The effects of oxidation by sodium hypochlorite (0, 0.8, 2, and 5%, NaOCl), the presence of endogenous proteins, and amylose content on waxy and common rice flours (WF, CF) and starches (WS, CS) were investigated in terms of in vitro starch digestibility, morphology and surface properties, and thermal and rheological characteristics. The concentration of NaOCl had an effect on all the samples including WF, CF, WS, and CS. The carbonyl and carboxyl group contents increased up to 25 and 10 folds (P < 0.05) of oxidized starches (WS, CS), respectively. Only mild oxidation (P < 0.05) occurred in flours (WF, WS). In addition, endogenous proteins were oxidized according to amino acid analysis and SDS–PAGE results. Glu+Gln, Gly, His, Arg, Tyr, and Lys were more sensitive to NaOCl oxidation. Disulfide bonds, hydrophobic force, and hydrogen bonds were involved in protein polymerization after NaOCl oxidative modification. In granular state, the in vitro starch digestibility of WF, WS, and CS decreased by 5% NaOCl oxidation. After gelatinization, only 2 and 5% oxidized WS had lower digestibility. Scanning electron microscopy and confocal laser scanning microscopy further demonstrated that protein existed on the surface of starch granules and had aggregation by oxidation. X-ray diffraction patterns showed the crystallinity of 5% oxidized flours and starches was reduced compared with all their non-oxidized samples. Thermal and rheological properties were analyzed by differential scanning calorimetry and rheometer, respectively. Starch gelatinization peak temperature of flours (WF, RF) was increased by 3 °C, but starches (WS, CS) had a significantly decrease by 8 °C. Viscoelastic patterns were dramatically changed by oxidation. Oxidized WF and CF had increased in both viscosity and elasticity by oxidation, whereas both WS and CS had significantly lower viscoelasticity after oxidative modification.

Baigiamojo magistro darbo tikslas – ištirti cheminių įmaišų poveikį reologinėms portlandcemenčio tešlos savybėms, panaudojant skirtingų tipų cementus. Darbe išnagrinėta lietuvių, užsienio mokslinė literatūra, aprašytos naudotos žaliavos, parinktos skirtingos cementinės tešlos sudėtys, kurios skiriasi cemento ir plastifikuojančios įmaišos tipu. Tyrimams naudotos šios medžiagos: AB „Akmenės cementas“ gamyklos portlandcementis CEM I 42,5 (N ir R ankstyvojo stiprumo), klinties portlandcementis CEM II/A-LL 42,5 N, plastiklis Centrament N3, naujausios kartos superplastiklis MC-PowerFlow 3140 ir vanduo. Ištirtas plastiklio ir superplastiklio poveikis portlandcemenčio tešlos vandens ir cemento (V/C) santykio pokyčiams ir sklidumui naudojant Sutardo viskozimetrą. Buvo tiriamos vienodo vandens ir cemento santykio portlandcemenčio tešlos su cheminėmis įmaišomis ir be jų. Tyrimai atlikti naudojant rotacinį viskozimetrą Rheotest NH 4.1 su bendraašiais cilindrais. Nustatytas cheminių įmaišų portlandcemenčio tešloje veiksmingumas, esant skirtingo tipo cementui. Pastebėta, kad portlandcemenčio tešlos dinaminis klampis gali būti reguliuojamas cheminėmis įmaišomis viso indukcinio hidratacijos periodo metu. Sukurta metodika portlandcemenčio tešlos reologinėms savybėms nustatyti bei parinktas reologinis modelis, kuris geriausiai apibūdina gautus tyrimų duomenis. Atlikus portlandcemenčio tešlos su cheminėmis įmaišomis ir be jų tyrimų rezultatų regresinę analizę, gautos klampio, tekėjimo lygtys... [toliau žr. visą tekstą] / The purpose of this thesis is to analyse the influence of chemical admixtures on the rheological properties of Portland cement paste, which differ depending on the type of cement used. In addition to the literature analysis, different cement paste compositions (differing in type of cement and plasticizers) were tested. Testing materials: Portland cement CEM I 42.5 (N and R early strength), limestone Portland cement CEM II/A-LL 42.5 N, plasticizer Centrament N3, the latest generation superplasticizer MC-PowerFlow 3140 and water. Research focused on effects of plasticizer and superplasticizer on water and cement (W/C) ratio and Portland cement paste slump-flow characteristics. Portland cement pastes with the same water-cement ratio with and without chemical admixtures were tested. Tests were carried out using a Suttard viscometer and rotation viscometer Rheotest NH 4.1 with coaxial cylinders. It was observed that viscosity of Portland cement paste can be controlled by chemical admixtures during the hydration induction period. The work provides analysis of the effectiveness of the chemical admixtures on the rheological properties of the Portland cement pastes, comparing it with a control composition of the Portland cement paste. Diagrams demonstrate changes in viscosity of the Portland cement pastes depending on the type and amount of the chemical admixtures. Obtained results were compared with the same consistence paste without admixtures. We created a new methodology of... [to full text]

