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Orientador: Solange Cadore / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-13T13:12:41Z (GMT). No. of bitstreams: 1 Matoso_Erika_D.pdf: 946241 bytes, checksum: 56f70c56da8e0c3fb10d01d26c121fb7 (MD5) Previous issue date: 2009 / Resumo: Os polímeros são um grupo importante de materiais de engenharia pela sua facilidade de produção e uma larga faixa de propriedades e aplicações. O acetato de polivinila (PVAc) é produzido pela polimerização do acetato de vinila em presença de um catalisador. Suas principais aplicações estão na indústria de tintas, vernizes e adesivos. Neste trabalho foi desenvolvido um método de digestão de amostras de acetato de polivinila (látex base PVAc) em emulsão aquosa para determinação de As, B, Ba, Bi, Cd, Cr, Cu, Fe, Hg, Ni, Pb, Sb, Se e Sn, utilizando a técnica de espectrometria de emissão ótica em plasma de argônio indutivamente acoplado (ICP OES). Foram testados diferentes procedimentos de digestão da amostra (calcinação, digestão ácida à baixa e à alta temperatura e digestão assistida por microondas em frasco fechado) com a finalidade de se obter o método mais exato, mais preciso, com maior sensibilidade e com um menor tempo. Os melhores resultados para a determinação dos elementos estudados em acetato de polivinila foram obtidos utilizando-se a digestão assistida por microondas em frasco fechado. Nas condições otimizadas, a solução após digestão apresentou 0,1% de CCR (conteúdo de carbono residual), as recuperações obtidas ficaram na faixa de 98 a 105% para o produto de base (PVAc), com desvio padrão relativo (RSD) na faixa de 1,0 a 5,1% e limites de quantificação entre 0,003 e 0,294 mg kg. A exatidão do método proposto foi avaliada, também, pela análise de material de referência certificado, com resultados considerados satisfatórios para a maioria dos elementos. A aplicação do método desenvolvido em amostras de cola com base PVAc mostrou valores abaixo do limite de quantificação (LOQ) para a maioria dos elementos analisados, com exceção de Fe, Cu, Cr e Ni. No entanto, para estes elementos, os valores encontrados estão abaixo daqueles recomendados pelas agências reguladoras. A determinação de Cu por GF AAS em amostras de PVAc, sem a etapa prévia de preparação de amostra, mostrou resultados satisfatórios de recuperação e uma maior sensibilidade, com limite de quantificação de 0,001 mg kg / Abstract: Polymers are an important group of engineering materials because they are easily produced and have many applications. Polyvinyl acetate is produced by polymerization of vinyl acetate in presence of a catalyst and finds numerous applications in the manufacture of emulsion paints, varnishes and adhesives. A digestion method for the determination of de As, B, Ba, Bi, Cd, Cr, Cu, Fe, Hg, Ni, Pb, Sb, Se e Sn by Inductively Coupled Argon Plasma Optical Emission Spectrometry (ICP OES) in samples of polyvinyl acetate water emulsions was developed. The sample was treated by different procedures in order to determine the best treatment. In this way, calcination, acid digestions at low and high temperature and digestion by microwave radiation were studied. The best results for the determination of elements in polyvinyl acetate were achieved using microwave digestion. Under optimum conditions, only 0.1% of total organic carbon (TOC) was found as residue and recoveries between 98 and 105% for base product (PVAc) with RSD between 1.0 and 5.1% and quantification limits between 0.003 and 0.294 mg kg were obtained. The accuracy was also evaluated analyzing certified reference materials with satisfactory results. The application of the developed method in PVAc glue samples showed lower results than quantification limits for most elements, except Fe, Cu, Cr and Ni. But the found values are lower than those recommended by regulation agencies. Cupper determination by GF AAS in PVAc samples without treatment showed good results for recoveries and better sensibility (quantification limit: 0,001 mg kg) / Doutorado / Quimica Analitica / Doutor em Ciências

Thesis is dealing with PVAC dispersion adhesives. Main objective of this thesis is to assess the influence of compression pressure on strenght of glued joint. For research were used two kinds of adhesives. Secondary task was also determine if one of used glues suits to normatively appointed denominations of classe of durability D3. Speciments were made according to norms ČSN EN 204 a ČSN EN 205, than they were gummed by selected glues using different compression pressures and exposed to appointed conditions, which corresponds to classes of durability D1, D2 and D3. Finally there were determined strenght of glued joints according to the same norms and evaluated the influence of compression pressure. Results from all measurments were registred per tables and graphs.

