This work presents an in-depth study of the crystal structures and hydrogen sorption potential of the Li - N - H and Li - Na - N - H systems. The structures of the materials have been studied using X-ray and neutron diffraction, Raman spectroscopy and inelastic neutron scattering. The behavior of the materials during heating was studied using variable temperature X-ray diffraction, intelligent gravimetric analysis in conjunction with neutron diffraction, intelligent gravimetric analysis combined with mass spectrometry and differential scanning calorimetry. The role of cation disorder in the Li - N - H (D) system has been explored, indicating that crystallographic ordering of the Li⁺ ions within lithium amide and lithium imide significantly affects the hydrogen sorption properties of the materials. Order-disorder transitions were observed both during hydrogen desorption from ordered LiNH₂ and during deuterium adsorption on ordered Li₂ND. Such transitions were not observed in disordered samples of the materials. The intrinsic disorder and the stoichiometry of Li - N - H(D) materials was shown to depend strongly on the techniques used during their synthesis. Studies regarding the synthesis, crystal chemistry and decomposition properties of the mixed Li / Na amides are presented. Two distinct mixed Li / Na amides of formulae Li₃Na(NH₂)₄ and LiNa₂(NH₂)₃ were observed in the LiNH₂ / NaNH₂ phase space. Na was also seen to be soluble in LiNH₂, forming sodium-doped LiNH₂ . Li₃Na(NH₂)₄ and Na-doped LiNH₂ were found to exhibit significant cation non-stoichiometry, whereas LiNa₂(NH₂)₄ was shown to exist as a line phase material. Thermogravimetric and calorimetric studies of the mixed Li / Na amides suggested that these materials decompose primarily with loss of H₂.

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Diferentes vidros alcalinos têm sido desenvolvidos para serem usados como eletrólitos sólidos na fabricação de baterias e em sensores químicos devido a sua elevada condutividade iônica. Entretanto, um efeito deletério para os dispositivos surge quando dois íons alcalinos distintos se encontram em uma mesma matriz vítrea. O fenômeno conhecido na literatura como efeito dos alcalinos mistos (mixed-alkali effect (MAE), em inglês) provoca uma variação não-linear em certas propriedades físicas, especialmente na condutividade elétrica, levando ao aparecimento de um profundo mínimo (ou máximo, dependendo da propriedade em estudo), à medida que a concentração relativa dos dois íons alcalinos presentes na rede vítrea varia. O MAE foi descoberto há mais de 100 anos e até hoje a sua real origem não é conhecida. As pesquisas ganharam um novo impulso com a necessidade de miniaturizar e aumentar a eficiência das baterias, para atender a demanda dos novos equipamentos eletrônicos, e com o desenvolvimento da computação, especialmente dos programas de modelagem e dinâmica molecular. Neste trabalho o objetivo foi produzir vidros boratos dos sistemas 50B2O315PbO(35-x)Li2OxNa2O e 50B2O315PbO(35-x)LiFxNaF e determinar a ocorrência e a intensidade do MAE, procurando correlacionar com a possível mudança da estrutura local. Os vidros foram produzidos pelo método de fusão/moldagem em atmosfera aberta. O caráter não-cristalino foi determinado por difração de raios X e a caracterização estrutural foi realizada utilizando-se das técnicas espectroscópicas vibracionais de Infravermelho (IV) e Raman. O estudo das propriedades físicas dos vidros foi realizado mediante a utilização das técnicas de espectroscopia de impedância (caracterização elétrica), calorimetria exploratória diferencial (determinação dos eventos térmicos) e pelo método de Arquimedes (obtenção da densidade). / Different alkali glasses have been developed because exhibit a high ionic conductivity and can be used as solid electrolytes in the fabrication of devices such as batteries and chemical sensors. However, a deleterious effect emerges when two alkali ions are present in the same glassy matrix. The phenomenon, named of the mixed alkali effect (MAE), causes a nonlinear variation of certain physical properties, especially for the electrical conductivity, with the emergence of a deep minimum (or maximum, depending of the property under study). The effect was discovered more than 100 years ago and even today its real origin remain unknown. The research gained new impetus due to need to miniaturize and to increase the efficiency of the batteries to answer the demands of new electronic equipment and with the development of computing, especially of the modeling and dynamic molecular softwares. In this work the goal was to produce the borate glass systems 50B2O315PbO(35-x)Li2OxNa2O and 50B2O315PbO(35-x)LiFxNaF and to determine the occurrence and intensity of the MAE, seeking to correlate with the possible change of the local structure. The glasses were produced by melting/modeling method in open atmosphere. The structural characterization was performed using Infrared (IR) and Raman vibrational spectroscopies. The study of the physical properties was carried out by impedance spectroscopy (electrical characterization), differential scanning calorimetry (to get the thermal events) and Archimedes method (to obtain the density).

