<p>The study focused on examining the effects of using nanoadditives (nano-TiO2 and colloidal silica) on the hydration kinetics, microstructure, mechanical properties, and durability of concretes, especially those containing fly ash and slag and cured at low (4°C) temperature. </p> <p>The results of the Vicat and isothermal calorimetery (IC) tests suggest that the addition of nano-TiO2 accelerates the hydration process of pastes. In addition, the results of the thermogravimetric analysis (TGA) indicated that the addition of nano-TiO2 increased the amount of hydration products in the pastes, with more notable increases observed in fly ash pastes. Moreover, X-ray diffraction (XRD) results revealed that the addition of nano-TiO2 reduced the mean size of calcium hydroxide (CH) crystals.  </p> <p>The interfacial transition zone (ITZ) of concretes with nano-TiO2 was found to be less cracked and less porous when compared to that of concrete without nano-TiO2. Furthermore, the energy dispersive X-ray (EDX) analyses of the outer hydration products around partially hydrated cement particles in fly ash concretes with nano-TiO2 revealed reduction in the values of Ca/Si atomic ratios when compared to the reference fly ash concrete. The image analysis results of the concrete air void system indicated slightly reduced air content, increased specific surface area (SSA), and decreased spacing factor (SF) in concretes with added nano-TiO2. </p> <p>The addition of nano-TiO2 was also found to enhance the compressive and flexural strengths of mortars and concretes. Nano-TiO2 also improved the resistivity and formation factor values of concretes containing fly ash. Moreover, the total volume of pores, as well as the values of water absorption, were also reduced as a result of addition of nano-TiO2. This was true for all types of concretes (i.e., with or without SCMs). Finally, the use of nano-TiO2 seemed to be more beneficial with respect to improving the scaling and freeze-thaw resistance of fly ash concretes compared to cement-only and slag concretes. </p> <p>Concretes with added nanosilica (colloidal silica) also developed higher compressive and flexural strengths when compared to reference concrete. Moreover, the total pores and permeability of concretes decreased due to the addition of nanosilica while the improvement in scaling resistance of these concretes was only slight. Furthermore, concretes with nanosilica were found to have higher percentage of finer air voids compared to reference concretes. Finally, the ITZ of concretes with nanosilica was found to have fewer defects and cracks compared to the reference concrete. </p> <p>In summary, this dissertation presents the results of a study on the multi-scale behavior of nanomodified concretes with and without SCMs cured at both room and low temperatures. Knowledge gained from this study would be helpful in developing concretes with denser and less porous microstructure, a more refined and better-distributed air void system, improved strength, reduced permeability, and enhanced scaling and freeze-thaw resistance, especially in cases when involving the use of SCMs and exposure to low early-age temperatures.</p>

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No. of bitstreams: 2 Dissertação - Mayara Queiroz Moraes - 2012.pdf: 2306074 bytes, checksum: 39f99dfabbb79296b809313dd0730f16 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2012-12-11 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Unlike the silica fume, whose benefits on the properties of the concretes are already widely known, little is known regarding nanosilica. This research offers an analysis of the contribution of different types of nanosilica in mechanical characteristics and workability maintenance of concretes, as well as an evaluation of the behavior of these additions when subjected to steam curing. For this, there were compared among themselves laboratory test results in concretes with different characteristics and different purposes (one of them suitable for production at batching plants and the other for metering precast elements). The results confirmed advantages for the simple addition of nanossílica at mechanical properties of concretes for batching plants with strengths above 40 MPa (a/c<0.52), but showed that the most advantageous situation consists in adding it together with sílica fume, since the concrete with both additions exceeded the reference concrete above 36 MPa (a/c<0.615), which highlights the importance of combining pozzolanic effect of silica fume, the creation of nucleation sites caused by nanossílica and better packaging mix, size distribution generated by the two additions give the folder.Regarding the maintenance of workability, the nanosilica dispersed in superplasticizer demonstrated satisfactory performance. In the analysis of concretes for precast elements, the addition of nanosilica dispersed superplasticizer and silica fume together was also the one which showed the best results in terms of resistance in 28 days of conventional curing. However, with steam curing, a great improvement was noted in the behavior of