Orientador: Theo Guenter Kieckbusch / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-15T03:53:55Z (GMT). No. of bitstreams: 1 Santana_AudireneAmorim_M.pdf: 25644258 bytes, checksum: 2a3ea9b288162061aea3ee83e2cfef3e (MD5) Previous issue date: 2010 / Resumo: O consumidor consciente tem dado preferência a alimentos processados de melhor qualidade nutricional e com vida de prateleira prolongada, sempre com a devida preocupação com os efeitos prejudiciais acumulativos ao meio ambiente do descarte de subprodutos. Filmes biodegradáveis estão inseridos neste contexto. Eles são produzidos a partir de polímeros naturais, principalmente polissacarídeos e proteínas, com potencial aplicação na indústria farmacêutica e alimentícia. O alginato é um polissacarídeo que tem extensa aplicação em biotecnologia devido a sua habilidade de formar géis fortes e insolúveis ao ser reticulado com Ca++. Essa reação é tão rápida e localizada, impedindo a posterior moldagem do gel em forma de filmes. Para a confecção de filmes insolúveis é necessário primeiro fabricar um filme de alginato de sódio de baixa reticulação com cálcio, já contendo plastificante, que é então exposto a uma solução contendo cálcio para completar a reticulação por difusão. Nesse contato, entretanto, a solução reticuladora pode solubilizar o plastificante e o filme formado não apresenta uma flexibilidade desejável. Assim, o objetivo deste estudo foi selecionar formulações para a confecção de filmes de alginato de cálcio estruturados com plastificantes que apresentem baixa tendência de lixiviação/solubilização em meios aquosos. O estudo enfocou primeiramente plastificantes convencionais (glicerol, manitol, xilitol, sorbitol, maltitol e poli-etileno glicol-300). Também foram considerados os açúcares simples (frutose, lactose e sacarose), ácido graxo de cadeia curta (ácido hexanóico), surfactante não-iônico (Tween 20) e solutos não-convencionais (etanolamina, lactato de sódio, triacetina e citrato de tributila). Apenas formulações que produziam filmes transparentes de boa manuseabilidade foram consideradas, e esse critério eliminou os filmes plastificados com poli-etileno glicol-300, maltitol, lactose, sacarose, frutose, etanolamina, lactato de sódio, Tween 20, triacetina e ácido hexanóico. A seleção definitiva de plastificantes considerou, o aspecto visual, conteúdo de umidade, solubilidade em água, permeabilidade ao vapor de água, grau de intumescimento, resistência à tração e alongamento dos filmes formados. Os plastificantes que produziram filmes que satisfizeram requisitos mínimos para esses atributos foram glicerol, xilitol, manitol e citrato de tributila. Filmes com esses plastificantes foram submetidos à determinação de observações microscópicas de sua estrutura (MEV) e de isotermas de sorção, cor e opacidade e temperatura de transição vítrea. Os resultados confirmaram a excelente ação plastificante do glicerol e um comportamento similar do xilitol. O manitol e o citrato de tributila formam filmes de baixa higroscopicidade, mas são pouco flexíveis. Um compromisso entre alta resistência mecânica, boa aparência e baixa solubilidade em água pode ser obtido usando uma mistura de citrato de tributila e glicerol / Abstract: Responsible consumers are looking for processed food with higher nutritional value and extended shelf live, without disregarding the damaging cumulative effects of sub products discharge on the environment. Biodegradable films are part of this concept. They are produced from natural polymers, mainly saccharides and proteins, with potential applications in the pharmaceutical or food industries. Alginates are polysaccharides with large applications in biotechnology due to their ability to form strong and insoluble gels when crosslinked with Ca++. This reaction is fast and localized, preventing subsequent casting of the gel in the form of a film. In order to produce smooth and insoluble films, a weekly reticulated film already containing the plasticizer is confectioned first, and then exposed to a calcium solution and the reticulation is complemented by diffusion. During the contact period, however, the solution is prone to leach the plasticizer, and the resulting film will not present the required flexibility. The objective of this study was to select