The use of fly ash as a supplementary cementitious material (SCM) has increased in the last century due to its various environmental benefits as a recycled product. Within the last 60 years, it has been found that it can be used to effectively control damage induced by Alkali-Silica Reaction. However, it is not completely understood how to properly assign a dosage of fly ash to control the reaction. This depends greatly on the fly ash characteristics (e.g. composition, particle size, and reactivity), the reactivity of the aggregate (e.g. high to low reactivity level) and the environmental exposure conditions. The characteristics of the fly ash depend on the coal source being burned and the burning conditions that result in the fly ash formation. A major concern when supplementing cement with fly ash for ASR mitigation is the effect of the alkali contribution of the fly ash to the concrete pore solution. Current test methods cannot accurately determine the alkali contribution of fly ashes and there is no standardized test method to doing so. When contributed by the implementation of a SCM, alumina has been found to play a role in the ability of an SCM to mitigate ASR-induced damage. It has been observed that fly ashes containing higher levels of alumina (18-25%) tend to improve concrete durabilty more effectively when compared to fly ashes with lower levels of alumina. Additionally, the use of metakaolin, which is composed of 45-50% alumina, has been found to lessen expansion with a lower percentage of cement replacement than would be required if fly ash is used. Furthermore, the use of fly ash with another SCM material, a high quality ultra-fine fly ash or alumino-siliceous metakaolin, in ternary blends may improve the performance of fly ash resulting in a broadening of the spectrum of SCMs usable for ASR mitigation. For successful use of SCMs, it is important to develop an understanding of the alkalisilica reaction and the ability of such SCMs to control expansion. This report provides an overview of alkali-silica reaction and the use of fly ash and metakaolin as SCMs to mitigate expansion due to the reaction, with an emphasis on the role of alumina when contributed from the two materials. / Graduation date: 2012

This research develops two novel experimental techniques based on nonlinear acoustics/ultrasound to provide an ultra-accelerated characterization of alkali-reactivity of aggregates. Alkali-silica reaction (ASR) is a deleterious reaction occurring between reactive siliceous minerals present in some aggregates and alkalis mainly contributed by the cement, but also present in some deicing chemicals. With increasing reports of ASR-induced damage in transportation structures, there is a critical need for fast and reliable test methods for the screening of aggregates and aggregate/paste combinations. Currently, the accelerated mortar bar test (AMBT), which measures expansion, is the most commonly used test method. Also used is the concrete prism test (CPT), another expansion-based method, which requires at least one year testing time, limiting the practical utility of this method. In addition, petrographic analysis can be performed to identify potentially reactive minerals in aggregates but requires training and may not be appropriate for assessment of aggregate/paste combinations. Finally, linear acoustic methods such as wave speed and attenuation measurements can be used for the assessment of ASR, but the sensitivity of linear acoustic methods to ASR-induced damage is considered to be relatively low. Therefore, critical limitations exist in the existing test methods. In light of recent advances in nonlinear acoustics (which are more sensitive to small-scale damage than linear acoustics), the purpose of this research is the development and assessment of an accelerated method for evaluating the potential for alkali reactivity in