Le projet de thèse a pour but de synthétiser de nouveaux matériaux siliciques à microstructure contrôlée en utilisant des procédés de polycondensation à basse température, et de développer de nouvelles approches de microfabrication 3D à haute résolution par excitation bi-photonique d’une formulation sol-gel. La synthèse de matériaux microstructurés est ici centrée sur le procédé sol-gel, impliquant des réactions d’hydrolyse-polycondensation. Les mtériaux les plus étudiés par ces approches en particulier dans le cadre d’un contrôle de la porosité sont préparés à partir de tetraéthoxide de silicium (TEOS)/ Le matériau est structuré généralement par des agent moléculaires structurants (« templates ») tels que les composés tensioactifs. Ces derniers sont en général éliminés, après condensation des silanols, par traitement thermique ou lavage afin de libérer la porosité et générer la structuration. Cette étape d’élimination des agents structurants est souvent problématique, en particulier au niveau industriel, car elle utilise soit des hautes températures, soit des quantités importantes de solvants. Il y a un enjeu important à développer des approches de microstructuration s’affranchissant de ces agents moléculaires structurants, cela représentant le principal objectif de cette thèse.Deux stratégies sont abordées aux cours de ce travail de recherche. La première implique l’utilisation de précurseurs organosilylés donc la structure moléculaire permet une microstructuration du matériau synthétisé. Cette partie explore l’utilisation de précurseurs de la famille des silsesquioxanes et leur transformation vers les matériaux. La deuxième approche propose d’évaluer pour la première fois l’utilisation de l’excitation biphotonique pour contrôler l’étape de condensation sol-gel par modification de pH au point focal d’un laser et ainsi apporter une résolution micrométrique à la structuration du matériau / The main goal of this research was the synthesis of new siliceous materials with controlled microstructures, using low-temperature polycondensation process, and develop the new approach towards 3D microfabrication under two-photon excitation of a sol-gel formulation. Synthesis of microstructured materials is based on the sol-gel process, i.e. hydrolytic polycondensation. Most known siliceous materials with controlled microstructure are synthesized from tetraethoxysilane (TEOS). The materials are generally structured by structuring molecular agents ("templates") such as surfactant compounds, which are then removed by heat treatment or washing with appropriate solvents. This stage of removal of structuring agents is often problematic, particularly at the industrial level, because it uses either high temperatures or large amounts of solvents. Therefore, new methods to obtain materials with controlled porosity without the need to use templates are still being developed. Two strategies are discussed during this research work. First one involved the use of organosilicon precursors with a define structure that at molecular level modify the structure of the final materials. The use of well-defined precursors (silsesquioxanes), in appropriate proportions, allows the control of the porosity of the obtained silica materials. The second approach investigated in this work is the local photo-induced structuration of silicon based pre-hydrolyzed precursors under two-photon excitation allowing high 3D resolution

Les bâtiments existants reposent sur un équilibre stable qui assure leur durabilité. Toute exécution de travaux de réhabilitation qui déplace cet équilibre peut être à l'origine de désordres. En ce sens, les travaux peuvent être qualifiés de pathogènes. Dans le cadre de rénovations énergétiques, la problématique de l'humidité dans les bâtiments existants nécessite donc une attention particulière. Il convient donc de fournir aux acteurs de la construction des modèles de simulation du comportement hygrothemique global des bâtiments et d'évaluer les risques de pathologies liées à l'humidité. L'élaboration de ces modèles passent par la résolution de problèmes non-linéaires, de grande échelles spatiales et temporelles, et parfois paramétrique. Ils sont donc complexes à résoudre et les méthodes de réduction de modèle permettent de répondre à cette problématique. Deux techniques de réduction de modèles ont été explorées: la Décomposition Orthogonale Propre (POD) et la Décomposition Générale Propre (PGD). Elles ont été appliquées sur des problèmes de diffusion non-linéaire, couplée chaleur et humidité, dans les matériaux poreux. Ces deux méthodes ont été évaluées et comparées sur les critères de réduction du coût numérique de résolution du problème et sur la précision de calcul de la solution. Sur la base de ces analyses, la PGD a été retenue pour la suite des travaux. Grâce à ses caractéristiques, la méthode PGD présente plusieurs avantages d'ordre structurel, recensés dans la littérature. Au chapitre 3, nous avons utilisé ces prérogatives pour