Les travaux de thèse ont porté sur la synthèse d’un MIP (polymère à empreintes moléculaires) spécifique d’un fongicide se trouvant dans la majorité des vins français : l’iprodione. Pour extraire l’iprodione à partir du vin, un challenge important se présentait : le milieu hydroalcoolique est un solvant dipolaire alors que l’interaction du MIP avec l’iprodione se base sur des interactions dipôle-dipôle. Les premières études d’extraction de l’iprodione ont été faites sur un MIP obtenu par polymérisation en masse à partir du méthacrylamide et de l'éthylène glycol diméthacrylate (EGDMA). Le MIP était plus efficace que le NIP (polymère non imprimé) dans des solutions hydroalcooliques ce qui vérifie que l’impression moléculaire était réussie. Un plan d’expériences 23 a été appliqué pour étudier l’influence de 3 facteurs de synthèse de MIP (la méthode de polymérisation, la nature de l'agent réticulant et le type de monomère fonctionnel) sur les propriétés de reconnaissance des polymères vis-à-vis de l’iprodione. 8 MIP et 8 NIP ont été ainsi synthétisés. Les isothermes d'adsorption de l'eau et de l’iprodione par les MIPs et les NIPs ont été déterminées. Des différences significatives entre les polymères ont été mises en évidences impliquant une relation entre l’adsorption de l’eau et l’adsorption de l’iprodione. La formation des empreintes moléculaires au sein des MIP a été démontrée par plusieurs techniques comme la calorimétrie différentielle à balayage et la résonance magnétique nucléaire. Les meilleures propriétés de reconnaissance de l’iprodione sont obtenues avec le MIP synthétisé par précipitation à partir du méthacrylamide comme monomère fonctionnel et de l’EGDMA comme réticulant. Ce MIP a été utilisé en extraction en phase solide (SPE) pour la pré-concentration de l’iprodione dans un vin blanc avec un facteur de pré-concentration égal à 6 et sa sélectivité par rapport à deux fongicides : le pyriméthanil et le procymidone a été démontrée. / The aim of this study was the synthesis of a MIP (molecularly imprinted polymer) specific for a fungicide that is found in the majority of the french wine: iprodione. The challenge for extracting iprodione from wine medium was that the hydoralcoholic solution is a dipolar solvent, whereas the interaction between the MIP and iprodione is based on dipolar interactions. The first extraction study of iprodione was made on a MIP synthesized by bulk polymerization using methacrylamide and ethylene glycol dimethacrylate (EGDMA). The MIP was found to be more efficient than the NIP (non-imprinted polymer) in hydroalcoholic solutions which demonstrates that the molecular imprinting was successful. Then we synthesized 8 MIPs and 8 NIPs following an 23 experimental design in order to study the influence of three synthesis factors (the polymerization method, the nature of the crosslinker and the type of the functional monomer) on the iprodione recognition properties of the polymers. The water and the iprodione adsorption isotherms for MIPs and NIPs were determined. The result showed significant differences between the polymers involving a relationship between the water adsorption and the adsorption of iprodione. The molecular imprinting has been demonstrated by several techniques such as the differential scanning calorimetry and the nuclear magnetic resonance. The best recognition properties of iprodione are obtained with the MIP which was synthesized by precipitation polymerization using methacrylamide as functional momonomer and EGDMA as crosslinker. This MIP was used in solid phase extraction (SPE) for pre-concentration of iprodione in a white wine with a pre-concentration factor of 6. Its selectivity versus two fungicides: procymidone and pyrimethanil has been demonstrated.

Le défi énergétique imposé par l’épuisement des énergies fossiles d’une part et par leur consommation croissante d’autre part, a favorisé l’apparition d’une gestion optimale de l’énergie basée sur l’utilisation de ressources propres et renouvelables telles que l’énergie solaire. Le secteur du bâtiment est le principal consommateur d’énergie. Une grande partie de cette énergie est consommée par les systèmes de chauffage. Par conséquent, une bonne gestion peut être réalisée grâce à l’utilisation des technologies de stockage thermochimique d’énergie. L’avantage principal d’utiliser ce type de système est la possibilité de stocker de la chaleur pendant la période de disponibilité maximale du rayonnement solaire, en été (étape de déshydratation) et la libérer pour chauffer une maison pendant la période hivernale (étape d’hydratation). L’amélioration des propriétés d’adsorption des matériaux pour le stockage thermochimique de la chaleur est l’objectif principal de ce travail. L’utilisation d’adsorbants poreux tels que les zéolithes dans le domaine du stockage saisonnier de la chaleur s’avère être une solution intéressante pour la réduction de la consommation d’énergie. Par ailleurs, le développement de nouveaux matériaux composites à base d’hydrate de sel a été étudié pour améliorer les capacités de stockage à la fois des matrices mésoporeuses et des hydrates salins. Une comparaison entre les