Biblioteca Digital

Spin-coated films of cellulose acetate (CA), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB) and carboxymethylcellulose acetate butyrate (CMCAB) have been characterized by ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The films were spin-coated onto silicon wafers, a polar surface. Mean thickness values were determined by means of ellipsometry and AFM as a function of polymer concentration in solutions prepared either in acetone or in ethyl acetate (EA), both are good solvents for the cellulose esters. The results were discussed in the light of solvent evaporation rate and interaction energy between substrate and solvent. The effects of annealing and type of cellulose ester on film thickness, film morphology, surface roughness and surface wettability were also investigated.

In the present study, films based on linter cellulose and chitosan were prepared using an aqueous solution of sodium hydroxide (NaOH)/thiourea as the solvent system. The dissolution process of cellulose and chitosan in NaOH/thiourea aqueous solution was followed by the partial chain depolymerization of both biopolymers, which facilitates their solubilization. Biobased films with different chitosan/cellulose ratios were then elaborated by a casting method and subsequent solvent evaporation. They were characterized by X-ray analysis, scanning electron microscopy (SEM), atomic force microscopy (AFM), thermal analysis, and tests related to tensile strength and biodegradation properties. The SEM images of the biofilms with 50/50 and 60/40 ratio of chitosan/cellulose showed surfaces more wrinkled than the others. The AFM images indicated that higher the content of chitosan in the biobased composite film, higher is the average roughness value. It was inferred through thermal analysis that the thermal stability was affected by the presence of chitosan in the films; the initial temperature of decomposition was shifted to lower levels in the presence of chitosan. Results from the tests for tensile strength indicated that the blending of cellulose and chitosan improved the mechanical properties of the films and that an increase in chitosan content led to production of films with higher tensile strength and percentage of elongation. The degradation study in a simulated soil showed that the higher the crystallinity...

Environmentally friendly biocomposites were successfully prepared by dissolving chitosan and cellulose in a NaOH/thiourea solvent with subsequent heating and film casting. Under the considered conditions, NaOH/thiourea led to chain depolymerization of both biopolymers without a dramatic loss of film forming capacities. Compatibility of both biopolymers in the biocomposite was firstly assessed through scanning electron microscopy, revealing an intermediate organization between cellulose fiber network and smoothness of pure chitosan. DSC analyses led to exothermic peaks close to 285 and 315 degrees C for the biocomposite, compared to the exothermic peaks of chitosan (275 degrees C) and cellulose (265 and 305 degrees C), suggesting interactions between chitosan and cellulose. Contact angle analyses pointed out the deformation that can occur at the surface due to the high affinity of the;e materials with water. T(2) NMR relaxometry behavior of biocomposites appeared to be dominated by chitosan. Other properties of films, as crystallinity, water sorption isotherms, among others, are also discussed. (C) 2010 Published by Elsevier Ltd.

The properties of films of carboxymethyl cellulose, CMC, of different degree of substitution, DS, have been examined by the use of perichromic indicators (probes). The film properties that have been determined are: empirical polarity, E-T(33); "acidity", alpha; "basicity", beta; and dipolarity/polarizability, pi*. This has been achieved by employing the following perichromic probes: 4-nitroaniline, 4-nitroanisole, 4-nitro-N,N-dimethylaniline, and 2,6-dichloro-4-(2,4,6-triphenyl-pyridinium-1-yl)phenolate, WB. The correlations between both E-T(33)- or pi* and DS were found to be linear; that between beta and DS is a second order polynomial; no obvious correlation was found between alpha and DS. The polarities of CMC films are in the range of those of butyl alcohols. As models for CMC, we have employed cellulose plus CMC of high DS; oxidized cellulose with degree of oxidation = 0.5; sodium glucuronate. The former model behaved akin to CMC, but the plots of the perichromic properties versus DS showed different slopes/intercepts. FTIR data and molecular dynamics simulations on the solvation of WB have shown that this difference can be traced to more efficient hydrogen bonding between the film of the model and the probe. This affects the intra-molecular charge-transfer energy of the latter...