répondre aux problématiques de complexité des modèles de simulation des bâtiments. Notre intérêt s'est concentré sur la réduction de la complexité numérique de problèmes multi-dimensionnels, sur la globalisation de problèmes locaux et sur la création de méta-modèle ou solution PGD paramétrique. Plusieurs cas académiques ont été considérés pour illustrer ces propos. Nous avons traité des problèmes de transferts non-linéaires dans les matériaux poreux et des problèmes de transferts multizone dans un bâtiment. Enfin, la dernière partie des travaux est axée sur la construction d'un modèle global articulant des modèles réduits PGD. Deux modèles sont construits. Le premier couple un modèle réduit enveloppe PGD avec un modèle complet multizone. Ces travaux ont été réalisés dans le cadre d'une collaboration avec le laboratoire LST de l'université PUCPR de Curitiba, Brésil. Ce partenariat a permis de bénéficier du modèle reconnu et validé Domus pour la simulation des transferts multizones. Les nombreuses possibilités du logiciel ont pu être exploitées. Deux cas d'études sont abordés. Le premier concerne la résolution d'un problème paramétrique pour l'étude de scénarios de réhabilitation en fonction de la perméabilité à la vapeur de l'isolant. Le second porte sur la modélisation globale d'un bâtiment bi-zone intégrant une simulation bi-dimensionnelle d'un pont thermique. Il est possible d'élaborer un modèle global présentant une plus grande réduction de la complexité du problème que celui réalisé avec Domus. Le deuxième modèle couple donc un modèle réduit PGD pour le problème enveloppe et une solution PGD paramétrique pour le problème multizone. Les performances de ce modèle ont été discutées en terme de précision de calcul de la solution et d'économie numérique de résolution du problème. La pertinence des méthodes de réduction de modèle pour la simulation du comportement des bâtiments a été montrée. En particulier, la méthode PGD permet d'apporter une nouvelle approche de résolution ces problèmes. / Excessive levels of moisture in buildings may damage the construction quality. Moisture also has an effect on indoor air quality and thermal comfort of the occupants. Thus moisture is a possible source of disorders in buildings. It is therefore important to continue developing numerical models to simulate the global hygrothermal behaviour of buildings. To achieve this aim, it is necessary to solve non-linear problems, with high space and time scales, with fine discretisation and sometimes parametric. This mathematical problems are complex to solve. Thus model reduction techniques and efficient ways of numerical simulation are worth investigations. Two techniques were assessed : the Proper Orthogonal Decomposition (POD) and the Proper Generalised Decomposition (PGD). They were first applied on non-liner coupled heat and mass transfers in porous materials. Both were compared and evaluated carrying about the reduction of the cost of resolution and the precision of the solution computed. Following this analysis, the PGD was selected for our next investigations. Due to it representation, the PGD method has several interesting features, already reviewed in literature.Thus, chapter 3 proposed to illustrate this advantages on different issues of modelling buildings hygrothermal behaviours. We focused on the reduction of the complexity of multi-dimensional problems, on the globalisation of local problems and on building PGD parametric solution or meta-model. Several academic case study were considered to illustrate these points. We analysed non-linear heat and mass transfers in porous materials and multizone air building transfers. In last part, we elaborated a PGD reduced order model to perform whole building energy simulation. Two different models were built. The first one associates a PGD model for envelope problem and a large original model for multizone problem. This work was done during a collaboration with the LST laboratory, at PUCPR University, Curitiba, Brazil. The main interest was the benefits of using their validated and admitted model Domus for solving multizone problem. Two case study were analysed. The first one analyse a parametric problem for the study of the retrofitting a building in function of the vapour permeability of the insulating material. The second one focused on the whole building energy simulation of a two-zone building with 2-dimension transfers in the wall assembly. A second global PGD reduced order model was elaborated, with a higher reduction of the numerical complexity of the problem. This model associates a PGD model for solving envelope problem and a PGD parametric solution for the multizone problem. The performance of this model was analysed investigating the numerical gain and the precision of the solution computed. In conclusion, the relevance of reduction model techniques for performing whole building energy simulation was revealed. The PGD method contributes to a new approach for solving this problems.