Ce travail de thèse concerne l’étude de dispersions de nanotubes de carbone (NTC) dans une matrice polymère afin d’obtenir des matériaux nanocomposites avec des propriétés améliorées. Dans la première partie, nous nous sommes intéressés à l’enrobage des NTC par des copolymères à blocs amphiphiles afin de faciliter la dispersion en solution aqueuse. L’influence de la structure chimique, de la composition et de la masse molaire des copolymères sur les propriétés a été étudiée. Dans une deuxième partie, l’incorporation des NTC dans une matrice polymère a été développée. Des procédés par voie aqueuse et par voie fondue ont été choisis afin de contrôler la répartition des NTC dans une matrice modèle de polyoxyde d’éthylène ainsi que dans des de polyéthylène ou de polyméthacrylate de méthyle. L’étude des propriétés physiques, notamment rhéologiques et électriques des nanocomposites à renfort de nanotubes a été réalisée. Ainsi les relations entre l’état des dispersions, la nature de l’enrobage et le mode d’élaboration des composites ont été établies. / This work is concerned with the study of carbon nanotubes (CNT) dispersions in a polymer matrix in order to obtain nanocomposite with unique properties. In the first part, we investigated the CNT wrapping by amphiphilic block copolymers to facilitate their suspension in aqueous solution. Based on the results, we could assess the effect on CNT dispersion quality of the molar mass of copolymers, the nature of the hydrophobic block and the length of hydrophilic block. In the second part, the incorporation of CNTs in polymer matrix was developed. Water or melt processing were chosen to control the distribution of CNTs in various polymer matrices (Polyethylene oxide, polyethylene and polymethyl methacrylate) through a prior wrapping of CNT. The studies of physical properties, including rheological and electrical properties, of nanocomposites were undertaken. Relationships between the state of dispersion, the nature of the coating and the method of preparation of composites were established.

Les exigences actuelles en terme de lubrification automobile imposent des formulations extrêmement complexes. Parmi tous les additifs présents dans l’huile, on peut noter le dithiocarbamate de molybdène et le dithiophosphate de zinc, additifs à action tribologique, à base de soufre et de phosphore. Pour des raisons environnementales, il est important de diminuer nettement voire d’éliminer la présence de ces deux éléments dans les huiles. Les matériaux à base de carbone présentent des propriétés tribologiques intéressantes mais n’ont jamais été entièrement étudiés. Dans cette étude nous nous sommes intéressés aux propriétés lubrifiantes des nanotubes de carbone (NTCs). Des nanotubes multi-parois ont été dispersés dans l’huile puis les propriétés rhéologiques et tribologiques des « nanolubrifiants » ont été étudiées. Nous nous sommes intéressés à leurs propriétés tribologiques dans deux régimes de lubrification : le régime limite et le régime élastohydrodynamique. Nous nous sommes tout d’abord focalisés sur les propriétés rhéologiques du mélange huile/NTCs.Les nanotubes de carbone possèdent une tendance à s’agréger sous la forme d’un réseau de taille micrométrique ce qui résulte en une nette augmentation de viscosité de l’huile de base. Cet effet épaississant pourrait éventuellement permettre aux NTCs de remplacer une partie de l’Améliorant d’Indice de Viscosité (AVI) habituellement additionné à l’huile de base. Néanmoins, nous avons mis en évidence un effet antagoniste avec les autres additifs de lubrification, tel que le dispersant, qui pourrait être un problème pour une telle utilisation. Nous nous sommes ensuite intéressés aux propriétés des NTCs dans le régime limite de lubrification. Les NTCs présentent des propriétés réductrices de l’usure et du frottement intéressantes sous certaines conditions. Les analyses effectuées laissent supposer un rôle du catalyseur dans le mécanisme de lubrification. Les nanotubes de carbone semblent d’un grand intérêt car, ils possèdent également des propriétés tribologiques en régime élastohydrodynamique (EHD). Le mécanisme de formation des films lubrifiants a été étudié en fonction des paramètres concentrations et vitesses d’entraînement: la propagation des agrégats de NTCs à travers le contact résulte en une augmentation locale de l’épaisseur de film lubrifiant. De plus, une réduction de frottement et un décalage dans l’apparition des premières traces d’usure ont été observés à la suite d’essais tribologiques. Le mécanisme d’action des NTCs en régime de lubrification EHD est proposé dans cette partie. Cependant, les interactions entre les NTCs et les additifs présents dans les lubrifiants entièrement formulés doivent être étudiés pour optimiser la formulation de lubrifiant à base de nanotubes de carbone. / The current requirements in automotive lubrication impose extremely complex formulation. Among all the additives present in oil, one can note the presence of molybdenum dithiocarbamateand zinc dithiophosphate, both tribological additives containing sulfur and phosphorous. For environmental reasons, it is important to reduce or eliminate the presence of these two elements contained in oil. Carbon based materials are expected to present interesting tribological properties but were never really fully investigated. In this study, we are being interested on the lubricant properties of nanometric Carbon NanoTubes (CNT). Multi wall carbon nanotube MWNTs have