Submitted by UILIAN GABALDI YONEZAWA null (uilian_yonezawa@yahoo.com.br) on 2016-05-16T21:16:30Z No. of bitstreams: 1 dissertação Final.pdf: 3612402 bytes, checksum: b582b0fd2450b9deae8e2a4e625add5a (MD5) / Approved for entry into archive by Ana Paula Grisoto (grisotoana@reitoria.unesp.br) on 2016-05-17T18:33:33Z (GMT) No. of bitstreams: 1 yonezawa_ug_me_ilha.pdf: 3612402 bytes, checksum: b582b0fd2450b9deae8e2a4e625add5a (MD5) / Made available in DSpace on 2016-05-17T18:33:33Z (GMT). No. of bitstreams: 1 yonezawa_ug_me_ilha.pdf: 3612402 bytes, checksum: b582b0fd2450b9deae8e2a4e625add5a (MD5) Previous issue date: 2016-03-04 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Os hidrogéis são polímeros hidrorretentores reticulados, que são capazes de reter e absorver grande quantidade de água. A combinação de polissacarídeos e nanoargila na matriz polimérica otimiza o desenvolvimento de materiais biodegradáveis e nanoestruturados que podem ser utilizados na agricultura. Nesta dissertação foram preparados e caracterizados hidrogéis nanoestruturados biodegradáveis, afim de aplicá-lo como um acelerador no crescimento de mudas de hortaliça. Os hidrogéis foram preparados fixando as concentrações de acrilamida (AAm) em 6% m/v e carboximetilcelulose (CMC) em 1% m/v, e incorporando diferentes concentrações de nanoargila cloisita-Na+. Diferentes quantidades de hidrogéis foram incorporadas ao substrato e investigado a sua eficiência no cultivo de alface. Foram analisadas as propriedades hidrofílicas e cinéticas em água destilada e em soluções salinas. Os hidrogéis demonstraram excelentes resultados de intumescimento. A incorporação de nanoargila na matriz do polímero aumentou a velocidade de absorção de água (indicada pelo aumento da constante cinética k) quando intumescido em água destilada. A formação das redes poliméricas foi confirmada pela análise de espectroscopia no infravermelho com transformada de Fourier (FTIR). A difração do raios-x (DRX) e a espectroscopia de energia dispersiva de Raios-X (EDX) permitiu avaliar a conformação das plaquetas de nanoargila e os elementos químicos presente nos nanocompósitos, respectivamente. A microscopia eletrônica de varredura (MEV) demonstrou uma morfologia de estruturas porosas, com formas bem definidas e tamanhos de poros heterogêneos. A análise térmica evidenciou uma estabilidade térmica abaixo de 200 ºC para todas as amostras analisadas. A aplicação do hidrogel como condicionador de solo demonstrou ser eficiente no cultivo de alface, se aplicado na dose ideal. A presença de nanoargila na matriz polimérica melhorou a germinação, o desenvolvimento e a qualidade das mudas testadas. Os resultados demonstram que os nanocompósitos são produtos promissores em meio de cultura que precisam de liberação controlada e de condicionadores de solo. / Hydrogels are water-retainer crosslinked polymers which are able to retain and absorb large quantities of water. The combination of polysaccharides and nanoclay in the polymeric matrix enhanced the development of nanostructured and biodegradable materials and it can be used in agriculture. In this work, nanostructured biodegradable hydrogels was prepared in order to improve germination and seedling quality of lettuce cultivation. The hydrogels were prepared by fixing the concentrations of acrylamide (AAm) in 6% w/v carboxymethylcellulose (CMC) in 1% w/v, containing different nanoclay Cloisite-Na+ concentrations. Different amounts of hydrogel were incorporated to the substrate and investigated their efficiency in lettuce cultivation. Hydrophilic and kinetic properties were investigated in distilled water and in saline solutions. The hydrogels showed excellent swelling degree results. Also, the incorporation of nanoclay in the polymer matrix increased the water absorption speed (indicated by an increase in kinetic constant k) when swollen in distilled water. The formation of polymer networks was confirmed by Fourier transform infrared spectroscopy (FTIR) analysis. The x-ray diffraction (XRD) and energy dispersive spectroscopy X-ray (EDX) corfimed the conformation of the nanoclay platelets and chemical elements present in the nanocomposite, respectively. The scanning electron microscopy (SEM) showed porous structures morphology with well-defined shapes, but with heterogeneity in the size. Thermal analysis showed thermal stability for all samples below 200 °C. The application of hydrogel as a soil conditioner confirmed the efficiency in lettuce cultivation if applied in an optimal dose. The presence of nanoclay in the polymeric matrix enhanced the germination, the development and the quality of the tested seedlings. The results showed that nanocomposites are promising products in a culture medium that need controlled release and soil conditioners.

