Dissertations / Theses on the topic 'Peritectic'

This thesis work deals with the volume changes during the solidification of cast irons and peritectic steels. The volume changes in casting metals are related to the expansion and/or contraction of the molten metal during solidification. Often, different types of shrinkage, namely macro- and micro-shrinkage, affect the casting quality. In addition to that, exposure of the metal casting to higher contraction or expansion during the solidification might also be related to internal strain development in samples, which eventually leads to surface crack propagation in some types of steel alloys during continuous casting. In consequence, a deep understanding of the mechanisms and control of the solidification will improve casting quality and production. All of the experiments during the entire work were carried out on laboratory scale samples. Displacement changes during solidification were measured with the help of a Linear Variable Displacement Transformer (LVDT). All of the LVDT experiments were performed on samples inside a sand mould. Simultaneously, the cooling curves of the respective samples during solidification were recorded with a thermocouple. By combining the displacement and cooling curves, the volume changes was evaluated and later used to explain the influence of inoculants, carbon and cooling rates on volume shrinkages of the casting. Hypoeutectic grey cast iron (GCI) and nodular cast iron (NCI) with hypo-, hyper- and eutectic carbon compositions were considered in the experiments from cast iron group. High nickel alloy steel (Sandvik Sanbar 64) was also used from peritectic steel type. These materials were melted inside an induction furnace and treated with different types of inoculants before and during pouring in order to modify the composition. Samples that were taken from the LVDT experiments were investigated using a number of different  methods in order to support the observations from the displacement measurements:  Differential Thermal Analysis (DTA), to evaluate the different phase present; Dilatometry, to see the effect of cooling rates on contraction for the various types of alloys; metallographic studies with optical microscopy; Backscattered electrons (BSE) analysis on SEM S-3700N, to investigate the different types of oxide and sulphide nuclei; and bulk density measurements  by applying Archimedes' principle. Furthermore, the experimental volume expansion during solidification was compared with the theoretically calculated values for GCI and NCI. It was found that the casting shows hardly any shrinkage during early solidification in GCI, but in the eutectic region the casting expands until the end of solidification. The measured and the calculated volume changes are close to one another, but the former shows more expansion. The addition of MBZCAS (Si, Ca, Zr, Ba, Mn and Al) promotes more flake graphite, and ASSC (Si, Ca, Sr and Al) does not increase the number of eutectic cells by much. In addition to that, it lowers the primary austenite fraction, promotes more eutectic growth and decreases undercooled graphite and secondary dendritic arm spacing (SDAS). As a result, the volume expansion changes in the eutectic region. The expansion during the eutectic growth increase with an increase in the inoculant weight percentage. At the same time, the eutectic cells become smaller and increase in number. The effect of the inoculant and the superheat temperature shows a variation in the degree of expansion/contraction and the cooling rates for the experiments. Effective inoculation tends to homogenize the eutectic structure, reducing the undercooled and interdendritic graphite throughout the structure. In NCI experiments, it was found that the samples showed no expansion in the transversal direction due to higher micro-shrinkages in the centre, whereas in the longitudinal direction the samples shows expansion until solidification was complete.   The theoretical and measured volume changes agreed with each other. The austenite fraction and number of micro-shrinkage pores decreased with increase in carbon content. The nodule count and distribution changes with carbon content. The thermal contraction of NCI is not influenced by the variation in carbon content at lower cooling rates. The structural analysis and solidification simulation results for NCI show that the nodule size and count distribution along the cross-sections at various locations are different due to the variation in cooling rates and carbon concentration. Finer nodule graphite appears in the thinner sections and close to the mold walls. A coarser structure is distributed mostly in the last solidified location. The simulation result indicates that finer nodules are associated with higher cooling rate and a lower degree of microsegregation, whereas the coarser nodules are related to lower cooling rate and a higher degree of microsegregation. As a result, this structural variation influences the micro-shrinkage in different parts. The displacement change measurements show that the peritectic steel expands and/or contracts during the solidification. The primary austenite precipitation during the solidification in the metastable region is accompanied by gradual expansion on the casting sides. Primary δ-ferrite precipitation under stable phase diagram is complemented by a severe contraction during solidification. The microstructural analysis reveals that the only difference between the samples is grain refinement with Ti addition. Moreover, the severe contraction in solidification region might be the source for the crack formation due to strain development, and further theoretical analysis is required in the future to verify this observation.