been dispersed in oil and the behaviour of the blends has been studied in terms of rheology and tribology. We investigated their friction properties in two regims of lubrification : boundary lubrification and elastohydrodynamic (EHD) lubrification. At first, we focused in rheological properties of the blend. Carbon NanoTubes (CNT) present the tendency to aggregate to form micrometric network and this results in an increase in the blend viscosity. This thickening effect could make it possible to replace part of the ViscosityIndex Improver traditionally added to base oil. Nevertheless we reported an antagonist effect with other additives such as dispersant which may be a problem for this purpose. Then we investigated lubricant properties of CNT in boundary regim. CNTs show interesting friction reducing and anti-wear properties in some conditions. The results obtained let suppose a role of the catalyst in the lubrication mechanism. CNT are also of great interest in reason of their potential tribological properties in EHD lubrification regim. The lubricant film formation has been investigated as a function of the speed and the CNT concentration : the propagation of the CNT through the contact results in a local increase in the film thickness. Moreover, a reduction in friction and a drift in the wear onset have been observed under controlled contact kinematics. A potentiel mechanism of lubrification is explained in this last part. However, the interaction between the carbon nanotubes and the other additives present in the fully formulated lubricant need to be carrefully investigated in order to be able in the future to optimise the formulation of new carbon nanotubes based lubricants.

Master's thesis topic: Influence of rheological characteristics of muscle tissue by musculus triceps surae by means of AEK practice Author: Bc. Karel Kupec Branch of study: Physiotherapy Disertation Tutor: PhDr. Petr Šifta, Ph.D. Year of Defense: 2013 Abstract: The target of this thesis was find out the effect of agistic-excentric contractions on muscle tension of musculus soleus compared with passive relaxation of musculus soleus. The assumption was, that agistic-excentric contraction reduce muscle tension of musculus soleus after anaerobic load. The contralateral lower limb was control limb for comparison agistic-excentric contraction and passive relaxation. Muscle tension was measured in laboratory in Faculty of Physical Education and Sport, Charles University: five students were measured. As a measurement method was used myotonometry, which simulated palpation. Measured data were displayed by using an analog-digital convertor and consequently evaluated. The results of this study found out positive effect of agistic-excentric contraction on muscle tension. Control form of relaxation, passive relaxation, didn't influence muscle tension so significantly. The results support the principle of hypotheses, that agisctic-exentric contraction approach affect muscle tension more positive than passive...

O desenvolvimento de filmes à base de biopolímeros tem sido bastante estudado devido aos problemas ambientais causados pelas embalagens de plásticos sintéticos. Dentre os biopolímeros, merece destaque a gelatina, que tem excelente propriedade filmogênica. Entretanto, até o presente momento, os filmes de gelatina apresentam limitações de propriedades mecânicas e, tem elevada sensibilidade à umidade. Uma alternativa para melhorar as propriedades desses filmes pode ser a utilização de nanopartículas como carga de reforço. Assim, os objetivos desta tese foram o desenvolvimento e a caracterização de filmes à base de gelatina, reforçados com nanopartículas. Especificamente, foram objetivos os seguintes estudos: avaliação do efeito da concentração de gelatina sobre as propriedades reológicas das soluções formadoras de filmes e de algumas propriedades físicas de filmes de gelatina, preparados com essas soluções formadoras de filmes com um aplicador automático de filmes; e estudo dos efeitos das concentrações de gelatina e de montmorilonita sobre as propriedades físicas de filmes nanocompósitos e de suas soluções formadoras. Em ambos os estudos, os filmes foram caracterizados imediatamente após a secagem e depois de 7 dias de acondicionamento. As soluções formadoras de filmes (SFF) foram preparadas com gelatina e glicerol, e as soluções formadoras de nanocompósitos (SFN), pela mistura de uma solução de gelatina com uma dispersão de montmorilonita em água, em ambos os estudos, em proporções e temperaturas convenientes. Após a homogeneização, as SFF ou SFN foram resfriadas até a temperatura adequada para aplicação em suportes de plexiglass com a ajuda de um espalhador automático de filmes, acoplado a um banho ultratermostatizado. A altura do espalhador foi mantida constante em 1,5 mm, e a velocidade de espalhamento foi fixada em 35 mm/segundo. Em seguida, as SFF ou SFN foram desidratadas a 30ºC por 24h, em estufa com circulação de ar. No primeiro estudo, as SFF foram preparadas com 5, 8, 11 e 14g de gelatina/100g de SFF e 30 g de glicerol/100g de gelatina, e na segunda parte da tese, as SFN foram preparadas com 5 e 8g de gelatina/100g de SFN, 30 g de glicerol/100g de gelatina