Orientador: Fauze Ahmad Aouada / Resumo: Os hidrogéis são polímeros hidrorretentores reticulados, que são capazes de reter e absorver grande quantidade de água. A combinação de polissacarídeos e nanoargila na matriz polimérica otimiza o desenvolvimento de materiais biodegradáveis e nanoestruturados que podem ser utilizados na agricultura. Nesta dissertação foram preparados e caracterizados hidrogéis nanoestruturados biodegradáveis, afim de aplicá-lo como um acelerador no crescimento de mudas de hortaliça. Os hidrogéis foram preparados fixando as concentrações de acrilamida (AAm) em 6% m/v e carboximetilcelulose (CMC) em 1% m/v, e incorporando diferentes concentrações de nanoargila cloisita-Na+. Diferentes quantidades de hidrogéis foram incorporadas ao substrato e investigado a sua eficiência no cultivo de alface. Foram analisadas as propriedades hidrofílicas e cinéticas em água destilada e em soluções salinas. Os hidrogéis demonstraram excelentes resultados de intumescimento. A incorporação de nanoargila na matriz do polímero aumentou a velocidade de absorção de água (indicada pelo aumento da constante cinética k) quando intumescido em água destilada. A formação das redes poliméricas foi confirmada pela análise de espectroscopia no infravermelho com transformada de Fourier (FTIR). A difração do raios-x (DRX) e a espectroscopia de energia dispersiva de Raios-X (EDX) permitiu avaliar a conformação das plaquetas de nanoargila e os elementos químicos presente nos nanocompósitos, respectivamente. A microscopia eletrônica... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Hydrogels are water-retainer crosslinked polymers which are able to retain and absorb large quantities of water. The combination of polysaccharides and nanoclay in the polymeric matrix enhanced the development of nanostructured and biodegradable materials and it can be used in agriculture. In this work, nanostructured biodegradable hydrogels was prepared in order to improve germination and seedling quality of lettuce cultivation. The hydrogels were prepared by fixing the concentrations of acrylamide (AAm) in 6% w/v carboxymethylcellulose (CMC) in 1% w/v, containing different nanoclay Cloisite-Na+ concentrations. Different amounts of hydrogel were incorporated to the substrate and investigated their efficiency in lettuce cultivation. Hydrophilic and kinetic properties were investigated in distilled water and in saline solutions. The hydrogels showed excellent swelling degree results. Also, the incorporation of nanoclay in the polymer matrix increased the water absorption speed (indicated by an increase in kinetic constant k) when swollen in distilled water. The formation of polymer networks was confirmed by Fourier transform infrared spectroscopy (FTIR) analysis. The x-ray diffraction (XRD) and energy dispersive spectroscopy X-ray (EDX) corfimed the conformation of the nanoclay platelets and chemical elements present in the nanocomposite, respectively. The scanning electron microscopy (SEM) showed porous structures morphology with well-defined shapes, but with heterogeneity in... (Complete abstract click electronic access below) / Mestre

Hydrogels are polymeric materials with chemically, physically or topologically crosslinked networks which have a capacity to absorb and retain water. They have been frequently used for many medical applications because of their useful physical properties such as oxygen permeability and excellent compatibility with living tissue and blood. The long term goal of this research is to develop a hydrogel system for potential use in reconstructive and plastic surgeries such as the closure of cleft palate defects and syndactyly (congenitally fused fingers or toes) repair. The medical requirements for such systems are not only a high degree of swelling, but also slow swelling rate, preferred direction of swelling (anisotropic swelling), appropriate mechanical strength, in addition to being biocompatible. A large degree of swelling would limit the number of surgical procedures required thereby reducing the cost and risk of surgery. A slow swelling rate can avoid tissue necrosis and help tissue growth during the tissue expansion process. Anisotropic swelling is required for specific surgical applications such as cleft palate repairs. Known to be biocompatible hydrogel systems, of a neutral gel system consisting of N-vinyl-2-pyrrolidinone (VP) and 2-hydroxyethyl methacrylate (HEMA) copolymers and an ionizable gel system of VP and acrylic acid (AA) copolymers were prepared using thermal and controlled UV-initiated polymerization. Using these VP/HEMA and VP/AA gel systems, various approaches to control their degree and rate of swelling were studied as a function of key controllable parameters. Their mechanical properties and structural characteristics determining their swelling behavior and mechanical properties also were investigated. Through these studies, how to control the key parameters that affect such swelling behavior was understood in addition to optimizing the gel systems for large degree of swelling, slow swelling rate, and mechanical integrity. Investigations into a number of methods to control the swelling rate were also undertaken for different VP/HEMA based gel systems. Multilayers of alternating gels and elastomer films (polybutadiene (PB) or polydimethylsiloxane (PDMS)) as well as gels encapsulated with the elastomer films were prepared. In addition, gels were prepared with inclusion of either silver nanoparticles or methacrylates with increasing the length of hydrophobic groups for the studies of swelling rate. In this work, two novel methods to control swelling direction (anisotropic swelling) of hydrogels were investigated. One method induces anisotropic swelling through structural gradients within the VP/HEMA gels synthesized by UV polymerization using gradient photomasks. A more promising method used stress induced anisotropic swelling for compressed VP/AA gels. The morphology-gradient VP/HEMA hydrogel system did not show large scale anisotropic swelling. However, the compressed VP/AA gels produced significant anisotropic swelling due to the controlled anisotropy of network morphology. A systematic study as a function of compression temperature, stain and strain rate was performed to derive an understanding of the anisotropic swelling behavior. These compressed gel systems produced not only a large degree of swelling and slow swelling rates but also high anisotropic swelling and proper mechanical stiffness of hydrogels. These materials are believed to be ideal candidates for tissue or skin expansion.

