Medidas de Termoluminescência (TL), Luminescência Opticamente Estimulada (LOE), EPR (Ressonância Paramagnética de Elétron) e RL (Radioluminescência) foram obtidas de amostras de óxido de alumínio e óxido de alumínio dopado com magnésio. As amostras foram calcinadas em três diferentes temperaturas (1100, 1350 e 1600°C) para observar a variação do comportamento das propriedades luminescentes. Ao final, constatou-se que a temperatura de calcinação é um parâmetro de grande importância para a produção de materiais dosimétricos, pois a amostra com melhores resultados LOE foi o material sem dopante tratada a 1600°C. Em trabalhos anteriores, a composição de óxido de alumínio dopado com magnésio havia apresentado nanoestruturas de aluminato de magnésio, observadas através de Microscopia Eletrônica de Transmissão (MET), que influenciaram a sensibilidade do material à radiação. Amostras de aluminato de magnésio puro e dopado com terras raras foram obtidas na forma de pó e calcinadas a 1100, 1350 e 1600°C. Medidas de TL e LOE de amostras irradiadas com fonte de partículas foram analisadas e comparadas com resultados de EPR e Difração de Raios-X (DRX). Como resultado, foi concluído que, nas condições trabalhadas, somente o elemento gadolínio proporcionou aumento de emissão LOE e TL no espectro visível. DRX indicou a formação dos compostos Al5Er3O12 e Al5Yb3O12; gadolínio e európio também formaram estruturas secundárias que não puderam ser determinadas. A partir do óxido de alumínio em pó, foram produzidos alvos para deposição de filmes finos empregando um sistema de sputtering magnetron e lâminas de silício monocristalino (100) tipo P para substrato. Parâmetros de deposição e de tratamento térmico foram variados de modo a produzir amostras com diferentes características. Curvas de TL foram levantadas e analisadas com relação aos resultados de DRX. Imagens de Microscopia Eletrônica de Varredura (MEV) foram obtidas de algumas amostras para visualizar o estado dos filmes depositados após tratamentos térmicos de 500 e 1100°C. Resultados mostraram a formação de picos de difração de a-Al2O3 em algumas das amostras espessas. Medidas de TL de amostras expostas à radiação ambiente exibiram picos de emissão em posições que variaram de acordo com a composição e espessura do filme depositado. / Thermoluminecent (TL), Optically Stimulated Luminescence (OSL), EPR (Electron spin Resonance) and Radioluminescence (RL) measurements were obtained from aluminum oxide and magnesium doped aluminum oxide samples. The samples were calcinated at three different temperatures (1100, 1350 and 1600°C) in order to observe variation of luminescent properties. As results, it was found that the calcination temperature is of great importance in the production of dosimetric materials, since the undoped sample calcinated at 1600°C showed the highest sensibility. In early works, magnesium doped aluminum oxide samples exhibited the formation of nanostructured layer composed by magnesium aluminate, observed using Transmission Electron Microscopy (TEM), which induced an increase of the luminescent properties. Samples of undoped and rare-earths doped magnesium aluminate, calcinated at 1100, 1350 and 1600°C, were produced. TL and OSL measurements were obtained from irradiated aliquots, analyzed and compared to EPR and XRD results. Results showed that, under the parameters used in this work, only gadolinium doped samples exhibited increase in TL and OSL emissions. XRD indicated the formation of Al5Er3O12 and Al5Yb3O12 structures in doped samples; gadolinium and europium doped samples also showed new structures, which couldnt be identified. Powder aluminum oxide was used to produce deposition targets, which were employed in the deposition of thin films over P type monocrystalline silicon (100) wafers. Variations of deposition parameters and heat treatment induced the formation of thin films with different characteristics, observed by XRD and luminescent analysis (TL). XRD results indicated the occurrence of alpha-Al2O3 in some of the thick films. Samples exposed to natural radiation produced TL emission in the visible spectrum.