aggregate and aggregate/paste combinations by combining advanced ultrasonic methods with standard test procedures. In fact, two nonlinear acoustic methods are developed under this research - nonlinear wave modulation spectroscopy (NWMS) and nonlinear impact resonance acoustic spectroscopy (NIRAS) - and are used to characterize the changes in material nonlinearity as a result of the progressive ASR damage during the standard mortar bar and concrete prism testing. Following the AMBT and CPT, nonlinear acoustic techniques are applied to both mortar bars and concrete prism samples. Nonlinearity parameters are defined as the indicator of growing ASR damage, and measurement results clearly show that these nonlinearity parameters are more sensitive to the ASR damage than the linear parameters used in the linear acoustic measurements, particularly at early ages. Different aggregates with varying alkali-reactivity are effectively distinguished with the proposed experimental techniques in a timely manner, particularly for those aggregates with similar levels of reactivity, as determined by AMBT. The effect of a Class C fly ash addition on nonlinear properties was also investigated using the NIRAS measurements through a comparison of test results between mortar samples blended with fly ash and without fly ash. As complementary supports of the experimental results, petrographic analyses and theoretical modeling are also performed, and these results are well correlated with results from the NWMS and NIRAS techniques. Through a comparison with results from accompanying expansion measurements and linear acoustic methods, the proposed nonlinear acoustic techniques show their advantages to accelerate the assessment of alkali-reactivity of aggregates. Under AMBT, reactive aggregates were identifiable as early as a few days of testing. With CPT, reactive aggregates were differentiated as early as a few weeks. Overall, the coupling of the developed nonlinear test methods with standard expansion tests suggests that test durations could be potentially reduced by half, especially for AMBT tests.

This research focuses on the characterization of damage accumulation in concrete specimens. Specifically, a nonlinear vibration technique is used to characterize the damage introduced by ongoing alkali-silica reactions (ASR). The nonlinear resonance testing consists of an analysis of the frequency response of concrete specimens subjected to impact loading. ASR introduces a third gel like phase, which can be expansive in the presence of moisture. The result of ASR is the formation of microcracks and debonding between aggregate and cement phases. Collectively, these changes act to increase the specimens' nonlinearity. As a result, it is found that the concrete samples exhibit nonlinear behavior; mainly a decrease in resonance frequency with an increasing level of excitation strain. The relationship between the amplitude of the response and the amount of frequency shift is used as a parameter to describe the nonlinearity of the specimen. The specimens used in this research are of varying reactivity with respect to ASR, which is induced in accordance with ASTM C 1293. The level of nonlinearity is used as a measure of damage caused by the progress of ASR throughout the one year test duration. These nonlinear resonance results are compared to the traditional measures of expansion described in the standard. The robustness and repeatability of the proposed technique is also investigated by repeated testing of samples assumed to be at a specific damage state. Finally, a petrographic staining technique is used to complement nonlinearity measurements and to further gain understanding of ASR. The results of this study show that the proposed nonlinear resonance methods are very sensitive to microstructural changes and have great potential for quantitative damage assessment in concrete.