e 0, 5, 10 e 15g de montmorilonita/100g de gelatina. As propriedades reológicas das SFF e SFN foram estudadas com testes estacionários e dinâmicos. As propriedades reológicas dasdispersões de montmorilonita em água também foram estudadas, bem como a determinação do tamanho médio das partículas e do potencial zeta. Os filmes foram caracterizados para conhecimento da espessura, umidade, propriedades mecânicas (testes de tração e perfuração), transições de fase, microestrutura das superfícies e da criofratura, cristalinidade, espectroscopia de infravermelho com transformada de Fourier (FTIR), hidrofobicidade, isoterma de sorção de vapor de água, solubilidade em água, permeabilidade ao vapor de água, ao O2 e CO2, cor, opacidade, brilho e propriedade de barreira a luz/UV, segundo os objetivos específicos de cada estudo. Em relação ao primeiro estudo, observou-se que a concentração de gelatina na SFF influenciou fortemente todas as propriedades reológicas e inclusive, as transições sol-gel e gel-sol, determinadas nos testes dinâmicos com varredura de temperatura. A concentração de gelatina na SFF aumentou linearmente a espessura dos filmes, sem, contudo afetar nitidamente a umidade, as transições de fases e nem as propriedades mecânicas obtidas nos testes de tração. A força na perfuração aumentou, mas esse efeito foi devido ao aumento da espessura dos filmes. Em relação ao estudo sobre nanocompósitos de gelatina, observou-se inicialmente que a montmorilonita dispersa em água apresentou diâmetro médio entre 204 e 344 nm, e potencial zeta variando em torno de -43mV. A carga de nanopartícula não afetou a viscosidade da dispersão em água, mas influenciou fortemente as propriedades reológicas e de transições de fases das SFN. A carga de nanopartículas também influenciou a espessura, as propriedades mecânicas e a hidrofobicidade dos filmes nanocompósitos, sem uma função nítida. Comportamento similar foi observado nos resultados da calorimetria diferencial de varredura, embora o padrão de cristalinidade, os espectros de FTIR e as microestruturas dos filmes tenham variado com a carga de montmorilonita. O filme nanocompósito produzido com 5g de gelatina/100g de SFN e 5g de montmorilonita/100g de gelatina apresentou melhores propriedades mecânicas e menor solubilidade em água. Esse filme foi submetido a caracterizações complementares com resultados típicos de filmes de gelatina. No geral, pode-se concluir que a montmorilonita pode melhorar as propriedades dos filmes de gelatina, porém, mais estudos serão necessários para se garantir perfeita dispersão da nanopartícula na matriz do filme. / The development of films based on biopolymers has been widely studied due to the environmental problems caused by synthetic plastic packaging. Among biopolymers, gelatin has to be outlined as it has excellent filmogenic properties. However, until now, the gelatin films have mechanical properties limitations and, high humidity sensitive. An alternative to improve the properties of these films may be the use of nanoparticles as load. Thus, the objectives of this thesis were the development and characterization of gelatin-based films, charged with nanoparticles. Specifically, the objectives were the following studies: evaluation of the effect of gelatin concentration on the rheological properties of the film-forming solutions and on some physical properties of the gelatin films prepared with those film forming solutions using a automatic spreader; and the study of the effect of the gelatin and montmorillonite concentrations on the physical properties of nanocomposite films and their film forming solutions. In both studies, the films were characterized immediately after drying and then after 7 days of conditioning. The film forming solutions (FFS) were prepared with gelatin and glycerol, and the nanocomposite film forming solutions (NFS), by blending the gelatin solution with the montmorillonite dispersion in water, for both studies, in convenient proportions and temperatures. After homogenization, the FFS or NFS were cooled to a proper temperature and applied on plexiglass plates with the help of an automatic spreader, attached to an ultra thermostatized bath. The height of the spreader was kept constant at 1.5 mm, and the spreading speed fixed at 35 mm/second. After that, the FFS or NFS were dehydrated at 30ºC for 24h, in an oven with air circulation. In the first study, the FFS were prepared with 5, 8, 11 and 14g of gelatin/100g of FFS and 30g of glycerol/100g of gelatin, and in the second part of the thesis, the NFS were prepared with 5 and 8g of gelatin/100g of NFS, 30 g of glycerol/100g of gelatin and 0, 5, 10 and 15g of montmorillonite/100g of gelatin. The rheological properties of the FFS and NFS were studied by steady and dynamic tests. The rheological properties of the montmorillonite dispersions in water were also studied, along with the average particle size and zeta potential determinations. The films were characterized to determine thickness, water content, mechanical properties (tensile and puncture tests), phase transitions, surface and cryo-fracture microstructure, crystallinity, Fourier transform infrared spectroscopy (FTIR), hydrophobicity, water vapor