différentes séries de matériaux de stockage thermochimiques sélectionnés et synthétisés a été réalisée, concernant l’impact de la nature et de la quantité de sel ajouté et des propriétés physicochimiques des matériaux poreux sur leurs densités de stockage de chaleur et leurs capacités de sorption d’eau. Afin de mieux comprendre le comportement d’adsorption-désorption, les différents types de matériaux de stockage sélectionnés ont été caractérisés d’un point de vue structural et textural en utilisant des techniques appropriées et par adsorption de la vapeur d’eau en utilisant un analyseur thermique TG-DSC 111 de Setaram. Des cycles successifs d’hydratation (à 20°C) / déshydratation (à 150°C) ont été effectués / The energy challenge imposed by exhaustion of fossil fuels and their increasing consumption has favored the emergence of optimal energy management based on the use of alternative resources such as solar energy. The household sector is the main consumer of energy. A large part of this energy is consumed by heating systems. Therefore, good management can be achieved through the use of thermochemical energy storage technology. The main advantage to use this type of system is the possibility to store heat during the maximum availability of solar radiation in summer (dehydration step) and release the energy on demand for heating houses in winter (hydration step). The improvement of the adsorption properties of materials for thermochemical heat storage is the main objective of this work. The use of porous adsorbents such as zeolites in the field of seasonal heat storage is an attractive solution for the reducing of energy consumption. On the other hand, the development of new composite materials based on hydrate salt is made to improve the heat storage capacities of both pure mesoporous host matrix and hydrate salt. A comparison among different series of thermochemical storage materials selected and synthesized was done by analyzing the impact of salt addition and physico-chemical properties of porous materials on the heat storage and water sorption performances. In order to understand the adsorption-desorption behavior, different kinds of materials were characterized in their structural, textural and surface properties by using appropriate techniques and by adsorption of water vapor using a Setaram TG-DSC 111 apparatus. Successive cycles of hydration (at 20°C) / dehydration (at 150 °C) were performed

<p>Prisusutvo&nbsp; arsena&nbsp; u&nbsp; podzemnim&nbsp; vodama,&nbsp; koje&nbsp; se&nbsp; primenjuju&nbsp; za vodosnabdevanje stanovni&scaron;tva je globalan problem. Različiti&nbsp; konvencionalni<br />procesi&nbsp; se primenjuju&nbsp; za&nbsp; uklanjanje&nbsp; arsena iz vode, uključujući koagulaciju i<br />flokulaciju,&nbsp; sorpciju,&nbsp; membransku&nbsp; filtraciju&nbsp; i&nbsp; jonsku&nbsp; izmenu.&nbsp; Uzimajući&nbsp; u<br />obzir relativnu nisku cenu, jednostavnu kontrolu procesa i održavanje, visok<br />stepen uklanjanja arsena, sorpcija se smatra jednom od najpodobnijih tehnika<br />za uklanjanje arsena u tretmanu vode za piće. Premda su na trži&scaron;tu dostupni<br />različiti&nbsp; sorbenti&nbsp; za&nbsp; uklanjanje&nbsp; arsena,&nbsp; postoji&nbsp; potreba&nbsp; za&nbsp; iznalaženjem&nbsp; i<br />razvojem&nbsp; novih&nbsp;<em> low-cost&nbsp;</em> sorbenata,&nbsp; a&nbsp; kojima&nbsp; bi&nbsp; se&nbsp; pak&nbsp; mogao&nbsp; obezbediti<br />visok stepen uklanjanja oba oksidaciona oblika&nbsp; arsena,&nbsp; i&nbsp; As(III) i As(V). Cilj<br />ovog rada bio je usmeren na sintezu i karakterizaciju novih sorbenata na bazi<br />gvožđa&nbsp; i&nbsp; mangana&nbsp; odnosno&nbsp; Fe-Mn&nbsp; binarnog&nbsp; oksida,&nbsp; ispitivanje&nbsp; njihovog<br />potencijala&nbsp; za&nbsp; uklanjanje&nbsp; arsena&nbsp; iz&nbsp; vode&nbsp; i&nbsp; utvrđivanje&nbsp; da&nbsp; li&nbsp; novosintetisani<br />sorbenti po pitanju efikasnosti, mogu konkurisati postojećim komercijalnim i<br />&scaron;iroko kori&scaron;ćenim sorbentima u tretmanima voda.<br />Metodom&nbsp; precipitacije,&nbsp; sintetisani&nbsp; su&nbsp; Fe-Mn&nbsp; binarni&nbsp; oksidi&nbsp; sa&nbsp; različitim Fe:Mn&nbsp; molskim&nbsp; odnosima&nbsp; 1:1,&nbsp; 3:1,&nbsp; 6:1&nbsp; i&nbsp; 9:1,&nbsp; dok&nbsp; su&nbsp; kombinacijom heterogene&nbsp; nukleacione&nbsp; tehnike&nbsp; i&nbsp; precipitacije,&nbsp; sintetisana&nbsp; i&nbsp; četiri&nbsp; sorbenta magnetnih&nbsp; svojstava&nbsp; (Mag,&nbsp; Mag-Fe,&nbsp; Mag-Mn,&nbsp; Mag-FeMn).&nbsp; Modifikacijom biopolimera&nbsp; Chitosana&nbsp; i&nbsp; GAC,&nbsp; sa&nbsp; Fe-Mn&nbsp; binarnim&nbsp; oksidom,&nbsp; razvijena&nbsp; su preostala&nbsp; dva&nbsp; materijala&nbsp; Chit-FeMn,&nbsp; odnosno&nbsp; GAC-FeMn.&nbsp; Sintetisani sorbenti su karakterisani različitim tehnikama i metodama (SEM/EDS, XRD,FTIR, BET).Fizičko-hemijskom karakterizacijom sintetisanih sorbenata ustanovljeno je da se Fe-Mn binarni oksidi i magnetni materijali, karakteri&scaron;u relativno velikim specifičnim&nbsp; povr&scaron;inama&nbsp; (109-300&nbsp; m²/g)&nbsp; i&nbsp; zapreminama&nbsp; mezopora (0,144-0,403&nbsp; cm ³ /g).