Diferentes vidros alcalinos têm sido desenvolvidos para serem usados como eletrólitos sólidos na fabricação de baterias e em sensores químicos devido a sua elevada condutividade iônica. Entretanto, um efeito deletério para os dispositivos surge quando dois íons alcalinos distintos se encontram em uma mesma matriz vítrea. O fenômeno conhecido na literatura como efeito dos alcalinos mistos (mixed-alkali effect (MAE), em inglês) provoca uma variação não-linear em certas propriedades físicas, especialmente na condutividade elétrica, levando ao aparecimento de um profundo mínimo (ou máximo, dependendo da propriedade em estudo), à medida que a concentração relativa dos dois íons alcalinos presentes na rede vítrea varia. O MAE foi descoberto há mais de 100 anos e até hoje a sua real origem não é conhecida. As pesquisas ganharam um novo impulso com a necessidade de miniaturizar e aumentar a eficiência das baterias, para atender a demanda dos novos equipamentos eletrônicos, e com o desenvolvimento da computação, especialmente dos programas de modelagem e dinâmica molecular. Neste trabalho o objetivo foi produzir vidros boratos dos sistemas 50B2O315PbO(35-x)Li2OxNa2O e 50B2O315PbO(35-x)LiFxNaF e determinar a ocorrência e a intensidade do MAE, procurando correlacionar com a possível mudança da estrutura local. Os vidros foram produzidos pelo método de fusão/moldagem em atmosfera aberta. O caráter não-cristalino foi determinado por difração de raios X e a caracterização estrutural foi realizada utilizando-se das técnicas espectroscópicas vibracionais de Infravermelho (IV) e Raman. O estudo das propriedades físicas dos vidros foi realizado mediante a utilização das técnicas de espectroscopia de impedância (caracterização elétrica), calorimetria exploratória diferencial (determinação dos eventos térmicos) e pelo método de Arquimedes (obtenção da densidade). / Different alkali glasses have been developed because exhibit a high ionic conductivity and can be used as solid electrolytes in the fabrication of devices such as batteries and chemical sensors. However, a deleterious effect emerges when two alkali ions are present in the same glassy matrix. The phenomenon, named of the mixed alkali effect (MAE), causes a nonlinear variation of certain physical properties, especially for the electrical conductivity, with the emergence of a deep minimum (or maximum, depending of the property under study). The effect was discovered more than 100 years ago and even today its real origin remain unknown. The research gained new impetus due to need to miniaturize and to increase the efficiency of the batteries to answer the demands of new electronic equipment and with the development of computing, especially of the modeling and dynamic molecular softwares. In this work the goal was to produce the borate glass systems 50B2O315PbO(35-x)Li2OxNa2O and 50B2O315PbO(35-x)LiFxNaF and to determine the occurrence and intensity of the MAE, seeking to correlate with the possible change of the local structure. The glasses were produced by melting/modeling method in open atmosphere. The structural characterization was performed using Infrared (IR) and Raman vibrational spectroscopies. The study of the physical properties was carried out by impedance spectroscopy (electrical characterization), differential scanning calorimetry (to get the thermal events) and Archimedes method (to obtain the density).

Atomic precision measurements provide a strong testing ground for new theoretical ideas and fundamental laws of physics. Measurement of the Lamb shift in the hydrogen atom is one of the best examples towards this -it resulted in the birth of QED in 1949 by Dyson, Feynman, Schwinger and Tomonaga. The precision measurements of the hyperfine structure in hydrogen and deuterium by Nafe, Nelson and Rabi indicated that the g-factor for the electron was not exactly 2 as predicted by Dirac, but slightly greater, due to QED effects. Thus the precision measurements are indispensable not only for developing new theory but also for the verification and fine-tuning of theoretical parameters. Precision measurement of hyperfine structure provide valuable information about the nucleus structure, which is helpful in fine tuning of atomic wave-functions used in theoretical calculations. The aim of the work reported in this thesis is the measurement of hyperfine frequency and the observation of hyperfine structure constant in alkali atoms and in Yb atom. This thesis is organized as follows. In Chapter 1, an introduction