nanosilica dispersed in water, which had not achieved good results with the conventional cure, while nanosilica dispersed in superplasticizer did not respond well to the process, possibly due to the shape of the polycarboxylate used in the dispersion of the particles. Probably, the nanosilica dispersed in water showed no significant pozzolanic activity levels, but with the rise of temperature and the agitation of the particles, the formation of nucleation sites was intensified. As the development of resistance in early ages, all additions had positive effects, but the best performance was observed on the concrete with the simple addition of nanosilica dispersed in superplasticizer. With this addition, the concrete has reached 40 MPa after only 12 hours of steam curing, within about four times lower than the reference concrete (44 hours), which suggests that its addition to the concrete could result in na almost four times greater productivity of a precast elements factory. / Ao contrário da sílica ativa, cujas vantagens nas propriedades do concreto já são amplamente conhecidas, pouco se sabe em relação à nanossílica. Esta pesquisa contempla uma análise da contribuição de diferentes tipos de nanossílica nas características mecânicas e de manutenção do abatimento de concretos, bem como uma avaliação do comportamento destas adições frente à cura térmica. Para isto, compararam-se entre si resultados de ensaios laboratoriais em concretos com diferentes traços e diferentes finalidades (produção em centrais dosadoras e fabricação de pré-moldados). Os resultados confirmaram vantagens para a adição simples de nanossílica quanto à resistência à compressão dos concretos para centrais com resistências acima de 40 MPa (a/c<0,52), mas mostraram que a melhor situação consiste na adição conjunta de sílica ativa e nanossílica, já que o concreto com a adição conjunta superou o de referência a partir de 36 MPa (a/c<0,615). Isso deixa clara a importância de aliar o efeito pozolânico da sílica ativa, a criação de pontos de nucleação ocasionada pela nanossílica e o melhor empacotamento da mistura, gerado pela distribuição granulométrica que as duas adições juntas conferem à pasta. Quanto à manutenção do abatimento, a nanossílica dispersa em aditivo superplastificante demonstrou desempenho satisfatório. Em relação aos concretos para pré-moldados, foi a adição conjunta de sílica ativa e nanossílica dispersa em superplastificante a que apresentou melhores resultados de resistência aos 28 dias de cura convencional. No entanto, com a cura térmica, notou-se melhora substancial do comportamento da nanossílica dispersa em água, que não havia atingido bons resultados com cura convencional, enquanto a nanossílica dispersa em superplastificante não respondeu bem ao processo, possivelmente por influência da forma do policarboxilato usado na dispersão das partículas. Provavelmente, a nanossílica dispersa em água não apresentou atividade pozolânica relevante, mas com a elevação da temperatura e a agitação das partículas, a formação de pontos de nucleação foi intensificada. Quanto ao desenvolvimento de resistências nas idades iniciais, todas as adições apresentaram efeitos positivos, mas o melhor desempenho foi observado no concreto com adição simples da nanossílica dispersa em superplastificante. Com ela, o concreto atingiu 40 MPa com apenas 12 horas de cura térmica, prazo quase quatro vezes menor do que o do concreto de referência (44 horas), o que leva a crer que sua adição ao concreto poderia implicar em uma produtividade quase quatro vezes maior de uma fábrica de elementos pré-moldados.

This diploma thesis deals with the study of isothermal crystallization of nanocomposite materials based on isotactic polypropylene (iPP) and nanosilica, depending on the volume fraction (0, 2, 4 and 6 %) and type of silica and the crystallization temperature. Fumed silica and four types of silica with different surface treatment were used as filler. The crystallization performed at temperatures 136, 138, 140 and 142 °C has been studied in-situ using polarized optical microscope and the crystallization rate was evaluated from the growing radius of spherulites. It can be stated that particles of silica have been inbuilt into the spherulites due to the linear growth of spherulites of all composite materials. The most significant increase of the crystallization rate of iPP was caused by fumed silica, the most significant decrease was caused by silica TS-720 at volume fraction 4 %. The crystallization rate (G) has been slightly increased with the increasing volume fraction of filler at 136 °C, the G slightly decreased at 138 °C and there was no trend of G for two higher temperatures. Also, it was not possible to exactly evaluate the influence of the surface treatments. The reason is the most probably uneven (non-homogenous) distribution of nanosilica as revealed thermogravimetric analysis. The crystallization kinetics was evaluated according to the Lauritzen-Hoffmann theory. The morphological part of the study showed that iPP was in ? and ß-structure and spherulites of ? phase were of the type I, II and mixed.

