abstract: Nuclear magnetic resonance (NMR) is an important phenomenon involving nuclear magnetic moments in magnetic field, which can provide much information about a wide range of materials, including their chemical composition, chemical environments and nuclear spin interactions. The NMR spectrometer has been extensively developed and used in many areas of research. In this thesis, studies in two different areas using NMR are presented. First, a new kind of nanoparticle, Gd(DTPA) intercalated layered double hydroxide (LDH), has been successfully synthesized in the laboratory of Prof. Dey in SEMTE at ASU. In Chapter II, the NMR relaxation studies of two types of LDH (Mg, Al-LDH and Zn, Al-LDH) are presented and the results show that when they are intercalated with Gd(DTPA) they have a higher relaxivity than current commercial magnetic resonance imaging (MRI) contrast agents, such as DTPA in water solution. So this material may be useful as an MRI contrast agent. Several conditions were examined, such as nanoparticle size, pH and intercalation percentage, to determine the optimal relaxivity of this nanoparticle. Further NMR studies and simulations were conducted to provide an explanation for the high relaxivity. Second, fly ash is a kind of cementitious material, which has been of great interest because, when activated by an alkaline solution, it exhibits the capability for replacing ordinary Portland cement as a concrete binder. However, the reaction of activated fly ash is not fully understood. In chapter III, pore structure and NMR studies of activated fly ash using different activators, including NaOH and KOH (4M and 8M) and Na/K silicate, are presented. The pore structure, degree of order and proportion of different components in the reaction product were obtained, which reveal much about the reaction and makeup of the final product. / Dissertation/Thesis / Ph.D. Physics 2013

This thesis deals with development of shrinkage reducing admixtures designed for alkali activated materials based on blast furnace slag. The main task of this work is to select the most suitable shrinkage reducing admixture based on experiments, in which can be observed minimal shrinkage and at the same time it will not adversely affect the properties of alkali activated blast furnace slag. In the experimental part of the work, test beams containing shrinkage reducing admixtures were prepared, in which the shrinkage and loss of weight were measured. Moreover, the mechanical properties of individual beams, such as tensile strength and compressive strength, were measured. Next, the surface tension of individual shrinkage reducing admixtures was measured in a mixture with pore solution. The hydration process of alkali activated materials under the action of reducing shrinkage admixtures was monitored by calorimetric analysis. The microstructure of the prepared samples was observed by scanning electron microscopy.

Alkali-activated materials (AAM) are construction materials with great potential, especially for their environmental friendliness, but also due to their mechanical properties. Therefore, it is appropriate to pay further attention to these binders. This diploma thesis deals with monitoring the effectiveness of plasticizers in connection with the surface chemistry of the alkali-activated slag system. Sodium hydroxide and sodium water glass were used as alkaline activators for the preparation of alkali-activated blast furnace slag-based systems. To study the effectiveness of the lignosulfonate plasticizer, yield stress, heat flow, adsorption and zeta potential were monitored depending on the amount and time that the plasticizer was added to the system. The results show that the type of activator used in the mixtures plays an important role. NaOH-activated samples revealed the best efficiency of lignosulfonate plasticizers. A key factor in studying the behavior of the studied mixtures was the measurement of the zeta potential, which provided insight into the surface charge of blast furnace slag particles related to the ability of lignosulfonate to adsorb on grains of alkali-activated slag.

Combination of fine ground granulated slag with proper alkaline activator gives alkali-activated slag – a material with remarkable properties. Theoretical part of the thesis deals with summarizing basic informations about alkali-activated slag, its properties, production and utilization. It also follows research devoted to effects of curing of alkali activated slag and shrinkage-reducing admixtures on its properties. Objective of the experimental part is to determine the influence of curing conditions on the mechanical properties and microstructure of alkali-activated slag. These properties are also monitored in alkali-activated slag with carbon nanotubes and hydroxypropylmethylcellulose as an shrinkage-reducing admixtures.

Alkali activated materials could be suitable alternative to construction materials based on ordinary Portland cement (OPC). Therefore, it is advisable to pursue these binders further on. Aim of this thesis is to clarify the effect of lignosulfonate-based plasticizer and polycarboxylate-based superplasticizer on the behaviour and nature of alkali activated materials. For the purposes of studying the efficiency of plasticizing additives, the change of workability of alkali activated blast furnace slag in dependence on time, effect of additives on mechanical properties as well as, with usage of isothermal calorimetry, their impact on kinetics of solidification and hardening had been observed. The stability of the plasticizing admixtures in a high alkaline environment such as water glass and sodium hydroxide had been studied using infrared spectrometry. As a last step, X-ray photoelectron spectroscopy (XPS) had been used while clarifying the chemical changes in the structure of plasticizing additives after adsorption to blast furnace slag.