&nbsp; Velika&nbsp; specifična&nbsp; povr&scaron;ina&nbsp; i&nbsp; razvijena&nbsp; mikroporozna struktura uočena je kod GAC-FeMn (996 m<br />² /g; 0,394 cm^{3 /}g). U poređenju sa ostalim&nbsp; sintetisanim&nbsp; sorbentima,&nbsp; Chit-FeMn&nbsp; je&nbsp; karakterisala&nbsp; najmanja specifična&nbsp; povr&scaron;ina&nbsp; i&nbsp; zapremina&nbsp; mezopora&nbsp; (1,99&nbsp; m<br />²/g;&nbsp; 0,014&nbsp; cm ³ /g).&nbsp; XRD analiza&nbsp; Fe-Mn&nbsp; binarnih&nbsp; oksida&nbsp; ukazala&nbsp; je&nbsp; da&nbsp; je&nbsp; fazna&nbsp; struktura&nbsp; sintetisanih Fe-Mn&nbsp; binarnih&nbsp; oksida&nbsp; slična&nbsp; ferihidratu&nbsp; dok&nbsp; je&nbsp; fazna&nbsp; struktura&nbsp; magnetnih materijala ukazala na prisustvo magemita.<br />Ispitivanja kinetike sorpcionog procesa ukazala su da je mehanizam sorpcije<br />As(III)&nbsp; i&nbsp; As(V)&nbsp; na&nbsp; sintetisanim&nbsp; sorbentima&nbsp; sloţena&nbsp; kombinacija&nbsp; povr&scaron;inske<br />hemisorpcije,&nbsp; koja&nbsp; se&nbsp; odvija&nbsp; kroz&nbsp; granični&nbsp; sloj&nbsp; čestica&nbsp; sorbenata&nbsp; i unutarčestične difuzije. Tome u prilog i&scaron;li su i rezultati FTIR analize kojima<br />je potvrđeno da se sorpcija arsena na sintetisanim sorbentima ostvaruje kroz<br />interakcije hidroksilnih grupa gvožđa prisutnih na povr&scaron;ini sorbenata i arsena.<br />Dodatno, pokazano je da se za razliku od sorpcije As(V), sorpcija As(III) na sorbentima&nbsp; koji&nbsp; pored&nbsp; oksida&nbsp; gvožđa&nbsp; sadrže&nbsp; i&nbsp; okside&nbsp; mangana&nbsp; (Fe-Mn binarni oksidi, Mag-FeMn, Mag-Mn,Chit-FeMn i GAC-FeMn) odvija u dva koraka. U prvom koraku As(III) se oksiduje do As(V), dok u drugom koraku, oksidovani&nbsp; As(V)&nbsp; mehanizmom&nbsp; ligandne&nbsp; izmene&nbsp; formira&nbsp; komplekse&nbsp; na povr&scaron;ini ovih sorbenata.<br />Afiniteti sorpcije Fe-Mn binarnih oksida (na osnovu K_d vrednosti)&nbsp; za As(III) opadali su u nizu Fe-Mn 3:1 &gt; Fe-Mn 1:1 &gt; Fe-Mn 6:1 &gt; Fe-Mn 9:1 odnosno kod&nbsp; As(V):&nbsp; Fe-Mn&nbsp; 6:1&nbsp; &gt;&nbsp; Fe-Mn&nbsp; 3:1&nbsp; &gt;&nbsp; Fe-Mn&nbsp; 9:1&nbsp; &gt;&nbsp; Fe-Mn&nbsp; 1:1.&nbsp; Kod magnetnih kompozita,&nbsp; najveća K_d vrednost za As(III) i As(V) ustanovljena je kod&nbsp; Mag-FeMn.&nbsp; Uop&scaron;teno,&nbsp; Kd<br />vrednosti&nbsp; za&nbsp; As(III),&nbsp; kod&nbsp; magnetnih kompozita,&nbsp; opadale&nbsp; su&nbsp; u&nbsp; nizu:&nbsp; Mag-FeMn&nbsp; &gt;&nbsp; Mag-Mn&nbsp; &gt;&nbsp; Mag&nbsp; &gt;&nbsp; Mag-Fe, Slično, afinitet sorbenata za As(V), opadao je na sledeći način: Mag-FeMn &gt; Mag&nbsp; &gt;&nbsp; Mag-Fe&nbsp; &gt;&nbsp; Mag-Mn.&nbsp; U&nbsp; poređenju&nbsp; sa&nbsp; neimpregniranim,&nbsp; K_d vrednosti bile su daleko veće kod obloţenih materijala, Chit-FeMn i GAC-FeMn, &scaron;to je ukazalo&nbsp; na&nbsp; značajan&nbsp; doprinos&nbsp; Fe-Mn&nbsp; binarnog&nbsp; oksida&nbsp; adsorpcionom kapacitetu neimpregniranih medija za As(III) i As(V). U&nbsp; odnosu&nbsp; na&nbsp; ostale&nbsp; ispitivane&nbsp; anjone,&nbsp; najveći&nbsp; uticaj&nbsp; na&nbsp; sorpciju&nbsp; oba&nbsp; oblika arsena&nbsp; na&nbsp; svim&nbsp; sintetisanim&nbsp; sorbentima&nbsp; uočen&nbsp; je&nbsp; kod&nbsp; fosfata,&nbsp; dok&nbsp; je&nbsp; uticaj nitrata i hlorida, u svim slučajevima bio bez značaja. Uticaj ispitivanih anjona na&nbsp; sorpciju&nbsp; As(III)&nbsp; i&nbsp; As(V)&nbsp; na&nbsp; Fe-Mn&nbsp; binarnim&nbsp; oksidima,&nbsp; magnetnim materijalima, Chit-FeMn kao i na sorpciju As(V) na GAC-FeMn, opadao je u nizu: fosfati &gt; silikati &gt; karbonati &gt; sulfati &gt; nitrati &gt; hloridi. Slično, uticaj ispitivanih&nbsp; anjona&nbsp; na&nbsp; sorpciju&nbsp; As(III)&nbsp; na&nbsp; GAC-FeMn&nbsp; je&nbsp; opadao&nbsp; na&nbsp; sledeći način: fosfati &gt; silikati &gt; sulfati &gt; karbonati &gt; nitrati &gt; hloridi.Primenom&nbsp; sme&scaron;e&nbsp; NaCl-NaOH-NaOCl&nbsp; odnosno&nbsp; primenom&nbsp; 0,1&nbsp; M&nbsp; i&nbsp; 0,5&nbsp; M&nbsp; rastvora NaOH, ustanovljeno je da se sintetisani sorbenti mogu jednostavno i&nbsp; efikasno&nbsp; regenerisati&nbsp; i&nbsp; vi&scaron;estruko&nbsp; primeniti,&nbsp; &scaron;to&nbsp; je&nbsp; od&nbsp; izuzetnog&nbsp; značaja&nbsp; sa ekolo&scaron;kog i ekonomskog aspekta.&nbsp; Najmanje smanjenje sorpcionog kapaciteta&nbsp; i za As(III) i za As(V), nakon pet ciklusa sorpcije -desorpcije, ustanovljeno je kod binarnog oksida sa Fe:Mn molskim odnosom 3:1 i Mag-FeMn.&nbsp; Na osnovu rezultata prikazanih u ovom radu, može se zaključiti da sintetisani sorbenti,&nbsp; Fe-Mn&nbsp; binarni&nbsp; oksidi&nbsp; i&nbsp; magnetni&nbsp; kompoziti,&nbsp; posebno&nbsp; Mag-FeMn, mogu&nbsp; biti&nbsp; efikasna&nbsp; i&nbsp; ekonomična&nbsp; alternativa&nbsp; skupim&nbsp; komercijalnim sorbentima&nbsp; i&nbsp; drugim&nbsp; sofisticiranim&nbsp; tehnologijama.&nbsp; Visok&nbsp; oksidacioni&nbsp; i sorpcioni kapacitet ovih&nbsp; materijala, koji obezbeđuje istovremeno uklanjanje&nbsp; oba oksidaciona oblika arsena daje veliku prednost ovim sorbentima i čini ih veoma&nbsp; atraktivnim&nbsp; i&nbsp; obećavajućim&nbsp; u&nbsp; tretmanu&nbsp; voda.&nbsp; Dodatni&nbsp; benefit<br />magnetnih&nbsp; sorbenata,&nbsp; pre&nbsp; svega&nbsp; Mag-FeMn,&nbsp; ogleda&nbsp; se&nbsp; u&nbsp; njegovoj jednostavnoj separaciji iz vodenog medijuma i recirkulaciji u sistemu. Glavne prednosti&nbsp; sintetisanih&nbsp; Chit-FeMn&nbsp; i&nbsp; GAC-FeMn,&nbsp; ogledaju&nbsp; se&nbsp; u&nbsp; mogućnosti&nbsp; njihove primene kao efikasne filtracione ispune.