Abstract Replacing the plastics in packaging applications with bio based and biodegradable cellulosic materials, especially all cellulose composites, would be a sustainable alternative. The main problem would be the non ecological and non economic nature of the processing required by all cellulose composites due to the use of toxic and expensive chemicals such as cellulose solvents. In addition, the raw materials typically studied for all cellulose composites have been highly specialized cellulosic pulps. This thesis therefore explores the possibility of using NaOH/urea as a cellulose solvent together with commercially available chemical pulps from the paper and board industry for the production of sustainable all cellulose composites materials. Furthermore, the effect of calendering and fibre orientation was investigated. The methods used for characterizing the materials were tensile strength measurements, X Ray diffraction, imaging and the short compression strength test. In connection with the X Ray diffraction measurements a method for evaluating the crystallinity of cellulose was modified from the literature and partly automated. The results show that NaOH/urea is a suitable solvent for producing all cellulose composites within a significant shorter time than reported in the literature. In addition, the tensile strength of the paper used for this purpose could be increased up to ten times and it is shown that the dissolution of cellulose fibres was indeed only partial. The efficiency of the treatment is nevertheless greatly dependent on the pulps used and their hemicellulose and lignin content. Further post-processing in the form of calendering is not recommended because it weakens the composites. / Tiivistelmä Fossiilisien muovien korvaaminen biopohjaisilla ja -hajoavilla materiaaleilla pakkausteollisuuden sovelluksissa on ympäristön kannalta kestävä vaihtoehto, varsinkin kun materiaalina käytetään itselujittuva selluloosakomposiitti (eng. all-cellulose composite). Tämän materiaalin teollinen valmistus ei kuitenkaan ole vielä ollut taloudellisesti kannattavaa eikä ympäristöystävällistä, koska selluloosan liuotukseen tarvitaan kalliita ja ympäristölle haitallisia kemikaaleja. Lisäksi raaka-aineena on aiemmin käytetty kalliita erikoisselluloosakuituja. Edellä mainituista syistä tässä väitöskirjatyössä tutkitaan itselujittuvien selluloosakomposiittien valmistusta käyttäen raaka-aineina kaupallisesti saatavilla olevia selluloosakuituja ja niiden liuottimena NaOH/urean vesiliuosta. Tämän liuottimen etuja ovat vähäinen myrkyllisyys, edullisuus ja riittävien määrien saatavuus teolliseen tuotantoon. Lisäksi työssä tutkitaan kalanteroinnin ja kuituorientaation vaikutusta komposiitin ominaisuuksiin. Käytettyjä analyysimenetelmiä ovat röntgendiffraktio, elektronimikroskoopilla kuvantaminen ja erityyppiset mekaaniset testit. Röntgendiffraktiomittausten tulosten arvioinnissa käytetään aiemmin raportoidusta menetelmästä kehitettyä osin automatisoitua selluloosan kiteisyyden määrittämisen menetelmää. Tulosten perusteella voidaan sanoa, että NaOH/urea on sopiva liuotin itselujittuvien selluloosakomposiittien valmistukseen ja sillä prosessia voidaan nopeuttaa huomattavasti muihin raportoituihin menetelmiin verrattuna. Raaka-aineena käytetyn paperin vetolujuus parani liuotinkäsittelyllä jopa kymmenkertaiseksi. Liuotinkäsittelyn tehokkuus riippui paljon käytettyjen selluloosakuitujen tyypistä ja niiden hemiselluloosa- ja ligniinipitoisuuksista.