L’encrassement des façades d’immeuble est causé par un phénomène d’altération biologique essentiellement esthétique. Leur vieillissement naturel favorise la colonisation de micro-organismes. La cinétique de biodétérioration dépend de plusieurs paramètres, tels que la situation géographique, les conditions environnementales et les caractéristiques physico-chimiques du matériau. L’objectif de la présente étude est d’établir un lien entre la composition chimique de mortiers à base de ciments et leur cinétique de colonisation par des microorganismes. Deux bancs d’essais sont utilisés : un banc d’essai in situ et un banc d’essai de biodétérioration accélérée de laboratoire. Deux ciments Portland (OPC) et deux ciments alumineux (CAC) de minéralogies différentes ont été sélectionnés. L’effet de la porosité, de la rugosité et de la carbonatation a également été étudié. Le microorganisme sélectionné pour les essais de laboratoire est l’algue Klebsormidium flaccidum qui se développe de manière prépondérante sur les façades en France. Les résultats obtenus en laboratoire et in situ montrent que la biocolonisation des mortiers à base de CAC est plus lente que celle des mortiers à base d’OPC. Lorsque la porosité augmente, la vitesse de biocolonisation augmente et l’effet de la composition chimique est en grande partie masqué. La biocolonisation des mortiers carbonatés se réalise plus rapidement que celle des mortiers non carbonatés surtout dans le cas des mortiers à base d’OPC. Enfin, les mortiers de surface rugueuse sont colonisés plus rapidement quelle que soit la formulation testée. Cet effet est plus marqué pour les mortiers exposés in situ que pour ceux testés en laboratoire. / The fouling of building-facade is caused by a main aesthetic phenomenon of biological weathering. The natural weathering favors the micro-organisms development. The biofouling kinetics depends on several parameters such as geographical situation, environmental conditions and physicochemical parameters of substrates. The main objective of this study is to highlight the influence of the mortar chemistry in relationship with its physical properties on the algal growth. The biofouling kinetics was followed on samples exposed outdoor and on samples tested in a laboratory bench which consists in spraying an algal culture on mortar specimens. In order to characterize the influence of the mortar chemistry on biofouling, two Portland cements (OPC) and two calcium aluminate cements (CAC) were tested. The influence of roughness, porosity and carbonation was also studied. The green algae Klebsormidium flaccidum were chosen for the accelerated laboratory tests because of its representativeness. The results obtain in laboratory and in situ show that CAC based mortars slow down the colonization kinetics compared to OPC based mortars. When porosity increases the biofouling kinetics increases and the effect of the mortars chemical composition is largely hidden. The carbonated mortars biofouling is achieved more quickly than uncarbonated ones especially for OPC based mortars. Finally, the rough surfaces are colonized faster whatever formulation tested. This parameter is mostly highlighted for in situ tests.

Polymerem impregnované cementové materiály představují zajímavou a perspektivní alternativu klasických portlandských cementových past. Hlavním zástupcem těchto materiálů jsou macrodefect-free (MDF) kompozity, složené z anorganického pojiva a organického polymeru. I přes řadu vynikajících mechanických vlastností je plné zavedení MDF kompozitů na trh omezené především z důvodu jejich relativně nízké odolnosti vůči vlhkosti. Jednou z možností jak zvýšit odolnost výsledného MDF vůči vlhkosti je „in situ“ síťování polymeru. V této práci byla připravena počáteční série MDF kompozitů na bázi hlinitanového cementu a polyvinylalkoholu se třemi typy organo-titanátových síťovacích činidel (Tyzory). Efekt modifikace MDF kompozitů byl hodnocen na základě zkoušek pevnosti v tahu za ohybu po uložení materiálů v různých vlhkostních podmínkách.

When firing calcium ceramic materials creates a new crystalline phase anorthite. It can significantly improve the properties of ceramic body. This work deals with the possibilities of development anortitové ceramics using non-plastic raw materials, particularly alumina cement compared with conventional ceramics based on mullite.

