Characterisation of phase composition, microstructure and microhardness of electroless nickel composite coating co-deposited with SiC on casting aluminium LM24 alloy substrate

Electroless Ni-P (EN) and composite Ni-P-SiC (ENC) coatings were developed on cast aluminium alloy, LM24. The coating phase composition, microstructure and microhardness were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM) and microhardness tester, respectively, on as-plated and heat-treated specimens. The original microstructure of the Ni-P matrix is not affected by the inclusion of the hard particles SiC. No formation of Ni-Si phase was observed upto 500°C of heat treatment. The microhardness is increased on incorporation of SiC in Ni-P matrix. The hardening mechanism is the formation of intermetallic phase Ni3P on annealing at elevated temperature. Overall, the composite coating (ENC) was found to be superior as compared to particles free (EN) coating in both as-deposited and heat-treated conditions.

Micro-scale abrasion behaviour of electroless Ni-P-SiC coating on aluminium alloy

Electroless nickel (EN) and electroless nickel composite (ENC) coatings were deposited on aluminium alloy substrate, LM24. The micro abrasion test was conducted to study the wear behaviour of the coatings with the effect of SiC concentration. Microhardness of the coatings was tested also. The wear scars were analysed using optical microscope and scanning electron microscope (SEM). The wear resistance was found to be improved in composite coating that has higher microhardness as compared to particles free and the bare aluminium substrate. In as-deposited condition for the composite coating, the wear volume increases on increase in SiC percentage in the coating but is found to be minimum for lower SiC percentage. The increase in hardness on heat treatment at 400°C is due to the hardening or grain coarsening with the formation Ni3P.

The potential of electron beam irradiation for simultaneous surface modification and bioresorption control of PLLA for medical device applications

Bioresorbable polymers have been widely investigated as materials exhibiting significant potential for successful application in the medical fields of bone fixation devices and drug delivery. Further to the ability to control degradation, surface engineering of polymers has been highlighted as a key method central to their development. Previous work has demonstrated the ability of electron beam (e-beam) technology to control the degradation profiles and bioresorption of a number of commercially relevant bioresorbable polymers (poly-l-lactic acid (PLLA), L-lactide/ DL-lactide co-polymer (PLDL) and poly(lactic-co-glycolic acid) (PLGA). This work investigates the further potential of e-beam technology to impart added biofunctionality through the manipulation of polymer (PLLA) surface properties. A Dynamatron Continuous DC e-beam unit (Synergy Health, UK), with beam energies of 0.5, 0.75, and 1.5 MeV, was used for the irradiation of PLLA samples with delivered surface doses of 150 or 500 kGy at each energy level. The chosen conditions reflect the need to achieve a specific surface modification for the control of surface degradation as demonstrated in previous work. Surface characterization was then performed using contact angle analysis, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and atomic force microscopy.
Results demonstrated a significant increase in surface wettability post e-beam treatment. In correlation with this, XPS data showed the introduction of oxygen-containing functional groups to the surface of PLLA. Raman spectroscopy indicated chain scission in the near surface region of PLLA. E-beam irradiation did not seem to affect the surface roughness of PLLA as a direct consequence of the treatment. In conclusion electron beam surface modification has been found to modify both the surface-to-bulk bioresorption profile and the surface hydrophilicity. Both could provide benefits in relation to the performance of implantable medical devices.

Modifications of Surface Properties of Beta Ti by Laser Surface Treatment

β -type Ti-alloy is a promising biomedical implant material as it has a low Young’s modulus but is also known to have inferior surface hardness. Various surface treatments can be applied to enhance the surface hardness. Physical vapour deposition (PVD) and chemical vapour deposition (CVD) are two examples of this but these techniques have limitations such as poor interfacial adhesion and high distortion. Laser surface treatment is a relatively new surface modification method to enhance the surface hardness but its application is still not accepted by the industry. The major problem of this process involves surface melting which results in higher surface roughness after the laser surface treatment. This paper will report the results achieved by a 100 W CW fiber laser for laser surface treatment without the surface being melted. Laser processing parameters were carefully selected so that the surface could be treated without surface melting and thus the surface finish of the component could be maintained. The surface and microstructural characteristics of the treated samples were examined using X-ray diffractometry (XRD), optical microscopy (OM), 3-D surface profile & contact angle measurements and nano-indentation test.