sorption isotherm, solubility in water, water vapor, O2 and CO2 permeabilities, color, opacity, gloss, and light/UV barrier properties, according to the objectives of each study. Regarding the first study, it was observed that the gelatin concentration in the FFS strongly influenced the rheological properties and even the sol-gel and gel-sol transitions, determined by the dynamic temperature scanning tests. The gelatin concentration provoked linear increasing of films thickness without, however, affecting discernibly the water content, the phase transitions neither the mechanical properties determined by the tensile tests. The puncture force increased, but this effect was due to the thickness increasing of the films. Regarding the gelatin nanocomposites study, it was initially observed that the montmorillonite dispersed in water had average diameter between 204 and 344 nm, and zeta potential varying around -43mV. The nanoparticle filling did not affect the viscosity of the water dispersion, but strongly influenced the rheological properties and the phase transitions of the NFS. The nanoparticle filling also affected the thickness, the mechanical properties and the hydrophobicity of the films, without a clear function. Similar behavior was observed for the differential scanning calorimetry results, although the crystalline pattern, the FTIR spectra and the microstructure of the films varied with the montmorillonite filling. The nanocomposite film produced with 5g of gelatin/100g of NFS and 5g of montmorillonite/100g of gelatin showed better mechanical properties and lower solubility in water. That film was submitted to further characterizations rendering results typical of gelatin films. In general, it can be concluded that the montmorillonite can improve the properties of gelatin films, however more studies will be necessary to guarantee the perfect dispersion of the nanoparticles within the film matrix.

A presente dissertação de mestrado visa avaliar e comparar o desempenho de um bioligante, obtido por processamento de material de origem vegetal, frente a ligantes asfálticos derivados do refino de petróleo. Nesse sentido, foram realizados ensaios objetivando a caracterização reológica dos ligantes e análise do comportamento mecânico de misturas usinadas destes ligante com agregados. Com auxílio de um reômetro de cisalhamento dinâmico (DSR) foram realizados os seguintes ensaios reológicos: cisalhamento oscilatório (para determinação do módulo complexo e do ângulo de fase); fluência e recuperação sob múltiplas tensões (MSCR); e varredura de amplitude linear (LAS). Uma avaliação do efeito do envelhecimento dos bioligante em comparação com um ligante convencional CAP 30/45 foi realizada com base em características reológicas e químicas. Dentre os ensaios mecânicos realizados nas misturas de ligantes com agregados usinadas a quente, tem-se: deformação permanente e módulo dinâmico. Os resultados reológicos mostram que o bioligante apresenta elevados módulos de cisalhamento dinâmico em altas frequências, mas é semelhante a um asfalto convencional nas baixas frequências. Os ensaios indicam que o bioligante pode vir a apresentar boa resistência à deformação permanente, semelhante à verificada em ligante asfáltico convencional (CAP 30/45). Tal semelhança de comportamento, entre os dois tipos de ligantes, foi igualmente verificada em ensaios mecânicos de determinação do afundamento em trilha de roda, realizados nas misturas usinadas a quente em laboratório. Os resultados reológicos de LAS indicam que o bioligante deve apresentar menor vida de fadiga. A temperatura do ensaio de envelhecimento de curto prazo interferiu significativamente na rigidez do bioligante, assinalando o expressivo efeito da temperatura de ensaio RTFOT na oxidação e na perda de voláteis do bioligante. Os índices de carbonila e de sulfóxido não se mostraram adequados para análise da oxidação e envelhecimento sofrido pelo bioligante envelhecido em diferentes condições. Os ensaios de módulo dinâmico de misturas usinadas de bioligante com agregados tendem a mostrar elevados valores, maiores que as misturas com asfalto convencional. Baseando-se na análise dos resultados reológicos e nas observações de comportamento mecânico das misturas usinadas a quente de bioligante e agregados é possível, portanto, constatar o potencial do emprego deste material inovador em camadas usinadas e compactadas de pavimentos. / This dissertation aims to evaluate and compare the performance of a biobinder obtained by processing plant material against asphalt binders derived from petroleum refining. Thus, tests were performed aiming at the rheological characterization of the binders and at the analysis of the mechanical behavior of hot mixtures processed with such binders and aggregates. With the use of Dynamic Shear Rheometer (DSR), the following rheological tests were carried out: Oscillatory shear (in order to determine the complex modulus and phase angle); the Multiple Stress Creep and Recovery (MSCR); and the Linear Amplitude Sweep (LAS). An evaluation of the biobinder aging effect in comparison to a conventional CAP 30/45 binder was performed based on rheological and chemical features. Among the