EU Sustainable Development Strategy planned to achieve improvement of life-quality by promoting sustainable production and consumption of raw materials. On November 2018, EU Commission presented a long-term strategy, aiming among others a climate-neutral economy by 2050. Cement production is contributing to 6-10% of the anthropogenic CO2 emissions. Thus, several strategies for total or partial replacement of Portland cement in concrete production have been developed. The use of supplementary cementitious materials (SCM) and alkali-activated materials (AAM) is considered the most efficient countermeasure to diminish CO2 emissions. The broadening of knowledge with particular attention to the sustainable goals is the primary requirement to be fulfilled when novel materials are investigated. This study aims to develop a novel clay-based binder that can be used as a sustainable alternative to produce SCM as well as AAM. Clay is a commonly occurring material, with large deposits worldwide. However, natural clay has a low reactivity and various compositions, depending, e.g. on the weathering conditions. The present research aims exactly at enhancing the reactivity of natural clays occurring in Sweden subjecting them to mechanical activation in a planetary ball mill. Ball milling (BM) is considered a clean technology able to enhance the reactivity of crystalline materials without resorting to high processing temperatures or additional chemicals. BM was able to induce amorphization in clay minerals and to transform the layered platy morphology to spherical shape particles. The efficiency of the process was strictly related to the used process parameters. Higher ball to processed powder (B/P) ratio, longer time of grinding and higher grinding speeds increased the degree of the obtained amorphization. However, an undesired extensive caking and agglomeration occurred in certain setups. The potential of activated clay as a SCM was investigated in specific case studies. The measured compressive strength results showed a direct correlation between the enhanced amorphization degree of the mechanically activated clay and the increased strength values. The pozzolanic activity was induced and enhanced after the mechanical activation of the clay. The reactivity was assessed by the strength activity index (SAI). Furthermore, preliminary tests have shown that the alkali activation of the processed clays produced solidified matrixes with considerable strength.