Ce travail de thèse a pour objectif d’élaborer de nouveaux matériaux composites (élastomères, adhésifs) en utilisant les nanocelluloses (NCC et NFC) comme renforts mécaniques biosourcés. Une méthode de fonctionnalisation des nanocelluloses en conditions aqueuses a d’abord été développée, dans le but ultime d’améliorer leur compatibilité avec les matrices polymères. La réaction, basée sur la transestérification des esters de vinyle, a été optimisée à partir de l’acétate de vinyle utilisé comme réactif modèle. Le greffage en conditions basiques s’est avéré efficace, mais a également conduit à la formation de poly(acétate de vinyle) (PVAc) comme produit secondaire. Pour pallier à ce problème, un deuxième protocole en conditions neutres a également été développé, mais des rendements moins bons ont été obtenus dans ce cas. Les nanocelluloses non modifiées et acétylées ont ensuite été dispersés dans une matrice caoutchouc naturel (NR) afin d’étudier l’impact de cette charge sur les performances thermomécaniques du matériau cru ou vulcanisé. Une amélioration des propriétés mécaniques a pu être observée en présence de NCC ou NFC, mais l’acétylation des nanoparticules n’a pas conduit à de meilleures performances. Enfin, une valorisation du PVAc produit lors de l’acétylation des nanocelluloses en conditions aqueuses basiques a été proposée. La dispersion des NCC acétylés dans le PVAc polymérisé in-situ a en effet permis de produire des composites aux propriétés améliorées. L’utilisation ultérieure de ces composites comme charge (mélange-maître) dans des matrices NR ou EVA a été discutée. / The objective of this research work consists in the elaboration of novel composite materials (elastomers, adhesives) using nanocelluloses (CNC and NFC) as biobased reinforcing fillers. A method allowing the functionalization of nanocelluloses in aqueous conditions was first developed, with the aim of ultimately improving their compatibility with polymer matrices. The reaction, based on the transesterification of vinyl esters, was optimized with vinyl acetate selected as model reactant. The grafting performed in basic aqueous conditions was efficient, but also led to the formation of poly(vinyl acetate) as a by-product. To limit this problem, a second protocol in neutral aqueous conditions was also developed, but lower yields were obtained in that case. The unmodified and acetylated nanocelluloses were then dispersed in a natural rubber matrix (NR), to study the impact of this filler on the thermomechanical performances of the crude and vulcanized material. An improvement of the mechanical properties was observed in the presence of NCC or NFC, but the acetylation of the nanoparticles did not enhance further the performances. Finally, a valorization of the PVAc produced during the acetylation of the nanocelluloses in basic aqueous conditions was proposed. The dispersion of the acetylated NCC in the PVAc polymerized in-situ indeed led to the production of composites with improved properties. The subsequent utilization of these composites as filler (master batch) in NR or EVA matrices was discussed.

The main aim of the thesis is the comparison of methods that are focused on assessment of solid woods boards' strength. The assessment is considered from a point of view of normative methods and it is determined at industrial oak and beech solid wood panels with PVAC dispersion glue. The thesis consists of two main parts. The first part is theoretical and it is focused on solid wood materials, wood bonding, technological factors and circumstances that influence the quality of adhesive joints. There are also mentioned basic types of adhesives used in furniture and wood industry as well as overview of standards dealing with quality of adhesive joints of wood materials in the theoretical part. The theoretical knowledge is used in the second part where is the methodology created. The methodology helps to find out the density, shear bond strength and percentage violation of adhesive joints of test samples. Finally, the results of analytical part are statistically evaluated and mutually compared and also compared with specialized literature.

The thesis deals with the influence of mixture of the mixed adhesive and dispersion PVAc adhesive for bonding strength in shear strength. For the testing were selected two economically very important wood species (the spruce and beech wood) which are used in construction, furniture and building industry. All samples were grouped by the type of adhesive and by the temperature used for 28 days conditioning. All samples were bonded with coating 120 g/m2. After bonding, pressing and conditioning to required temperature were all samples subjected to a test, which examines the bonding strength in shear. The thesis deals with the comparison of the results and examines the effect of the adhesive mixture to bonding strength.

This study aims to compare the strength of bonding joint and bonding quality depending on the proportion of violations. The first part contains a research of various types of adhesives. Based on the research, two types of adhesive were chosen - the PVAC and UF adhesives. These adhesives are used directly in manufacturing of solid wood panels. Our test samples were made of beech wood and oak wood using both types of adhesive, four groups of samples altogether. The thesis contains an analysis of the requirements for bonding strength as well as production of samples from solid wood panel. According to current standards, the tests were performed to determine the density, moisture content, strength of bonding joint, the bonding quality and proportion of violations.