mechanical tests carried out on binder and aggregate hot mixtures, there were: Rutting, and Dynamic Modulus tests. Rheological results show that the biobinder presents high dynamic shear modulus at high frequencies; however, it is similar to conventional asphalt at low frequencies. Tests indicate that the biobinder may present good resistance to permanent deformation, similar to that observed in conventional (CAP 30/45) asphalt binder. Such similarity in behavior in both types of binders was also verified in mechanical rutting tests performed on the hot mixtures in the laboratory. The LAS rheological results indicate that the biobinder must present a lower fatigue life. The temperature of the short-term aging test significantly interfered with the stiffness of the biobinder, pointing out the meaningful effect of the RTFOT test temperature on the oxidation and on the loss of volatiles from the biobinder. The carbonyl and sulphoxide rates were not adequate for the analysis of the oxidation and aging suffered by the biobinder aged under different conditions. Dynamic modulus assays of biobinder and aggregate hot mixtures tend to show higher values, higher than mixes with conventional asphalt. Based on the analysis of the rheological results, and on the observations of the mechanical behavior of biobinder and aggregate hot mixes, it is possible, therefore, to verify the potential of using this innovative material in hot-mix and compacted pavement layers.

O presente trabalho propõe o entendimento do comportamento no estado fresco de argamassas colantes, com base na caracterização reológica e físico-química de diferentes composições comerciais, servindo de base para analisar o fenômeno de deslizamento, a partir do ensaio estabelecido na norma brasileira. Para isso, foi utilizado o ensaio “Squeeze flow" (escoamento por compressão axial), empregado na caracterização de argamassas de revestimento no laboratório de microestrutura do CPqDCC da EPUSP, como ferramenta de análise do comportamento de argamassas colantes. Neste ensaio, o escoamento do material decorre da aplicação de uma carga de compressão sobre a amostra no estado fresco, a qual ocasiona deslocamentos no seu interior devido a esforços de cisalhamento radiais originados durante o fluxo. O critério de seleção das argamassas colantes comerciais (tipo AC-I) se baseou nos resultados do ensaio de deslizamento, escolhendo-se duas com resultado muito abaixo do limite especificado, duas com resultado próximo do limite e outras duas com resultado acima do mesmo. A composição química e física foi caracterizada com o objetivo de embasar a análise dos resultados obtidos no “Squeeze flow". A separação da fração fina das argamassas na peneira no.200 contribuiu para o conhecimento da viscosidade da pasta e da sua influência no comportamento reológico das argamassas. Foi observado que as argamassas estudadas apresentam diferenças de composição físico-química e de comportamento reológico. As diferenças de comportamento reológico das argamassas decorrem, provavelmente, de ação sinérgica de alguns parâmetros da composição, com destaque para a distribuição granulométrica. O “Squeeze flow" mostrou-se uma ferramenta adequada na caracterização das argamassas colantes e contribuiu para explicar o deslizamento estabelecido na norma brasileira, pela proposição de modelos hipotéticos de comportamento. / Present thesis proposes the study of plastic-state behaviour of dry-set mortars based on the rheological and physicochemical characterization of different commercially available dry-set mortar compositions. Such characterization served as basis for the analysis of dry-set mortar slip phenomena using the tests recommended by brazilian standards (NBR). The Squeeze Flow test (slip by axial compression) originally used for coating mortars characterization by the EPUSP CPqDDC Microstructure Laboratory was adopted as a test tool for analysing the dry-set mortar behaviour. In the mentioned test the material slip is obtained by compressing the sample in its plastic state which caused internal displacements due to radial shearing tensions originated during the mentioned slip. The dry-se mortars (all of them AC-I type) used in the study were selected based in the slip tests results against brazilian standards specified limits resulting in the selection of two dry-set mortars below the specified limit, two dry-set mortars close to the specified limit and dry-set mortars above the specified limit. Chemical and physical compositions were characterized in order to serve as basis for Squeeze Flow results analysis. Fine fraction segregation, using number 200 sieve contributed to understanding of plastic-state mortar viscosity and its influence in mortar rheological behaviour. It was observed diverse physicochemical and rheological behaviour among the studied dry-set mortars. The rheological behaviour diversity of dry-set mortars were due to the synergy among some composition parameters, specially the granular distribution. The Squeeze Flow was considered a suitable tool for the characterization of dry-set mortars and contributed to develop hypotetical behaviour models that allowed to explain the slip as stated by brazilian standards.