The subject of the doctoral thesis is the study of moisture resistance of macro-defect-free (MDF) composites based on calcium-aluminate cement and polyvinylalcohol used as polymer. MDF cements are perspective materials providing unique properties relative to traditional cement pastes with great potential to incoming constructional utilization. But it is known that MDF cements exhibit sensitivity to water, with swelling and reduction of strength. Therefore the work is aimed in monitoring of an organic polymer effect on the moisture resistance of MDF materials and phase changes. The effects of three different organotitanate cross-linking agents on the properties were investigated. The organotitanate-modified MDF cement samples exhibited improved moisture resistance as compared to the standard samples when exposed to 100 % relative humidity or water at laboratory conditions. The influence of composition at different curing on the properties of model MDF cement samples was observed. The characterization of MDF samples was based especially on test of flexural strength, XRD, DTA/TGA and EGA, EDS and scanning electron microscopy analyses.

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.

The self-assembly of magnesium aluminate spinel as a result of dewetting an overlaid thin film of (chiefly) gold was investigated. Thin films of gold were deposited on single-crystalline spinel substrates and were heat-treated to dewet gold film which led to self-assembly of intricate structures consisting of faceted spherical particles atop of frustums. The current work was conducted in continuation of previous studies which reported formation of such intricate structures. The most recent studies had evidently overruled a pure gold self-assembly scenario as was pointed out in preliminary investigations. It was in fact proven that these structures consist of three distinct parts: (i) a single or polycrystalline gold faceted sphere, (ii) quasi-phase interfacial bilayer, and (iii) a crystalline MgAl2O4 necking structure spontaneously risen from spinel substrate. In the current work, samples were produced through different film deposition methods of sputter, thermal evaporation, and e-beam evaporation coating which underwent thermal annealing to induce dewetting of gold film and subsequent self-assembly of intricate structures. Several characterization methods such as electron microscopy, X-ray energy dispersive spectroscopy, electron energy loss spectroscopy, and atom probe tomography were utilized to survey the different features of the intricate structures with focus on chemical analysis of the gold-spinel interface. The results rejected the previous findings about formation of interface complexion at the boundary of gold-spinel. It was found out that gold-spinel interface is in fact an ordinary metal-oxide boundary with sharp atomic distinction and no inter-diffusion or formation of interfacial complexion. It was further discovered that dewetting pure gold thin films does not result in formation of spinel self-assembly and existence of elemental impurities of copper (Cu) in the initial film is vital in development of such structures. Finally, it was concluded that chemical composition of metallic overlayer and the heat treatment parameters most fundamentally influence formation and physical characteristics of those self-assembled structures. / Thesis / Master of Applied Science (MASc)

Uma das abordagens para minimizar o volume de captação de água potável e o descarte de efluentes é o reuso da água dentro da unidade industrial através de técnicas avançadas de tratamento como o sistema de osmose reversa, porém esse sistema exige um afluente com uma baixa quantidade de sólidos, além de outros requisitos. A água residuária utilizada nesse estudo é proveniente de uma empresa do ramo metal-mecânico que utiliza processos de coagulação-floculação-sedimentação como forma de remover os sólidos antes de um sistema de osmose reversa. A proposta deste trabalho foi avaliar três diferentes coagulantes (aluminato de sódio, cloreto férrico e uma mistura de dois coagulantes comerciais, Procytrat 100A e Procytrat 300) em processos de coagulação-floculação e separação de sólidos da fase líquida por sedimentação e flotação por ar dissolvido e também comparar os custos aproximados dos processos envolvidos. Foram realizados ensaios em testes de jarros e flotateste e com os dados obtidos construíram-se diagramas de coagulação-floculação e escolhidas as regiões de maior remoção de sólidos. Através das regiões escolhidas, foram