calcium alginate film forming formulations structured with plasticizers that show low solubilization/leaching susceptibilities in aqueous environments. The study examined initially the more conventional plasticizers (glycerol, mannitol, xylitol, sorbitol maltitiol, polyethylene glycol (PEG 300)). Consideration was then given to the simpler sugars (like fructose, lactose and sucrose), short chain fatty acids (hexanoico acid), non ionic surfactant (Tween 20) and non conventional solutes like ethanolamine, sodium lactate, triacetin and tributyl citrate. The final selection of adequate plasticizers was based on visual aspect, moisture content, solubility in water, water vapor permeability, degree of swelling in water, tensile strength and elongation of the films. The plasticizers that produced films with an adequate compromise within these attributes were glycerol, xylitol, mannitol and tributyl citrate. Films containing these plasticizers were submitted to microscopic observations of their structure (MEV), and their sorption isotherms, color and transparency, and glass transition temperature were determined. The results confirmed the excellent and powerful plasticizing effect of glycerol and a similar behavior of xylitol. Mannitol and tributyl citrate form films with lower hygroscopicity, but are less flexible. A compromise between high mechanical resistance, attractive appearance and low solubility in water can be obtained with a mixture of tributyl citrate and glycerol / Mestrado / Engenharia de Processos / Mestre em Engenharia Química

Orientador: Carlos Raimundo Ferreira Grosso / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-23T08:09:57Z (GMT). No. of bitstreams: 1 Braga_AndreaHelenaFerreira_D.pdf: 2190091 bytes, checksum: 46376779b7866dd62ac05c2a6abc7be6 (MD5) Previous issue date: 2013 / Resumo: A eficiente combinação entre proteínas e polissacarídeos produz filmes biodegradáveis com melhores propriedades funcionais, a interação associativa entre os grupamento presentes na cadeia polimérica dos biopolímeros gera uma rede polimérica mais coesa e resistente. Esta associação, em geral, ocorre através das interações eletrostáticas entre os biopolímeros que é controlada pelas condições de pH, força iônica e proporção estequiométrica dos polimeros, entre outros parâmetros. O objetivo deste trabalho foi utilizar o método de coacervação na elaboração de filmes a base de gelatina-quitosana (GEL/QUI), gelatina-pectina (GEL/PEC) e de gelatina-goma arábica (GEL/GAR) com o intuito de promover maiores interações intermoleculares entre os biopolímeros, formando filmes mais resistentes mecanicamente e menos susceptíveis a ação da água. O desenvolvimento deste trabalho pode ser dividido em: 1-) Análise da solução filmogênica de GEL/QUI ou PEC ou GAR (em várias proporções estequiométricas): nesta etapa foi feito um estudo para definir o pH de coacervação para cada formulação utilizando o ?-potencial zeta. No pH de coacervação ocorre a máxima interação eletrostática entre os biopolímeros gerando carga elétrica neutra para a solução filmogênica (?-potencial zeta igual a zero), devido a neutralização da carga elétrica positiva (-NH4+) com a carga elétrica negativa (-COO-) dos biopolímeros. 2-) Elaboração dos filmes coacervados foi realizada em várias proporções estequiométricas no seu devido pH de coacervação. 3-) Caracterização dos filmes de acordo com o aspecto visual, propriedades mecânicas, permeabilidade ao vapor de água (PVA), solubilidade em água (SOL), umidade (UMI) e opacidade (Op). Análises complementares de difração de raio-X (DRX), espectroscopia de infravermelho (FTIR), microscopia eletrônica de varredura (MEV) e calorimetria diferencial de varredura (DSC) foram realizadas em alguns filmes. 4-) Seleção dos filmes: foi escolhida a proporção estequiométrica que produziu filmes com maior resistência mecânica, menor PVA e SOL. 5-) Concentração do material polimérico: na formulação selecionada foram testadas maiores concentrações de material polimérico (4, 6, 8 e 10%) com o intuito de reduzir o tempo de secagem dos filmes coacervados. Estes filmes foram novamente caracterizados (propriedades mecânicas, PVA, SOL e UMI). A concentração de material polimérica escolhida para prosseguir o estudo associou o menor tempo de secagem sem alterar a PVA e SOL dos filmes. 