Mechanical behaviour of AISiC nano composites produced by Ball Milling and Spark Plasma Sintering

Neste trabalho foram produzidos nanocompósitos de AlSiC misturando alumínio puro com nano partículas de SiC com diâmetro de 45 – 55 nm, usando, de forma sequencial, a técnica da metalurgia do pó e a compactação por “ Spark Plasma Sintering”. O compósito obtido apresentava grãos com 100 nm de diâmetro, encontrandose as partículas de SiC localizadas, principalmente, nas fronteiras de grão. O nanocompósito sob a forma de provetes cilíndricos foi submetido a testes de compressão uniaxial e a testes de nanoindentação para analisar a influência das nanopartículas de SiC, da fração volúmica de ácido esteárico e do tempo de moagem, nas propriedades mecânicas do material. Para efeitos de comparação, utilizouse o comportamento mecânico do Al puro processado em condições similares e da liga de alumínio AA1050O. A tensão limite de elasticidade do nanocompósito com 1% Vol./Vol. de SiC é dez vezes superior à do AA1050. O refinamento de grão à escala nano constitui o principal mecanismo de aumento de resistência mecânica. Na realidade, o Al nanocristalino sem reforço de partículas de SiC, apresenta uma tensão limite de elasticidade sete vezes superior à da liga AA1050O. A adição de 0,5 % Vol./Vol. e de 1 % Vol./Vol. de SiC conduzem, respetivamente, ao aumento da tensão limite de elasticidade em 47 % e 50%. O aumento do tempo de moagem e a adição de ácido esteárico ao pó durante a moagem conduzem apenas a um pequeno aumento da tensão de escoamento. A dureza do material medida através de testes de nanoindentação confirmaram os dados anteriores. A estabilidade das microestruturas do alumínio puro e do nanocompósito AlSiC, foi testada através de recozimento de restauração realizado às temperaturas de 150 °C e 250 °C durante 2 horas. Aparentemente, o tratamento térmico não influenciou as propriedades mecânicas dos materiais, excepto do nanocompósito com 1 % Vol./Vol. de SiC restaurado à temperatura de 250 °C, para o qual se observou uma redução da tensão limite de elasticidade na ordem dos 13 %. No alumínio nanocristalino, a tensão de escoamento é controlada pelo efeito de HallPetch. As partículas de SiC, são segregadas pelas fronteiras do grão e não contribuem para o aumento de resistência mecânica segundo o mecanismo de Orowan. Alternativamente, as nanopartículas de SiC constituem um reforço das fronteiras do grão, impedindo o seu escorregamento e estabilizando a nanoestrutura. Deste modo, as propriedades mecânicas do alumínio nanocristalino e do nanocompósito de AlSiC poderão estar relacionadas com a facilidade ou dificuldade do escorregamento das fronteiras de grão, embora não seja apresentada prova explícita deste mecanismo à temperatura ambiente.

Assessing the combined effect of land management and wildfire on runoff and soil erosion in north central Portugal