</p> / <p>The&nbsp; presence&nbsp; of&nbsp; inorganic&nbsp; arsenic&nbsp; in&nbsp; groundwater&nbsp; used&nbsp; for&nbsp; drinking&nbsp; water supply&nbsp; is&nbsp; a&nbsp; global&nbsp; problem.&nbsp; Different&nbsp; techniques&nbsp; such&nbsp; as&nbsp; oxidation, coagulation,&nbsp; adsorption,&nbsp; ion&nbsp; exchange,&nbsp; and&nbsp; membrane&nbsp; filtration&nbsp; have&nbsp; been developed&nbsp; and&nbsp; applied&nbsp; for&nbsp; arsenic&nbsp; removal&nbsp; from&nbsp; aqueous&nbsp; media.&nbsp; Among these&nbsp; technologies,&nbsp;&nbsp; adsorption&nbsp; is&nbsp; regarded&nbsp; as&nbsp; one&nbsp; of&nbsp; the&nbsp; most&nbsp; promising approaches to remove arsenic from water because of its high efficiency, low cost, simplicity of operation. Although many sorbents for arsenic removal are available on the market, there is still a need to identify and develop new&nbsp; lowcost&nbsp; sorbents which are highly effective in removing both oxidation states of arsenic, As(III) and As(V). This dissertation therefore presents the synthesis and&nbsp; characterization&nbsp; of&nbsp; ten&nbsp; new&nbsp; iron&nbsp; and&nbsp; manganese&nbsp; based&nbsp; sorbents specifically developed for effective As removal. The Fe- Mn binary oxides were prepared with Fe:Mn molar ratios of 1:1, 3:1,6:1 and 9:1, while four heterogeneous magnetic composites (Mag, Mag-Fe,Mag-Mn,&nbsp; Mag-FeMn)&nbsp; were&nbsp; synthesized&nbsp; by&nbsp; combining&nbsp; the&nbsp; heterogeneous nucleation&nbsp; technique&nbsp; with&nbsp; precipitation.&nbsp; The&nbsp; remaining&nbsp; two&nbsp; materials, Chit-FeMn&nbsp; and&nbsp; GAC-FeMn,&nbsp; were&nbsp; created&nbsp; by&nbsp; modifying&nbsp; the&nbsp; Chitosan&nbsp; and GAC&nbsp; biopolymers&nbsp; with&nbsp; Fe-Mn&nbsp; binary&nbsp;&nbsp; oxide&nbsp; (Chit-FeMn&nbsp; and&nbsp; GAC-FeMn).Multiple&nbsp; techniques&nbsp; were&nbsp; applied&nbsp; to&nbsp; determine&nbsp; the&nbsp; physical&nbsp; and&nbsp; chemical characteristics&nbsp; of&nbsp; the&nbsp; resulting&nbsp; sorbents&nbsp; (including&nbsp; SEM/EDS,&nbsp; XRD,&nbsp; FTIR and BET analyses). In order to establish which sorbents show&nbsp; the greatest promise for application during&nbsp; drinking&nbsp; water&nbsp; treatment,&nbsp; the&nbsp; sorption&nbsp; capacity&nbsp; of&nbsp; the&nbsp; sorbents,&nbsp; theAs(III)&nbsp; and&nbsp; As(V)&nbsp; sorption&nbsp; mechanisms,&nbsp; and&nbsp; the&nbsp; impact&nbsp; of&nbsp; various&nbsp; factors relevant to arsenic sorption, including the regeneration potential and the reuse potential of the sorbents, were all investigated in&nbsp; batch experiments. During the physical characterisation, the Fe-Mn binary oxides and magnetic materials&nbsp; were&nbsp; found&nbsp; to&nbsp; have&nbsp; relatively&nbsp; large&nbsp; specific&nbsp; surface&nbsp; areas (109-300 m 2 /g) and mesopore volumes (0.144-0.403 cm 3 /g).&nbsp; A large specific surface&nbsp; area&nbsp; and&nbsp; microporous&nbsp; structure&nbsp; was&nbsp; observed&nbsp; for&nbsp; GAC-FeMn&nbsp; (996 m 2 /g;&nbsp; 0.394&nbsp; cm 3 /g).&nbsp; In&nbsp; comparison&nbsp; with&nbsp; the&nbsp; other&nbsp; synthesized&nbsp; sorbents,&nbsp; Chit-FeMn has the smallest specific surface area and pore volume (1.99 m 2 /g; 0.014&nbsp; cm 3 /g).&nbsp; XRD&nbsp; analyses&nbsp; of&nbsp; the&nbsp; Fe-Mn&nbsp; binary&nbsp; oxides&nbsp; indicated&nbsp; that&nbsp; the phase&nbsp; structure&nbsp; of&nbsp; the&nbsp; synthesized&nbsp; Fe-Mn&nbsp; binary&nbsp; oxides&nbsp; was&nbsp; similar&nbsp; to ferrihydrate,&nbsp; while&nbsp; the&nbsp; phase&nbsp; structure&nbsp; of&nbsp; the&nbsp; magnetic&nbsp; materials&nbsp; showed&nbsp; a good agreement with the XRD diffractogram of maghemite. Investigations into As sorption process kinetics have shown that the sorption mechanism&nbsp; for&nbsp; both&nbsp; As(III)&nbsp; and&nbsp; As(V)&nbsp; on&nbsp; the&nbsp; synthesized&nbsp; sorbents&nbsp; is&nbsp; a combination&nbsp; of&nbsp; surface&nbsp; hemisorption,&nbsp; which&nbsp; takes&nbsp; place&nbsp; through&nbsp; the boundary&nbsp; layer&nbsp; of&nbsp; sorbent&nbsp; particles,&nbsp; and&nbsp; intracellular&nbsp; diffusion.&nbsp; The&nbsp; FTIR analyses&nbsp; confirmed&nbsp; that&nbsp; arsenic&nbsp; sorption&nbsp; was&nbsp; accomplished&nbsp; through&nbsp; the interactions&nbsp; of&nbsp; the&nbsp; hydroxyl&nbsp; groups&nbsp; of&nbsp; iron&nbsp; present&nbsp; on&nbsp; the&nbsp; surface&nbsp; of&nbsp; the sorbents and arsenic. In contrast to the sorption of As(V), it was also shown that&nbsp; As(III)&nbsp; sorption&nbsp; onto&nbsp; sorbents&nbsp; containing&nbsp; manganese&nbsp; oxides&nbsp; (Fe-Mn binary&nbsp; oxides,&nbsp; Mag-FeMn,&nbsp; Mag-Mn,&nbsp; Chit-FeMn&nbsp; and&nbsp; GAC&nbsp; -FeMn)&nbsp; takes place in two steps. In the first step As(III) is oxidized to As(V), while in the second&nbsp; step,&nbsp; the&nbsp; oxidized&nbsp; As(V)&nbsp; forms&nbsp; complexes&nbsp; on&nbsp; the&nbsp; surface&nbsp; of&nbsp; the sorbents via ligand exchange. The&nbsp; Fe-Mn&nbsp; binary&nbsp; oxide&nbsp; sorption&nbsp; capacities&nbsp; (expressed&nbsp; as&nbsp; Kd values)&nbsp; for As(III)&nbsp;&nbsp; followed the trend Fe-Mn 3:1 &gt; Fe-Mn 1:1 &gt; Fe-Mn 6:1 &gt; Fe-Mn 9:1, whereas the&nbsp; As(V) trend was Fe-Mn 6:1 &gt; Fe-Mn 3:1 &gt; Fe-Mn 9:1 &gt; Fe-Mn 1:1. In the magnetic&nbsp; composites, the largest&nbsp; Kd value for As(III) and As(V) was&nbsp; obtained&nbsp; for&nbsp; Mag-FeMn.