Esta tese está dividida em duas partes. Na Parte I, blendas de polietileno maleado (M-PE) e butirato acetato de celulose (CAB) (5-50% em massa) e compósitos de polietileno (PE) ou M-PE e 20% em massa de celulose, acetato de celulose (CA), propionato acetato de celulose (CAP) ou CAB foram preparados em um misturador. As estruturas e propriedades das misturas foram estudadas através de ensaios mecânicos, calorimetria exploratória diferencial, microscopia eletrônica de varredura, extração com solvente seletivo seguida de espectroscopia FTIR e difração de raios-X (XRD). As blendas M-PE/CAB e os compósitos PE/polissacarídeo e M-PE/polissacarídeo não apresentaram mudanças significativas nos valores da temperatura de fusão (Tm) quando comparados aos valores de Tm do PE e do M-PE. Dados de XRD mostraram que a adição das cargas não causou mudança na estrutura cristalina do PE ou M-PE, mas aumentou a região amorfa dos materiais, indicado que a miscibilidade ocorre na parte amorfa do PE. Compósitos preparados com M-PE apresentaram tensão no escoamento e elongação superiores do que os preparados com PE, evidenciando o efeito compatibilizante do anidrido maléico. Na parte II, o efeito de dois bons solventes, acetona e acetato de etila...

O presente trabalho visou o estudo da modificação química da celulose de linter (obtida de fonte de rápido crescimento e considerada a celulose de maior pureza isolada de fontes vegetais) através da sua derivatização em meio homogêneo, buscando-se a obtenção de materiais com características bem definidas e via um método que apresente boa reprodutibilidade. Dentre os derivados de celulose, os acetatos têm importância industrial significativa. No presente trabalho, acetatos de celulose obtidos no sistema de solvente cloreto de lítio/dimetilacetamida (LiCl/DMAc), com diferentes graus de substituição (GS) foram caracterizados através de 1H NMR, espectroscopia na região do infravermelho, viscosimetria e análises térmicas (DSC e TG). Através de métodos quantitativos aplicados às curvas termogravimétricas pode-se obter parâmetros cinéticos relacionados à decomposição térmica como a energia de ativação (Ea). Os resultados para os acetatos mostraram que conforme o GS aumenta, aumenta o grau de substituição de C2 e C3, e observa-se também aumenta Ea. Acetatos de celulose com diferentes GS foram utilizados para a obtenção de filmes a partir do mesmo sistema de solvente. Visando à obtenção de biocompósitos...

Filmes foram preparados com êxito dissolvendo e misturando quitosana com celulose de sisal no sistema de solvente NaOH/tiouréia. Nenhum solvente residual foi encontrado nos filmes preparados, conforme mostrado por análise elementar (S) e absorção atômica (Na). Os filmes foram caracterizados por técnicas como espectroscopia na região do infravermelho com transformada Fourier, difração de raios-X e análise térmica (TG, DSC e DMTA). A compatibilidade de ambos biopolímeros foi avaliada por microscopia eletrônica de varredura, em cujas imagens o filme de biocompósito mostrou uma organização intermediária entre a rede de fibra de celulose e a homogeneidade do filme de quitosana. Interações com água foram estudadas por medida de ângulos de contatos de uma gota d'água com a superfície do filme, isoterma de absorção de umidade e relaxometria de RMN T2. A análise de ângulo de contato mostrou uma deformação que pode ocorrer na superfície devido a alta afinidade destes materiais com a gota d'água. O sistema de solvente NaOH/tiouréia levou a despolimerização de ambos biopolímeros, mas sem provocar perda da capacidade de formação de filme dos mesmos. Resultados de índice de cristalinidade sugeriram que as interações entre quitosana e o solvente foram mais intensas do que as interações entre celulose e o solvente. Os resultados de relaxometria de RMN T2 do biocompósitos mostrou que as características da quitosana prevaleceram sobre as da celulose no que se refere as interações com água. Acetatos de celulose de sisal com diferentes graus de substituição foram preparados em meio homogêneo (DMAc/LiCl como sistema de solvente) e caracterizados por RMN 1H (determinação do grau de substituição)...

Considerando o grande interesse na produção de materiais provenientes de fontes renováveis, biocompatíveis e que combinem as propriedades de dois ou mais componentes em um único material, buscou-se contribuir para com estudos sobre a incorporação de nanopartículas (NPs) de magnetita (Fe3O4) em filmes preparados a partir de polpa celulósica de sisal e de acetatos obtidos usando esta polpa. Pretendeu-se obter filmes compósitos com boas propriedades magnéticas e com propriedades mecânicas similares ou melhores que aquelas dos filmes puros. Optou-se por polpa celulósica de sisal pelo fato de a planta ser largamente produzida no país, além de ter rápido crescimento e fibras com alto teor de celulose. A magnetita foi escolhida devido a sua baixa toxicidade quando comparada as NPs metálicas e pelo seu potencial de aplicação em diversas áreas, incluindo a médica. A magnetita foi obtida por decomposição térmica (método do poliol) e caracterizada via microscopia eletrônica de transmissão (MET), difração de raios X (DRX) e por magnetometria via SQUID (superconducting quantum interference device). Os resultados indicaram que as NPs preparadas corresponderam a um sistema de partículas esféricas e monodispersas, com diâmetro médio de 5...

