A fundamental theoretical and experimental study on calcium sulphate scale formation in hydrometallurgical solutions containing various minerals was conducted. A new database for the Mixed Solvent Electrolyte (MSE) model of the OLI Systems® software was developed through fitting of existing literature data such as mean activity, heat capacity and solubility data in simple binary and ternary systems. Moreover, a number of experiments were conducted to investigate the chemistry of calcium sulphate hydrates in laterite pressure acid leach (PAL) solutions, containing Al2(SO4)3, MgSO4, NiSO4, H2SO4, and NaCl at 25–250ºC. The database developed, utilized by the MSE model, was shown to accurately predict the solubilities of all calcium sulphate hydrates (and hence, predict scaling potential) in various multicomponent hydrometallurgical solutions including neutralized zinc sulphate leach solutions, nickel sulphate–chloride solutions of the Voisey’s Bay plant, and laterite PAL solutions over a wide temperature range (25–250°C). The stability regions of CaSO4 hydrates (gypsum, hemihydrate and anhydrite) depend on solution conditions, i.e., temperature, pH and concentration of ions present. The transformation between CaSO4 hydrates is one of the common causes of scale formation. A systematic study was carried out to investigate the effect of various parameters including temperature, acidity, seeding, and presence of sulphate/chloride salts on the transformation kinetics. Based on the results obtained, a mechanism for the gypsum–anhydrite transformation below 100°C was proposed. A number of solutions for mitigating calcium sulphate scaling problems throughout the processing circuits were recommended: (1) operating autoclaves under slightly more acidic conditions (~0.3–0.5 M acid); (2) mixing recycled process solutions with seawater; and (3) mixing the recycling stream with carbonate compounds to reject calcium as calcium carbonate. Furthermore, aging process solutions, saturated with gypsum, with anhydrite seeds at moderate temperatures (~80°C) would decrease the calcium content, provided that the solution is slightly acidic.

The presented work deals with research in the field of sulfate binders on the anhydrite base. Conceptually, it is divided into a general theory of sulfate binders and anhydrite mortar compounds, which is describing in detail the using of anhydrite mortar compounds on the poured floor screeds, and then the experimental part, where is made the mineralogical analysis of seven different gypsum resources and subsequent is monitored the effect of two sulfate exciters on the achieved technological properties and hydration process.

Anhydrit II (AII) wird industriell hauptsächlich als Bindemittel bei der Fußbodenestrich-Herstellung eingesetzt. Zur Beschleunigung der Abbindereaktion und der daraus resultierenden schnelleren Verfestigung des Fußbodens wird Kaliumsulfat als Additiv verwendet. Im Rahmen dieser Arbeit wurden anorganische Salze (Sulfate und Chloride) im Vergleich zu Kaliumsulfat hinsichtlich ihrer beschleunigenden Wirkung auf die Abbindereaktion von AII untersucht, um eine mögliche Alternative und einen Mechanismus für die Wirkungsweise der Additive angeben zu können. Unter den verwendeten Salz-Additiven wurde keine Alternative zu K2SO4 für die industrielle Anwendung gefunden. Als Ursache für die beschleunigende Wirkung von K2SO4 wird die Bildung des Doppelsalzes Syngenit auf der Anhydrit-Oberfläche angenommen. Durch epitaktische Beziehungen von Kristallflächen oder den Zerfall des Syngenits wird die heterogene Gips-Keimbildung begünstigt und die Abbindereaktion beschleunigt.