&nbsp; Generally,&nbsp; the&nbsp; Kd values&nbsp; for&nbsp; As(III)&nbsp; in&nbsp; the magnetic composites decreased in the series: Mag-FeMn &gt; Mag-Mn &gt; Mag &gt; Mag-Fe.&nbsp; Similarly,&nbsp; the&nbsp; affinity&nbsp; of&nbsp; the&nbsp; sorbents&nbsp; for&nbsp; As(V)&nbsp; was&nbsp; as&nbsp; follows: Mag-FeMn&nbsp; &gt;&nbsp; Mag&nbsp; &gt;&nbsp; Mag-Fe&nbsp; &gt;&nbsp; Mag- Mn.&nbsp; In&nbsp; comparison&nbsp; to&nbsp; the&nbsp; nonimpregnated&nbsp; materials,&nbsp; the&nbsp; Kd values&nbsp; were&nbsp; much&nbsp; higher&nbsp; for&nbsp; the&nbsp;&nbsp; boated materials,&nbsp; Chit-FeMn&nbsp; and&nbsp; GAC-FeMn,&nbsp; demonstrating&nbsp; the&nbsp; significant advantage&nbsp; Fe-Mn&nbsp; binary&nbsp; oxides&nbsp; provide&nbsp; in&nbsp; increasing&nbsp; As(III)&nbsp; and&nbsp; As(V)&nbsp; adsorption capacities. One&nbsp; of&nbsp; the&nbsp; most&nbsp; problematic&nbsp; limiting&nbsp; factors&nbsp; in&nbsp; applying&nbsp; adsorption technologies during drinking water treatment is the presence of other water constituents which interfere with the adsorption process.&nbsp; Investigations into the inhibitory effect of competive anions on the adsorption of both forms of arsenic&nbsp; revealed&nbsp; that&nbsp; phosphates&nbsp; were&nbsp; the&nbsp; worst&nbsp; offenders&nbsp; in&nbsp; terms&nbsp; ofreducing&nbsp; the&nbsp; arsenic&nbsp; removal&nbsp; efficacy&nbsp; of&nbsp; sorbents&nbsp; investigated.&nbsp; From&nbsp; the largest&nbsp; to&nbsp; the&nbsp; smallest&nbsp; negative&nbsp; influence&nbsp; of&nbsp; the&nbsp; anions&nbsp; investigated,&nbsp; for As(III)&nbsp; and&nbsp; As(V)&nbsp; adsorption&nbsp; on&nbsp; Fe-Mn&nbsp; binary&nbsp; oxides,&nbsp; magnetic&nbsp; materials and Chit-FeMn, as well as As(V) adsorption on GAC-FeMn, the order was: phosphates &gt; silicates &gt; carbonates &gt; sulfates &gt; nitrates &gt; chlorides, with the presence&nbsp; of&nbsp; the&nbsp; latter&nbsp; two&nbsp; anions&nbsp; proving&nbsp; almost&nbsp; irrelevant&nbsp; to&nbsp; the&nbsp; As adsorption&nbsp; process.&nbsp; Similarly,&nbsp; the&nbsp; negative&nbsp; influence&nbsp; of&nbsp; anions&nbsp; on&nbsp; As(III) sorption on GAC-FeMn was: phosphates &gt; silicates &gt; sulphates &gt; carbonates &gt; nitrates &gt; chlorides. Another&nbsp; issue&nbsp; with&nbsp; applying&nbsp; adsorption&nbsp; in&nbsp; real&nbsp; treatment&nbsp; conditions&nbsp; is&nbsp; the need to regularly&nbsp; regenerate and/or replace the spent sorbent. In this work, a simple&nbsp; and&nbsp; efficient&nbsp; process&nbsp; for&nbsp; sorbent&nbsp;&nbsp; rfegeneration&nbsp; is&nbsp; demonstrated.&nbsp; This regeneration&nbsp; process&nbsp; can&nbsp; be&nbsp; applied&nbsp; to&nbsp; the&nbsp; sorbents&nbsp; investigated&nbsp; multiple times, and uses an NaCl-NaOH-NaOCl mixture, or 0.1 M and 0.5 M NaOH solutions.&nbsp; This&nbsp; finding&nbsp; is&nbsp; of&nbsp; great&nbsp; importance&nbsp; from&nbsp; an&nbsp; ecological&nbsp; and economic point of view. The minimum reduction in the sorption capacity for both As(III) and As(V), after five sorption-regeneration cycles, was found in&nbsp; the&nbsp; binary&nbsp; oxide&nbsp; with&nbsp; a&nbsp; 3:1&nbsp; Fe:Mn&nbsp; molar&nbsp; ratio&nbsp; and&nbsp; Mag-FeMn.&nbsp; Arsenic sorption&nbsp; behaviour&nbsp; was&nbsp; also&nbsp; investigated&nbsp; using&nbsp; real&nbsp; groundwater&nbsp; samples, with the results demonstrating the great potential of 3:1 Fe-Mn binary oxide and Mag- FeMn. However, Chit-FeMn and GAC-FeMn were less effective at adsorbing As from the groundwater samples.Based on the results presented in this dissertation, it can&nbsp; be concluded that the synthesized&nbsp; sorbents,&nbsp; especially&nbsp; the&nbsp; Fe-Mn&nbsp; binary&nbsp; oxides&nbsp; and&nbsp; magnetic composites,&nbsp; and&nbsp; Mag-FeMn&nbsp; in&nbsp; particular,&nbsp; can&nbsp; be&nbsp; efficient&nbsp; and&nbsp; economical alternatives&nbsp; to&nbsp; expensive&nbsp; commercial&nbsp; sorbents&nbsp; and&nbsp; other&nbsp; sophisticated&nbsp; As removal&nbsp; technologies.&nbsp; The&nbsp; high&nbsp; oxidation&nbsp; and&nbsp; sorption&nbsp; capacity &nbsp; of&nbsp; these materials,&nbsp; which&nbsp; ensure&nbsp; the&nbsp; simultaneous&nbsp; removal&nbsp; of&nbsp; arsenic&nbsp; with&nbsp; both oxidation states, is a large advantage for these sorbents and makes them very attractive&nbsp; and&nbsp; promising&nbsp; for&nbsp; application&nbsp; in&nbsp; drinking&nbsp; water&nbsp; treatment.&nbsp; An additional&nbsp; benefit of the magnetic sorbents, primarily Mag-FeMn, is the ease with&nbsp; which&nbsp; they&nbsp; may&nbsp; be&nbsp; separated&nbsp; from&nbsp; the&nbsp; aqueous&nbsp; medium,&nbsp; allowing&nbsp; for simple&nbsp; recirculation within a system. Similarly,&nbsp; the main advantages of&nbsp; the synthesized Chit- FeMn and GAC-FeMn are reflected in their application as effective filtration media.</p>