Atualmente o maior impacto ambiental do concreto como material de construção origina-se das emissões de CO2 durante a produção do cimento. Uma das alternativas atualmente utilizadas para minimizar este impacto, é a utilização de adições minerais como substituição ao cimento. Entre as diferentes adições utilizadas, o uso de fíler calcário parece ser uma alternativa interessante para melhorar a sustentabilidade do uso do concreto na construção. Consequentemente, o presente estudo foca a análise do impacto da substituição do cimento por fílers de origem calcária (dolomita) no comportamento do concreto em estado fresco e endurecido, especialmente focando-se numa avaliação reológica e na retração por secagem do material. Para tal fim, foram formulados três microconcretos com teores de fíler calcário de 80%, 60% e 20% em relação ao peso dos finos totais (cimento mais fíler calcário). O teor de finos totais e de água foram mantidos constantes para todas as formulações resultando em misturas com similar volume de pasta. O comportamento reológico das misturas foi avaliado num reômetro de movimento planetário. Foram moldados corpos de prova para caracterização mecânica e acompanhamento da retração por secagem. A porosidade das pastas também foi avaliada usando a porosimetria por intrusão de mercúrio. As propriedades reológicas como a tensão de escoamento e a viscosidade foram influenciadas pelo teor de substituição de cimento por fílers. Maiores volumes de fílers na pasta produziram menores tensões de escoamento e, por consequência, maiores valores de abatimento foram obtidos. No entanto, a viscosidade plástica aumentou com teor de fílers. No estado endurecido, a maior substituição de cimento por fílers diminui a intensidade da retração por secagem devido ao menor teor de cimento na pasta e a modificações na estrutura porosa do material. Os resultados experimentais da retração foram comparados com os valores obtidos pelos modelos de previsão da retração: ACI 209, CEB-FIP, B3 e GL2000. Observou-se que os modelos superestimam os valores da retração conforme aumenta a substituição de cimento por fílers na pasta. Portanto, esses modelos devem ser calibrados considerando outros fatores, tais como: a quantidade de fíler utilizado em substituição de cimento. Esta consideração poderia otimizar o uso dos modelos em fase de projeto para verificar se os valores da retração esperados estão dentro dos limites normalmente aceitos. / Currently the biggest environmental impact of concrete as a building material originates in CO2 emissions during the production of cement. For this reason, one of the alternatives currently used to reduce these emissions is the use of mineral additions as cement replacement. Among the different additions used, the use of limestone fillers to replace cement appears to be an interesting alternative for improve the sustainability of the concrete used in construction. Consequently, this study focuses on the analysis of the impact of the replacement of cement by limestone fillers in fresh and hardened concrete, especially focusing on rheological behavior and shrinkage of the material. To this end, three microconcretos were formulated with fillers limestone content of 80%, 60% and 20% by weight relative to the total fine (limestone fillers and cement). The total content of fine and water were held constant for all formulations resulted in mixtures with similar volume of paste. The rheological behavior of the mixes was evaluated in a planetary motion rheometer. For mechanical characterization and measurement of shrinkage, specimens were molded. The porosity of the pastes was also evaluated using mercury intrusion porosimetry. The rheological properties such as yield stress and viscosity were influenced by the amount of cement that was replaced by fillers. Further filers volumes in the pulp produced smaller flow stress and, consequently, higher allowance values were obtained. Larger volumes of filler in the paste produced lower yield stresses and, consequently, higher slump values were obtained. However, the plastic viscosity increased with filers content. In the hardened condition, the largest cement replacement by limestone fillers reduced the intensity of shrinkage due to the lower content of cement paste and changes in the porous structure of the material. The experimental results of shrinkage were compared with the values obtained by shrinkage prediction models: ACI 209, CEB-FIP, B3 and GL2000. It was observed that the models overestimate the shrinkage values with increasing cement replacement by limestone fillers. Therefore, these models must be calibrated considering other factors such as the amount of fillers used as cement replacement This consideration would optimize the use of these models in the design phase to verify that the values of the expected shrinkage are within the limits normally accepted.