A presente tese tem por objetivo contribuir para o conhecimento do comportamento dependente do tempo das rochas de anidrita e gipso. O maior interesse é fornecer argumentos convincentes sobre os mecanismos físicos responsáveis pelas deformações lentas observadas em algumas escavações subterrâneas realizadas em maciços dessas rochas na Europa, aspecto este que hoje está bastante confuso e escassamente estudado. A hipótese central desta pesquisa é que o comportamento dependente do tempo das rochas de anidrita e gipso deve-se parcial e/ou totalmente às propriedades reológicas (fluência) e não exclusivamente a expansão decorrente da transformação anidrita – gipso como a maioria dos autores sustenta. Este problema será analisado a partir de uma perspectiva experimental através de ensaios específicos. Os ensaios de expansão axial livre em rochas de anidrita permitiram concluir que quando submersas em água destilada, experimentam diminuição de volume por dissolução. Já as amostras de anidrita em contato com solução saturada em 'CA'SO IND.4' mostram uma relação não linear entre deformação axial e o tempo indicando uma taxa de expansão que decresce com o tempo. As taxas de expansão axial variam entre 0,3 e 2,4%/ano. A novidade é que esta expansão se deve à deposição de uma camada contínua formada por neocristais de gipso e não a expansão por hidratação da anidrita como acontece com os argilominerais. O mecanismo de transformação consiste na dissolução da anidrita e posterior precipitação do gipso em condições de sobre-saturação da solução. A transformação mineralógica acontece, na natureza, em condições propícias de temperatura e saturação da solução com íons 'CA POT.2+' e 'SO IND.4'POT.2-'. Propõe-se uma teoria alternativa sobre deformações lentas de maciços sulfáticos baseada na força de cristalização decorrente da deposição de cristais de gipso nas juntas do maciço rochoso. Propõe-se utilizar as formulações termodinâmicas propostas para expansão de concretos por crescimento de etringita e gipso. Os ensaios de fluência uniaxial sob compressão axial constante mostram que ambos os tipos de rochas sulfáticas apresentam comportamentos elasto-visco-plásticos e taxas de deformação axial e lateral da ordem de '10 POT.-12' a '10 POT.-10' 'S POT.-1'. A deflagração da fluência secundária acontece sob tensões de 4 – 6 MPa para gipsitas e de 25 – 40 MPa para anidritas. As análises sobre os possíveis mecanismos de deformação por fluência foram inconsistentes e nenhuma conclusão definitiva foi atingida. Aparentemente a baixas tensões atuariam mecanismos de difusão e dissolução por pressão. A tensões intermediárias dominariam mecanismos de deslocamentos intra e intercristalinos e a altas tensões as rochas deformariam por propagação de microfissuramento. Ensaios de fluência acoplados a sensores de emissão acústica mostram a manifestação de eventos microssísmicos que usualmente se atribuem à propagação de microfraturas mas que podem dever-se a outros mecanismos. Tanto as taxas de expansão axial como de fluência são compatíveis com as taxas de convergência medidas em algumas obras subterrâneas escavadas em maciços sulfáticos, verificando a hipótese central da pesquisa / The purpose of this thesis is to contribute for the knowledge of time-dependent behavior of sulfatic rocks of anhydrite and gypsum. Emphasis is given to provide straightforward arguments about physical mechanisms responsible for creep observed in some underground excavations in those rocks in Europe. Explanation for this phenomena is