feitas as comparações de eficiência de remoção e custos para cada coagulante estudado. Verificou-se que os diagramas de coagulação-floculação-sedimentação foram os que apresentaram as regiões de maior área com turbidez remanescente menor que 2%, principalmente para os coagulantes cloreto férrico e a mistura Procytrat 100A + Procytrat 300, chegando a alcançar valores próximos a 0,5%. A opção mais econômica foi alcançada com custo de cloreto férrico, na dosagem de 200 mg/L, pH igual a 8,3 e turbidez remanescente igual a 0,6%, de R$0,47/\'M POT.3\' de água tratada. Os diagramas de coagulação-floculação-flotação apresentaram regiões de turbidez remanescente com áreas bem mais reduzidas se comparadas aos diagramas de coagulação-floculação-sedimentação, sendo que não foram atingidos valores de turbidez remanescente menores que 1,5%. Os menores valores de turbidez remanescente para o processo de flotação foram encontrados utilizando-se como coagulante a mistura Procytrat 100A + Procytrat 300, sendo a opção mais econômica alcançada para pH igual a 3,3, dosagem de 60 mg/L e turbidez remanescente igual a 1,6%, com custo de R$0,33/\'M POT.3\' de água tratada. De um modo geral, para todos os coagulantes testados, as regiões escolhidas nos diagramas de coagulação-floculação-flotação, cujos valores de turbidez remanescente foram menores, estavam concentradas em valores de pH baixos (3,2 a 5,5), dosagens de coagulante reduzidas (10 a 80 mg/L) e dosagens de alcalinizante também reduzidas (0 a 60 mg/L de Ca(\'OH)IND.2\'). Esse comportamento foi contrário ao apresentado pelos diagramas coagulação-floculação-sedimentação cujos valores de turbidez remanescente foram menores em valores de pH mais altos (6,5 a 8,5), maiores dosagens de coagulante (40 a 380 mg/L) e altas dosagens de alcalinizante (100 a 400 mg/L de Ca(\'OH)IND.2\'). / One approach to minimize the consumption of drinking water and effluent disposal is the reuse of water within the plant through advanced treatment techniques such as reverse osmosis system, however, this system requires an affluent with a low amount of solids and other requirements. The wastewater used in this study comes from a metalworking company that uses coagulation-flocculation-sedimentation process as a way to remove the solids before a reverse osmosis system. The purpose of this study was to evaluate three different coagulants (sodium aluminate, ferric chloride and a mixture of two commercial coagulants, Procytrat 100A and Procytrat 300) in the process of coagulation-flocculation and separation of solids from the liquid phase by sedimentation and dissolved air flotation and also compare the approximate costs of the processes involved. Jar tests and flotatests were performed and the coagulation-flocculation diagrams were built. In the coagulation-flocculation diagrams were selected areas of higher solids removal. Through the chosen regions, comparisons were made of removal efficiency and cost study for each coagulant. It was found that the diagrams of coagulation-flocculation-sedimentation presented the areas of higher turbidity remaining area with less than 2%, mainly for the coagulants ferric chloride and the mixture Procytrat 100A + Procytrat 300, reaching values close to 0.5 %. The most economical option was achieved at a cost of ferric chloride at a dosage of 200 mg/L, pH 8.3, and the remaining turbidity equal to 0.6%, from R$ 0.47/\'M POT.3\' treated water. The diagrams of coagulation-flocculation-flotation showed regions with turbidity remaining areas much reduced compared to the diagrams of coagulation-flocculation-sedimentation, and the turbidity remaining values were more than 1.5%. The lower values of turbidity remaining for the flotation process were found using the mixture Procytrat 100A + Procytrat 300, and the most economical option was reached for a pH of 3.3, dosage of 60 mg/L and remaining turbidity equal to e 1.6%, at a cost of R$ 0.33/\'M POT.3\' of treated water. In general, for all coagulants tested, the selected regions in the diagrams of coagulation-flocculation-flotation, whose remaining turbidity values were lower, were concentrated in low pH values (3.2 to 5.5), dosages of coagulant reduced (10 to 80 mg/L) and dosages of alkaline also reduced (0 to 60 mg/L of Ca(\'OH)IND.2\'). This behavior was contrary to the diagrams presented by coagulation-flocculation-sedimentation whose remaining turbidity values were lower in higher pH values (6.5 to 8.5), larger amounts of coagulant (40 to 380 mg/L) and high doses of alkaline (100 to 400 mg/L Ca(\'OH)IND.2\').