O presente trabalho visou à valorização da fibra lignocelulósica de sisal, focando principalmente em seu componente majoritário, a celulose, através da síntese de ésteres de celulose e também na preparação de diferentes materiais. A escolha dessa fonte lignocelulósica deveu-se a sua disponibilidade no país, sendo o Brasil o maior produtor e exportador mundial, e por se tratar de uma fonte de fibras com alto teor de celulose e de curto ciclo de crescimento. A síntese de ésteres de celulose com diferentes tamanhos de cadeia (acetatos, butanoatos e hexanoatos) e grau de substituição (GS) foi explorada, em meios homogêneo e heterogêneo, visando à identificação de condições que levassem aos melhores rendimentos. Em meio homogêneo, utilizando DMAc/LiCl como sistema de solvente e anidridos ácidos como agentes esterificantes, a síntese de ésteres de celulose com diferentes tamanhos de cadeia e GS (0,2-3,0) foi possível, apenas ajustando-se a razão MolAnidrido/MolCelulose. Em meio heterogêneo, diferentes rotas de síntese foram exploradas. Com o uso do sistema anidrido ácido/iodo metálico (catalisador), apenas ésteres de cadeia curta (acetatos) puderam ser obtidos com alta eficiência. Na busca de rotas alternativas para a obtenção de ésteres de cadeias mais longas...

IEEE Electron Device Letters, VOL. 29, NO. 9,; Abstract—In this letter, we report for the first time the use of a sheet of cellulose-fiber-based paper as the dielectric layer used in oxide-based semiconductor thin-film field-effect transistors(FETs). In this new approach, we are using the cellulose–fiber-based paper in an “interstrate” structure since the device is built on both sides of the cellulose sheet. Such hybrid FETs present excellent operating characteristics such as high channel saturation mobility (> 30 cm2/Vs), drain–source current on/off modulation ratio of approximately 104, near-zero threshold voltage, enhancement n-type operation, and subthreshold gate voltage swing of 0.8 V/decade. The cellulose-fiber-based paper FETs’ characteristics have been measured in air ambient conditions and present good stability, after two months of being processed. The obtained results outpace those of amorphous Si thin-film transistors (TFTs) and rival with the same oxide-based TFTs produced on either glass or crystalline silicon substrates. The compatibility of these devices with large-scale/large-area deposition techniques and low–cost substrates as well as their very low operating bias delineates this as a promising approach to attain high-performance disposable electronics like paper displays...

The goal of this work was to investigate the production and properties of hybrid materials based on poly(lactic acid) (PLA), employing microcrystalline cellulose (MCC) and organophilic silica (R972) as fillers. The composites were obtained by solution casting to form films. Each nanoparticle was incorporated at 3 wt. %, relative to the polymer matrix. In this experiment, four films were obtained (PLA, PLA/MCC, PLA/R972 and PLA/MCC/R972). The films properties were evaluated by X-ray diffractometry, nuclear magnetic resonance, Fourier transform infrared spectroscopy and mechanical properties. The results showed that each nanoparticle, added individually or both combined, had different effect on the final properties of the films. Microcrystalline cellulose can act as nucleating agent for the crystallization of PLA. Silica promoted an increase in rigidity, due to the strong intermolecular forces, while MCC addition promoted an increase in the molecular mobility of the polymeric chains. The PLA/MCC/R972 film showed the highest crystallinity degree and tensile modulus. This film presented a T1H value between both values found for PLA/MCC and PLA/R972 films. The results indicated that silica R972 could promote a decrease of the surface tension between PLA and cellulose.

The objective of this research was to develop and characterize composite biofilms produced using wheat gluten and cellulose acetate phthalate. Biofilms act as barriers to moisture and oxygen diffusion through the film. The films were prepared with different thicknesses and component concentrations and were analyzed for water vapor and oxygen permeabilities, water and acid solubilities and mechanical properties. Results showed that the mixture improved film characteristics more than each of the individual components alone. The 1:1 mixture had properties of better permeability to water and oxygen. The composite films were completely soluble in water and acid, with the exception of the film with the highest gluten concentration, which was 50% soluble in water and acid. An increase in gluten concentration in the composite films resulted in a decrease in tensile strength. There was no significant difference in elongation at break between the composite films. No difference in thickness was detected either. Results showed that the mixture improved the characteristics more than of the individual components alone.