Le travail décrit dans ce manuscrit s’inscrit dans le cadre de la gestion de déchets nucléaires, de faible activité à vie longue (FA-VL), composés d’alliage de magnésium et de graphite, produits pendant l’exploitation de la première génération de réacteurs nucléaires en France. Il s’agit d’étudier la possibilité de leur immobilisation par cimentation et de comprendre le comportement des colis ainsi fabriqués tout au long de leur vie. Plusieurs mécanismes couplés sont à considérer : l’alliage de magnésium peut se corroder au sein de la matrice d’enrobage, en particulier lors du couplage galvanique avec le graphite. La croissance de produits de corrosion autour du métal et la restriction des déformations propres de la matrice cimentaire engendrent des contraintes à l’intérieur du matériau. La vérification de certaines exigences de sureté (stabilité dimensionnelle du colis et faible production d’hydrogène) nécessite donc le développement d’un outil numérique pouvant prédire le comportement mécanique des colis. En particulier, un mortier de laitier activé à la soude, qui présente un intérêt particulier, est examiné. Ce liant appartient à la famille des matériaux alcali-activés dont la modélisation numérique du comportement est peu abordée dans la littérature. La construction du modèle numérique passe ainsi par une large campagne expérimentale (caractérisation du comportement thermo-chemo-mécanique du mortier de laitier alcali-activé et de la corrosion du magnésium dans les matrices cimentaires) puis par un travail d’homogénéisation par éléments finis pour pouvoir déterminer les propriétés de l’ensemble (mortier + déchets) et mener des simulations à l’échelle du colis. Concernant le premier axe d’étude expérimentale, un faible échauffement accompagne l’avancement des réactions d’hydratation, ce qui est bénéfique vis-à-vis des contraintes internes résultantes de l’auto-restriction des déformations thermiques au sein des structures massives. Néanmoins, les déformations de retrait endogène montrent un développement important à long terme. Ceci peut générer des contraintes internes dans le colis (en présence de restrictions), mais la grande capacité de fluage du matériau empêche la fissuration. Concernant le deuxième axe d’étude expérimentale, le mortier de laitier activé est comparé avec deux autres mortiers à base de CEM I, pour évaluer le comportement à la corrosion de l’alliage de magnésium. Les observations microscopiques montrent que la corrosion galvanique de l’alliage est particulièrement agressive dans les mortiers à base de CEM I (corrosion localisée se manifestant par des creusements et des microstructures en feuillets) contre une corrosion uniforme, mais faible dans le mortier de laitier alcali-activé. La cinétique de corrosion est déterminée en utilisant des techniques gravimétriques et électrochimiques. Les résultats de ces deux types de mesure sont complémentaires et témoignent également d’une faible corrosion dans le mortier de laitier activé. De plus, ils montrent une certaine passivation du métal au-delà de 6 mois d’enrobage. Cette propriété spécifique du mortier de laitier activé peut être expliquée par une grande résistivité électrique par rapport aux mortiers de CEM I déterminée en analysant les données de spectroscopie d’impédence électrochimiques. Ensuite, des premières simulations simplifiées par éléments finis à l’échelle mésoscopique sont effectuées sur Cast3m, pour modéliser l’effet mécanique du développement de la corrosion sur le mortier d’enrobage. Plusieurs paramètres sont intégrés comme la cinétique de corrosion de l’alliage ainsi que la nature des produits formés et leurs propriétés mécaniques, identifiées par des observations MEB/EDS et nano-indentation. Les résultats indiquent que les contraintes générées dans la matrice d’enrobage n’entrainent pas d’endommagement. / The operation phase of the first generation of nuclear reactors in France has generated magnesium and graphite long lived low-level wastes (LLW-LL). Their conditioning in a hydraulic binder matrix is being addressed. In order to study the behavior of these packages, several coupled mechanisms have to be considered: the magnesium alloy can corrode within the encapsulating matrix, especially when galvanic coupling with the graphite occurs. The corrosion of the metal results in the development of corrosion products. The growth of corrosion products around the metal and the restriction of the hydraulic binder’s delayed strains may lead to the generation of internal stresses. The verification of certain safety requirements (dimensional stability of the package and low hydrogen production) is therefore essential. It requires the development of a numerical model able to predict the behavior of these packages.In particular, a sodium hydroxide activated blast furnace slag mortar is being addressed. It belongs to the family of alkali-activated materials for which the modelling of ageing behavior is rarely approached. Hence, the construction of the numerical model involves a large experimental campaign covering the thermo-chemo-mechanical behavior of the alkali-activated mortar and the corrosion of magnesium in hydraulic binders. Meso-scale homogenization calculations are undertaken in order to determine upscaled properties of the mix (matrix + wastes) and carry out simulations on the scale of the packages.Regarding the first experimental study axis, a relatively low hydration heat is measured. This is beneficial with respect to the internal stress generated from the self-restriction of the thermal strains within massive structures.Nevertheless, the materials undergoes a particular autogenous shrinkage strains showing an increase even at long term. However, its basic creep strains are shown to be important which could result in stress relaxation and avoids damage related to shrinkage restriction.Regarding the metal’s corrosion behavior in the alkali-activated mortar, it is compared to the one in two different ordinary Portland cement (OPC) based mortars. Microscopic observations are conducted on samples especially designed to monitor the galvanic corrosion of the alloy. They show the aggressiveness in OPC mortars (localized corrosion manifested by holes and layered microstructure) against limited homogeneous corrosion in alkali-activated mortar. Additionnaly, corrosion kinetics are determined using different experimental methods: mass loss and electrochemical measurements. The complementary results of these two types of measurements also show a low corrosion in the alkali-activated slag mortar with a passive state of the metal achived at 6 months of embedment. This advantage of slag mortar is explained by a high electrical resistivity with respect to OPC mortars, determined by electrochemical impedance spectroscopy.Finite element simulations are performed using Cast3m software on meso-scale in order to evaluate the mechanical effect of the corrosion layer development on the surrounding matrix. The corrosion kinetics of the alloy, the nature of corrosion products and their mechanical properties identified using SEM/EDS and nano-indentation techniques are implemented. The calculations indicate low stress generation in the alkali-activated mortar.

yes / The present paper reports the testing of 12 alkali-activated mortars and a control ordinary portland cement (OPC) mortar. The main aim is to develop cementless binder activated by sodium silicate powder. An alkali quality coefficient combining the amounts of main compositions of source materials and sodium oxide (Na2O) in sodium silicate is proposed to assess the properties of alkali activated mortars, based on the hydration mechanism of alkali-activated pastes. Fly ash (FA) and ground granulated blast-furnace slag (GGBS) were employed as source materials. The ratio of Na2O-to-source material by weight for different mortars ranged between 0.038 and 0.164; as a result, alkali quality coefficient was varied from 0.0025 to 0.0365. Flow loss of fresh mortar, and shrinkage strain, compressive strength and modulus of rupture of hardened mortars were measured. The compressive strength development of alkali activated mortar was also compared with the design equations for OPC concrete specified in ACI 209 and EC 2. Test results clearly showed that the flow loss and compressive strength development of alkali-activated mortar were significantly dependent on the proposed alkali quality coefficient. In particular, a higher rate of compressive strength development achieved at early age for GGBS-based alkali-activated mortar and at long-term age for FA-based alkali-activated mortar. In addition, shrinkage strain and modulus of rupture of alkali-activated mortar were comparable to those of OPC mortar.