Philosophiae Doctor - PhD / In this thesis, regioregularpoly( 3-hexylthiophene) (rr-P3HT) polymer was used as a light absorption and electron donating material, while the C60 fullerene and its derivative [6,6]-phenyl C61-butyric acid methyl ester (PCBM) were used as electron acceptor materials. The effect of solvent to control the degree of mixing of the polymer and fullerene components, as well as the domain size and charge transport properties of the blends were investigated in detail using P3HT:C60 films. The photo-physical, structural and electrical transport properties of the polymer blends were carried out according to their ratios. A distinctive photoluminescence (PL) quenching effect was observed indicating a photo-induced electron transfer. In this thesis, the effect of solvents on the crystallization and interchain interaction of P3HT and C60 fullerene films were studied using XRD, UV-vis, PL, Raman and FTIR spectroscopy. The polymer blends formed with non-aromatic solvents exhibited an improved crystallinity and polymer morphology than that formed with aromatic solvents. An improved ordering was demonstrated in the polymer films spin coated from non-aromatic solvents. This indicates that the limited solubility of rr P3HT in a marginal solvent such as non-aromatic solvents can offer a strategy to obtain highly ordered crystal structures and lead directly to optimal morphologies on the films. / South Africa

Ferrierite zeolite has a specific crystalline structure that gives unique catalytic properties that enable the selective isomerization of n-butene to isobutene and selective cracking of n-paraffins in the range of gasoline, mainly producing light olefins (ethylene and propylene). This study focused on assessing the formation and crystal growth method of transport through vapor phase (VTP) for fixed conditions of temperature, Si / Al and time of crystallization. In the work variables were used: structural directors, source of aluminum and % seeds. The experiments showed synthesis for transport method in phase steam with addition of seeds presented satisfactory results. Most of the samples synthesized in the work exhibited high crystalline percentage, with superior values to 90%, when compared with the commercial pattern. The results of crystalline percentage of synthesized materials indicated that there is an outstanding influence of the source of aluminum (sulfate of aluminum or pseudoboehmite) about the crystallization of the ferrierite zeolite for the transport method in vapor phase in the pyrrolidine presence as organic director, however when the director is the ethylenediamine this fact is almost imperceptible. / Fundação de Amparo a Pesquisa do Estado de Alagoas / A zeólita ferrierita apresenta uma estrutura cristalina específica que lhe confere propriedades catalíticas únicas, que possibilitam a isomerização seletiva de n-buteno em isobuteno e o craqueamento seletivo de n-parafinas, na faixa da gasolina, produzindo principalmente olefinas leves (eteno e propeno). O presente trabalho dirigi-se a avaliação da formação e crescimento cristalino através do método de transporte de fase vapor (VTP), para condições fixas de temperatura, razão de Si/Al e tempo de cristalização. No trabalho foram utilizadas as variáveis: direcionadores estruturais, fonte de alumínio e teor de sementes. Os experimentos mostraram que a síntese pelo método de transporte em fase vapor com a adição de sementes apresentaram resultados satisfatórios. A maioria das amostras sintetizadas no trabalho exibiu alta percentagem de cristalinidade, com valores superiores a 90%, quando comparados com o padrão comercial. Os resultados de cristalinidade dos materiais sintetizados indicaram que há uma influência marcante da fonte de alumínio (sulfato de alumínio ou pseudobohemita) sobre a cristalização da zeólita ferrierita pelo método de transporte em fase vapor na presença de pirrolidina como direcionador orgânico, contudo quando o direcionador é a etilenodiamina este feito é quase imperceptível.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The enthalpy of fusion of a perfect crystal of cellulose acetate was calculated in this thesis. In order to do so, cellulose samples from different sources were acetylated through the heterogenous acetilation methodology. The cellulose acetate samples were characterized by differencial scanning calorimetry (DSC) and by wide angle X-ray diffraction (WAXD). The X-ray diffractograms were deconvoluted into halos and peaks using the Pseudo-Voigt peak function of program Origin® 7.0. Two hypotheses were proposed in order to fit the deconvolution patterns into the two-phase model. In the first, the amorphous regions of the material was considered to be represented by the area of the halo located at 21º and the crystalline area by the maxima at 8º, 11º, 13º and 16º. In the second hypothesis, the amorphous region was considered to be represented by the areas of the maxima at 11º and 21º, and the crystalline region by the maxima at 8º, 13º and 16º. The WAXD crystallinities of the samples were then calculated from these values. The first hypothesis was ignored for presenting a very high crystallinity value for a sample that did not present an enthalpy of fusion. The second hypothesis was used, but the linear regression that defined the relationship between the enthalpy of fusion and the crystallinity of the materials was forced through zero. Through this relationship, the enthalpy of fusion of a perfect crystal of cellulose acetate was calculated to be 58.8 J/g. / A entalpia de fusão de um cristal perfeito