L’EVOH est un copolymère thermoplastique semi-cristallin composé de segments de polyéthylène et d’alcool polyvinylique de proportion variable. Grâce notamment à une importante densité d’énergie cohésive lui conférant d’excellentes propriétés barrière à l’oxygène et aux arômes en condition anhydre, ce matériau est aujourd’hui largement utilisé dans l’élaboration d’emballages alimentaires multicouches. Sa grande sensibilité à l’eau, provoquant une détérioration importante des propriétés du matériau en conditions hydratées, reste cependant la principale problématique liée à son utilisation actuelle. Dans ce contexte, les travaux ont dans un premier temps porté sur la compréhension approfondie du comportement d’hydratation de l’EVOH afin de mettre en évidence des relations propriétés-structure, ce qui n’avait pas été réalisé jusqu’à présent. Deux axes de recherches ont ensuite été développés dans le but d’améliorer les propriétés barrière du matériau aussi bien à l’état anhydre qu’à l’état hydraté, tout en conservant une bonne transparence et une tenue mécanique correcte: le mélange de polymère d’une part, et l’approche nanocomposite d’autre part. Le choix de la voie fondu, procédé de mise en œuvre peu décrit dans la littérature pour ces systèmes, et celui des charges ont été guidés par la possibilité de transposer facilement les études à l’échelle industrielle / EVOH is a semi-crystalline thermoplastic copolymer composed of polyethylene and polyvinyl alcohol segments in various contents. Thanks to an important cohesive energy density leading to excellent oxygen and food aromas barrier properties in anhydrous state, this material is currently widely used in the elaboration of multilayer food packaging. Its high moisture sensitivity, causing an important deterioration of the properties of the material in hydrated conditions, still constitutes the main inconvenient for its current use. In this context, the studies were firstly focused on the detailed comprehension of the hydration behavior of EVOH in order to underline properties-structure relations, which was still unrealized. Two research axes were then developed in order to improve the barrier properties of the material in both dry and hydrated states, while remaining mechanical behavior and transparency stable: the polymers blend, on the one hand, and the nanocomposite approach on the other hand. The choice of the melting way, rarely described in the literature for these systems, and the one of the fillers nature were dictated by the possibility to easily transpose the experiments to an industrial scale

Indiana University-Purdue University Indianapolis (IUPUI) / Calcium phosphate-filled restorative materials were developed to provide calcium (Ca) and phosphate (PO4) ions, which have been proposed to enhance remineralization of demineralized tooth structure. Recently, tricalcium phosphate (TCP)-filled restorative materials were introduced as an alternative to amorphous calcium phosphate. The TCP filler has a more crystalline structure than ACP and is therefore potentially stronger. The aim of the present study was to examine TCP-filled restorative resins at different concentration levels at different time intervals to characterize the concentrations of Ca and PO4 ions released, and to measure the water sorption (WS) of these resins. An in vitro study was conducted by formulating resin composite using TCP as the filler mixed with EBPADMA, HmDMA, and HEMA as the resin matrix. One-hundred- sixty samples were prepared, 40 samples of each filler concentration (30 percent, 40 percent, 50 percent, and 60 percent) by weight. From each filler concentration, 5 samples of each of the 8 time points (time intervals of 4 h, 8 h, 12 h, 24 h, 3 d, 7 d, 14 d, and 21 d) were immersed in 100-ml deionized water. Calcium and PO4 ions were measured using atomic absorption spectroscopy and light spectroscopy, respectively. Water sorption (WS) was measured according to ISO 4049 specification and then the WS and the diffusion coefficient were calculated. The significance level was set at p = 0.001. The results indicated that Ca and PO4 ion release increased with increasing filler level at a rate faster than being linear. In addition, WS results were very high and failed to meet the ISO 4049 specification requirement. Diffusion coefficient results were also high. One-way ANOVA test for only 21-day data revealed that there is a statistically significant difference in filler level percent, and two-way ANOVA testing revealed that there is a statistically significant interaction between time and filler level percent on the Ca, PO4 released and WS. It can be concluded that the concentrations of Ca and PO4 released and WS were affected by composition of the monomers, filler level and type, dispersion, and the absence of coupling agent. Although this TCP-filled restorative material may release Ca and PO4, it cannot serve as a restorative material due to high WS values. Further study is needed to improve the material and evaluate its ability in promoting remineralization of the tooth structure in order for it to serve its purpose.