to the importance of Alkali atoms and Yb atom in the field of precision measurement will be discussed. The scope of this thesis is also discussed in this chapter. In Chapter 2, an introduction to hyperfine structure starting from the beginning of the atomic physics will be discussed. We have discussed about the LS-coupling, jj-coupling, and the influence of the atomic nucleus on atomic spectra. We have also discussed the Zeeman effect and Doppler broadening. In chapter 3, the detail of experimental technique used in this thesis as copropagating satabs, hyperfine frequency measurement using AOM scan, AOM lock and ring cavity has been discussed. Experimental technique to observe the EIT signal in two electron Yb system has been discussed, which can be improved the precision in frequency measurement because of the narrow line-width. In chapter 4, we describe the co-propagating saturated-absorption spectroscopy and its application in frequency measurement. Saturated-absorption spectroscopy (satabs) in a vapor cell is a standard technique used to stabilise the laser frequency. In normal satabs we are getting some extra peaks known as a crossover peaks because laser interact with different velocity group in a vapor cell. In satabs the crossover peaks are stronger and often swamp the true peaks. So we have developed a technique of co-propagating satabs to remove the spurious peak, which has several advantages over conventional satabs. The co-propagating satabs signal appears on a flat background (Doppler-free) with good signal-to-noise ratio and does not have the problem of crossover resonances in between hyperfine transitions. We have adapted this technique to make measurements of hyperfine intervals by using one laser along with an acousto-optic modulator (to produce the scanning pump beam). In chapter 5, we describe the measurement of the hyperfine interval in the 2P1/2 state of 7Li using the SAS technique in hot Li vapor. This technique produces spurious ground crossover resonances that are more prominent that the real peaks. So we have used this ground crossover to measure the hyperfine interval using AOM locking technique. We have developed a technique to measure the absolute frequencies of optical transitions by using an evacuated Rb-stabilized ring-cavity resonator as a transfer cavity. In chapter 6, we study the wavelength-dependent errors due to dispersion at the cavity mirrors by measuring the frequency of the same transition in the Cs D 2 line (at 852 nm) at three cavity lengths. The spread in the values shows that dispersion errors are below 30 kHz, corresponding to a relative precision of 10−10 . We give an explanation for reduced dispersion errors in the ring-cavity geometry by calculating errors due to the lateral shift and the phase shift at the mirrors, and show that they are roughly equal but occur with opposite signs. In chapter 7, we describe precision measurement of hyperfine structure in the 3P2 state of 171,173Yb, and see an unambiguous signature of the magnetic octupole coefficient C in 173Yb. The frequencies of the 3P23S1 transition at 770 nm → are measured using a Rb-stabilized ring-cavity resonator with an accuracy of 200 kHz. In 173Yb we obtain the hyperfine coefficients as A = − 742.11(2) MHz and B = 1339.2(2) MHz, which represent a two orders-of-magnitude improvement in precision, and C = 0.54(2) MHz. Using atomic-structure calculations for two-electron atoms, we extract the nuclear moments quadrupole Q =2.46(12)b and octupole Ω = 34.4(21)b × µN . The observation of nuclear octupole moment in two-electron atoms, to the best of our knowledge, was never reported before. In 171Yb we obtain the hyperfine coefficient A = 2678.49(8) MHz. Using this measurement as well as the previous measurement of A coefficient from our lab, we have compared the hyperfine anomalies for 1P1, 3P1 and 3P2 states. In chapter 8, we describe the EIT in two electron system of 174Yb from 1S0(Fg = 0) 3P1(Fe = 1). We have observed the EIT in degenerate two level system and → after lifting the degeneracy by applying the magnetic field we are getting five peaks. We have also observed the EIT in 173Yb. In 173Yb there are three degenerate two level system Fg =5/2 Fe =3/2, Fg =5/2 Fe =5/2, Fg =5/2 Fe =7/2. →→→ We have observed the same type of EIT signal for all the three transitions Fg = FFe = F, ±F + 1. → In Chapter 9, we give a broad conclusion to the work reported in this thesis and suggest future avenues of research to continue the work started here.