Materiais com luminescência persistente são normalmente baseados em aluminatos e silicatos dopados com íons Eu2+, portanto buscam-se novos materiais com diferentes dopantes. Consequentemente, os materiais BaAl2O4:Eu2+,TR3+ (R: La-Lu) foram preparados pelo método de combustão com temperaturas de ignição entre 400 e 600 °C, assim como pelo método cerâmico a 1500 °C. Os sistemas mais versáteis CdSiO3:TR3+ foram preparados apenas pelo método cerâmico a 950 °C. Para estudar a estrutura e a pureza de fase dos materiais utilizou-se espectroscopia de absorção no infravermelho, difração de raios X (método do pó) e microscopia eletrônica de varredura. Os estados de oxidação e o ambiente ao redor dos íons terras raras foram investigados com a espectroscopia de absorção de raios X com radiação Síncrotron (XANES e EXAFS). As propriedades da luminescência persistente dos fósforos foram investigadas com as técnicas de termoluminescência (TL), fotoluminescência e espectroscopia com radiação Síncrotron na região do UV-UV vácuo. Baseado nas medidas de TL, a estrutura dos defeitos dos materiais BaAl2O4:Eu2+,TR3+ (TR: Nd e Dy) e CdSiO3:TR3+ (TR: Pr, Gd e Tb) mostrou-se ideal para a luminescência persistente a temperatura ambiente. Os espectros de XANES indicaram a presença dos estados divalente e trivalente do Eu dopado na matriz BaAl2O4, enquanto que apenas íons TR3+ co-dopantes foram observados (exceto CeIV). O íon Eu3+ pode estar presente devido ao processo de migração do elétron do íon Eu2+ para a banda de condução durante o processo de excitação. Em contraste, para o sistema CdSiO3:TR3+, foram observadas apenas as espécies trivalentes TR3+, excluindo, portanto, a oxidação direta TR3+→TRIV. Apenas a transição interconfiguracional 4f65d1→4f7 do íon Eu2+ foi observada na luminescência persistente dos materiais BaAl2O4:Eu2+,TR3+. Por outro lado, para a matriz CdSiO3 dopada com íons Pr3+ e Tb3+, apenas as transições 4fn-4fn foram observadas, sem a presença da banda de emissão defeitos observada tanto no espectro de emissão sob excitação no UV como no espectro de luminescência persistente do CdSiO3:Gd3+. O band gap das matrizes BaAl2O4 (6,5 eV) e CdSiO3 (5,28 eV) foi obtido com a espectroscopia de excitação no UV-UV vácuo. A posição dos níveis de energia dos íons TR2+/3+ determinada com o auxílio da banda de transferência de carga ligante metal (LMCT) O2-(2p)Eu3+ confirmou o papel dos elétrons como carregadores de carga no mecanismo da luminescência persistente dos íons Eu2+, Pr3+ e Tb3+. Por fim, os mecanismos da luminescência persistente foram desenvolvidos, e, apesar de serem diferentes, os mecanismos para os íons Eu2+, Tb3+ e Pr3+ apresentaram princípios similares. Esta semelhança confirma a solidez da interpretação dos dados experimentais dos materiais com luminescência persistentes dopados com Eu2+ e encoraja a expansão de modelos similares para outros materiais com luminescência persistente no futuro. Cálculos teóricos com, por exemplo, método DFT poderão no futuro ser utilizados para refinar o modelo, diminuir o trabalho experimental e para descobrir novos modelos para sistemas que o atual modelo não pode ser aplicado, como no caso dos materiais dopados com Eu3+. / Persistent luminescent materials are usually based on Eu2+ doped aluminates or silicates, though novel materials with different dopants are seeked for. Accordingly, BaAl2O4:Eu2+,R3+ (R: La-Lu) materials were prepared by the combustion method with ignition temperatures between 400 and 600 °C as well as with the solid state reaction at 1500 °C. The more versatile CdSiO3:R3+ systems were prepared only with the solid state reaction at 950 °C. Infrared absorption spectroscopy, X-ray powder diffraction and Scanning Electron Microscopy techniques were used to study the structure and phase purity of the materials. The oxidation states of the rare earths and their environment were investigated with synchrotron radiation X-ray absorption spectroscopy (XANES and EXAFS). The