe₄S₄]-cluster. The mutant ferredoxin with a [Fe₄S₄]-cluster and triscarbene ligand have been characterized by multiple spectroscopic techniques. The reconstruction of an H-cluster mimic has not yet been achieved, due to the difficulty of obtaining crystallographic evidence and the ambiguity of the EPR results.

钯配合物催化烯烃氧化合成酮类物质的研究进展

本文系统地评述了钯配合物催化烯烃氧化合成酮类物质的研究进展。综述了改进 Wacker类催化剂催化活性的几种方法。总结了烯烃氧化合成酮类物质反应的几种典型催化体系及其作用机理。着重介绍了 Pd( ) /HPA(杂多酸 )、Pd( ) /Fe Pc(酞菁铁 )、 Pd( ) /HQ(氢醌 ) /Fe Pc、Pd( ) /HQ /HPA、Pd( ) /Cu SO4 /HPA等 Wacker类催化体系在烯烃氧化合成酮类物质中的应用 ;对 Pd( ) /LCo NO2 、Pd Cl2 ( Me CN) 2 /Cu Cl、Pd( OAc) 2 /吡啶、氟两相等非 Wacker类催化体系在烯烃氧化合成酮类物质中的应用也作了讨论

The Influence of Structural Modeshape Variability on Limit Cycle Oscillation Behaviour

Modal analysis is a popular approach used in structural dynamic and aeroelastic problems due to its efficiency. The response of a structure is compo
sed of the sum of orthogonal eigenvectors or modeshapes and corresponding modal frequencies. This paper investigates the importance of modeshapes on the aeroelastic response of the Goland wing subject to structural uncertainties. The wing undergoes limit cycle oscillations (LCO) as a result of the inclusion of polynomial stiffness nonlinearities. The LCO computations are performed using a Harmonic Balance approach for speed, the modal properties of the system are extracted from MSC NASTRAN. Variability in both the wing’s structure and the store centre of gravity location is investigated in two cases:- supercritical and subcritical type LCOs. Results show that the LCO behaviour is only sensitive to change in modeshapes when the nature of the modes are changing significantly.

Prediction of Transonic LCOs using an Aeroelastic Harmonic Balance Method

This work proposes a novel approach to compute transonic Lim
it Cycle Oscillations using high fidelity analysis. CFD based Harmonic Balance methods have proven to be efficient tools to predict periodic phenomena. This paper’s contribution is to present a new methodology to determine the unknown frequency of oscillations, enabling HB methods to accurately capture Limit Cycle Oscillations (LCOs); this is achieved by defining a frequency updating procedure based on a coupled CFD/CSD Harmonic Balance formulation to find the LCO condition. A pitch/plunge aerofoil and delta wing aerodynamic and respective linear structural models are used to validate the new method against conventional time-domain simulations. Results show consistent agreement between the proposed and time-marching methods for both LCO amplitude and frequency, while producing at least one order of magnitude reduction in computational time.

Transonic Nonlinear Aeroelastic Simulations Using An Harmonic Balance Method

This paper presents an approach to compute transonic Limit Cycle O
scillations using a coupled Harmonic Balance formulation based on the Euler equations for fluid dynamics and finite element models. The paper will investigate the role of aerodynamic (shocks) and structural nonlinearities in driving the limit cycle behaviour. Part icular attention will be given to nonlinear interactions for subcritical LCOs. The Aero elastic Harmonic Balance formulation, allows for solutions of the coupled structural dynamics and CFD system at a reduced cost.

Analysis of Transonic Limit Cycle Oscillations under Uncertainty

For the computation of limit cycle oscillations (LCO) at transonic speeds, CFD is required to capture the nonlinear flow features present. The Harmonic Balance method provides an effective means for the computation of LCOs and this paper exploits its efficiency to investigate the impact of variability (both structural a nd aerodynamic) on the aeroelastic behaviour of a 2 dof aerofoil. A Harmonic Balance inviscid CFD solver is coupled with the structural equations and is validated against time marching analyses. Polynomial chaos expansions are employed for the stochastic investiga tion as a faster alternative to Monte Carlo analysis. Adaptive sampling is employed when discontinuities are present. Uncertainties in aerodynamic parameters are looked at first followed by the inclusion of structural variability. Results show the nonlinear effect of Mach number and it’s interaction with the structural parameters on supercritical LCOs. The bifurcation boundaries are well captured by the polynomial chaos.