The water sorption of the films of polyacrylic acid, guar gum, gellan gum and PAA-guar, PAA-gellan mixtures of different compositions, prepared at 25°C and 70°C, was studied. The chemical potentials of water Δμ1, polymer component Δμ2, the average Gibbs energy of interaction of polymers and mixtures with water Δgm, the average Gibbs mixing energy of PAA and guar, PAA and gellan Δgx have been determined. It is established that the increase in the preparation temperature significantly enhances the films’ sorption capacity in relation to water. It is determined that the Gibbs mixing energy of polyacrylic acid with guar and gellan are negative for all component ratios (Δgx <0). The second derivative of Gibbs energy for PAA-guar mixtures has different signs, and in a wide range of concentrations of the mixture it is negative. This indicates the absence of compatibility and the formation of two-phase colloidal systems in mixtures of guar with PAA. In contrast to this for PAA-guar mixtures the second derivative of Gibbs energy is positive for all component ratios. This indicates the polymer compatibilityю The increase in the preparation temperature of mixtures leads to an increase in the interaction of the components in the two-phase system, which may be related to the reduction in size of the associates of macromolecules of guar in aqueous solutions. / Изучена равновесная сорбция паров воды пленками полиакриловой кислоты ПАК, гуара геллана и смесями ПАК-гуар разного состава, приготовленными при 25 °C и 70 °C. Рассчитаны разности химических потенциалов воды Δμ1, полимерных компонентов Δμ2, средние удельные энергии Гиббса взаимодействия полимеров и смесей с водой Δgm и друг сдругом Δgx. Установлено, что повышение температуры приготовления пленок значительно увеличивает их сорбционную способность по отношению к воде. Обнаружено, что энергии Гиббса смешения гуара и геллана с полиакриловой кислотой отрицательны при всех соотношениях компонентов (Δgx < 0). Вторая производная энергии Гиббса по составу имеет разные знаки, и для системы гуар – ПАК в широкой области концентраций смеси она отрицательна. Это свидетельствует об отсутствии совместимости и образовании двухфазных коллоидных систем в смесях гуара с ПАК. В противоположность этому для системы ПАК-геллан величина положительна во всей области составов. Это свидетельствует о совместимости полимеров. При этом повышение температуры приготовления смесей приводит к усилению взаимодействия компонентов в двухфазной системе, что может быть связано с уменьшением размеров ассоциатов макромолекул гуара в водных растворах при повышении температуры.

0 comportamento higroscópico do suco de laranja liofilizado, e aditivado com malto-dextrinas e lactose, e de misturas mecânicas do suco liofilizado com os aditivos secos, foi estudado através da cinética e das isotermas de sorção de água, em diferentes temperaturas. Avaliou-se as características espectrais no visível e ultravioleta, e o teor de vitamina C, de amostras de suco de laranja liofilizado expostas a diferentes umidades relativas e temperaturas. Estudou-se a influência do valor de pH e natureza do tampão sobre a retenção do limoneno emulsionado em soluções de lactose, liofilizadas. A liofilização praticamente não alterou o teor de vitamina C e as características espectrais do suco de laranja, mas aumentou o valor monomolecular da malto-dextrina (dextrose equivalente de 9 a 12%). A lactose liofilizada apresentou-se no estado amorfo. Os teores de umidade de equilíbrio das misturas aditivadas liofilizadas, foram menores que os das misturas mecânicas. Os aditivos reduziram a sorção de umidade em função do tempo. A retenção do limoneno foi influenciada pela sua concentração inicial, sendo que ocorreu a major perda, durante a liofilização na major concentração utilizada. / The higroscopic behavior of freeze-dried orange juice, with added maltodextrins and lactose and mechanical mixtures with this additives was studied through the kinetics and isoterms of water sorption in different temperatures. It was evaluated the spectral characteristics, in the visible and ultraviolet range, and the vitamin C content from samples of freeze-dried orange juice exposed at different relative humidities and temperatures. It was studied the influence of pH and buffer composition, on the limonene retention of freeze-dried emulsions. The spectral characteristics and vitamin C content showed no alterations after liofilization the maltodextrin (9-12 % dextrose equivalent monomolecular value increased. Freezedried lactose was amorphous. The equilibrium humidity content of the samples with additives were reduced when compared with mechanical mixtures. The additives also reduced the rate of water sorption. The limonene retention during freeze-drying was influenced by the initial concentration of the emulsion. The greater concentration studied showed the lower retention value.