The work deals mainly with preparation protocol of nanocomposites. The task of this work is to study structural and procedural parameteres that control the dispersion of nanoparticles in polymer solution to be able to prepare desired spatial organization of nanoparticles. The work resolves the effect of various components such as polymer matrices, nanoparticles and solvent, in which matrices and nanoparticles are blended. Used components control final dispersion state of nanoparticles and it influences also properties of investigated materials such as glass transition temperature, stiffness and rheological properties.

Lead is a naturally occurring element that has high atomic weight (207u) and density (11.3 g/cm3). Their multiple industrial, domestic, agricultural, medical and technological applications have led to their wide distribution in the environment, raising concerns over their potential effects on human health and the environment. At present, extensive application of nanosilica in environmental pollution treatment has led to the development of silica extraction methodologies out of various chemical and waste products. In this study, nanosilica is synthesized by sol-gel method from tetraethoxysilane (TEOS) with base catalysts and volumetric ratio TEOS/C2H5OH/H2O/NH4OH: 5/30/1/1 and identified characteristics by some modern techniques such as Energy-dispersive Xray spectroscopy (EDX), Fourrier Transformation Infrared (FTIR) and X-ray diffraction (XRD), Scanning electron micrograph (SEM), field emission scanning electron microscopy (FESEM). The results showed that the prepared SiO2 nanoparticles were amorphous phase with the average size about 60-100 nm and can be used as an immediately utilization for lead treatment. At the pH of 5, shaking within 1 hours with speed 150rpm/min, lead treatment efficiency is 96.17% for initial Pb2+ concentration 10 mgPb2+/L. Maximum adsorption concentration Qmax = 30.3mg/g, and adsorbent and adsorbate constant b = 0.868 L/g. Therefore, extracted nanosilica from TEOS has high lead treatment efficiency. In addition, synthesis nanosilica from rice husk with similar characteristics is a new research approach to improve application and economic value of the material. / Chì là nguyên tố tự nhiên có khối lượng nguyên tử cao(207 đvC), tỉ trọng lớn (11,3 g/cm3) và được ứng dụng phổ biến trong công nghiệp, nông nghiệp, sinh hoạt, y tế và công nghệ. Việc sử dụng rộng rãi chì trong nhiều lĩnh vực làm tăng mối quan ngại về tác động tiềm tàng của chúng đối tới sức khỏe con người và môi trường. Hiện nay việc áp dụng rộng rãi nanosilica vào xử lí ô nhiễm môi trường đã và đang dẫn đến sự phát triển của các phương pháp tách chiết silica từ hóa chất và các phế phụ phẩm. Trong nghiên cứu này, nanosilica được tổng hợp bằng phương pháp sol-gel từ tetraetoxysilan (TEOS) với xúc tác bazo theo tỷ lệ thể tích TEOS/C2H5OH/H2O/NH4OH là 5/30/1/1 và xác định các đặc tính bằng một số kỹ thuật hiện đại như phổ tán sắc năng lượng tia X (EDX), quang phổ hồng ngoại (FTIR) và nhiễu xạ tia X (XRD), kính hiển vi điện tử quét (SEM), kính hiển vi điện tử quét phát xạ trường (FESEM). Kết quả cho thấy các hạt nano SiO2 tách chiết được có pha vô định hình với kích thước trung bình khoảng 60-100 nm và được sử dụng trực tiếp cho xử lí chì. Tại điều kiện pH=5, lắc trong 1 giờ với tốc độ 150 vòng/phút, hiệu quả xử lý chì đạt 96,17% đối với nước nhiễm kim loại chì có nồng độ ban đầu là 10mgPb2+/L. Lượng hấp phụ cực đại Qmax = 30,3mg/g; hằng số đặc trưng của chất hấp phụ và chất bị hấp phụ b = 0,868L/g. Như vậy, hiệu quả xử lý kim loại chì của vật liệu nano silica được tổng hợp từ TEOS là rất cao. Bên cạnh đó, nghiên cứu chế tạo nanosilica từ vỏ trấu với các đặc tính tương tự là một hướng đi mới giúp nâng cao tính ứng dụng và giá trị kinh tế của vật liệu.