Abstract About 4 Mt of ladle slag is generated in steelmaking processes in Europe per year, a large proportion of which (80%) is placed in landfills or stored. This pattern is expected to continue without further research for their valorisation due to increasing demand for quality steel products worldwide. Ladle slag (LS) produced in Finland possesses large amounts of calcium and aluminium and mineralogical phases which can exhibit cementitious capabilities and can be utilized in applications where expensive commercial cements are currently being used. The aim of this thesis is to investigate the properties of ladle slag in different activation pathways, including alkali activation and use as a hydraulic binder with gypsum. The results showed that ladle slag can be used alone as a precursor in alkali activation or as the sole binder or a co-binder with gypsum in hydraulic binding. Depending on the activation pathway, compressive strength between 35–92 MPa can be achieved after 28 days. The reaction properties of alkali activated ladle slag are characterized, and it is confirmed through X-ray diffraction (XRD) that the reaction product after alkali activation is mainly an x-ray amorphous (calcium aluminate silicate hydrate-like) phase. Characterization techniques (SEM, XRD, TGA and NMR) used to analyze the LS paste binder with just water showed the hydration products of ladle slag to be dicalcium aluminate octahydrate (C₂AH₈), tricalcium aluminate hexahydrate (C₃AH₆), gibbsite (AH₃) and stratlingite (C₂ASH₈) was also identified after a prolonged period of hydration. Furthermore, it was found that to minimize the conversion, the ideal water-to-binder ratio is 0.35. The conversion mechanism is reduced at this ratio and the strength is slightly affected. Another pathway that can be used to annul the conversion of calcium aluminate hydrates formed in LS paste is through the addition of gypsum to the LS paste system to produce an ettringite-rich binder (C₆A\(\bar{S}\)₃H₃₂). When ettringite is formed in place of calcium aluminate hydrates the strength increases, frost resistance is improved, and drying shrinkage is enhanced. Lastly, a potential application of ladle slag as a refractory material was also investigated. / Tiivistelmä Euroopassa syntyy vuosittain noin 4 Mt terästeollisuden sivutuotetta, JV-kuonaa, josta 80 % läjitetään tai kaatopaikoitetaan. Maailmanlaajuisesti syntyvän kuonan määrä tulee todennäköisesti kasvamaan laadukkaiden terästuotteiden ennustetun kysynnän kanssa. Tämän vuoksi kuonalle tulisi löytää hyötökäyttökohde, jota vältyttäisiin läjitykseltä. JV-kuona sisältääkin suuria määriä kalsiumia ja alumiinia sekä mineralogisia faaseja, joilla on sementtimäisiä ominaisuuksia. Näin kuonaa voitaisiin käyttää sovelluksissa, joissa tällä hetkellä käytetään kalliita kaupallisia sementtejä. Tämän väitöskirjan tarkoituksena oli tutkia JV-kuonan ominaisuuksia sementtimäisenä sideaineena alkali-aktivoinnissa sekä hydraulisena sideaineena yksinään että kipsin kanssa sekoitettuna. Väitöskirjan tulokset osoittivat, että JV-kuonaa voidaan käyttää prekursorina alkali-aktivoinnissa tai hydraulisena sideaineena pelkästään veden kanssa tai yhdessä kipsin ja veden kanssa. Saavutetut puristuslujuuset vaihtelivat 35 ja 92 MPa:n välillä, jotka vastaavat normaalin ja erityislujan betonin lujuuksia. JV-kuonan reaktiotuotteet alkali-aktivonnin jälkeen analysoitiin XRD- ja FTIR-analyyseillä. Tuloksista nähtiin, että alkali-aktivoinnin jälkeen reaktiotuote on sementin kaltainen kalsium-aluminatti-silikaati-hydraati (C-A-S-H) -tyyppinen faasi. XRD-, SEM-, TGA- ja NMR-analyysit osoittivat JV-kuonan hydrataatiotuotteiden olevan erilaisia kalsium-aluminaattihydraatteja (C₂AH₈, C₃AH₆, AH₃ ja C₂ASH₈). Tämän vuoksi työssä tutkittiin eri vesi–kuona-suhteita, ja havaittiin, että kun käytetään alhaista kuona-vesi –suhdetta (0,35), reaktiotuoteiden muutos vähenee ja lujuus paranee. Toinen tapa, jolla voidaan estää reaktiotuotteiden muuttuminen, on kipsin lisäys: lisäämällä kipsiä tuotetaan runsaasti ettringiittiä (C₆A\(\bar{S}\)₃H₃₂). Kun ettringiittiä muodostuu kalsium-aluminaattihydraattien sijaan, lujuus kasvaa, pakkaskestävyys paranee ja kuivumiskutistuma paranee. Väitöskirjan viimeisessä osiossa tutkittiin JV-kuonan mahdollista käyttöä tulenkestävänä materiaalina ja huomattiin, että sen tulenkestävyysominaisuudet vaihtelevat käytetyn aktivointityypin mukaan.

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