This paper reports the development of an Alkali Activated Binder (AAB) with an emphasis on the performance and the durability of the AAB-matrix. For the development of the matrix, the reactive components granulated slag and coal fly ash were used, which were alkali activated with a mixture of sodium hydroxide (2 - 10 mol/l) and aqueous sodium silicate solution (SiO2/Na2O molar ratio: 2.1) at ambient temperature. A sodium hydroxide concentration of 5.5 mol/l revealed the best compromise between setting time and mechanical strengths of the AAB. With this sodium hydroxide concentration, the compressive and the 3-point bending tensile strength of the hardened AAB were 53.4 and 5.5 MPa respectively after 14 days. As a result of the investigation of the acid resistance, the AAB-matrix showed a very high acid resistance in comparison to ordinary Portland cement concrete. In addition, the AAB had a high frost resistance, which had been validated by the capillary suction, internal damage and freeze thaw test with a relative dynamic E-Modulus of 93% and a total amount of scaled material of 30 g/m2 after 28 freeze-thaw cycles (exposure class: XF3).

Made available in DSpace on 2017-07-21T20:43:50Z (GMT). No. of bitstreams: 1 Luiz Cezar Lima Junior.pdf: 4959123 bytes, checksum: 8ba169401ed3c8565f7d14d0d74e19c1 (MD5) Previous issue date: 2016-08-29 / Geopolymers, or ‘inorganic polymers’, considered an alternative cementing system to the convention Portland cement, are formed due to the dissolution, under a high alkali solution, of natural raw materials containing aluminosilicate species. The product of this reaction is the obtainment of a synthetic aluminosilicate product, manufactured under low temperature or even at room temperature. A wide range of materials can be used as precursors as well as alkali activators. The present work focuses on the obtainment of inorganic polymers with innovative precursors, based on different residues of several industrial sectors, such as glass manufacturing, ceramic claddings, and also with local minerals found in abundance on the region of the Campos Gerais. The development of an alternative cementing system will be directly applied on materials to be used as external cladding of steel/wood-based modular structures for residential/commercial buildings, replacing similar materials made from ordinary Portland cement, aiming and industrial application for this product. The obtained product presented similar/superior physical-mechanical properties when compared to its opponent products, with an average flexural strength of 11,73 MPa and a water absorption of 13,50%, being the first value intermediate and the second the best in comparison with commercial products. The use of temperature during curing cycle for increasing the properties of the geopolymeric cement was successfully tested, resulting on more dense and stable structures. Samples showed an increase in flexural strength from 1,83 MPa to 10,15MPa comparing curing cycles at room temperature and at 65ºC, which indicates that temperature works as a setting accelerator for the tested recipe of geopolymers. / Geopolímeros, ou ‘polímeros inorgânicos’, considerados um sistema cimentante alternativo ao cimento Portland convencional, são materiais formados a partir da dissolução de matérias-primas naturais à base de aluminossilicatos em uma solução alcalina. O resultado desta reação é a formação de um aluminossilicato sintético, produzido a baixas temperaturas ou mesmo sob temperatura ambiente. Diferentes matérias-primas naturais e sintéticas podem ser utilizadas como precursores e fonte de álcalis. O presente trabalho tem por objetivo o desenvolvimento de polímeros inorgânicos a partir de precursores inovadores, utilizando-se de resíduos de diversos setores da indústria, tais como da fabricação de vidro, da indústria de revestimentos cerâmicos, e também de insumos locais disponíveis em abundância na região dos Campos Gerais. O sistema cimentante obtido foi utilizado para a obtenção de placas de revestimento em construções em estrutura modular de aço ou madeira, substituindo produtos similares produzidos a partir de cimento Portland convencional, e visando uma aplicação industrial deste. O produto obtido apresentou propriedades físico-mecânicas semelhantes e até superiores às dos produtos concorrentes, com uma resistência à flexão média de 11,73 MPa e uma absorção de umidade média de 13,50%, sendo o primeiro valor intermediário e o segundo o melhor dentre os produtos comerciais. O uso de temperatura para aumento das propriedades físico-mecânicas do cimento geopolimérico foi testado com sucesso, resultando em estruturas mais compactas e estáveis. Houve um aumento de resistência mecânica de 1,83 MPa para 10,15 MPa comparando-se ciclos de cura sob temperatura ambiente e a 65ºC, indicando que a temperatura funciona como um acelerador de cura dos geopolímeros testados.