6-) Adição do plastificante: nesta etapa foi avaliado o tipo de plastificante (triacetina e glicerol) e a sua concentração (2,5, 5, 7,5, 10, 15, 20, 25 e 30g de plastificante/100g de material polimérico). Os filmes coacervados de GEL/QUI foram elaborados em pH alcalino (pH de coacervação entre 6,2-7,2) por combinar um polissacarídeo catiônico (QUI) com a GEL. Formulações com maior teor de GEL (10:1 e 20:1 de GEL/QUI) confere ao filme coacervado maior resistência à ruptura, flexibilidade e menor PVA. As análises de difração de raio-X e de FTIR evidenciam a presença de interações eletrostáticas atrativas entre as cadeias da gelatina e a quitosana. Ao comparar os filmes coacervados com os filmes compostos (sem ajuste de pH) verificou-se que o método de coacervação conferiu ao filme maior tensão na ruptura, menor PVA e menor SOL. Ao aumentar a concentração de material polimérico de 2% para 6% constatou-se redução pela metade do tempo de secagem, além de promover maior resistência a ruptura e menor PVA. Os filmes coacervados de GEL/PEC e GEL/GAR foram elaborados em pH ácido (pHcoacervação igual a 4,0 e 4,5-5,0, respectivamente), isto ocorre devido a interação do grupo carboxil (-COO-) dos polissacarídeos aniônicos com o grupo amina (-NH4+) da GEL, já que a proteína encontra-se carregada positivamente somente em pHs abaixo do seu ponto isoelétrico - pI (pI da GEL 4,8-5,2). Para filme coacervado de GEL/PEC, somente a solução filmogênica contendo 20:1 de GEL/PEC apresentou-se homogênea e com em condição de coacervação (pHcoacervação=4,0). O espectro de FTIR do filme coacervado de GEL/PEC (20:1) mostrou que o grupo carboxil da PEC pode estar interagido com o grupo amina da GEL gerando novos grupamentos amida (1630 e 1530 cm-1). A incorporação do glicerol foi mais eficiente na matriz polimérica da GEL/PEC do que a triacetina, isto foi comprovado pela análise visual e pela difração de raio-X. Filmes coacervados de GEL/GAR apresentaram-se coesos, uniformes e homogêneos. Filmes coacervados com alto teor de GEL mostraram-se mais resistentes e flexíveis e menos solúveis em água do que as formulações com menor teor de GEL (1:1 e 2:1 de GEL/GAR), resultados confirmados pelas análises de FTIR, DSC e DRX. O método de coacervação formou filmes mais resistentes mecanicamente e a ação da água do que nos filmes não coacervados (sem ajuste de pH). O aumento da concentração do material polimérico de 2 para 6% reduziu o tempo de secagem do filme de GEL/GAR (10:1) pela metade sem alterar suas propriedades funcionais. Todos os filmes coacervados de GEL/QUI, PEC ou GAR, de modo geral, apresentaram o mesmo comportamento frente a a adição do plastificante. A adição do glicerol foi mais eficiente devido sua melhor incorporação na matriz polimérica produzindo filmes coacervados mais flexíveis, mais resistentes, com menor PVA e mais transparentes do que os filmes coacervados contendo triacetina. Os resultados apresentados neste trabalho confirmam a eficiencia do método de coacervação em melhorar a compatibilidade, e consequentemente, intensificando a interação eletrostáticas entre a proteína e o polissacarídeo. Isto reflete diretamente nas propriedades funcionais dos filmes coacervados, pois a maior interação entre os biopolímeros promove a formação de uma rede polimérica mais densa e coesa, gerando filmes com maior TR, menor PVA, menor ELO e em alguns formulações mais resistentes a ação da água (menor SOL) / Abstract: The efficient combination of proteins and polysaccharides produces biodegradable films with improved functional properties; the associative interaction between the groupings present in the polymer chain of biopolymers generates a more cohesive and resistant polymer network. This association generally occurs through electrostatic interactions between the biopolymers which is controlled by the conditions of pH, ionic strength and stoichiometric ratio of polymers, among other parameters. The aim of this study was to use the coacervation method in developing films based on gelatin-chitosan (GEL/QUI), on gelatin-pectin (GEL/PEC) and on gelatin-gum arabic (GEL/GAR), in order to promote greater intermolecular interactions between biopolymers, forming mechanically stronger films and less susceptible to the action of water. The development of this work can be divided into: 1-) Analysis of the film solution GEL/QUI or PEC or GAR (in various stoichiometric ratios): in this step a study was done to determine the pH of coacervation for each formulation using ?