de acetato de celulose foi calculada nessa dissertação. Para isso, amostras de celulose de diferentes origens foram acetiladas através do método de acetilação heterogêneo. As amostras de acetato de celulose foram caracterizadas por calorimetria diferencial de varredura (DSC) e difração de raios-X a alto ângulo (WAXD). Os difratogramas de raios-X foram deconvoluídos em halos e picos utilizando a função pico Pseudo-Voigt do programa Origin® 7.0. Duas hipóteses foram propostas para que as deconvoluções estivessem de acordo com o modelo de duas fases. Na primeira, foi considerado que a parte amorfa do material era representada pela área do halo localizado em 21º e a área cristalina pela soma das áreas dos máximos em 8º, 11º, 13º e 16º. Na segunda hipótese, a região amorfa foi considerada como sendo representada pelas áreas dos máximos em 11º e 21º, e a região cristalina pelos máximos em 8º, 13º e 16º. A partir desses valores se calculou a cristalinidade das amostras de acetato de celulose via WAXD. A primeira hipótese foi desconsiderada por apresentar um valor muito alto de cristalinidade para uma amostra que não apresentou entalpia de fusão. A segunda hipótese foi utilizada, porém a regressão linear que definiu a relação entre a entalpia de fusão e cristalinidade dos materiais foi forçada a passar pela origem. Através dessa relação, calculou-se a entalpia de fusão de um cristal perfeito de acetato de celulose como sendo 58,8 J/g. / Mestre em Química

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-07-20T18:09:16Z No. of bitstreams: 1 stephanebandeirapedrodefarias.pdf: 4932119 bytes, checksum: eb701a000af1e9eb174352777a07aab2 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-08-09T13:09:32Z (GMT) No. of bitstreams: 1 stephanebandeirapedrodefarias.pdf: 4932119 bytes, checksum: eb701a000af1e9eb174352777a07aab2 (MD5) / Made available in DSpace on 2017-08-09T13:09:32Z (GMT). No. of bitstreams: 1 stephanebandeirapedrodefarias.pdf: 4932119 bytes, checksum: eb701a000af1e9eb174352777a07aab2 (MD5) Previous issue date: 2011-02-28 / Os hidróxidos duplos lamelares (HDL) são também conhecidos como argilas aniônicas, devido à possibilidade de intercalação de espécies aniônicas no espaço interlamelar. Essa nomenclatura se refere às características estruturais, onde se destaca a presença de dois tipos de cátions metálicos na lamela destes compostos. Encontra-se, na literatura, outro termo bastante utilizado para designar esses materiais, compostos do tipo hidrotalcita. Apresentam formula geral MII1-xMIIIx(OH)2(Am-)x/m.nH2O, que pertencem a família de HDL. Muitos HDL envolvendo misturas de diferentes cátions divalente podem ser preparados e são chamados de Hidróxidos Lamelares Ternários (HLT) ou Quaternários, dependendo da quantidade de cátions na lamela. Sintetizou-se hidrotalcitas por diversos métodos de síntese obtendo diferentes graus de cristalinidade. Os resultados mostraram que, apesar de simples, a síntese feita sem controle de pH produz compostos pouco cristalinos. No entanto, usando um tratamento hidrotérmico posterior é possível aumentar a cristalinidade destes compostos. Foi possível ainda sintetizar hidróxidos triplos lamelares, substituindo parte do magnésio por metais da primeira série de transição, a partir da hidrólise de uréia. A formação do HLT é favorecida quando a taxa de substituição do metal M2+ é baixa, até no máximo 50%. A difração de raios X possibilita uma boa caracterização desses materiais. Dados de alta qualidade foram obtidos a partir de uma fonte de radiação síncrotron, no LNLS (Laboratório Nacional de Luz Sincrotron), e com eles utilizou-se o método de Rietveld para tratamento dos dados de difração de raios X e fazer o estudo da decomposição térmica dos hidróxidos ternários lamelares. Este técnica se mostra extremamente eficiente e confiável para análise qualitativa e quantitativa de fases cristalinas. / The layered double hydroxides (LDH) are also known as anionic clays, due to the possibility of intercalation of anionic species in the interlayer space. This nomenclature refers to the structural characteristics, which presents two types of metallic cations in the lamella of these compounds. Another term commonly used to designate these materials is hydrotalcitelike compounds. They present general formula MII1-xMIIIx(OH)2(Am-)x/m.nH2O, belonging to LDH family. Many LDH involving mixtures of different divalent cations can be prepared and are called Ternary Layered Hydroxides (TLH) or Quaternary, depending on the amount of cations in the lamella. It was synthesized hydrotalcites by several synthesis methods with different crystallinity degrees. The results showed that, although simple, the synthesis performed without pH control produces poorly crystalline compound. However, using a hydrothermal treatment can further increase the crystallinity of these compounds. It was possible to synthesize triple layered hydroxides by replacing part of the magnesium by the first series of transition metal, with the urea synthesis hydrolysis. The formation of the HLT is favored when the rate of replacement of the metal M2 + is low, up to a maximum of 50%. The X-ray diffraction provides a better characterization of these materials. Highquality data were obtained from a synchrotron radiation source at LNLS (National Laboratory of Synchrotron Light), and use the Rietveld Method for data treatment of X-ray diffraction and observe the thermal decomposition of hydroxides triple layered. This technique shows an extremely efficient and reliable technique for qualitative and quantitative analysis of crystalline phases.