not clear yet and studies about them are still scarce. The backbone idea behind this research is that the time-dependent behavior of anhydrite and gypsum is totally or at least partially due to rheological properties, and not exclusively due to swelling resulting from the anhydritegypsum transformation. This problem was investigated experimentally with specific tests. Free swelling tests on anhydrite led to the conclusion that when immersed into distilled water, volume decrease due to dissolution is observed. Anhydrite samples in contact with a saturated solution of 'CA'SO IND.4' present a nonlinear relationship between axial strain and time, indicating swelling rate decreasing with time. Axial swelling rates vary between 0,3% and 2,4%/year. The new concept is that this swelling is due to the deposition of a continuous layer of gypsum composed by gypsum neo-crystals, and not due to hydration swelling of anhydrite, a usual with clay minerals. The transformation mechanism consists of anhydrite dissolution and later precipitation of gypsum under over-saturation condition of the solution. The mineralogical transformation takes place in nature under favorable conditions of temperature and solution saturation with 'CA POT.2+' and 'SO IND.4'POT.2-' ions. An alternative theory is proposed about creep of sulfatic rock masses based on crystallization forces resulting from the deposition of gypsum crystals in the rock masses joints. The use of thermodynamic formulations is proposed for concrete swelling due to the growth of ettringite and gypsum. Uniaxial compression creep tests show that both types of sulfatic rocks present elasto-visco-plastic behavior and axial and lateral strain rates of the order of '10 POT.-12' to '10 POT.-10' 'S POT.-1'. Triggering of secondary creep takes places under stresses of the order of 4 – 6 MPa for gypsum and 25 – 40 MPa for anhydrite. The analyses about the possible creep mechanisms were not consistent and no definite conclusion has been reached get. Apparently under low stresses diffusion and pressure dissolution mechanism dominate. Under intermediate stresses, intra- and inter crystalline displacement mechanisms seem to dominate, and under high stresses rock deform due to microcrack propagation. Creep tests monitored with acoustic emission devices show the occurrence of microseismic events attributed to microcrack propagation. Both axial swelling and creep rock are compatible with convergence rocks measured in some underground works excavated in sulfatic rock masses, following the central idea of this thesis

Die Adsorption von Additiven an den Oberflächen eines Kristallisates wird als eine hauptsächliche Ursache für die Beeinflussung von Kristallwachstum und Morphologie angesehen und spielt bei vielen Kristallisationsprozessen eine entscheidende Rolle. Gerade für die Calciumsulfate, die im Millionen-Tonnen-Maßstab jährlich in Deutschland verarbeitet werden, stellt der Additiv-Einsatz einen Hauptkostenfaktor dar, während gleichzeitig die Additivwirkung mechanistisch nicht ausreichend gut verstanden und damit derzeit nicht vorhersagbar ist. Zur Erlangung eines besseren Verständnisses wurden mit Hilfe von molekulardynamischen Computersimulationen die Prozesse in den Grenzflächen zwischen festen Calciumsulfaten und wässriger Additivlösung auf atomarer Ebene analysiert. Wesentlicher Untersuchungsschwerpunkt war dabei die Rolle des polaren Lösungsmittels Wasser auf die Wechselwirkung zwischen verschiedenen ionischen Additivspezies und den Salzkristallen.