En el trabajo con el título "Analytical study of accelerated light ageing and cleaning effects on acrylic and PVAc dispersion paints used in Modern and Contemporary Art" se han empleado diferentes técncias analíticas con el fin de optimizar protocolos experimentales para la caracterización de la estabilidad de acrílicos y acetatos de polivinilo (PVAc) frente a ensayos de envejecimeinto acelerado y tratamientos de limpieza. El estudio de los procesos de degradación causados por la exposición a la luz se ha desarrollado sobre una amplia seria de muestras acrílicas y vinílicas expuestas a dos tipos de envejecimiento acelerado con condiciones de envejecimiento artificail representativas de un envejecimiento natural. La información química y mecánica obtenida por ambos ensayos de envejecimiento acelerado permitió identificar procesos de degradación específicos tales como entrecruzamiento o escisión de cadenas. Las conclusiones obtenidas de forma general apuntan que los acrílicos son materiales más estables que los vinílicos y los estireno-acrílicos. Asimsismo, en este estudio se han aborado los efectos de los tratamientos de limpieza bien de base acuosa, bien con disolventes orgánicos, en las propiedades físico-qúimicas en muestras acrílicas y vinílicas. También se han evaluado otros métodos de limpieza tales como geles o emulsiones. Los resultados indican que los tratamientos acuosos extraen aditivos, afectan la morfología e inducen cambios en las propiedades mecánicas de las muestras. Estos efectos pueden ser reducidos con el uso de sistemas alternativos de limpieza. / De Sousa Ramos Félix Silva, M. (2011). Analytical study of accelerated light ageing and cleaning effects on acrylic and PVAc dispersion paints used in Modern and Contemporary Art [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/13829

Les nanofibrilles de cellulose (NFC), obtenus par oxydation TEMPO des microfibrilles de cellulose native sous forme de suspensions colloïdales aqueuses, sont des nanoparticules biosourcées ayant des propriétés rhéologiques et optiques particulièrement séduisantes pour la conception de nanomatériaux à haute performance. Le but principal de cette étude était de contrôler et optimiser les conditions de préparation de ces NFCs extraites du rachis de palmier dattier en examinant le temps d'oxydation et le nombre de passe à travers l'homogéinsateur.La réussite de la réaction a été démontrée par spectroscopies FT-IR. Le taux de groupements carboxyliques a été calculé par dosage conductimétrique et était compris entre 221 et 772 µmol/g d'anhydroglucose. Les études morphologiques montrent que NFCs oxydées sont assez bien individualisés grâce à l'introduction des charges négatives à leur surface qui induisent des forces de répulsion électrostatique entre les fibrilles. Une attention particulière a été accordée à la viscoélasticité des suspensions NFC oxydées TEMPO dont le suivi a été réalisé par un rhéomètre ARES-G2TA. Ces nanocharges ont ensuite été incorporées au sein d'un thermoplastique (PVAc), puis les matériaux nanocomposites obtenus ont été caractérisés par MEB, ATG, DSC, DMA et par des tests mécaniques. / The cellulose nanofibrils (CNF), obtained by TEMPO oxidation of native cellulose microfibrils as colloidal aqueous suspensions, are biosourced nanoparticles having rheological and optical properties well adapted for the conception of new nanomaterials with high performance.The main purpose of this study was to control and optimize the conditions for preparing these NFCs extracted from date palm tree by examining the oxidation time and the number of passes through the homogenizer..The success of the reaction was demonstrated by FT-IR spectroscopy. The rate of the carboxylic groups has been calculated by conductometric titration and ranged between 221 and 772 mol / g of anhydroglucose. Morphological studies show that oxidized CNFs are very individualized by introducing negative charges on their surfaces that induce electrostatic repulsion forces between the fibrils. Particular attention has been given to the viscoelasticity of oxidized-TEMPO CNF suspensions whose monitoring was carried out by a rheometer ARES-G2TA. These nanocharges were incorporated in a thermoplastic (PVAc) and nanocomposite materials obtained were characterized by SEM, TGA, DSC, DMA and mechanical testing.

A majority of research within the field of energetic materials have been centered around the stable crystalline phase, whilst there has been less about the amorphous phase and the implications of these types of material. In this study, Molecular Dynamics simulations with the General Amber Force Field (GAFF) is used to predict fundamental properties of the nitramine explosives HMX and CL-20 in the amorphous phase. Amorphous structures are obtained by compressing a molecular gas to 4 GPa followed by relaxation and equilibration. The simulations indicate that the amorphous phases of HMX and CL-20 have lower densities than the corresponding crystal phases, 12.7% and 7.3% respectively. Both HMX and CL-20 was found to compress more easily when subject to external pressure, the difference was most significant for HMX.As a second part of this study an amorphous composition of CL-20/HMX/Polyvinylacetate(PVAc) (50/45/5 -wt%) was studied. This was obtained by compressing a molecular gas to varying pressures followed by relaxation and equilibration. Results indicate that the simulated density around 1.64 [g/cm3 ] fall close to experimental observations of 1.7 [g/cm3 ]. The density was observed to not vary significantly for pressures higher than 0.4 [GP a] in accordance to experimental data.