This diploma thesis deals with preparation and testing of biodegradable materials for use in the packaging indrustry. The task of this work is to prepare set of laboratory made films based on wheat starch, glycerol, polyvinyl alcohol with the addition of a suitable additive, which has been selected as citric acid. A suitable composition meeting the requirements of the packaging foils has been found. Quaternary blends from all components achieve the best results. It has been found that citric acid can influence the chemical structure and thus affect the mechanical and thermal properities and also the degree of solubility. The films were characterized in terms of mechanical properities by tensile testing and thermal stability by means of thermogravimetric analysis with respect to the phase structure. The structure was characterized by Fourier transform infrared spectroscopy and confocal laser scanning microscopy. The biodegradability of the film was tested by its solubility in aqueous medium.

<p style="text-align: justify;">U ovom radu sintetisani su hidrogelovi na osnovu akrilamida i akrilne kiseline, radikalnom polimerizacijom, primenom konvencionalne i mikrotalasne metode sinteze. Varirani su početni odnosi monomera i udeo umreživača, u cilju ispitivanja uticaja sastava reakcione sme&scaron;e na svojstva dobijenih hidrogelova. Optimizovani su uslovi sinteze u mikrotalasnom polju kao brže, jednostavnije i ekonomičnije metode. U cilju uspostavljanja korelacije između mehanizma sinteze, strukture i svojstava dobijenih hidrogelova, primenom relevantnih metoda karakterizacije, upoređena su apsorpciona, reolo&scaron;ka, toplotna i strukturna svojstva hidrogelova dobijenih dvema metodama.&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; Ustanovljeno je da se mikrotalasnom metodom sinteze na brži i jednostavniji način uz smanjen utro&scaron;ak vremena i energije dobijaju hidrogelovi konkurentni onima koji se dobijaju konvencionalnim zagrevanjem u vodenom rastvoru. Drugi deo doktorata obuhvata sintezu hidrofilnih polimernih mreža na osnovu natrijum karboksimetilceluloze (NaCMC) i karboksilnih kiselina, od kojih je jedna serija sintetisana prožimanjem linearnim kopolimerima akrilamida i akrilne kiseline u cilju povećanja potencijala primene u floku-lacione svrhe. Rezultati ispitivanja svojstava bubrenja, strukturnih toplotnih i flokulacionih svojstava pokazali su međusobno slaganje. Dobijeni rezultati pokazali su da od primenjenih karboksilnih kiselina, linunska kiselina u udelu od 15% u odnosu na masu NaCMC daje hidrogelove najboljih svojstava. Kombinacijom ove mreže sa kopolimerom akrilamida i akrilne kiseline u masenom odnosu 10/90, stvara se teorijska platforma za dobijanja flokulanta koji bi mogao da pokaže visoku efikasnost u preči&scaron;ćavanju vode u kojoj dominiraju pozitivno naelektrisane čestice, pravilnim izborom parametara flokulacije.</p> / <p>In this paper, hydrogels based on acrylamide and acrylic acid were synthesized using conventional and microwave synthetic methods via free-radical polymerization. The initial monomers ratio and amount of crosslinking agent were varied in order to investigate the effect of the composition of the reaction mixture on the properties of the obtained hydrogels. The conditions of synthesis in the microwave field as faster simpler and more economical method have been optimized. In order to establish a correlation between the mechanism of synthesis, structure and properties of the obtained hydrogels using the relevant methods of characterization, the absorption, rheological, thermal and structural properties of the hydrogels obtained by the two methods were compared. It has been found that the microwave synthesis is a faster and simpler method, which enables reduced consumption of time and energy and produces hydrogels competitive to those ones obtained by conventional heating in aqueous solution. The second part of the thesis includes the synthesis of hydrophilic polymer networks based on sodium carboxymethylcellulose (NaCMC) and carboxylic acids, whereby one series is synthesized by interpenetration of the network using the linear acrylamide and acrylic acid copolymers in order to increase the potential application of hydrogels for flocculation purposes. The results of measurements of swelling, structural, thermal and flocculation properites have shown mutual agreement. The obtained results have shown that among applied carboxylic acids, citric acid in the amount of 15% per mass of NaCMC, has given the hydrogels with the best properties. The Combination of this network with a copolymer of acrylamide and acrylic acid in a mass ratio of 10/90 has created a theoretical platform for the production of flocculant which could show high efficacy in purifying of water dominated by positively charged particles.</p>