The salient feature of liquid crystal elastomers and networks is strong coupling between orientational order and mechanical strain. Orientational order can be changed by a wide variety of stimuli, including the presence of moisture. Changes in the orientation of constituents give rise to stresses and strains, which result in changes in sample shape. We have utilized this effect to build soft cellulose-based motor driven by humidity. The motor consists of a circular loop of cellulose film, which passes over two wheels. When humid air is present near one of the wheels on one side of the film, with drier air elsewhere, rotation of the wheels results. As the wheels rotate, the humid film dries. The motor runs so long as the difference in humidity is maintained. Our cellulose liquid crystal motor thus extracts mechanical work from a difference in humidity.

Die (Lager-)Stabilität ausschließlich mit Ethylcellulose (EC) stabilisierter, gießfähiger W/O-Emulsionen mit Octyldodecanol als Ölphase ist für eine praktische Anwendung nicht ausreichend. Ziel der vorliegenden Arbeit ist – aufbauend auf eine systematische Charakterisierung – eine Optimierung der Grenzflächenstabilisierung ausschließlich mit Ethylcellulose stabilisierter, gießfähiger W/O-Emulsionen. Mit Hilfe von Messungen der dynamischen Grenzflächenspannungen und Grenzflächen-rheologie (Grenzflächendilatationsrheologie und -scherrheologie) in Abhängigkeit von der Ethylcellulose-Konzentration und der Temperatur kann die prinzipielle Eignung des lipophilen Celluloseethers zur Stabilisierung von W/O-Emulsionen bestätigt werden. Das Grenzflächenverhalten von EC ist sehr komplex und unterscheidet sich erheblich vom Adsorptionsverhalten von Hypromellose (Hydroxypropylmethylcellulose, HPMC) an der O/W-Grenzfläche: so zeigt Ethylcellulose bei Messung der dynamischen Grenzflächenspannung in gleicher Konzentration deutlich längere Induktionszeiten als HPMC. Des Weiteren senkt der lipophile Celluloseether die Grenzflächenspannung bei Raumtemperatur merklich stärker ab als der hydrophile Vertreter dieser Substanzgruppe. Dabei wird bei EC unabhängig von der Polymerkonzentration stets der gleiche Gleichgewichtswert der Grenzflächenspannung erreicht. Bei einer Erhöhung der Temperatur auf 40 °C und 60 °C zeigt Ethylcellulose ein temperaturabhängiges...

O verniz acrílico Paraloid B72TM é um termoplástico que atua como um bom adesivo formando filmes claros. Tem sido usado em conservação e restauração de bens culturais desde os anos 50. Por apresentar Tg próximo a 40°C, no Brasil, algumas substâncias podem ficar adsorvidas à superfície de camadas pictóricas envernizadas. Nesse caso, a limpeza tradicional (palito com algodão e solventes) pode acarretar danos (penetração do solvente, abrasão, etc.) à obra de arte. A limpeza por métodos aquosos (géis e emulsões) pode deixar resíduos que interagem com os materiais originais. Por outro lado, a utilização de nano-géis magnéticos é bastante restrita e de difícil acesso. Esse trabalho tem por objetivo o desenvolvimento de filmes adsorventes de celulose/SBA-15 para retirada do verniz Paraloid B72TM, onde se fizer necessário. Esses filmes foram empregados sobre miméticos (pinturas originais de diferentes técnicas e obras confeccionadas para estudo envernizadas com Paraloid B72TM) para verificação de sua eficácia. As matérias primas, os miméticos e os filmes adsorventes, antes e após a aplicação, foram caracterizadas por técnicas físico-química e analíticas [análise térmica (TG/DTG e DTA); espectroscopia no infravermelho (FTIR); microscopia eletrônica de varredura (MEV); microscopia eletrônica de transmissão (MET); espectroscopia de fluorescência de raios X (XRF)...