Landlebende Pflanzen weisen differenzierte Gewebetypen auf, die neben der Aufrechterhaltung physiologischer Stoffwechselvorgänge äußeren mechanischen Belastungen standhalten müssen. Durch zweckmäßige Verteilung von Festigkeitsgeweben über den Sprossquerschnitt erlangen Pflanzen die notwendigen Versteifungen und Stabilitäten. Zur ortsaufgelösten Darstellung der unterschiedlichen Pflanzengewebe wird auf die Methode der Ramanspektroskopie zurückgegriffen. Dazu werden valide ramanspektroskopische Methoden entwickelt, die die Bestimmung der Cellulosekristallinität sowie die Quantifizierung des Lignins und der Hemicellulosen zum Ziel haben. Am Beispiel eines Pflanzenquerschnittes des Gemeinen Flachs Linum usitassimum werden die spektroskopischen Methoden angewandt und die Verteilung der unterschiedlichen Gewebetypen aufgezeigt und diskutiert.

Dynamique du polyamide dans l'état solide en présence de solvants: Les polyamides sont une famille de polymères thermoplastiques semi-cristallins largement utilisés dans l'industrie automobile grâce à leur excellente stabilité thermique et propriétés mécaniques. Cependant, ces propriétés peuvent être affectées par la sorption de l'eau présente dans l'atmosphère ou de l'éthanol présent dans les biocombustibles. Les cinétiques de sorption et la sorption à l'équilibre dépendent des mécanismes d'interaction entre le solvant et le polyamide et des mécanismes de sorption et de diffusion. La diffusion et la sorption de solvants dans les polyamides sont des phénomènes complexes à cause de l'existence d'interactions spécifiques (liaisons hydrogène), d'hétérogénéités dynamiques dans la phase amorphe, de changements dans la dynamique du polymère en présence de solvants et de l'existence d'une phase cristalline. Puisque l'accessibilité de la phase amorphe peut avoir une influence sur les mécanismes de diffusion et de sorption, la diffusion et la sorption de différents solvants (eau, alcools de tailles différentes) ont été comparés dans un polyamide 100% amorphe et son homologue semi-cristallin. Nous avons confirmé que la phase amorphe d'un polymère semi-cristallin n'est pas entièrement accessible à l'eau, ce qui est en accord avec la littérature. Une deuxième partie de cette étude a été consacrée à la relation entre la diffusion de solvants et la dynamique de la phase amorphe. Premièrement, nous avons mis en évidence que les mécanismes de diffusion Fickien et non-Fickien peuvent être expliqués par la variation des coefficients de diffusion avec la concentration de solvant. Deuxièmement, l'influence de la relaxation du polymère a été évaluée par Spectroscopie Diélectrique. Une simple comparaison des échelles de temps de la diffusion et de la relaxation alpha, associée à la transition vitreuse, indique que les deux phénomènes ne sont pas directement corrélés. Cependant, la diffusion semble corrélée à la relaxation secondaire beta, qui décrit la dynamique locale des groupements amide en présence d'eau / Dynamics in the solid state in presence of solvents: Polyamides are a family of semi crystalline thermoplastic polymers widely employed in the automotive industry due to its excellent thermal stability and mechanical properties. However, polyamide can be significantly affected by the absorption of low molecular weight penetrants like water. The rate of sorption and amount of absorbed solvent depend on the mechanisms of interaction between solvent and polyamide, along with sorption and diffusion mechanisms. Diffusion and sorption of solvents in polymers can be very complex because of the existence of specific interactions (non-polar or polar), dynamic heterogeneities in the amorphous phase, modification of the polymer dynamics induced by the solvents and different crystalline phases. In polyamide/solvent systems, all of these factors have to be taken into account. A first part of this study focused on the accessibility of the amorphous phase in semicrystalline polyamides. A comparison between a 100% amorphous polyamide and its semicrystalline counterpart of equivalent chemical structure suggests that the amorphous phase in semi-crystalline polyamide is not entirely accessible to the solvents. A second part of this study focused on the diffusion mechanisms of water and ethanol in polyamide. Fickian or non- Fickian diffusion mechanisms could be explained by the variation of the diffusion coefficients as a function of solvent concentration. Moreover, the relationship between water diffusion and the dynamics of the amorphous phase in polyamide was investigated. A simple comparison of dielectric characteristic relaxation times with the timescale of diffusion suggests that diffusion and polyamide alpha relaxation (associated to the glass transition) should not be directly correlated. However, diffusion is correlated to the secondary beta relaxation, which encompasses the local chain dynamics of hydrogen bonded amide groups in the presence of water. A mechanism of diffusion based on the trapping of water molecules between neighboring sorption sites (amide groups) is proposed in these strongly interacting polymers