Neste trabalho propomos uma nova formulação micromecânica para descrever escoamentos monofásicos em meios porosos viscoelásticos. Na abordagem proposta consideramos o meio poroso por dois níveis de porosidade (micro e macroporos), onde os efeitos de relaxação e fluência da matriz porosa são advindos da drenagem secundária do fluido residente nos microporos. A derivação do modelo macroscópico é obtida via técnicas de homogeneização de estruturas periódicas aplicadas à mudança a partir do modelo micromecânico composto por uma matriz poroelástica circundada por uma rede conexa de macroporos. Neste contexto o nosso principal resultado consiste na conjugação do modelo de suas escalas com a análise assintótica da formulação variacional do problema micromecânico posto no domínio da célula unitária periódica. Mostramos que esta combinação de técnicas fornece o decaimento dos núcleos de convolução das equações constitutivas homogeneizadas para as tensões efetivas da fase sólida e para a porosidade viscosa além de estabelecer a dependência constitutiva para o tempo de relaxação do processo de compactação secundária da matriz. Simulações numéricas são obtidas descretizando os problemas de célila locais via métoco de elementos finitos e ilustram as taxas de decaimento obtidas na análise

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Submitted by Letícia Fernanda Rasteiro null (leticiarasteiro@gmail.com) on 2017-08-14T18:29:34Z No. of bitstreams: 1 Dissertação - Letícia (repositório).pdf: 7126379 bytes, checksum: fb6b61701c972d4a6fedad35c81492ba (MD5) / Approved for entry into archive by LUIZA DE MENEZES ROMANETTO (luizamenezes@reitoria.unesp.br) on 2017-08-18T20:29:00Z (GMT) No. of bitstreams: 1 rasteiro_lf_me_araiq.pdf: 7126379 bytes, checksum: fb6b61701c972d4a6fedad35c81492ba (MD5) / Made available in DSpace on 2017-08-18T20:29:00Z (GMT). No. of bitstreams: 1 rasteiro_lf_me_araiq.pdf: 7126379 bytes, checksum: fb6b61701c972d4a6fedad35c81492ba (MD5) Previous issue date: 2017-07-28 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Este trabalho descreve a avaliação de óxidos mistos porosos de vanádio e molibdênio na reação de desidratação oxidativa do glicerol a ácido acrílico em uma única etapa. O trabalho divide-se em duas partes, em que na primeira tem-se a síntese, caracterização e avaliação catalítica dos materiais inicialmente sem tensoativos para posterior aplicação das condições ideias encontradas nesta etapa na segunda etapa, sendo ela a síntese, caracterização e avaliação catalítica dos materiais porosos. Na preparação dos materiais sem tensoativos variou-se a atmosfera de síntese e de tratamento térmico, mostrando que diferentes fases cristalinas eram formadas para cada condição distinta e por meio do método de Rietveld fez-se a quantificação dessas fases cristalinas formadas para cada amostra. Ao correlacionar as fases cristalinas presentes em cada amostra com os resultados catalíticos, observou-se que o melhor resultado se deu para aquela sintetizada e tratada termicamente em atmosfera de O2, no qual a fase Mo4,65V0,35O14 era predominante. Avaliou-se também a acidez dos materiais, porém os mesmos apresentaram poucas quantidades de sítios ácidos totais. Analisou-se também as condições para a reação catalítica, variando-se a temperatura e a atmosfera de reação. Por meio de todo o estudo das melhores condições concluiu-se que sintetizar e tratar termicamente em atmosfera de O2 leva aos melhores resultados catalíticos e que realizar a reação catalítica em atmosfera de O2 a 320°C melhora ainda mais a atividade catalítica do material. Através de uma análise após a reação notou-se que não houve formação de compostos carbonáceos e que o equilíbrio na quantidade das fases contendo o vanádio nas formas reduzida e oxidado é o responsável pela melhor atividade catalítica encontrada e que a presença de V+4 é imprescindível para a etapa de oxidação de acroleína a ácido acrílico. Na segunda etapa do trabalho, avaliou-se a influência da inserção dos poros no material pela adição de tensoativos à síntese em que se obteve os melhores resultados catalíticos na reação da desidratação oxidativa do glicerol. Sintetizou-se os catalisadores com 3 diferentes tensoativos em 3 razões tensoativo/(Mo+V) distintas, nas condições encontradas na parte 1 do trabalho. Caracterizou-se os materiais por difração de raios-X, dessorção de amônia a temperatura programada, porosimetria de mercúrio, picnometria de hélio, termogravimetria e fisissorção de nitrogênio. Observou-se a formação das fases cristalinas iguais ao do material de referência (MoV-O2(O2)), como já esperado e o aumento da porosidade para todos os catalisadores. Os materiais apresentaram acidez total menor do que a da referência porém com aumento na quantidade de sítios mais fortes. Não se observou a formação de coque nas amostras analisadas após a reação. Observou-se uma melhora significativa nos resultados catalíticos comparados aos catalisadores sem poros, principalmente para o catalisador SDS-0,10, alcançando uma seletividade para ácido acrílico de 56% e 100% de conversão, mostrando que os objetivos iniciais do trabalho foram alcançados. / This work describes