Este trabalho de doutorado teve como objetivo estudar o potencial de uso do amido, farinha e nanofibras obtidos a partir de bananas verdes da variedade Terra (Musa paradisiaca) na elaboração de filmes biodegradáveis. Na primeira etapa do trabalho, o amido e a farinha de banana foram caracterizados quanto às propriedades físicoquímicas, funcionais e térmicas. Ambas as matérias-primas apresentaram considerável conteúdo de amido (94,8 e 83,2%, respectivamente) com alto teor de amilose (35,0 e 23,1%, respectivamente) e amido resistente (49,5 e 50,3%, respectivamente), além de fibras, proteínas e lipídios. Numa segunda etapa, filmes a partir de farinha de banana foram elaborados segundo um planejamento experimental. Os resultados obtidos foram analisados estatisticamente empregando a metodologia de superfície de resposta, que juntamente com a função de desejabilidade permitiu a obtenção da formulação e condições de processo ótimas (concentração de glicerol de 19%, temperatura de processo de 81 ºC, temperatura de secagem de 54 ºC e umidade relativa de 48%). Os filmes produzidos sob essas condições apresentaram tensão na ruptura de 9,2 MPa, elongação de 24,2%, módulo de Young de 583,4 MPa, permeabilidade ao vapor de água de 2...

Antimicrobial active packaging delays or inhibits microorganism growth in packed products, and it can be used in a variety of food systems. The objective of the present research was to develop packaging incorporated with natural antimicrobial agents (active film). The effects of the active film on the spoilage, pathogenic microorganism counts, pH and color of the refrigerated chicken breast cuts were analyzed. Cellulose acetate-based active films incorporating two concentrations (20% and 50%, v/w) of rosemary (Rosmarinus officinalis L.) essential oil were manufactured and placed in contact with the chicken breast cuts for six days. An analysis of variance and mean comparison tests (Tukey's test, p<0.05) were performed on the results. The films that contained 20% essential oil and were intercalated with chicken breast samples did not demonstrate significant effects on the control of psychrotrophic or total coliform microorganisms during the storage period; however, the films incorporated with 50% essential oil demonstrated efficacy toward the control of coliforms during the storage of the samples (6 days, 2 ± 2ºC). The pH was related to the psychrotrophic microorganism count and was not influenced by the treatment. The color was not influenced by the time of storage or the treatment. The results demonstrate that active films incorporating 50% rosemary essential oil are effective at controlling certain microorganisms in chicken breast cuts.

The interaction between a lignin film and a cellulose sphere has been measured using the colloidal probe force technique as a function of aqueous electrolyte solution conditions. The lignin film was first studied for its roughness and stability using atom

Food and beverage packaging has been the target of an intensive conceptual revolution in the past twenty years, moving further away from the mere passive barriers highly dependent on petrochemical-based raw materials. The recent trends of the state of the art food packages consist of smart packages that are preferentially green manufactured due to environmental concerns, and edible, making it more practical to consume and simultaneously minimizing the resultant waste. Some of these smart packages are able to diagnose and inform “in real-time” the consumer/retailer of the encased food’s quality (intelligent packaging). Other packages are responsible for an active interaction with the food or food’s atmosphere increasing the products shelf life, improving its organoleptic and/or health properties (active packaging). The food and beverage packaging market is estimated to represent 1 trillion dollars by 2015 in the United States alone, making this field of research an interesting area to explore.The main goal of this work is to produce a novel edible packaging film with antimicrobial properties. The purpose of including a food grade antimicrobial compound is to delay the growth of microbial flora and thus increasing the food’s safety and delaying its spoilage. For the packaging main raw material we have chosen the bacterial cellulose...

A systematic study of the surface forces between a cellulose sphere and cellulose thin films of varying crystallinity has been conducted as a function of ionic strength and pH. Semicrystalline cellulose II surfaces and amorphous cellulose films were prepared by spin-coating of the precursor cellulose solutions onto oxidized silicon wafers before regeneration in water. Crystalline cellulose I surfaces were prepared by spin-coating wafers with aqueous suspensions of sulfate-stabilized cellulose I nanocrystals. These preparation methods produced thin, smooth films suitable for surface forces measurements. The interaction with the cellulose I was monotonically repulsive at pH 3.5, 5.8, and 8.5 and at 0.1, 1, and 10 mM ionic strengths. This was attributed to the presence of strongly ionizable sulfur-containing groups on the cellulose nanocrystal surfaces. The amorphous film typically showed a steric interaction up to 100 nm away from the interface that was independent of the solution conditions. A range of surface forces were successfully measured on the semicrystalline cellulose II films; attractive and repulsive regimes were observed, depending on pH and ionic strength, and were interpreted in terms of van der Waals and electrostatic interactions. Clearly...