As argamassas colantes são produtos constituídos por areia natural ou artificial, ligantes e aditivos químicos que cumprem uma função de adesivo para assentamento de revestimentos em pisos e paredes. Sob o ponto de vista reológico, a argamassa colante é um material multifásico formado por uma pasta que envolve agregados minerais. Atualmente, o único teste preconizado em norma a fresco é o ensaio de deslizamento, que apesar de ter baixo custo e relativa facilidade de execução em laboratório. As grandes desvantagens desse método são: imprecisão e a baixa repetibilidade, além de ser insuficiente para efetuar uma avaliação mais completa desses produtos no estado fresco. Assim, técnicas de caracterização reológica (Squeeze Flow, Pull Out Flow e reometria rotacional) foram especificadas e aplicadas, como alternativa tecnológica para avaliação de argamassas colantes. Porém, o potencial da configuração tradicional do ensaio de Squeeze Flow e a reometria rotacional foram pouco explorados neste tipo de argamassa. Neste estudo foi necessário empreender ajustes de configuração. O objetivo desta dissertação foi o de aplicar métodos de caracterização reológica em argamassas colantes de mercado (ACI e ACIII) de certo fabricante e ACI formulada em laboratório composta por areias com morfologias diferentes que permitissem identificar suas características relevantes no estado fresco, avaliar a influência dos parâmetros experimentais do método de Squeeze Flow (principalmente em relação à configuração e parâmetros), avaliar a adesividade das argamassas no estado fresco e aplicar o método de reometria rotacional para avaliação das energias de mistura e reológica. Os experimentos para avaliação das configurações e parâmetros do ensaio de Squeeze Flow e Pull Out Flow mostraram que tais métodos foram sensíveis para diferenciar as argamassas e refletiram o que, na prática, é percebido: ACIII (Argamassa Colante do Tipo III) tem maior consistência que ACI (Argamassa 7 Colante do Tipo I), além de mostrar que são sensíveis às diferentes taxas de deslocamento, teores de água e morfologia de agregados. Já a reometria rotacional mostrou-se sensível para identificar e diferenciar a cinética de mistura das argamassas colantes ACI e ACIII. Os resultados indicaram que o tempo de mistura de 150 segundos foi eficiente e suficiente para homogeneizar e estabilizar as argamassas testadas, e que a argamassa do tipo ACI apresenta maior dificuldade de mistura e resulta em uma suspensão com maior viscosidade e tensão de escoamento do que a argamassa ACIII. Por fim, a aplicação dos métodos de caracterização reológica em argamassas ACI compostas por areias com morfologias diferentes, indicou que o método de Squeeze Flow mostrou ser sensível para diferentes teores de água, em argamassas compostas por areia artificial. As curvas de carga de compressão da argamassa ACI com areia artificial mostraram serem superiores às formuladas argamassas com areia natural, indicando que, com a mesma proporção de insumos e teor de água (volume), as argamassas não possuem perfis reológicos similares. / Adhesive mortars are products constituted of natural or artificial sand, binder (cement) and chemical additives which serve as an adhesive for laying floor and wall tiles. From the rheological point of view, the adhesive mortar is a multiphase material consisting of a paste that coats mineral aggregates. Currently, the only test done is the slip test, which has low cost and has a relatively easy execution. The disadvantage of this method is not to have a good repeatability and is not sufficient to evaluate products in fresh state. Thus, techniques of rheologic characterization (flow squeeze, pull out flow and rotational rheometry) were applied as technologic alternatives for evaluation of adhesive mortars. However, the potential of the traditional configuration of the Squeeze Flow test and rotational rheometry were not explored in this type of product due to the requirement of configuration settings. The purpose of this dissertation is to apply advanced methods for rheological characterization of adhesive mortars in order to identify important characteristics of fresh-state application; evaluation of the influence of the squeeze-flow experimental method (mainly due to configuration and parameters); applied rheometry techniques to evaluate the mixing energy; and to evaluate the adhesiveness of fresh mortars. The evaluation of the configuration and parameters of the Squeeze Flow and Pull Out Flow showed that the methods were sensible enough to differentiate mortars in the same way that is perceived in practice: ACIII has greater consistency than ACI, also shows that are sensitive to different rates of displacement, water content and morphology of aggregates. The mixing and rotational rheometry showed that the method is sensitive to identify and differentiate the kinetics of mixing for ACI and ACIII mortars. The results indicate that the mixing time of 150 seconds was effective to homogenize and disperse the mortars. The mixing and flow torque values are higher for ACI than for ACIII, indicating that ACI is more difficult to be mixed and has a higher viscosity and yield stress than ACIII.