-zeta potential. At pH of coacervation occurs maximum electrostatic interaction between biopolymers generating a neutral electric charge for filmogenic solution (? - zeta potential of zero), due to neutralization of the positive charge (-NH4+) with negative charge (-COO-) of biopolymers. 2-) Development of coacervated films was held in various stoichiometric ratios in its proper pH of coacervation. 3-) Characterization of films according to the visual appearance, mechanical properties, permeability to water vapor (PVA) water solubility (SOL), humidity (UMI) and opacity (Op). Complementary analyzes of X-ray diffraction (XRD), infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and differencial scanning calorimetry (DSC) were performed in some films. 4-) Selection of films: it was chosen a Stoichiometric ratio which produced films with higher mechanical strength and lower PVA SOL. 5-) Concentration of polymeric material: higher concentration of polymeric material (4, 6, 8, and 10% ) were tested in the selected formulation in order to reduce the drying time of the coacervated films. These films were further characterized (mechanical properties, PVA, SOL and UMI). The concentration of polymeric materials chosen for further study associated the lowest drying time without changing the SOL and PVA films. 6-) Addition of plasticizer: In this step the type of plasticizer (triacetin or glycerol) and its concentration was evaluated (2.5, 5, 7.5, 10, 15, 20, 25 and 30g plasticizer/100g polymeric material). The coacervated films GEL/CHI were prepared at alkaline pH (pH of coacervation between 6.2-7.2) by combining a cationic polysaccharide (QUI) with GEL. Formulations with higher content of gel (10:1 and 20:1 GEL/QUI) gave the coacervated film higher tensile strength, flexibility and less PVA. The analysis of X- ray diffraction and FTIR showed the presence of attractive electrostatic interactions between the chains of gelatin and chitosan. Comparing coacervated films with composite films (without pH adjustment) it was found that the coacervation method gave the highest film tensile strength, lower PVA and lower SOL. By increasing the concentration of polymeric material from 2% to 6% a reduction by half of the drying time was found promoting a greater resistance to breakage and lower PVA. The coacervate films GEL/PEC and GEL/GAR were prepared in acidic pH (pH of coacervation equal to 4.0 and 4.5 to 5.0, respectively), this occurs due to interaction carboxyl group (-COO-) of anionic polysaccharides with amino group (-NH4+) of GEL, since the protein is positively charged at pHs only below its isoelectric point - pI (pI of 4.8 to 5.2 GEL). To coacervate film GEL/PEC, only film solution containing 20:1 GEL/PEC appeared homogeneous and in condition coacervation (pH of coacervation = 4.0). The FTIR spectrum of the coacervated film GEL/PEC (20:1) showed that the carboxyl group of the PEC may have been interacted with the amino group generating new clusters of GEL amide (1630 and 1530 cm-1). The incorporation of the glycerol was more efficient in the polymer matrix of GEL/PEC than triacetin. It was confirmed by visual analysis and by X -ray diffraction. Films coacervated GEL/GAR presented themselves cohesive, uniform and homogeneous. Coacervated films with high gel content were more resistant and flexible and less soluble in water than the formulations with lower content of gel (1:1 to 2:1 GEL/GAR), which was confirmed by analysis of FTIR, DSC and XRD. The coacervation method formed films more mechanical and water resistant than in the non coacervated films. (without pH adjustment). Increasing the concentration the polymeric material from 2 to 6 % reduced the drying time of the film GEL/GAR (10:1) by half without altering their functional properties. All coacervated films GEL/QUI, PEC or GAR, in general, showed the same behavior in addition of plasticizer. The addition of glycerol was more efficient because of its better incorporation into the polymer matrix coacervated producing more flexible