A presente tese tem por objetivo contribuir para o conhecimento do comportamento dependente do tempo das rochas de anidrita e gipso. O maior interesse é fornecer argumentos convincentes sobre os mecanismos físicos responsáveis pelas deformações lentas observadas em algumas escavações subterrâneas realizadas em maciços dessas rochas na Europa, aspecto este que hoje está bastante confuso e escassamente estudado. A hipótese central desta pesquisa é que o comportamento dependente do tempo das rochas de anidrita e gipso deve-se parcial e/ou totalmente às propriedades reológicas (fluência) e não exclusivamente a expansão decorrente da transformação anidrita – gipso como a maioria dos autores sustenta. Este problema será analisado a partir de uma perspectiva experimental através de ensaios específicos. Os ensaios de expansão axial livre em rochas de anidrita permitiram concluir que quando submersas em água destilada, experimentam diminuição de volume por dissolução. Já as amostras de anidrita em contato com solução saturada em 'CA'SO IND.4' mostram uma relação não linear entre deformação axial e o tempo indicando uma taxa de expansão que decresce com o tempo. As taxas de expansão axial variam entre 0,3 e 2,4%/ano. A novidade é que esta expansão se deve à deposição de uma camada contínua formada por neocristais de gipso e não a expansão por hidratação da anidrita como acontece com os argilominerais. O mecanismo de transformação consiste na dissolução da anidrita e posterior precipitação do gipso em condições de sobre-saturação da solução. A transformação mineralógica acontece, na natureza, em condições propícias de temperatura e saturação da solução com íons 'CA POT.2+' e 'SO IND.4'POT.2-'. Propõe-se uma teoria alternativa sobre deformações lentas de maciços sulfáticos baseada na força de cristalização decorrente da deposição de cristais de gipso nas juntas do maciço rochoso. Propõe-se utilizar as formulações termodinâmicas propostas para expansão de concretos por crescimento de etringita e gipso. Os ensaios de fluência uniaxial sob compressão axial constante mostram que ambos os tipos de rochas sulfáticas apresentam comportamentos elasto-visco-plásticos e taxas de deformação axial e lateral da ordem de '10 POT.-12' a '10 POT.-10' 'S POT.-1'. A deflagração da fluência secundária acontece sob tensões de 4 – 6 MPa para gipsitas e de 25 – 40 MPa para anidritas. As análises sobre os possíveis mecanismos de deformação por fluência foram inconsistentes e nenhuma conclusão definitiva foi atingida. Aparentemente a baixas tensões atuariam mecanismos de difusão e dissolução por pressão. A tensões intermediárias dominariam mecanismos de deslocamentos intra e intercristalinos e a altas tensões as rochas deformariam por propagação de microfissuramento. Ensaios de fluência acoplados a sensores de emissão acústica mostram a manifestação de eventos microssísmicos que usualmente se atribuem à propagação de microfraturas mas que podem dever-se a outros mecanismos. Tanto as taxas de expansão axial como de fluência são compatíveis com as taxas de convergência medidas em algumas obras subterrâneas escavadas em maciços sulfáticos, verificando a hipótese central da pesquisa / The purpose of this thesis is to contribute for the knowledge of time-dependent behavior of sulfatic rocks of anhydrite and gypsum. Emphasis is given to provide straightforward arguments about physical mechanisms responsible for creep observed in some underground excavations in those rocks in Europe. Explanation for this phenomena is not clear yet and studies about them are still scarce. The backbone idea behind this research is that the time-dependent behavior of anhydrite and gypsum is totally or at least partially due to rheological properties, and not exclusively due to swelling resulting from the anhydritegypsum transformation. This problem was investigated experimentally with specific tests. Free swelling tests on anhydrite led to the conclusion that when immersed into distilled water, volume decrease due to dissolution is observed. Anhydrite samples in contact with a saturated solution of 'CA'SO IND.4' present a nonlinear relationship between axial strain and time, indicating swelling rate decreasing with time. Axial swelling rates vary between 0,3% and 2,4%/year. The new concept is that this swelling is due to the deposition of a continuous layer of gypsum composed by gypsum neo-crystals, and not due to hydration swelling of anhydrite, a usual with clay minerals. The transformation mechanism consists of anhydrite dissolution and later precipitation of gypsum under over-saturation condition of the solution. The mineralogical transformation takes place in nature under favorable conditions of temperature and solution saturation with 'CA POT.2+' and 'SO IND.4'POT.2-' ions. An alternative theory is proposed about creep of sulfatic rock masses based on crystallization forces resulting from the deposition of gypsum crystals in the rock masses joints. The use of thermodynamic formulations is proposed for concrete swelling due to the growth of ettringite and gypsum. Uniaxial compression creep tests show that both types of sulfatic rocks present elasto-visco-plastic behavior and axial and lateral strain rates of the order of '10 POT.-12' to '10 POT.-10' 'S POT.-1'. Triggering of secondary creep takes places under stresses of the order of 4 – 6 MPa for gypsum and 25 – 40 MPa for anhydrite. The analyses about the possible creep mechanisms were not consistent and no definite conclusion has been reached get. Apparently under low stresses diffusion and pressure dissolution mechanism dominate. Under intermediate stresses, intra- and inter crystalline displacement mechanisms seem to dominate, and under high stresses rock deform due to microcrack propagation. Creep tests monitored with acoustic emission devices show the occurrence of microseismic events attributed to microcrack propagation. Both axial swelling and creep rock are compatible with convergence rocks measured in some underground works excavated in sulfatic rock masses, following the central idea of this thesis

During the production of concrete is important the careful selection of raw materials. Nowadays, we are trying in the production to minimize the economic burden and to maximize the use of secondary raw materials. This work is focused on the use of secondary raw materials from the energy industry in construction for the preparation of hydraulic binders. As the main raw materials were used different power plant fly ash from fluidized combustion. The composition of these secondary materials is quite different from conventional high-temperature ash, due to mixing with water they solidify and harden. Experiments were performed with three lodge fly ash from electrostatic precipitators of the fluidized combustion and one high-temperature fly ash. This work is focused on the possibility of monitoring the use of these secondary materials in construction, especially when tests were evaluated characteristics of strength and speed of setting and hardening.

The object of the thesis is a description of preparation process, realization and subsequent treatment of floors based on calcium sulphate, including problems related to the issue. The aim of the work is to closely acquaint the reader with methods used in diagnostics of flooring failures and defects in the housing and civic construction, including practical applications of these methods on real structures. The work also includes experimental analysis of a real floor construction during local load effect.

Die Adsorption von Additiven an den Oberflächen eines Kristallisates wird als eine hauptsächliche Ursache für die Beeinflussung von Kristallwachstum und Morphologie angesehen und spielt bei vielen Kristallisationsprozessen eine entscheidende Rolle. Gerade für die Calciumsulfate, die im Millionen-Tonnen-Maßstab jährlich in Deutschland verarbeitet werden, stellt der Additiv-Einsatz einen Hauptkostenfaktor dar, während gleichzeitig die Additivwirkung mechanistisch nicht ausreichend gut verstanden und damit derzeit nicht vorhersagbar ist. Zur Erlangung eines besseren Verständnisses wurden mit Hilfe von molekulardynamischen Computersimulationen die Prozesse in den Grenzflächen zwischen festen Calciumsulfaten und wässriger Additivlösung auf atomarer Ebene analysiert. Wesentlicher Untersuchungsschwerpunkt war dabei die Rolle des polaren Lösungsmittels Wasser auf die Wechselwirkung zwischen verschiedenen ionischen Additivspezies und den Salzkristallen.:1. Einleitung und Zielsetzung 1 2. Literatur 6 2.1. Kristallstrukturen der Calciumsulfate 7 2.2. Kristallmorphologie und relevante Kristallflächen 10 2.2.1. Kristallwachstum und Morphologie der Calciumsulfate 10 2.2.2. Theoretische Methoden zur Morphologievorhersage 13 2.2.3. Morphologievorhersage für die Calciumsulfate 18 2.3. Struktur von Mineral-Wasser-Grenzflächen 20 2.3.1. Experimentelle Untersuchungen 20 2.3.2. Simulationen 25 2.4. Morphologiebeeinflussung der Calciumsulfate durch Additive 26 2.4.1. Additive für Calciumsulfate und deren Wirkungsweise 26 2.4.2. Beeinflussung der Gipsmorphologie durch Zitronensäure und Aminosäuren 28 2.5. Stand der Technik von Adsorptionssimulationen 31 2.5.1. Methodenüberblick 31 2.5.2. Molekulardynamische Adsorptionssimulationen 33 2.5.3. Modellierungen und Simulationen der Calciumsulfat-Additiv- Wechselwirkung 44 3. Methodik 47 3.1. Simulationsbasis 49 3.1.1. Randbedingungen und Annahmen 49 3.1.2. Simulationsmethoden und -parameter 51 3.1.3. Kraftfeld 55 3.1.4. Erstellen von Simulationsboxen 60 3.2. Simulationen zur Morphologievorhersage 65 3.2.1. Durchgeführte Simulationen 66 iiiInhaltsverzeichnis 3.2.2. Berechnung der Morphologie im Vakuum 68 3.2.3. Berechnung der Morphologie in Lösung 69 3.2.4. Zusammenfassung 72 3.3. Simulationen der CaSO 4 -Wasser-Grenzfläche 74 3.3.1. Durchgeführte Simulationen 74 3.3.2. Charakterisierung der Oberflächenstabilität 75 3.3.3. Strukturelle Charakterisierung der Hydratationsschichten 77 3.3.4. Kinetische Charakterisierung der Hydratationsschichten 82 3.3.5. Thermodynamische Charakterisierung der Hydratations- schichten 83 3.3.6. Zusammenfassung 87 3.4. Simulation der Adsorption 89 3.4.1. Durchgeführte Simulationen 89 3.4.2. Berechnung der Adsorptionsenergie 103 3.4.3. Berechnung der Freien Adsorptionsenergie 106 3.4.4. Zusammenfassung 112 4. Ergebnisse und Diskussion 114 4.1. Morphologievorhersage und Flächenauswahl 115 4.1.1. Die Morphologie im Vakuum 115 4.1.2. Die Morphologie in Lösung 123 4.1.3. Flächenauswahl 126 4.2. Die Mineral-Wasser-Grenzfläche 127 4.2.1. Oberflächenstabilität 127 4.2.2. Strukturelle Charakterisierung der Hydratationsschichten 133 4.2.3. Kinetische Charakterisierung der Hydratationsschichten 153 4.2.4. Thermodynamische Charakterisierung der Hydratations- schichten 162 4.2.5. Einfluss der Simulationsmethodik 166 4.3. Die Adsorption 167 4.3.1. Einfluss des Lösungsmittels 167 4.3.2. Einfluss des Additivs 176 4.3.3. Einfluss der Fläche 186 4.3.4. Einfluss der Simulationsmethodik 201 5. Zusammenfassung und Ausblick 211 ivInhaltsverzeichnis Abkürzungsverzeichnis V-1 Literaturverzeichnis V-6 Abbildungsverzeichnis V-34 Tabellenverzeichnis V-38 A. Methoden A-1 A.1. Erstellen von Simulationsboxen mit Kristallschichten A-2 A.1.1. Randbedingungen A-2 A.1.2. Erstellen der Elementarzelle A-3 A.1.3. Erstellen der Oberflächenelementarzelle A-3 A.2. Voruntersuchungen zur Adsorption A-8 A.2.1. Ausgangssituation A-8 A.2.2. Finden energetisch günstiger Konformationen A-11 A.2.3. Berechnung der Freien Adsorptionsenergie A-13 A.2.4. Berechnung der Adsorptionsenergie A-23 A.3. Clusteranalyse A-24 B. Tabellen B-1 C. Abbildungen C-1