Thesis summarizes the problems of production and use of stretch film. The change of strength, ductility and relative relaxation effect in different times of drawing from role in three weeks was observed. Further, change of strength and ductility due to changes in the rate of deformation, exposure to accelerated aging in a UV chamber and changes in the loading direction were observed. Mechanical tests were realized on a tensile tester, relaxation tests on DMA and crystallinity changes were observed on the DSC. Relationship between chemical composition of stretch film and mechanical and thermomechanical properties were studied. It was found that chemical composition essential for stretch film properties. However, due to the impossibility to distinguish effects of chemical composition and process parameters was impossible to find clear relation describing this relationship.

No description available.

Micronisation of active pharmaceutical ingredients (APIs) to achieve desirable quality attributes for formulation preparation and drug delivery remains a major challenge in the pharmaceutical sciences. It is therefore important that the relationships between crystal structure, the mechanical properties of powders and their subsequent influence on processing behaviour are well understood. The aim of this project was therefore to determine the relative importance of particle attributes including size, crystal quality and morphology on processing behaviour and the characteristics of micronised materials. It was then subsequently intended to link this behaviour back to crystal structure and the nature of molecular packing and intermolecular interactions within the crystal lattice enabling the identification of some generic rules which govern the quality of size reduced powders. In this regard, different sieve fractions of lactose monohydrate and crystal variants of ibuprofen and salbutamol sulphate (size, morphology and crystal quality) were investigated in order to determine those factors with greatest impact on post-micronisation measures of particle quality including particle size, degree of crystallinity and surface energy. The results showed that smaller sized feedstock should typically be used to achieve ultrafine powders with high crystallinity. This finding is attributed to the reduced number of fracture events necessary to reduce the size of the particles leading to decreases in milling residence time. However the frequency of crystal cracks is also important, with these imperfections being implicated in crack propagation and brittle fracture. Ibuprofen crystals with a greater number of cracks showed a greater propensity for comminution. Salbutamol sulphate with a high degree of crystal dislocations however gave highly energetic powders, with reduced degree of crystallinity owing to the role dislocations play in facilitating plastic deformation, minimising fragmentation and extending the residence of particles in the microniser. Throughout these studies, morphology was also shown to be critical, with needle like morphology giving increased propensity for size reduction for both ibuprofen and salbutamol sulphate, which is related to the small crack propagation length of these crystals. This behaviour is also attributed to differences in the relative facet areas for the different morphologies of particles, with associated alternative deformation behaviour and slip direction influencing the size reduction process. Molecular modelling demonstrated a general relationship between low energy slip planes, d-spacing and brittleness for a range of materials, with finer particle size distributions achieved for APIs with low value of highest d-spacings for identified slip planes. The highest d-spacing for any material can be readily determined by PXRD (powder x-ray diffraction) which can potentially be used to rank the milling behaviour of pharmaceutical materials and provides a rapid assessment tool to aid process and formulation design. These studies have shown that a range of crystal properties of feedstock can be controlled in order to provide micronised powders with desirable attributes. These include the size, morphology and the density of defects and dislocations in the crystals of the feedstock. Further studies are however required to identify strategies to ensure inter-batch consistency in these attributes following crystallisation of organic molecules.