0 comportamento higroscópico do suco de laranja liofilizado, e aditivado com malto-dextrinas e lactose, e de misturas mecânicas do suco liofilizado com os aditivos secos, foi estudado através da cinética e das isotermas de sorção de água, em diferentes temperaturas. Avaliou-se as características espectrais no visível e ultravioleta, e o teor de vitamina C, de amostras de suco de laranja liofilizado expostas a diferentes umidades relativas e temperaturas. Estudou-se a influência do valor de pH e natureza do tampão sobre a retenção do limoneno emulsionado em soluções de lactose, liofilizadas. A liofilização praticamente não alterou o teor de vitamina C e as características espectrais do suco de laranja, mas aumentou o valor monomolecular da malto-dextrina (dextrose equivalente de 9 a 12%). A lactose liofilizada apresentou-se no estado amorfo. Os teores de umidade de equilíbrio das misturas aditivadas liofilizadas, foram menores que os das misturas mecânicas. Os aditivos reduziram a sorção de umidade em função do tempo. A retenção do limoneno foi influenciada pela sua concentração inicial, sendo que ocorreu a major perda, durante a liofilização na major concentração utilizada. / The higroscopic behavior of freeze-dried orange juice, with added maltodextrins and lactose and mechanical mixtures with this additives was studied through the kinetics and isoterms of water sorption in different temperatures. It was evaluated the spectral characteristics, in the visible and ultraviolet range, and the vitamin C content from samples of freeze-dried orange juice exposed at different relative humidities and temperatures. It was studied the influence of pH and buffer composition, on the limonene retention of freeze-dried emulsions. The spectral characteristics and vitamin C content showed no alterations after liofilization the maltodextrin (9-12 % dextrose equivalent monomolecular value increased. Freezedried lactose was amorphous. The equilibrium humidity content of the samples with additives were reduced when compared with mechanical mixtures. The additives also reduced the rate of water sorption. The limonene retention during freeze-drying was influenced by the initial concentration of the emulsion. The greater concentration studied showed the lower retention value.

Des films nanocomposites amidon / argent ont été préparés par deux voies de génération vertes de nanoparticules d'argent. La première voie, dite ex situ, consiste à préparer tout d'abord une solution colloïdale d'argent qui est ensuite redispersée dans une matrice amidon plastifiée glycérol. Les nanoparticules d'argent colloïdales sont synthétisées en solution aqueuse par réduction du nitrate d'argent par du glucose en présence d'amidon stabilisant. La seconde voie, dite in situ, consiste à disperser le nitrate d'argent dans le film amidon plastifié et le réduire directement dans le film par traitement thermique en présence ou non de réducteur. L'influence du taux de glucose réducteur, du temps de synthèse et de la température a été étudiée en termes de taille, distribution de taille et dispersion des nanoparticules d'argent dans les films nanocomposites ex situ et in situ. Tout en gardant des paramètres de procédé comparables, les deux voies de nanostructuration des films amidon/argent ont également été comparées en termes de structure, de propriétés thermiques et de transport. Enfin, l'incorporation de charges montmorillonites a également été étudiée dans les deux voies de génération des nanoparticules métalliques. L'ensemble des travaux a permis de valider les deux voies de génération vertes menant à des nanoparticules d'argent dispersées de manière homogène et de tailles moyennes inférieures à 30 nm. La voie in situ à 85°C se distingue par des nanoparticules d'argent cristallines et de très petites tailles (inférieures à 10 nm) avec une interface amidon/argent cohésive particulière qui permettent d'améliorer les propriétés barrières aux gaz et à l'eau avec une diminution de perméabilité observée jusqu'à 90% / The present work reports a strategy involving the preparation of silver nanoparticles in a biodegradable polymer stemming from either an ex situ or an in situ method, using in both cases a completely green chemistry process. The influence of the reducing agent concentration and the silver nanoparticles generation route is investigated on the structure, the morphology and the properties of the nanocomposite films. In both routes, silver nanoparticles with a diameter below 30 nm were highlighted in the nanocomposite films. For all nanocomposite films, no modification on the crystalline structure of the starch matrix is observed in the presence of silver. The in situ generation route allowed to obtain the smallest silver nanoparticles with a diameter below 10 nm. Crystalline silver nanoparticles were obtained only from the in situ generation route at the temperature of 85°C. The introduction of montmorillonites in both generation routes was also studied. The decrease of the water sorption and the improvement of water and oxygen barrier properties were found to be not dependent on the reducing agent concentration but mainly on the presence of the crystalline structure of the silver nanoparticles. Thus, significant enhancement of the barrier properties were finally obtained for the in situ nanocomposite films thanks to an efficient interaction between the crystalline silver nanoparticles and the starch matrix

Les travaux de recherche réalisés, dans le cadre de la préparation de cette thèse consiste à préparer une nouvelle famille de polyesters ionomères furanique incorporant dans leur structure d’une part des unités aromatiques sulfonées et d’autre part des unités pyridiniques. Ce Choix est justifié principalement par les trois considérations suivantes : (i) la présence d’unités sulfonées dans la structure du poly (téréphtalate d’éthylène) confère à ce genre de polymère des propriétés physico-chimiques spécifiques favorisant son utilisation dans divers secteurs industriels dont principalement celui du détergents et celui des textiles, (ii) la présence d’unité furanique pourrait conduire à la biodégradabilité des matériaux dont on envisage leur préparation, (iii) la présence d’unités pyridiniques confère à ce genre de polymère des propriétés optoélectroniques (conductivité électrique, photoconductivité et propriétés luminescentes) permettant son utilisation dans diverses applications dont principalement le secteur spatiale et aéronautique. / The research conducted for the preparation of this thesis is devoted to develop a new family of furanic copolyesters incorporating in their structure sulfonated and pyridinic units. This choice is justified mainly by the following three considerations: (i) the presence of sulfonated units in the poly(ethylene-terephthalate) structure gives to this kind of polymer a specific physicochemical properties favoring its use in various industrial sectors in a detergents and in textiles domains (ii) the presence of furanic unit could lead to the biodegradability of these materials (iii) Pyridinic units confer to these polymers an optoelectronic properties (electrical conductivity, photoconductivity and luminescent properties) favoring its use in various applications , in the space and aeronautics fields.