Strong and sometimes extreme responses in runoff and soil erosion following wildfires have been reported worldwide. However, in the case of North-Central Portugal, little research had been carried out regarding the hydrologic and erosive impacts of several land management activities in recently burnt areas (such as ground preparation, post-fire logging or post-fire mitigation treatments). This study aims to assess post-fire runoff and soil erosion response on Eucalypt and Maritime pine plantations during the first, second and third years following wildfires. The effect of several pre-fire ground preparation operations (ploughed down-slope, contour ploughed and inclined terraces), post-fire logging activities (on both the eucalypt and pine plantations), as well as the application of hydromulch (a post-fire emergency treatment) on overland flow and soil erosion were compared to burnt but undisturbed and untreated areas. The intensive monitoring of runoff, soil erosion and selected soil properties served to determine the main factors involved in post-fire runoff and soil erosion and their spatial and temporal variation. Soil water repellency deserved special attention, due to its supposed important role for overland flow generation. Repeated rainfall simulation experiments (RSE’s), micro-scale runoff plots and bounded sediment fences were carried out and/or installed immediately after the wildfire on seven burnt slopes. Micro-scale runoff plots results under natural rainfall conditions were also compared to the RSE’s results, which was useful for assessing the representativeness of the data obtained with artificial rainfall. The results showed comparable runoff coefficient (20-60%) but lower sediment losses (125-1000 g m-2) than prior studies in Portugal, but especially outside Portugal. Lower sediment losses were related with the historic intensive land use in the area. In evaluating these losses, however, the shallowness and stoniness of the soils, as well as the high organic matter fraction of the eroded sediments (50%) must not be overlooked. Sediment limited erosion was measured in all the ploughed sites, probably due to the time since ploughing (several years). The disturbance of the soil surface cover due to post-fire logging and wood extraction substantially increased sediment losses at both the pine and eucalypt sites. Hydromulch effectiveness in reducing the runoff (70%) and sediment losses (83%) was attributed to the protective high coverage provided by hydromulch. The hydromulch significantly affected the soil cover and other soil properties and these changes also reduced the soil erosion risk. The rainfall amount was the main factor explaining the variance in runoff. However, a shift from rainfall amount to rainfall intensity was detected when either the surface cover or the infiltration capacity (hydrophilic conditions) increased. Sediment losses were controlled by rainfall intensity and surface cover. The role of soil water repellency on runoff generation was not consistent; the overall repellency levels alone were not enough to assess its hydrological impact. Soil water repellency explained runoff generation in the specific-sites model better than in the overall model. Additionally, soil moisture content was a better predictor for soil water repellency than antecedent rainfall. The natural rainfall results confirmed that RSE’s were able to capture the specific sediment losses and its organic matter content as well as the differences between the ploughed and unploughed sites. Repeated RSE’s also captured the seasonal variations in runoff and sediment losses attributed to soil water repellency. These results have implications for post-fire soil erosion modelling and soil conservation practices in the region, or areas with the same land use, climate and soil characteristics. The measured sediment loss, as well as the increasing frequency of ploughing in recently burnt and unburnt eucalypt stands, suggests ploughing is not an effective as a soil conservation measure. Logging activities with less impact are recommended in order to maintain the forest litter protecting the soil surface. Due to its high effectiveness in reducing runoff and soil erosion, hydromulch is recommended for highly sensitive and vulnerable areas.

Alkali-free bioactive glasses for bone regeneration

Bioactive glasses and glass-ceramics are a class of third generation biomaterials which elicit a special response on their surface when in contact with biological fluids, leading to strong bonding to living tissues. The purpose of the present study was to develop diopside based alkali-free bioactive glasses in order to achieve good sintering behaviour, high bioactivity, and a dissolution/ degradation rates compatible with the target applications in bone regeneration and tissue engineering. Another aim was to understand the structure-property relationships in the investigated bioactive glasses. In this quest, various glass compositions within the Diopside (CaMgSi2O6) – Fluorapatite (Ca5(PO4)3F) – Tricalcium phosphate (3CaO•P2O5) system have been investigated. All the glasses were prepared by melt-quenching technique and characterized by a wide array of complementary characterization techniques. The glass-ceramics were produced by sintering of glass powders compacts followed by a suitable heat treatment to promote the nucleation and crystallization phenomena. Furthermore, selected parent glass compositions were doped with several functional ions and an attempt to understand their effects on the glass structure, sintering ability and on the in vitro bio-degradation and biomineralization behaviours of the glasses was made. The effects of the same variables on the devitrification (nucleation and crystallization) behaviour of glasses to form bioactive glass-ceramics were also investigated. Some of the glasses exhibited high bio-mineralization rates, expressed by the formation of a surface hydroxyapatite layer within 1–12 h of immersion in a simulated body fluid (SBF) solution. All the glasses showed relatively lower degradation rates in comparison to that of 45S5 Bioglass®. Some of the glasses showed very good in vitro behaviour and the glasses co-doped with zinc and strontium showed an in vitro dose dependent behaviour. The as-designed bioactive glasses and glass–ceramic materials are excellent candidates for applications in bone regeneration and for the fabrication of scaffolds for tissue engineering.