the evaluation of porous vanadium and molybdenum mixed oxides in the one-step glycerol oxydehydration to acrylic acid. The work was separated in two parts, where the first one is the synthesis, characterization and catalytic evaluation of the materials initially without the pores for later application of the ideal conditions found in this stage in the second stage, being it the synthesis, characterization and catalytic evaluation of porous materials. In the materials preparation without pores, the synthesis and heat treatment atmosphere was varied, showing that different crystalline phases were formed for each distinct condition and by means of the Rietveld refinement method the crystalline phases formed for each sample were quantified. By correlating the crystalline phases present in each sample with the catalytic results, it was observed that the best result was obtained for the one synthesized and thermally treated in O2 atmosphere, in which the Mo4.65V0.35O14 crystalline phase was predominant. The acidity of the materials was also evaluated, but they presented few amounts of total acid sites. The conditions for the catalytic reaction were also analyzed by varying the reaction temperature and the reaction atmosphere. Throughout the study of the best conditions it was concluded that synthesizing and thermally treating in O2 atmosphere leads to the best catalytic results and that performing the catalytic reaction in an O2 atmosphere at 320°C further improves the catalytic activity of the material. It was observed that there was no formation of carbonaceous compounds and that the equilibrium in the amount of the phases containing the vanadium in the reduced and oxidized forms is responsible for the best catalytic activity found and that the presence of V+4 is essential for the oxidation step of acrolein to acrylic acid. In the second stage of the work, was evaluated the material porosity influence in the glycerol oxydehydration to acrylic acid. The catalysts were synthesized with 3 different surfactants in 3 different surfactant/(Mo + V) ratios, under the ideal conditions found in part 1 of the work. The materials were characterized by X-ray diffraction, temperature programmed desorption of ammonia, mercury porosimetry, helium pycnometry, thermogravimetry and nitrogen physisorption. The formation of the same crystalline phases as that of the reference (MoV-O2(O2)) was observed for the porous catalysts, as already expected and was observed an increase in the porosity to all the catalysts prepared with surfactants. The materials presented lower total acidity than the reference, but with an increase in the number of strongest sites. No coke formation was observed in the analyzed samples after the reaction. The catalytic tests performed in the best conditions seen in part 1 of this work showed a significant improvement in the catalytic results compared to the non-porous catalysts, especially for the SDS-0.10 catalyst, achieving 56% of selectivity for acrylic acid and 100% of conversion, showing that the initial objectives of the work were achieved. / CNPq: 152447/2015-6

Thesis submitted in fulfillment of the requirements for the degree Doctor of Technology: Mechanical Engineering Cape Peninsula University of Technology, 2013 / Fluid flow through a porous channel and cylindrical pipe walls are important area of research due to its wide applications in transpiration cooling, gaseous diffusion technology, cooling of rocket, mechanized irrigation and filtration processes. It is therefore necessary to examine the effect of Navier slip, combined effects of buoyancy forces and variable viscosity on the entire flow structure. Analyzing the magneto- hydrodynamics (MHD) of unsteady flow with buoyancy effect and also investigate numerically the entropy generation in an unsteady flow through porous pipe. We have also examined the thermal stability and entropy generation in the system. The problems were investigated theoretically using appropriate mathematical models for both transient and steady state scenario. Both analytical techniques and numerical methods are employed to tackle the model nonlinear equations derived from the law of conservation of mass, momentum and energy balance. Some definitions of terms to come across and introduction to fluid flow are given in chapter 1, together with literature reviews, statement of problem and objectives of the study. Chapter 2 lays the foundation for basic fundamental equations governing fluid flow. In chapter 3, the combined effect of suction/injection and asymmetric Navier slip on the entropy generation rate for steady flow of an incompressible viscous fluid through a porous channel subjected to different temperature at the walls are investigated. Chapter 4 analyze combined effects of buoyancy forces together with Navier slip on the entropy generation in a vertical porous channel wall with suction/injection wall. Analysis of MHD unsteady flow through a porous pipe with buoyancy effects are carried out in chapter 5, while chapter 6 investigates numerically entropy generation of unsteady flow through a porous pipe with suction and chapter 7 gives concluding remarks.