Made available in DSpace on 2016-12-08T17:19:23Z (GMT). No. of bitstreams: 1 Andrea Luciane M Soares.pdf: 1356785 bytes, checksum: 08654c7f08e5db11d8746af3551cd3ed (MD5) Previous issue date: 2014-07-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This work investigates the effect by partial replacement of nanosilica (nS) of Portland cement on the mechanical, physical, chemical and microstructural Portland cement mortar properties. For better understanding of the effects and a more detailed analysis of the results, the 33-1 fractional factorial design to design of experiments was used with three factors, each at three levels: nS content cement replacement (1, 2 and 3wt. %), water/cement ratio (1.1, 1.4 and 1.7 weight) and the aggregate/cement ratio (7.04 factor, 8.53 and 10.05 weight). The processing of the nine mortar mixtures was performed according to standards of the manufacture of such construction materials (composition, mixing, molding, curing and specimen preparation). Mechanical properties were evaluated in the fresh state (flow table) and in the hardened state (compressive strength at 7, 28 and 90 days of curing). In order to correlate the compressive strength with the microstructural characteristics, physic, chemical and microstructural characterization was performed. X-ray diffraction (XRD), infrared spectroscopy (FTIR), thermal (TG/DTA) and scanning electron microscopic with energy-dispersive X-ray spectrometry (SEM/EDS) analyses were used on selected samples. The use of fractional factorial design and the response surface methodology was found to be in the design the experimental and statistical analyses. The addition of nS affects the mechanical properties of mortars, both in the fresh, and in the hardened state. Materials with adequate workability for use in construction industry (consistency of 230 ± 10 mm) and high compressive strength after 7 (&#8805; 3 MPa) and 28 days of curing (&#8805; 6 MPa) were obtained with the following composition: 1.5 wt. % nS, 1.3 water/cement ratio and aggregate/cement ratio kept constant of 10.1. The physical-chemical and microstructural characterization showed that nS contributes to improve the packing of the amorphous calcium silicate hydrate (C-S-H) and crystalline phases matrix and aggregate. Moreover, nS participates in the hydration reactions of Portland cement due to its reaction with calcium hydroxide. Thus, a more cohesive matrix and less calcium hydroxide contributes to lower porosity, thus reducing permeability, which contributes for better durability of the mortars containing nS. / Este trabalho investiga o efeito da substituição parcial de cimento Portland por nanosílica (nS) nas propriedades mecânicas, físico-químicas e microestruturais de argamassas de cimento Portland. Para melhor compreensão dos efeitos e uma análise mais detalhada dos resultados, foi usado o planejamento fatorial fracionado 33-1 para projeto dos experimentos. No projeto foram utilizados três fatores, cada qual em três níveis: o teor de nS em substituição ao cimento (1%, 2% e 3% em massa), a proporção de água/cimento (1,1; 1,4 e 1,7 em massa) e o fator agregado/cimento (7,04; 8,53 e 10,05 em massa). O processamento das nove misturas de argamassas foi realizado de acordo com as normas de fabricação desses materiais de construção civil (pesagem, mistura, moldagem, cura e preparação de corpos de prova). Propriedades mecânicas foram avaliadas no estado fresco (índice de consistência) e no estado endurecido (resistência mecânica à compressão em 7, 28 e 90 dias de cura). Com o objetivo de correlacionar a resistência à compressão com as características microestruturais, foi realizada a caracterização físico-química e microestrutural, por meio de análises de raios X (DRX), espectroscopia de infravermelho por transformada de Fourier (FTIR), análises térmicas (TG) e análise térmica diferencial (ATD) e de microscopia eletrônica de varredura (MEV/EDS) em amostras selecionadas. O uso do projeto fatorial fracionado se mostrou eficiente para o planejamento experimental e análises estatísticas juntamente com o uso da metodologia de superfície de resposta. A adição de nS nas argamassas afeta as propriedades mecânicas das argamassas, tanto no estado fresco, como no endurecido. Materiais com trabalhabilidade adequada para uso na construção civil (índice de consistência de 230 ± 10 mm) e elevada resistência à compressão após 7 (&#8805; 3MPa) e 28 dias de cura (&#8805; 6 MPa) foram obtidas com as seguintes composições: 1,5% de nS, 1,3 água/cimento e 10,1 agregado/cimento. A caracterização físico-química e microestrutural mostrou que a nS contribui para melhorar o empacotamento da matriz formada pelo silicato de cálcio hidratado amorfo (C-S-H), fases cristalinas e os agregados. Além disso, a nS participa das reações de hidratação do cimento Portland, por meio do consumo de hidróxido de cálcio. Dessa forma, uma matriz mais coesa e menos hidróxido de cálcio contribui para uma menor porosidade, reduzindo a permeabilidade, que se traduz numa melhor durabilidade das argamassas contendo nS.