Optimisation du traitement thermomécanique de pièces d’acier fabriquées par métallurgie des poudres

Le forgeage de préformes fabriquées par métallurgie des poudres nous permet d’atteindre une densification voisine de la densité théorique ce qui a comme incidence directe une amélioration substantielle des propriétés mécaniques finales des pièces, notamment la résistance en fatigue. La démarche préconisée pour améliorer cette performance critique de pièces forgées par métallurgie des poudres consiste à optimiser leurs caractéristiques métallurgiques et leur densité concomitante. À ce propos, une nouvelle formulation d’acier MP a été développée et caractérisée. La stratégie de développement portait sur l’utilisation d’éléments de microalliage préalliés, comme le vanadium et le niobium. Pour ce faire, on a optimisé le paramètre de mise en œuvre primordial, qui est la température de forgeage, afin d’obtenir une fine taille de grains à la fin du cycle du traitement réalisé accompagnée d’une densité élevée des pièces forgées. Une série de traitements d’austénisation sur une gamme étendue de température variant entre 900 °C à 1250 °C a été effectuée ce qui nous a permis par la suite de connaître, pour chaque mélange, l’évolution de la taille des grains en fonction de la température d’austénisation. La nouvelle formulation de composition chimique a démontré un impact marqué quant au contrôle de la taille de grains en fonction de la température d’austénitisation. Une étude comparative nous a permis d’identifier la température de forgeage la plus appropriée pour ce type de pièces et de dégager la méthodologie à suivre en fonction des propriétés mécaniques et microstructurales.

Determination of the Maximum Rate of Eccrine Sweat Glands’ Ion Reabsorption Using the Galvanic Skin Conductance to Local Sweat Rate Relationship

Purpose The purpose of the present study was to develop and describe a simple method to evaluate the rate of ion reabsorption of eccrine sweat glands in human using the measurement of galvanic skin conductance (GSC) and local sweating rate (SR). This purpose was investigated by comparing the SR threshold for increasing GSC with following two criteria of sweat ion reabsorption in earlier studies such as 1) the SR threshold for increasing sweat ion was at approximately 0.2 to 0.5 mg/cm2/min and 2) exercise-heat acclimation improved the sweat ion reabsorption ability and would increase the criteria 1. Methods Seven healthy non-heat-acclimated male subjects received passive heat treatment both before and after 7 days of cycling in hot conditions (50% maximum oxygen uptake, 60 min/day, ambient temperature 32°C, and 50% relative humidity). Results Subjects became partially heat-acclimated, as evidenced by the decreased end-exercise heart rate (p<0.01), rate of perceived exhaustion (p<0.01), and oesophageal temperature (p=0.07), without alterations in whole-body sweat loss, from the first to the last day of training. As hypothesised, we confirmed that the SR threshold for increasing GSC was near the predicted SR during passive heating before exercise heat acclimation, and increased significantly after training (0.19 ± 0.09 to 0.32 ± 0.10 mg/cm2/min, p<0.05). Conclusions The reproducibility of sweat ion reabsorption by the eccrine glands in the present study suggests that the relationship between GSC and SR can serve as a new index for assessing the maximum rate of sweat ion reabsorption of eccrine sweat glands in humans.