films, tougher, with less PVA and more transparent than coacervated films containing triacetin. The results presented here confirm the efficiency of the coacervation method to improve the compatibility, thus intensifying the electrostatic interaction between protein and polysaccharide. This highly reflects in the functional property of coacervated films, since the bigger interaction among biopolymers promotes the formation of more dense and united polymeric net, generating films with higher TR, smaller PVA, less ELO in some formulations and more resistant to the action of water (less SOL) / Doutorado / Consumo e Qualidade de Alimentos / Doutora em Alimentos e Nutrição

Cette étude se situe dans le contexte industriel de l’utilisation de superplastifiants pour la réalisation de bétons haute performance. Pour mieux comprendre le mode d’action des molécules fluidifiantes nous avons utilisé un système modèle constitué de suspensions de particules de carbonate de calcium l’une commerciale et constituée de microparticules et l’autre synthétisée au LPMC et constituée de nanoparticules. L’étude a porté sur cinq molécules organiques : quatre de type polyméthacrylates greffés polyoxyéthylène (PCP) avec des longueurs de greffons différentes et un diphosphonate polyoxyéthylène : OPTIMA100. La caractérisation des grandeurs pertinentes des fluidifiants comme leurs complexations vis-à-vis des ions ; leurs degré d’ionisation, leurs tailles, leurs affinités avec le solvant ou encore leurs capacités d’adsorption sur les surfaces a été effectuée. D’importantes différences d’efficacité de ces fluidifiants vis-à-vis de la rhéologie et de la sédimentation des deux types de suspension ont été mises en évidence. Ces différences de comportements on été interprétées grâce à la caractérisation effectuée sur les fluidifiants et à la modélisation des forces interparticulaires. / This study deals with the industrial context where the superplasticizers are used to manufacture the high performance cements. To better understand the action mode of plasticizing molecules, we used a model system which consists of calcium carbonate particles suspensions: in one hand, commercial microparticles suspension, and in the other hand, self synthesized nanoparticles suspensions. The study focuses on the use of five organic plasticizers: four types of polymethacrylates grafted polyoxyethylene (PCP) with different lengths of grafts, and a diphosphonate polyoxyethylene (OPTIMA100).Characterization of the plasticizers relevant parameters such as their complextation with the ions, their ionization degree, their size, their affinity with the solvent and their adsorption ability on the particles surfaces was performed. Significant differences in the effectiveness of these thinners regarding to the rheology and sedimentation of the two types of suspension were identified. These discrepancies in the behavior were interpreted by means of; the characterization performed on the thinners, and modeling of interparticle forces.

The topic of this dissertation was the preparation of a high-quality sulphate binder based on secondary raw materials. For this purpose, the work was primarily focused on the laboratory preparation of beta gypsum from the selected industrial gypsum, the design of the technological process of production and its verification by pilot tests. In the next step, the thesis dealt with the modification of beta gypsum by a selected set of liquefiers. In addition to commercial dehumidifiers, the possible beta casting of beta gypsum was tested by increasing the zeta potential of the gypsum suspension. At the end, a complete complex of construction products was developed based on laboratory and semi-prepared beta plasters, consisting of gypsum plasters, mastics, gypsum premix and small plaster casts.

The project elaborated in frame of engineering studies branch N2332-00. The project is submitting design of technology production sand mixture with cement binder – Portland binder CEM I 42,5 N. Pursuant to of the literary pursuit a problem of the sand mixture with cement binder was tested few sand mixture. As optimal composition it turned out application sand mixture with 2 % CaCl2 content and 1 – 2 % Dextrin content. Sand mixture with cement has good moulder and regenerating.