This work deals with the study of the influence of metallocene type polypropylene (mPP) molecular weight on isothermal crystallization of its nanocomposites filled with hydrophobic and hydrophilic nanosilica (1 and 2 vol.%). Real amount of nanosilica was determined by thermogravimetry. Isothermal crystallization was performed on differential scanning calorimeter (DSC) at 119–125 °C and observed in-situ under optical polarizing microscope (POM) at 128 °C using hot stage. The increase of mPP crystallinity degree in time was determined on DSC and spherulite type and growth rate was determined using POM. Supramolecular surface structure of the original and isothermally crystallited nanocomposites was observed directly or after chemical etching (mixture of mineral acids with KMnO4) on confocal laser scanning microscope. The crystal structure of mPP was in all tested materials verified by X-ray diffraction.

Tato dizertační práce se zabývá přípravou a charakterizací nanokompozitních polymerních pěn se zaměřením na strukturu materiálu a aplikaci v 3D tisku. Cílem práce je studium materiálu s vysoce organizovanou hierarchickou strukturou – od nanoměřítka, přes mikroskopickou strukturu po makroskopická tělesa. V první části práce byly řešeny strukturní vlastnosti nanokompozitů připravených z polymerních skel roztokovou metodou. Byl hledán obecně platný trend, pomocí kterého by bylo možné předpovídat disperzi nanočástic v kompozitu. Ukázalo se, že řídícím faktorem může být závislost na rozdílu parametrů rozpustnosti polymeru a rozpouštědla. Tento poznatek byl ověřen na systémech obsahujících různé nanočástice, polymery a rozpouštědla. Se znalostí principů pro řízení struktury nanokompozitů byly připraveny nanokompozity impaktního polystyrenu plněného nanosilikou. Tyto nanokompozity posloužily jako základ pro přípravu polymerních nakompozitních pěn. Porézní struktury bylo dosaženo pomocí termálního chemického nadouvadla azodikarbonamidu. Z těchto materiálů byly extrudovány filamenty, které byly následně zpracovány pomocí 3D tisku do požadovaných tvarů a vypěněny. Výsledkem byla hierarchická struktura s organizací struktury od nano (organizace nanočástic), přes mikro (struktura dvoukomponentní polymerní směsi a struktura pěny) po makroměřítko (struktura pěny a design 3D tisku). Byl pozorován vliv nanočástic na strukturu a termální a mechanické vlastnosti polymerních pěn. Nanočástice fungují při tvorbě pěny jako nukleační činidlo, na jejich povrchu snadno dochází k tvorbě pórů, takže s obsahem nanočástic v materiálu bylo vytvořeno více menších pórů, což napomohlo k homogenitě pěnové struktury. Přítomnost nanočástic změnila povrchovou energii zrn nadouvadla, díky čemuž docházelo k jeho rozkladu za nižích teplot a pěnění bylo i rychlejší. Nanočástice mají zároveň potenciál vyztužit stěny pěny a zlepšit tak mechanické vlastnosti. 3D tisk je oblíbená a hojně rozšířená technika, díky své jednoduchosti je v mnoha laboratořích a zkušebnách, proto roste poptávka po filamentech se speciálními vlastnostmi. Materiál vyvinutý v této dizertační práci je v podstatě hotovým a charakterizovaným produktem, který by mohl přispět k uspokojení této pohledávky.