persistent luminescence properties of the phosphors were investigated with thermoluminescence (TL), photoluminescence and synchrotron radiation UV-VUV spectroscopy. Based on the TL measurements, the trap structure for BaAl2O4:Eu2+,R3+ (R: Nd and Dy) and CdSiO3:R3+ (R: Pr, Gd and Tb) is ideal for room temperature persistent luminescence. The XANES spectra indicated the presence of both divalent and trivalent europium doped in the BaAl2O4 host, while only trivalent rare earth co-dopants were observed (except CeIV). Eu3+ may be present because of in situ charging of persistent luminescence. In contrast for the CdSiO3:R3+ system, only the trivalent R3+ species were observed, thus excluding the direct R3+→RIV (R: Pr and Tb) oxidation. Only the typical interconfigurational 4f65d1→4f7 transition of Eu2+ ion was observed in the persistent luminescence of BaAl2O4:Eu2+,R3+ materials. On the other hand, for the Pr3+ and Tb3+ doped CdSiO3, only 4fn-4fn transitions were observed with no traces of the defect band emission observed in either the conventional UV excited or persistent luminescence spectra of CdSiO3:Gd3+. The band gap energy for the hosts BaAl2O4 (6.5 eV) and CdSiO3 (5.28 eV) were obtained with the UV-VUV excitation spectroscopy. The R2+/3+ energy levels positions determined with the aid of the O2-(2p)→Eu3+ ligand to metal charge transfer transition (LMCT) confirmed the role of electrons as the charge carriers in the mechanism of Eu2+, Pr3+ and Tb3+ persistent luminescence. Finally, the persistent luminescence mechanisms were constructed and, despite the differences, the mechanisms for Eu2+, Tb3+ and Pr3+ proved to be rather similar. This similarity confirms the solidity of the interpretation of experimental data for the Eu2+ doped persistent luminescence materials and encourages the expansion of similar models for other persistent luminescence materials in the future. Theoretical calculations by e.g. DFT method can be used to refine the model, to decrease experimental work and to find different models for systems where the present model evidently fails, e.g. Eu3+ doped materials.

In calcium aluminate cement (CAC) systems the hydration process is different than portland cement (PC) systems. The hydration products of CAC are subjected to conversion depending on temperature, moisture, water-cement ratio, cement content, etc. Consequently, strength of CAC system can be seriously reduced. However, presence of other inorganic binders or additives may alter the hydration process and improve various properties of CAC based composites. The objective of this study is to investigate the temperature effect on the behaviour of CAC based composite binders. Throughout this research, several combinations of CAC-PC, CAC-gypsum, CAC-lime, CAC-ground granulated blast furnace slag (CAC-GGBFS) were studied. These CAC based composite binders were subjected to seven different curing regimes and their strength developments were investigated up to 210 days. In addition, the mechanism of strength development was examined by XRD analyses performed at 28 and 210 days. Finally, some empirical relationships between strength-time-curing temperatures were formulated. Experimental results revealed that the increase in ambient temperature resulted in an increase in the rate of conversion, thereby causing drastic strength reduction, particularly in pure CAC mix. It has been observed that inclusion of small amount of PC, lime, and gypsum in CAC did not induce conversion-free CAC binary systems, rather they resulted in faster conversion by enabling rapid formation of stable C3AH6 instead of metastable, high strength inducing CAH10 and C2AH8. On the other hand, in CAC-GGBFS mixes, the formation of stable straetlingite (C2ASH8) instead of calcium aluminate hydrates hindered the conversion reactions. Therefore, CAC-GGBFS mixes, where GGBFS ratio was over 40%, did not exhibit strength loss due to conversion reactions that occurred in pure CAC systems.