Prediction of Limit Cycle Oscillations Using an Implicit Aeroelastic-Harmonic Balance Method

This work proposes a extends a novel approach to compute tran sonic Limit Cycle Oscillations using high fidelity analysis. CFD based Harmonic Balance methods have proven to be efficient tools to predict periodic phenomena. This paper’s contribution is to present a methodology to determine the unknown frequency of oscillations using an implicit for- mulation of the HB method to accurately capture Limit Cycle Oscillations (LCOs); this is achieved by defining a frequency updating procedure based on a coupled CFD/CSD Harmonic Balance formulation to find the LCO condition. A pitch/plunge aerofoil and respective linear structural models is used to exercise the new method. Results show consistent agreement between the proposed and time-marching methods for both LCO amplitude and frequency.

Investigation of Limit Cycle Oscillations Using Aeroelastic-Harmonic Balance Method

This work investigates limit cycle oscillations in the transonic regime. A novel approach to predict Limit Cycle Oscillations using high fidelity analysis is exploited to accelerate calculations. The method used is an Aeroeasltic Harmonic Balance approach, which has been proven to be efficient and able to predict periodic phenomena. The behaviour of limit cycle oscillations is analysed using uncertainty quantification tools based on polynomial chaos expansions. To improve the efficiency of the sampling process for the polynomial-chaos expansions an adaptive sampling procedure is used. These methods are exercised using two problems: a pitch/plunge aerofoil and a delta-wing. Results indicate that Mach n. variability is determinant to the amplitude of the LCO for the 2D test case, whereas for the wing case analysed here, variability in the Mach n. has an almost negligible influence in amplitude variation and the LCO frequency variability has an almost linear relation with Mach number. Further test cases are required to understand the generality of these results.

Desenvolvimento de sistemas de medição interferométrica para a calibração de distanciómetros

Dissertação para obtenção do Grau de Mestre em Mestrado Integrado em Engenharia Mecânica

Análise metrológica de acabamento de superfícies aplicada a componentes mecânicos

Uma das tarefas mais relevantes deste trabalho foi a análise dos resultados de medição obtidos sobre os padrões de rugosidade, que permitiu identificar tendências dos resultados de medição de parâmetros de rugosidade pré-definidos, em função das condições de medição (ex.: comprimento total de medição, inclinação, tipo de apalpador). O estudo de quanto um valor de inclinação diferente do definido como critério de aceitação, influencia o valor do parâmetro de rugosidade em avaliação, foi um outro objectivo. Os resultados contribuíram para uma melhor definição das condições a ter em consideração aquando da calibração de padrões de rugosidade, bem como para uma melhor reprodutibilidade dos resultados obtidos (exactidão de medição) e redução do balanço de incertezas. Com a verificação e calibração in situ de um rugosímetro industrial, concluiu-se acerca da importância que a calibração tem nos equipamentos de medição de rugosidade (perfilómetros de contacto ou rugosímetros), através da avaliação da compatibilidade de resultados obtidos com um rugosímetro do Laboratório Nacional de Metrologia (LNM) e de um rugosímetro industrial. Dos trabalhos efectuados, averiguou-se a importância das normas técnicas que constituem a base do serviço de calibração de padrões de rugosidade, bem como da calibração dos sistemas de medição dos rugosímetros, nos resultados de medição e controlo de qualidade das superfícies. A calibração deve ser efectuada periodicamente e antes de qualquer medição da superfície em análise, através da utilização de padrões de rugosidade calibrados para os parâmetros a controlar. Estes podem variar de superfície para superfície. O trabalho desenvolvido no decurso da elaboração da Dissertação decorreu principalmente no Laboratório de Comprimento (LCO) do Departamento de Metrologia do Instituto Português da Qualidade (IPQ), em particular na área de trabalho do Laboratório correspondente à “Forma e Rugosidade”, em estreita colaboração com o Departamento de Engenharia Mecânica e Industrial (DEMI) da FCT/UNL. Simultaneamente, a verificação e a calibração de um rugosímetro industrial in situ foi possível graças à estreita colaboração existente entre a FCT/UNL-DEMI e o Instituto de Ciência e Engenharia de Materiais e Superfícies (ICEMS). Posteriormente à calibração do rugosímetro, as rugosidades de superfícies típicas de componentes mecânicos, obtidos por diferentes processos de fabrico (fundição, polimento e corte por serra), foram medidas, encontrando-se dentro da gama expectável de rugosidades

Les freins à l'adoption d'une approche d'éco-conception dans le processus de développement de produits: le cas des petites et moyennes entreprises

Scientifiques, gouvernements, entreprises et consommateurs s’entendent aujourd’hui pour dire que le système naturel est déréglé, que l’activité industrielle en est la cause principale. L’éco-conception est une manière de concevoir des biens ou des services en diminuant leurs impacts sur l’environnement et la société. De plus en plus présente dans les grandes entreprises où, associée à une gestion intégrée de l’environnement, elle procure des bénéfices non négligeables et une image de marque, l’éco-conception a beaucoup de difficultés à s’implanter dans les petites et moyennes entreprises. Dans ce travail, nous avons cherché à comprendre les raisons de ces difficultés. Deux approches ont été utilisées, l’une basée sur une analyse documentaire des rapports de RSE de dix entreprises, grandes et petites, de différents secteurs d’activité, qui nous a permis de fixer le cadre et le formalisme de la démarche de recherche, l’autre sur le principe d’entretiens semi-dirigés à partir de questions ciblées. Après une présentation générale de ce qu’est l’éco-conception et quelle en est la problématique appliquée aux PME (chapitre 2), nous précisons le cadre méthodologique de la recherche (chapitre 3) et exposons ses résultats (chapitre 4). Nous montrons que les freins à l’adoption de l’éco-conception dans les PME sont multiples et complexes, tant la diversité de ces entreprises est grande et difficile à synthétiser. En soulignant les freins, les leviers, les risques et les opportunités liés à l’intégration des principes de développement durable dans ces entreprises, nous faisons un portrait global de la situation actuelle et des difficultés rencontrées par ces PME pour adhérer à ces principes.

Mamès, profèsorn oun kindèr likht. Éducation en petite enfance en CPE. Le cas des femmes hassidiques Belz en services de garde en milieu familial accrédités.

La présente thèse est construite en trois parties. La première partie est précédée du chapitre 1 qui présente les premières données du travail de terrain sur les femmes hassidiques Belz, l’éducation des jeunes enfants et l’histoire de la communauté. La première partie est composée de trois chapitres qui analysent les notions relatives à la petite enfance, notamment sa définition et sa conception à travers l’histoire humaine récente et selon différentes cultures. Le chapitre 2 examine la question de la petite enfance en soi et des conditions qui la définissent. Le chapitre 3 analyse l’institutionnalisation de la petite enfance dans le monde moderne contemporain. Le chapitre 4 analyse l’avènement de la norme scientifique et son impact sur la petite enfance en ce qui a trait à l’éducation et au développement. Ces chapitres analysent notamment l’éducation en petite enfance en CPE (Centres de la petite enfance) au Québec. La deuxième partie de la thèse, composée aussi de trois chapitres, présente les paradigmes scientifiques et les cadres conceptuels dominants en petite enfance. Le chapitre 5 explique l’impact du « néolibéralisme » ou de la modernité avancée en petite enfance. Le chapitre 6 présente le nouveau paradigme du « postfondamentalisme » en petite enfance et le chapitre 7, celui de l’éco-éducation ainsi que la posture de « l’écosophie » en petite enfance. Ce dernier propose une application pédagogique de l’éco-éducation et de l’écosophie en petite enfance. La troisième partie fait état du travail de terrain en anthropologie au sein de la communauté féminine des Hassidim Belz de Montréal, notamment au sein des services de garde en milieux familial accrédités par le ministère de la Famille du Québec. Elle se divise en deux chapitres. Le chapitre 8 analyse l’incident de la Directive contre l’enseignement religieux en services de garde subventionnés. Le chapitre 9 propose les résultats du travail de terrain sur la philosophie de vie et la spiritualité des femmes hassidiques Belz de Montréal. La conclusion générale intègre le paradigme de l’éco-éducation et la posture de « l’écosophie » en petite enfance à la philosophie de vie et la spiritualité des femmes hassidiques Belz de Montréal. Elle propose un « réenchantement » du développement et de l’éducation en petite enfance.

Toxicity of Effluent from a Titanium Dioxide Factory on some Marine Animals

Toxicity of effluent from a titanium dioxide factory containing sulphuric acid residue with soluble iron metallic salts and insoluble material such as silica, etc. on fishes, decapods and molluscs was studied. The effluent caused changes in pH and oxygen depletion of the sea water. Sublethal effects of the precipitate of ferrous salts were also studied. Dilutions of effluent up to 1:150 were LC100 for all organisms used while 1:200 dilution was LC50 for fishes at 36 hr and for other organisms at 48 hr. But death of organisms at this concentration was caused by pH changes and oxygen depletion and did not account for the effects of the precipitate. Below this level precipitation started soon after mixing with sea water causing death of organisms by choking their gills and siphons. Dilutions,< 1:1000 were 96 hr LCO.