Establishing the main Guidelines for Cast Steel to Produce Truck Parts

Este trabalho foi realizado na Scania CV AB e teve como principal objectivo estabelecer uma diretriz sobre a possível utilização de aços vazados. Existe uma grande necessidade na realização deste trabalho, de forma a apoiar os engenheiros de projecto no seu processo de selecção dos materiais mais adequados, para produzir componentes mais leves e de elevado desempenho. Esta diretriz apresenta informação relacionada com propriedades mecânicas, processos de fundição, vazabilidade, tipologia de defeitos, tratamentos térmicos, soldabilidade e tratamentos superficiais dos aços vazados. Este trabalho foi limitado, na seleção de materiais para componentes do camião, a aços vazados que poderiam ser aplicados em dois componentes específicos: um componente estrutural da carroçaria sujeito a esforços de fadiga e a um colector de gases de combustão, sujeito a fluência, oxidação, fadiga por corrosão, fadiga-térmica e fadiga-mecânica. Foi realizado um benchmark focado nestes dois componentes de forma a saber que materiais são utilizados de momento por outras empresas concorrentes. Foi realizada ainda uma análise sobre possíveis materiais que possam ser aplicados em cada componente referido. Foi conduzida uma caracterização no estado bruto de fundição de um aço inoxidável vazado usado para produzir um protótipo do colector de gases. Esta caracterização consistiu numa análise microestrutural e medição de macro e microdurezas. Além da caracterização inicial, foram aplicados um conjunto de tratamentos térmicos, de forma a estudar a possibilidade de eliminar os carbonetos presentes inicialmente nas fronteiras de grão. As principais conclusões deste trabalho são que o aço vazado apresenta potencial para ser uma escolha válida em diversas aplicações, devido a um leque alargado de propriedades apresentadas tipicamente por este material. Relativamente a aplicações estruturais, o aço vazado é vantajoso comparativamente ao ferro fundido, quando são requeridos, por exemplo, soldabilidade e elevada resistência, combinada com elevada tenacidade à fractura. Para componentes sujeitos a elevadas temperaturas de serviço, o aço inoxidável vazado é vantajoso quando usado a temperaturas superiores a 750°C, apesar do seu elevado custo. O tratamento térmico composto por um recozimento de solubilização seguido de envelhecimento, elimina quase na totalidade os carbonetos presentes nas fronteiras de grão e verifica-se um aumento de dureza através de uma precipitação de carbonetos finamente dispersos na matriz, que poderão também aumentar a resistência à fluência.

Immersioultraäänitutkimuksen kehittäminen

Teräksenvalmistajilta edellytetään jatkuvasti panostusta laadun ja laadunvarmistuksen kehittämiseen. Teräksen laatu ja puhtaus korostuvat varsinkin silloin, kun terästä käytetään vaativiin käyttökohteisiin, kuten autoteollisuuden tarpeisiin. Ultraäänitarkastusmenetelmää käytetään laadun-varmistuksessa teräksen sisävikojen etsimiseen. Ultraäänitarkastuksessa lähetetään suuritaajuuksista ääntä kappaleeseen. Ääni etenee materiaalissa ja heijastuu erilaisista epäjatkuvuuskohdista. Luotaimeen palaavaa ääntä analysoimalla saadaan tietoa teräksestä ja sen sisävioista. Ultraäänitarkastuksen ongelmana on vian tyypin määrittäminen hankaluus sekä herkkyys tutkittavan materiaalin aineominaisuuksille. Työn tavoitteena oli immersioultraäänitarkastuksen kehittäminen sovellettuna teräksenvalmistajan tarpeisiin. Materiaalin aineominaisuuksista tutkittiin seostuksen vaikutusta. Teräslajit tarkastettiin valssitilaisena, karkaistuna ja normalisoituna. Lisäksi tutkittiin kappaleen pinnankarheuden ja -muodon vaikutusta tarkastukseen. Vikatyyppien tunnistamisen mahdollisuuksia ultra-äänitarkastuksessa selvitettiin käyttäen FFT- taajuusanalyysiä. Erilailla lämpökäsitellyillä teräslajeilla näytti eniten tuloksiin vaikuttavan terästen raekoko. Valssitilaisilla teräksillä raekoko on suuri, jolloin ultraääni vaimenee voimakkaasti teräksessä. Huomattavaa kuitenkin oli, että mikäli lämpö-käsittelyillä ei teräksen raekokoa saada juuri pienennettyä, ei myöskään vaimeneminen vähene. Tämän vuoksi lämpökäsittely ei välttämättä ole aina tarpeellinen valmisteltaessa ultraääninäytteitä. Fourier’n taajuusanalyysissä huomattiin olevan eroavaisuuksia verrattaessa huokosista ja sulkeumista palaavien kaikujen taajuusspektrejä. Näiden tulosten perusteella näyttäisi olevan mahdollista käyttää FFT- menetelmää ultraääni-tarkastuksessa vikojen luokitteluun.