Orientador: Osvaldo Luís Manzoli / Resumo: Materiais porosos constituem uma grande gama de materiais que podem ser encontrados na natureza ou em forma artificial. Rochas reservatório é um exemplo importante desse tipo de material, sendo o estudo delas a motivação principal desse trabalho. O estudo de rochas reservatório, de onde são extraídos gases e petróleo, consiste em um problema físico no qual os sistemas mecânico e hidráulico são acoplados. O acoplamento ocorre pois as deformações (no sistema mecânico) inuenciam as pressão (no sistema hidráulico), que por sua vez inuenciam as tensões (sistema mecânico). As equações governantes do sistema mecânico são mostradas e as do hidráulico deduzidas. Para a resolução do problema, o Método dos Elementos Finitos (MEF) foi utilizado para ambos os sistemas físicos, logo, as equações governantes são apresentadas em sua forma fraca e, então, aproximada pelo MEF. Numericamente, o acoplamento pode ser tratado de diferentes maneiras, seja considerando um dos sistemas de maneira bem pobre tal como fórmulas empíricas simplistas, seja considerado os sistemas de maneira individual, ou então de maneira completa. Essa última maneira de considerar um acoplamento, o acoplamento total, é formulada, programada e testada nesse trabalho. Para validar a implementação, dois problemas foram analisados: Problema de Terzaghi e Problema Mandel, ambos com solução analítica conhecidas. Os resultados obtidos numericamente comparados aos analíticos indicam que o método totalmente acoplado foi bem implem... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Porous materials constitute a wide range of materials that can be found in nature and arti cially. Reservoir rock is an important example of this kind of material, which is the main motivation of this work. The study of reservoir rocks, from which gases and oil are extracted, consists of a physical problem in which mechanical and hydraulic systems are coupled. The coupling occurs because the deformations (in the mechanical system) in uence the pressure (in the hydraulic system), which in turn in uence the stresses (mechanical system). The governing equations of the mechanical system are shown and those of the hydraulic system are deduced. To solve the problem, the Finite Element Method (FEM) is used for both physical systems, so the governing equations are presented in their weak form and then approximated according to the FEM. Numerically, the coupling can be handled in di erent ways, either by considering one of the systems in a very poor way by using simplistic empirical formulas, by considering the systems individually, or in a complete manner. The latter one, the fully-coupled treatment, is formulated, programmed and tested in this work. To validate the implementation, two problems has been analyzed: Terzaghi Problem and Mandel Problem, both with known analytical solutions. The comparison between the results obtained numerically and analytically indicates that the fully coupled method has been well implemented in both 2D and 3D cases. The numerical oscillation existing i... (Complete abstract click electronic access below) / Mestre

Ce travail avait pour but de développer un nouveau type de matériaux basés sur des complexes polyelectrolytes. Ces matériaux ont été obtenus par l’ultracentrifugation des complexes soit d’origine naturelle ou soit d’origine synthétique. Le système de polyélectrolytes ainsi que les conditions dans lesquelles ces matériaux peuvent être obtenus, suivi par le choix du système optimal pour des études complémentaires ont été décrits. PAA / PAH CoPECs a été choisi comme systèmes modèles de synthèse et ses propriétés physico chimiques (composition, structure et les propriétés mécaniques) ont été décrits ici en détails. Nous avons montré que les propriétés de la composition, la structure et mécanique de le PAA/PAH CoPECs peut être contrôlée en modifiant les conditions d’assemblage (pH, concentration des polyélectrolytes, [NaCl], la vitesse et la commande de l’addition). Également, les conditions environnementales ([NaCl] et pH) ont également été utilisés pour contrôler la taille des pores et porosité des PAA/PAH CoPECs . Enfin, leur capacité à servir de support pour l’immobilisation d’enzymes a également été étudiée. Nous avons optimise les conditions d’assemblage afin de maintenir le maximum quantité de l’enzyme dans le complexe. Nous avons également démontré que CoPECs fournit la stabilisation à long terme, ainsi que la protection de l’enzyme à des températures élevées. Ainsi, PAA / PAH CoPECs sont des candidats potentiels pour être utilisé comme des supports pour l’ingénierie tissulaire et pour l’immobilisation d’enzymes. / This work was aimed to the develop of a new kind of materials of polyelectrolytes complexes. These materials were obtained by the ultracentrifugation of complexes either of natural or synthetic origin. The polyelectrolytes systems as well as the conditions under which these materials could be obtained, followed by the selection of the optimal system to further studies was described. PAA/PAH CoPECs was chosen as synthetic model systems and its physiochemical properties (composition, structure and mechanical properties) were here deeply described. We demonstrated that the composition, structure and mechanical properties can be controlled by changing the assembly conditions (pH, concentration of the polyelectrolytes, [NaCl], speed and order of addition). Moreover, the environmental conditions ([NaCl] and pH) were also used to control the porosity and pores size of the PAA/PAH CoPECs. Finally their ability to serve as scaffold for enzyme immobilization was also studied. We optimized the assembly conditions to keep the maximum of the activity. We also demonstrated that the CoPECs structure provides the stabilization in long term as well as the protection of the enzyme from high temperature. Thus, PAA/PAH CoPECs is a potential and suitable candidates as scaffold for tissue engineering and for the immobilization of enzymes.

Made available in DSpace on 2014-10-09T12:35:57Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:48Z (GMT). No. of bitstreams: 0 / O desenvolvimento de biomateriais com estrutura porosa visa permitir uma boa ancoragem biológica através do crescimento do tecido ósseo no interior dos poros, além de no caso de algumas ligas de titânio, proporcionar valores de módulo elástico semelhantes ao do osso, prevenindo assim o insucesso por reabsorção óssea na interface com o implante. O objetivo deste estudo foi avaliar o processamento de implantes porosos à base de titânio produzidos por metalurgia do pó, utilizando polímeros naturais como aditivos (albumina, amidos de arroz, batata, milho e a gelatina), e analisar a osteointegração desses implantes por ensaio in vivo. Foram obtidas, amostras de titânio comercialmente puro (Ticp) e da Liga Ti-13Nb-13Zr pelos processos de space-holder e suspensão; os polímeros naturais foram removidos termicamente (350°C/1h) previamente a sinterização (1300°C/1h e 1300°C/3h, respectivamente). As metodologias de processamento utilizando aditivos de baixo custo propiciaram a obtenção de implantes metálicos porosos de maneira simplificada, com porosidades diferenciadas, boa homogeneidade estrutural, grau de porosidade adequado (entre 40% e 60%), distribuição e tamanho dos poros conforme o polímero natural formador. Na caracterização biológica, o teste in vitro de citotoxicidade validou a utilização dos implantes para a realização do teste in vivo. A avaliação da osteointegração foi realizada em coelhos da raça New Zealand em períodos de 49 dias. Na análise histológica por microscopia eletrônica de varredura e fluorescência, foram obtidos os resultados quantitativos e qualitativos da osteointegração, com crescimento ósseo em todos os implantes, apresentando osteocondutividade. Os melhores resultados ocorreram em implantes com porosidade homogênea, e com tamanho médio de poros entre 100 e 200 μm. Assim, os materiais porosos de titânio e da liga Ti-13Nb-13Zr produzidos com os polímeros naturais (amido de arroz, amido de batata, amido de milho, gelatina e albumina), permitiram a nutrição e manutenção necessárias para a sobrevivência das células, comprovando a osteointegração e osteocondução dos implantes desenvolvidos. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP