<p>Black liquors are presently combusted in recovery boilers where the inorganic cooking chemicals are recovered and the energy in the organic material is converted to steam and electricity. A new technology, developed by Chemrec AB, is black liquor gasification (BLG). BLG has more to offer compared to the recovery boiler process, in terms of on-site generation of electric power, liquid fuel and process chemicals. A prerequisite for both optimization of existing processes and the commercialization of BLG is better understanding of the physical and chemical processes involved including interactions with the refractory lining. The chemistry in the BLG process is very complex and to minimize extensive and expensive time-consuming studies otherwise required accurate and reliable model descriptions are needed for a full understanding of most chemical and physical processes as well as for up-scaling of the new BLG processes. However, by using these calculated model results in practice, the errors in the state of the art thermochemical data have to be considered. An extensive literature review was therefore performed to update the data needed for unary, binary and higher order systems. The results from the review reviled that there is a significant range of uncertainty for several condensed phases and a few gas species. This resulted in experimental re-determinations of the binary phase diagrams sodium carbonate-sodium sulfide (Na2CO3-Na2S) and sodium sulfate-sodium sulfide (Na2SO4-Na2S) using High Temperature Microscopy (HTM), High Temperature X-ray Diffraction (HT-XRD) and Differential Thermal Analysis (DTA). For the Na2CO3-Na2S system, measurements were carried out in dry inert atmosphere at temperatures from 25 to 1200 °C. To examine the influence of pure CO2 atmosphere on the melting behavior, HTM experiments in the same temperature interval were made. The results include re-determination of liquidus curves, in the Na2CO3 rich area, melting points of the pure components as well as determination of the extent of the solid solution, Na2CO3(ss), area. The thermal stability of Na2SO3 was studied and the binary phase diagram Na2SO4-Na2S was re-determined. The results indicate that Na2SO3 can exist for a short time up to 750 °C, before it melts. It was also proved that a solid/solid transformation, not reported earlier, occurs at 675 ± 10 °C. At around 700 °C, Na2SO3 gradually breaks down within a few hours, to finally form the solid phases Na2SO4 and Na2S. From HTM measurements a metastable phase diagram including Na2SO3, as well as an equilibrium phase diagram have been constructed for the binary system Na2SO4-Na2S. Improved data on Na2S was experimentally obtained by using solid-state EMF measurements. The equilibrium constant for Na2S(s) was determined to be log Kf(Na2S(s)) (± 0.05) = 216.28 – 4750(T/K)–1 – 28.28878 ln (T/K). Gibbs energy of formation for Na2S(s) was obtained as ΔfG°(Na2S(s))/(kJ mol–1) (± 1.0) = 90.9 – 4.1407(T/K) + 0.5415849(T/K) ln (T/K). The standard enthalpy of formation of Na2S(s) was evaluated to be ΔfH°(Na2S(s), 298.15 K)/(kJ mol–1) (± 1.0) = – 369.0. The standard entropy was evaluated to be S°(Na2S(s), 298.15 K)/(J mol–1 K–1) (± 2.0) = 97.0. Analyses of used refractory material from the Chemrec gasifier were also performed in order to elucidate the stability of the refractory lining. Scanning electron microscopy (SEM) analysis revealed that the chemical attack was limited to 250-300 μm, of the surface directly exposed to the gasification atmosphere and the smelt. From XRD analysis it was found that the phases in this surface layer of the refractory were dominated by sodiumaluminosilicates, mainly Na1.55Al1.55Si0.45O4.</p>

<p>The function of titanium- and nickel-silicides is to lower the series resistance and contact resistivity in gate, source and drain contacts of an integrated circuit transistor. </p><p>With decreasing dimensions, the low resistivity C54 TiSi₂ is not formed and stays in its high resistivity phase C49. It was found that a layer of niobium interposed between titanium and silicon, which is supposed to promote the C54 phase, led to the formation of the high resistivity C40 (Ti,Nb)Si₂ in both small and large contacts. </p><p>Increased interest in Si_1-xGe_x layers led to the inclusion of the Ni-Si-Ge system in this project. The interaction between nickel and poly-Si_0.42Ge_0.58 was found to be different from nickel and poly-silicon in the meaning of the phases formed during high temperature annealing. High-resistivity NiSi₂ was formed at 750°C, but nickel and Si_0.42Ge_0.58 formed no disilicide. A massive out-diffusion of germanium from the NiSi_1-uGe_u resulted in agglomeration at lower temperatures than for NiSi. This was ascribed to the larger enthalpy of formation for nickel reacting with silicon than with germanium. Ternary phase diagrams, with and without the disilicide phase, were calculated. According to the tie lines, NiSi_1-uGe_u will be in thermodynamic equilibrium with Si_1-xGe_x when u is smaller than x. This was confirmed experimentally, where a balanced germanium concentration in NiSi_1-uGe_u and Si_1-xGe_x, stabilized the germanosilicide. When nickel interacted with strained and relaxed silicon-germanium it was established that a strained substrate led to a morphologically unstable NiSi_1-uGe_u. The germanosilicide was highly textured on both (001) and (111) substrates. The texturing was explained by the absence of Ni(SiGe)₂ which forced NiSiGe to reorient so as not to resemble a digermanosilicide at the film/substrate interface. NiSi_0.82Ge_0.18 formed on p⁺-Si_0.82Ge_0.18 in CBKs grew laterally under the SiO₂, defining the contact hole. The contact resistivity extracted by 3D modelling was 5×10^-8 Ωcm².</p>

Phase behaviour information is essential for the development and optimization of hydrocarbon resource production, transport and refining technologies. Experimental data sets for mixtures containing heavy oil and bitumen are sparse as phase behaviour data are difficult to obtain and cost remains prohibitive for most applications. A computational tool that predicts phase behaviours reliably for mixtures containing such ill-defined components, over broad temperature, pressure and composition ranges would play a central role in the advancement of bitumen production and refining process knowledge and would have favourable impacts on the economics and environmental effects linked to the exploitation of such ill-defined hydrocarbon resources. Prior to this work, predictive computational methods were reliable for dilute mixtures of ill-defined constituents. To include a much wider range of conditions, three major challenges were addressed. The challenges include: creation of a robust and accurate numerical approach, implementation of a reliable thermodynamic model, and speciation of ill-defined constituents like Athabasca Bitumen Vacuum Residue (AVR). The first challenge was addressed by creating a novel computational approach based on a global minimization method for phase equilibrium calculations. The second challenge was tackled by proposing a thermodynamic model that combines the Peng-Robinson equation of state with group contribution and related parameter prediction methods. The speciation challenge was addressed by another research group at the University of Alberta. Pseudo components they proposed were used to assign groups and estimate thermodynamic properties. The new phase equilibrium computational tool was validated by comparing simulated phase diagrams with experimental data for mixtures containing AVR and n-alkanes. There is good qualitative and quantitative agreement between computed and experimental phase diagrams over industrially relevant ranges of compositions, pressures and temperatures. Mismatch was only observed over a limited range of compositions, temperatures and pressures. This computational breakthrough provides, for the first time, a platform for reliable phase behaviour computations with broad potential for application in the hydrocarbon resource sector. The specific computational results can be applied directly to solvent assisted recovery, paraffinic deasphalting, and distillation and refining processes for Athabasca bitumen a strategic resource for Canada. / Chemical Engineering

Due to climatic change, increasing thermal loads inbuildings and rising living standards, comfort cooling inbuildings is becoming increasingly important and the demand forcomfort cooling is expanding very quickly around the world. Theincreased cooling demand results in a peak in electrical powerdemand during the hottest summer hours. This peak presents newchallenges and uncertainties to electricity utilities and theircustomers. Cool thermal storage systems have not only the potential tobecome one of the primary solutions to the electrical powerimbalance between production and demand, but also shift coolingenergy use to off-peak periods and avoid peak demand charges.It increases the possibilities of utilizing renewable energysources and waste heat for cooling generation. In addition, acool storage can actually increase the efficiency of combinedheat and power (CHP) generation provided that heat drivencooling is coupled to CHP. Then, the cool storage may avoidpeaks in the heat demand for cooling generation, and this meansthat the CHP can operate at design conditions in most oftime. Phase Change Materials (PCMs) used for cool storage hasobtained considerable attention, since they can be designed tomelt and freeze at a selected temperature and have shown apromising ability to reduce the size of storage systemscompared with a sensible heat storage system because they usethe latent heat of the storage medium for thermal energystorage. The goal of this thesis is to define suitable PCM candidatesfor comfort cooling storage. The thesis work combines differentmethods to determine the thermophysical properties oftetradecane, hexadecane and their binary mixtures, anddemonstrates the potential of using these materials as PCM forcomfort cooling storage. The phase equilibrium of the binarysystem has been studied theoretically as well asexperimentally, resulting in the derivation of the phasediagram. With knowledge of the liquid-solid phase equilibriumcharacteristics and the phase diagram, an improvedunderstanding is provided for the interrelationships involvedin the phase change of the studied materials. It has beenindicated that except for the minimum-melting point mixture,all mixtures melt and freeze within a temperature range and notat a constant temperature, which is so far often assumed in PCMstorage design. In addition, the enthalpy change during thephase transition (heat of fusion) corresponds to the phasechange temperature range; thus, the storage density obtaineddepends on how large a part of the phase change temperaturerange is valid for a given application. Differential Scanning Calorimetery (DSC) is one frequentlyused method in the development of PCMs. In this thesis, it hasbeen found that varying results are obtained depending on theDSC settings throughout the measurements. When the DSC runs ata high heating/cooling rate it will lead to erroneousinformation. Also, the correct phase transition temperaturerange cannot be obtained simply from DSC measurement. Combiningphase equilibrium considerations with DSC measurements gives areliable design method that incorporates both the heat offusion and the phase change temperature range. The potential of PCM storage for peak shaving in differentcooling systems has been demonstrated. A Computer model hasbeen developed for rapid phase equilibrium calculation. The useof phase equilibrium data in the design of a cool storagesystem is presented as a general methodology. Keywords:Comfort cooling, peak shaving, PCM, coolthermal storage system, DSC, phase change temperature range,the heat of fusion, phase equilibrium, phase diagram. Language:English

The function of titanium- and nickel-silicides is to lower the series resistance and contact resistivity in gate, source and drain contacts of an integrated circuit transistor. With decreasing dimensions, the low resistivity C54 TiSi2 is not formed and stays in its high resistivity phase C49. It was found that a layer of niobium interposed between titanium and silicon, which is supposed to promote the C54 phase, led to the formation of the high resistivity C40 (Ti,Nb)Si2 in both small and large contacts. Increased interest in Si1-xGex layers led to the inclusion of the Ni-Si-Ge system in this project. The interaction between nickel and poly-Si0.42Ge0.58 was found to be different from nickel and poly-silicon in the meaning of the phases formed during high temperature annealing. High-resistivity NiSi2 was formed at 750°C, but nickel and Si0.42Ge0.58 formed no disilicide. A massive out-diffusion of germanium from the NiSi1-uGeu resulted in agglomeration at lower temperatures than for NiSi. This was ascribed to the larger enthalpy of formation for nickel reacting with silicon than with germanium. Ternary phase diagrams, with and without the disilicide phase, were calculated. According to the tie lines, NiSi1-uGeu will be in thermodynamic equilibrium with Si1-xGex when u is smaller than x. This was confirmed experimentally, where a balanced germanium concentration in NiSi1-uGeu and Si1-xGex, stabilized the germanosilicide. When nickel interacted with strained and relaxed silicon-germanium it was established that a strained substrate led to a morphologically unstable NiSi1-uGeu. The germanosilicide was highly textured on both (001) and (111) substrates. The texturing was explained by the absence of Ni(SiGe)2 which forced NiSiGe to reorient so as not to resemble a digermanosilicide at the film/substrate interface. NiSi0.82Ge0.18 formed on p+-Si0.82Ge0.18 in CBKs grew laterally under the SiO2, defining the contact hole. The contact resistivity extracted by 3D modelling was 5×10-8 Ωcm2.

Black liquors are presently combusted in recovery boilers where the inorganic cooking chemicals are recovered and the energy in the organic material is converted to steam and electricity. A new technology, developed by Chemrec AB, is black liquor gasification (BLG). BLG has more to offer compared to the recovery boiler process, in terms of on-site generation of electric power, liquid fuel and process chemicals. A prerequisite for both optimization of existing processes and the commercialization of BLG is better understanding of the physical and chemical processes involved including interactions with the refractory lining. The chemistry in the BLG process is very complex and to minimize extensive and expensive time-consuming studies otherwise required accurate and reliable model descriptions are needed for a full understanding of most chemical and physical processes as well as for up-scaling of the new BLG processes. However, by using these calculated model results in practice, the errors in the state of the art thermochemical data have to be considered. An extensive literature review was therefore performed to update the data needed for unary, binary and higher order systems. The results from the review reviled that there is a significant range of uncertainty for several condensed phases and a few gas species. This resulted in experimental re-determinations of the binary phase diagrams sodium carbonate-sodium sulfide (Na2CO3-Na2S) and sodium sulfate-sodium sulfide (Na2SO4-Na2S) using High Temperature Microscopy (HTM), High Temperature X-ray Diffraction (HT-XRD) and Differential Thermal Analysis (DTA). For the Na2CO3-Na2S system, measurements were carried out in dry inert atmosphere at temperatures from 25 to 1200 °C. To examine the influence of pure CO2 atmosphere on the melting behavior, HTM experiments in the same temperature interval were made. The results include re-determination of liquidus curves, in the Na2CO3 rich area, melting points of the pure components as well as determination of the extent of the solid solution, Na2CO3(ss), area. The thermal stability of Na2SO3 was studied and the binary phase diagram Na2SO4-Na2S was re-determined. The results indicate that Na2SO3 can exist for a short time up to 750 °C, before it melts. It was also proved that a solid/solid transformation, not reported earlier, occurs at 675 ± 10 °C. At around 700 °C, Na2SO3 gradually breaks down within a few hours, to finally form the solid phases Na2SO4 and Na2S. From HTM measurements a metastable phase diagram including Na2SO3, as well as an equilibrium phase diagram have been constructed for the binary system Na2SO4-Na2S. Improved data on Na2S was experimentally obtained by using solid-state EMF measurements. The equilibrium constant for Na2S(s) was determined to be log Kf(Na2S(s)) (± 0.05) = 216.28 – 4750(T/K)–1 – 28.28878 ln (T/K). Gibbs energy of formation for Na2S(s) was obtained as ΔfG°(Na2S(s))/(kJ mol–1) (± 1.0) = 90.9 – 4.1407(T/K) + 0.5415849(T/K) ln (T/K). The standard enthalpy of formation of Na2S(s) was evaluated to be ΔfH°(Na2S(s), 298.15 K)/(kJ mol–1) (± 1.0) = – 369.0. The standard entropy was evaluated to be S°(Na2S(s), 298.15 K)/(J mol–1 K–1) (± 2.0) = 97.0. Analyses of used refractory material from the Chemrec gasifier were also performed in order to elucidate the stability of the refractory lining. Scanning electron microscopy (SEM) analysis revealed that the chemical attack was limited to 250-300 μm, of the surface directly exposed to the gasification atmosphere and the smelt. From XRD analysis it was found that the phases in this surface layer of the refractory were dominated by sodiumaluminosilicates, mainly Na1.55Al1.55Si0.45O4.

This research addresses and illuminates a little understood region of miscible polymer mixtures and demonstrates a new means of separating wax from such blends. The method, termed Deformation Induced Phase Segregation potentially eliminates need of toxic processing solvents for wax removal or recovery in these types of blends. Previous theories of polymer combinations address them exclusively as solutions or as blends, two independent classes having very different behaviors. This study provides bridge connecting these two classes by identifying crossover points between them and the behaviors exhibited therein. The blends of this form were found to be semi-miscible, forming a homogenous phase in the melt but a two-phase system in the solid, with the rheological behavior influenced by the polymer's molecular weight and architecture. It also demonstrates practical promise of this regime by introducing a mechanical compression process to separate the wax phase from such a type of blend. This process potentially permits production of ultra-high molecular weight polyethylene (UHMwPE) films and fibers by melt processing, thereby obviating need of otherwise essential but expensive and environmentally unfriendly toxic solvents.

The complete and accurate thermodynamic and kinetic description of any systemis crucialfor understanding and predicting its properties. A particular interest is in systemsthat are used for some practical applications and have to be constantly improved usingmodification of their composition and structure. This task can be quite accuratelysolved at a fundamental level by density functional theory methods. Thesemethods areapplied to two practically important systems Fe-Cr and TiC-ZrC.The elastic properties of pure iron and substitutionally disordered Fe-Cr alloy are investigatedas a function of temperature and concentration using first-principles electronicstructurecalculations by the exact muffin-tin orbitals method. The temperature effectson the elastic properties are included via the electronic, magnetic, and lattice expansioncontributions. It is shown that the degree of magnetic order in both pure iron andFe90Cr10 alloy mainly determines the dramatic change of the elastic anisotropy of thesematerials at elevated temperatures. A peculiarity in the concentration dependence ofthe elastic constants in Fe-rich alloys is demonstrated and related to a change in theFermi surface topology.A thermodynamic model for the magnetic alloys is developed from first principles andapplied to the calculation of bcc Fe-Cr phase diagram. Various contributions to the freeenergy (magnetic, electronic, and phonon) are estimated and included in the model. Inparticular, it is found that magnetic short range order effects are important just abovethe Curie temperature. The model is applied for calculating phase equilibria in disorderedbcc Fe-Cr alloys. Model calculations reproduce a feature known as a Nishizawahorn for the Fe-rich high-temperature part of the phase diagram.The investigation of the TiC-ZrC system includes a detailed study of the defect formationenergies and migration barriers of point defects and defect complexes involvedin the diffusion process. It is found, using ab initio atomistic simulations of vacancymediateddiffusion processes in TiC and ZrC, that a special self-diffusion mechanism isoperative for metal atom diffusion in sub-stoichiometric carbides. It involves a noveltype of a stable point defect, a metal vacancy ”dressed” in a shell of carbon vacancies.It is shown that this vacancy cluster is strongly bound and can propagate through thelattice without dissociating. / <p>QC 20120604</p> / HERO-M

The availability of high quality thermodynamic data on solid solutions and compounds present in multicomponent systems assists in optimizing processing parameters for synthesis, and in evaluating stability domains and materials compatibility under different conditions. Several oxide systems of technological interest, for which thermodynamic data was either not available or is inconsistent were selected for study. Thermodynamic properties of phases present in the binary systems Nb-O and Ta-O were measured in the temperature range from 1000 to 1300 K using solid state electrochemical cells based on (Y2O3) ThO2 as the electrolyte. Based on these measurements and more recent data on heat capacity and phase transitions reported in the literature, Gibbs energy of formation for NbO, NbO2, NbO2.422, Nb2O5-x and Ta2O5 were reassessed. Significant improvements in the data for NbO2, Nb2O5 and Ta2O5 are suggested. The pseudo binary system MoO2-TiO2 was investigated because of the inconsistency between the phase diagram and thermodynamic properties of the solid solution reported in the literature. Based on new electrochemical measurements, a new improved phase diagram for the system MoO2-TiO2, incorporating recently discovered monoclinic to tetragonal phase transition in MoO2 at 1533 K, is presented. Isothermal section of the phase diagram for the ternary systems Cr-Rh-O and Ta-Rh-O and thermodynamic properties of ternary oxides CrRhO3 and TaRhO4 were measured for the first time in the temperature range from 900 to 1300 K. Phase relations for these systems have been computed as a function of oxygen potential at fixed temperature and as a function of temperature at selected oxygen partial pressures. Metal-spinel-corundum three-phase equilibrium in the Ni-Al-Cr-O system at 1373 K has been explored because of its relevance to high temperature corrosion of super alloys. The Gibbs energy of mixing of spinel solid solution was derived from the tie-line data and is compared with the values calculated from cation distribution models. An oxygen potential diagram is developed for the decomposition of spinel solid solution to nickel and corundum solid solution at 1373 K under reducing conditions. The high temperature thermodynamic properties of the phases present in quaternary systems Ca-Co-Al-O and Ca-Cu-Ti-O have been measured by solid state electrochemical cells based on stabilized zirconia. Gibbs energies of formation of the quaternary oxides Ca3CoAl4O10 in the temperature range from 1150 to1500 K and CaCu3Ti4O12 in the range from 900 to 1350 K are presented. Chemical potential diagrams have been computed for the system Al2O3-CaO-CoO at 1500 K. The oxygen potential corresponding to the decomposition of the complex perovskite CaCu3Ti4O12 (CCTO) has been calculated as a function of temperature from the emf of the cell. The effect of the oxygen partial pressure on the phase relations in the pseudo-ternary system CaO-(CuO/Cu2O)-TiO2 at 1273 K has been evaluated. The phase diagrams are useful for the control of the secondary phases that form during synthesis of CCTO, a material exhibiting colossal dielectric response.

Silicium wird während des Ätzvorgangs von Solar-Wafern mit HF-HNO3-Mischungen hauptsächlich zu Hexafluorosilicat (SiF62-) umgewandelt, welches sich negativ auf den Ätzabtrag, die Reaktivität der Ätzlösung und die Oberflächeneigenschaften der Wafer auswirkt. Möglichkeiten, das Silicium als SiF62- abzutrennen, sollten in dieser Arbeit untersucht werden. Voraussetzung für Abtrennungsuntersuchungen war eine quantitative Bestimmung des SiF62- in Ätzlösungen mittels Ramanspektrometrie. Als Abreicherungs-möglichkeiten des Siliciums in Form von Hexafluorosilicat wurden einerseits das Ausfrieren als Hydrat der Hexafluorokieselsäure (H2SiF6•nH2O) und andererseits die Fällung als K2SiF6 untersucht. Die experimentellen Ergebnisse wurden jeweils gestützt durch thermodynamische Modellierungen: die Tieftemperaturphasendiagramme wurden durch eine modifizierte BET-Modellierung bestätigt, die Löslichkeiten durch Nutzung des SIT-Ansatzes. Demnach erwies sich die Ausfällung als K2SiF6 als ökonomisch günstigste Variante.