Isolation and partial characterization of a complementary protein from the mycoparasite, Piptocephalis virginiana, which specifically binds to two glycoproteins b and c of the host cell surface

Presence of surface glycoprotein in Piptocephalis virginiana that recognizes the host glycoproteins band c, reported earlier from our laboratory, was detected by immunofluorescence microscopy. Germinated spores of P. virginiana treated with Mortierella pusilla cell wall protein extract, primary antibodies prepared against glycoproteins band c and FITC-goat anti-rabbit IgG conjugate showed fluorescence. This indicated that on the surfaces of the biotrophic mycoparasite P. virginiana , there might be a complementary molecule which recognizes the glycoproteins band c from M. pusilla. Immunobinding analysis identified a glycoprotein of Mr 100 kDa from the mycoparasite which binds with the host glycoproteins band c, separately as well as collectively. Purification of this glycoprotein was achieved by (i) 60% ammonium sulfate precipitation, (ii) followed by heat treatment, and (iii) Sephadex G-IOO gel filtration. The glycoprotein was isolated by preparative polyacrylamide gel electrophoresis by cutting and elution. The purity of the protein ·was ascertained by SDS-PAGE and Western blot analysis. Positive reaction to periodic acid-Schiff reagent revealed the glycoprotein nature of this 100 kDa protein. Mannose was identified as a major sugar component of this glycoprotein by using a BoehringerMannheim Glycan Differentiation Kit. Electrophoretically purified glycoprotein was used to raIse polyclonal antibody in rabbit. The specificity of the antibody was determined by dot-immunobinding test and western-blot analysis. Immunofluorescence mIcroscopy revealed surface localization of the protein on the germ tube of Piptocephalis virginiana. Fluorescence was also observed at the surfaceJ of the germinated spores and hyphae of the host, M. pusilla after treatment with complementary protein from P. virginiana, primary antibody prepared against the complementary protein and FITC-goat anti-rabbit IgG conjugate.

Elucidation of the components involved in the antioxidant activity of honey

Canadian honeys were analyzed for sugar concentration, honey colour, total phenolic content, the level of brown pigments, and antioxidant activity in order to elucidate the main components involved in the antioxidant activity of honey. By employing size-exclusion chromatography in combination with activity-guided fractionation, it was demonstrated that the antioxidant components are of high molecular weight (HMW), brown in colour and absorb at both 280nm and 450nm. The presence of brown HMW antioxidant components prompted an investigation on the influence of heattreatment on the Maillard reaction and the formation of melanoid ins. Heat-treatment of honey resulted in an increase in the level of phenolics in the melanoidin fractions which correlated with an increase in antioxidant activity. The preliminary results of this study suggest for the first time that honey melanoidins underlie the antioxidant activity of unheated and heat-treated honey, and that phenolic constituents are involved in the melanoidin structure and are likely incorporated by covalent or non-covalent interaction.