The development of acrylonitrile-butadiene-styrene (ABS) resins for use in rotational molding would provide a medium performance material, thus opening doors to new markets for the rotational molding industry. Unfortunately, ABS resins have shown serious problems during the rotational molding process, namely discoloration, bridging, and poor impact strength. It is believed that these effects are due to degradation of the carbon-carbon double bond in the butadiene, through attack by either oxygen or heat. Previous efforts have shown some success in addressing these issues. However, additional improvements are necessary to make ABS resins commercially viable to rotational molders. This study, fourth in a series of similar projects conducted though Brigham Young University, was focused on remediation of the ABS difficulties via two different approaches. First, a survey of several additives was performed with the intent of investigating four different strategies: increased protection from oxygen, decreased butadiene concentration, increased butadiene concentration, and promotion of flow. The best formulation was achieved when 15 wt % of a benzoate ester (XP-2280 available though ChemPoint) was blended into MAGNUM 342 EZ, an ABS resin (The Dow Chemical Company). This formulation showed the best balance between increased impact strength and improvement of cosmetic properties. Second, optimization of several rotational molding processing parameters was executed. These included particle size distribution of the resin, drying of the resin, internal mold atmosphere, and oven temperature. It was found that using coarse particle sizes (ground at 20-mesh rather than the industry standard of 35-mesh) increased the impact strength by about 19%. None of the other parameters proved to have a significant effect upon the system, except for the use of a nitrogen atmosphere, which lowered the impact strength. Final properties testing of this best formulation at the optimal processing conditions showed increased impact strength from 2 ft-lbs (the previous best value) to 8 ft-lbs. There was also a marginal decrease in surface hardness (95 to 78 on the Rockwell R scale) and yield tensile strength (3,900 psi to 3,300 psi). Larger differences were observed in flexural modulus (200,000 psi to 110,000 psi) and heat distortion temperature (95°C to 61°C). Therefore, these formulation and processing changes show a trade-off where stiffness and thermal stability (i.e. flexural modulus and heat distortion temperature) can be sacrificed for an increase in toughness and aesthetics, made manifest by increased impact strength, elimination of bridging, and eradication of discoloration.

Glucose, as the most plentiful sugar in nature, is a renewable resource and possesses excellent record in health safety. Levulinic acid is a platform chemical which plays an important role  in  biomass transformation and reactive intermediates. Both glucose and levulinic acid can be produced by biomass conversion with green processing techno logies. Due to the rising needs for bio-based, eco-friendly and non-toxic plasticizers, glucose levulinates as bio­ plasticizers were synthesized from glucose and levulinic acid, by utilizing microwave radiation or conventional condensation reaction (direct-heating method ). Acid number for the reaction liquor was measured by acid-base titration to follow the decrease of acid groups due to the reaction and the trend in  the acid number within reaction time displayed the process of esterification and possible sensitivity of the reaction rate to reaction scale. It showed that microwave radiation had superior ability in  enhancing reaction speed but it was also more sensitive to reaction scale and generated more diverse prod ucts  than the direct-heating method. Besides, the process of reaction and formation  of ester  bonds was  followed  and confirmed by FT IR. The achieved levulinate products were extracted by 2-pro panol and ethyl acetate. The practices showed several serio us problems in 2-propanol extraction, including high dosage required  for  NaCl and solvent and difficulties in purification. The ethyl acetate proved to be a suitable solvent for this study and the  extrac ted  product s  from  the Con-24hrs  and Micro-3/4/5/6/7hrs  were  characterized  by  1H  NMR,  13C N :tvlR. and LDI-MS. The results from spectrum suggested the presence of GL,. and G J .'l. type of levulinates. That means the glucose levulinates were  successfully  synthesized  although  the  dehydration side reaction of glucose was inevitable leading to the generation of glucosidic bonds. In addition, BG (mixture of glucose and glycosidic levulinates) was evaluated by so lution casting of starch and PVC. In order to minimize the microbial contaminations in solution casting of  starch, a  modified  method  was raised and applied. The results showed that 40% BG had goo d miscibility with starch and the conclusion was further proved by DSC measurements, while the BG performed poor miscibility with  PVC.

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Poly(vinyl chloride)(PVC) wire and cable insulation has poor thermal stability, causing the plasticizer to separate from the PVC chain and produce an oily residue, lowering the tensile elongation at break and thus increasing brittleness. We have added 4 wt.% of three different types of cross-linking agents and antioxidants, as well as mixtures of both, to improve the thermal stability of the plasticizer and tensile properties of PVC after thermal exposure. We performed tensile tests, tribological tests, profilometry, scanning electron microscopy(SEM) and water absorption determination before and after thermal exposure at 136 ℃ for 1 week. After adding the agents, elongation at break increased by 10 to 20 % while the wear rate and water absorption were lower than for the control sample. Less voids are seen in the SEM images after adding these two kinds of agents. The thermal resistance of the PVC cable insulation is best enhanced by combinations of cross-linking agents and antioxidants.