Facteurs cognitifs liés à l'acquisition du lexique orthographique

La présente thèse a pour objectif d’étudier le rôle des facteurs cognitifs (traitement phonologique et visuoattentionnel et mémoire lexicale orthographique) dans l’acquisition des connaissances orthographiques implicites et explicites. Afin d’examiner les liens entre les différents facteurs cognitifs et les connaissances orthographiques, une étude longitudinale a été réalisée à l’aide d’un échantillon de 338 enfants suivis de la maternelle 5 ans à la fin de la deuxième année du primaire. À la fin de la maternelle, les enfants ont été évalués à l’aide d’une épreuve d’orthographe approchée et d’épreuves évaluant les facteurs cognitifs en jeu dans l’apprentissage du langage écrit (traitement phonologique, traitement visuoattentionnel et mémoire à court et à long terme). Les connaissances lexicales orthographiques explicites de ces mêmes enfants ont été évaluées en fin de première et de deuxième années. Le premier article de cette thèse rapporte les données d’une étude réalisée auprès des enfants scolarisés en maternelle 5 ans. Cette étude vise l’établissement d’un lien entre, d’une part, la capacité de traitement phonologique, visuoattentionnel et de mémoire lexicale orthographique et, d’autre part, les connaissances orthographiques implicites des enfants qui n’ont pas encore eu d’enseignement formel de l’écriture. Les résultats indiquent que, contrairement à ce qui a été longtemps avancé, la capacité de traitement phonologique n’est pas le seul facteur cognitif à intervenir, puisque la capacité de mémoire lexicale orthographique à long terme ainsi que la capacité visuoattentionnelle contribuent de façon importante et indépendante à l’acquisition des connaissances orthographiques implicites des enfants de la maternelle 5 ans. La mémoire lexicale orthographique est même le facteur qui apporte la plus forte contribution. La deuxième étude de cette thèse vise à déterminer, parmi les facteurs cognitifs évalués en maternelle, celui ou ceux qui permettent de prédire les connaissances orthographiques explicites ultérieures, c'est-à-dire celles de première et de deuxième années du primaire. Les résultats de cette deuxième étude indiquent que les préalables nécessaires à l’acquisition des connaissances orthographiques lexicales sont les capacités de traitement phonologique ainsi que les capacités de la mémoire à court et à long terme. La troisième étude de cette thèse a pour but de mettre en lumière le rôle prédictif que joue le niveau des connaissances orthographiques des enfants de maternelle quant au niveau ultérieur de leurs connaissances orthographiques en première et deuxième années, en lien avec les capacités cognitives qui sous-tendent l’apprentissage du langage écrit, en particulier le traitement phonologique, le traitement visuoattentionnel et la mémoire lexicale orthographique. Les résultats de cette dernière étude permettent de montrer que, parmi les facteurs évalués en maternelle, le niveau des connaissances orthographiques implicites apporte une contribution unique à l’ensemble du niveau des connaissances orthographiques ultérieures. L’influence des connaissances orthographiques précoces sur l’acquisition ultérieure n’est pas surprenante. En effet, la première étude avait montré que le niveau de ces connaissances est fonction non seulement de la capacité de mémoire orthographique lexicale mais également de la capacité de traitement phonologique et visuottentionnel. Les résultats issus de ces trois études présentent un intérêt non négligeable dans la compréhension de l’acquisition du langage écrit. En effet, ces recherches ont permis de montrer qu’avant même l’apprentissage formel de l’écrit, l’enfant témoigne de connaissances implicites non négligeables sur la langue écrite et que c’est à partir de ces connaissances que s’élaboreront ses connaissances explicites ultérieures. Ces connaissances sont tributaires de multiples facteurs parmi lesquels la capacité de mémoire lexicale orthographique, facteur cognitif dont la contribution n’avait pas été démontrée jusqu’à présent. Les résultats de cette recherche montrent qu’il est possible d’envisager des outils de dépistage précoce qui permettront d’identifier les enfants à risque de présenter des difficultés spécifiques d’apprentissage du langage écrit. Ce dépistage permettrait de mettre en place des interventions mieux ciblées et précoces, ce qui réduirait ainsi l’impact des difficultés sur les apprentissages scolaires.

Synthesis and characterization of main-chain bile acid-based degradable polymers

Les acides biliaires sont des composés naturels existants dans le corps humain. Leur biocompatibilité, leur caractère amphiphile et la rigidité de leur noyau stéroïdien, ainsi que l’excellent contrôle de leurs modifications chimiques, en font de remarquables candidats pour la préparation de matériaux biodégradables pour le relargage de médicaments et l'ingénierie tissulaire. Nous avons préparé une variété de polymères à base d’acides biliaires ayant de hautes masses molaires. Des monomères macrocycliques ont été synthétisés à partir de diènes composés de chaînes alkyles flexibles attachées à un noyau d'acide biliaire via des liens esters ou amides. Ces synthèses ont été réalisées par la fermeture de cycle par métathèse, utilisant le catalyseur de Grubbs de première génération. Les macrocycles obtenus ont ensuite été polymérisés par ouverture de cycle, entropiquement induite le catalyseur de Grubbs de seconde génération. Des copolymères ont également été préparés à partir de monolactones d'acide ricinoléique et de monomères cycliques de triester d’acide cholique via la même méthode. Les propriétés thermiques et mécaniques et la dégradabilité de ces polymères ont été étudiées. Elles peuvent être modulées en modifiant les différents groupes fonctionnels décorant l’acide biliaire et en ayant recours à la copolymérisation. La variation des caractéristiques physiques de ces polymères biocompatibles permet de moduler d’autres propriétés utiles, tel que l’effet de mémoire de forme qui est important pour des applications biomédicales.