QC 20170228

In dieser Arbeit wurde der Einfluss der Schmelzkonvektion auf das erstarrende Gefüge von peritektischen Nd-Fe-B – und TiAl-Legierungen mit Hilfe neuartiger Methoden untersucht. Da die magnetischen und mechanischen Eigenschaften dieser technisch relevanten Legierungen stark vom Gefüge und insbesondere vom Volumenanteil der properitektischen Phase abhängen, sind diese Untersuchungen von großem Interesse. Auf der Basis der numerischen Simulationen der Schmelzkonvektionsmoden und des elektromagnetischen Problems in einer induktiv beheizten Schmelze, die am Forschungszentrum Dresden-Rossendorf durchgeführt wurden, wurden am IFW Dresden neuartige Versuchsaufbauten entwickelt, die die Modifizierung der Konvektion in einer Metallschmelze ermöglichen. Dies sind ein Aufbau zur erzwungenen Schmelzrotation in einem Tiegel und eine modifizierte Floating-Zone-Anlage. Die erzwungene Schmelzrotation, bei der der Schmelztiegel mit einer definierten Frequenz rotiert, führt in Übereinstimmung mit der Simulation zu einer starken Reduzierung der Konvektion in Abhängigkeit von der Frequenz. Diese Methode wurde auf Nd-Fe-B-Legierungen angewendet mit dem Ziel, die Bildung der unerwünschten weichmagnetischen Eisenphase zu unterdrücken bzw. deren Volumenanteil zu reduzieren. Im Ergebnis konnte der Volumenanteil der properitektischen Phase mit diesem Verfahren um 38.5 % reduziert werden. Das dendritische Gefüge wurde einer ausführlichen statistischen Analyse unterzogen, bei der die Abstände der sekundären Dendritenarme (SDAS) gemessen wurden. Es konnte gezeigt werden, dass die SDAS sich mit steigender Frequenz der Tiegelrotation, was einer reduzierten Schmelzkonvektion entspricht, verringern. Die Verringerung des Volumenanteils der properitektischen Eisenphase und der SDAS wird mit dem reduzierten konvektiven Massentransport unter reduzierter Schmelzkonvektion erklärt. Starke interdendritische Strömung reduziert die Dicke der Diffusionsgrenzschicht um die properitektische Phase. Dadurch wird der Stofftransport durch die Grenzschicht erleichtert. Kleinere Dendritenarme werden in die Schmelze zurückgeschmolzen, wodurch sich der Abstand zwischen den verbleibenden Dendritenarmen vergrößert. Eine Floating-Zone-Anlage, die das tiegelfreie Prozessieren von Metallschmelzen erlaubt wurde so modifiziert, dass mit Hilfe eines Doppelspulensystems eine zusätzliche wohl definierte elektromagnetische Kraft eingebracht wird, über die eine sehr intensive (Zweiphasenrührer in Parallelschaltung) bzw. stark verringerte Strömung (Doppelspule in Reihenschaltung) in der Schmelze eingestellt werden kann. Die experimentellen Ergebnisse der Untersuchungen am Nd-Fe-B-System mit der Doppelspule in Reihenschaltung zeigten, dass sich bei einem optimalen Spulenabstand von 5,1 mm die geringste Schmelzkonvektion ergab, wobei der Anteil des a-Eisen-Volumenanteils weiter verringert werden konnte. Im Gegensatz dazu wurde mit dem Zweiphasenrührer in Parallelschaltung eine sehr starke Schmelzkonvektion mit einem maximalen Volumenanteil der a-Eisen-Phase eingestellt, wobei durch die starke Rührung ein Wechsel der Morphologie von dendritisch zu globular zu beobachten war. Die Untersuchungen zum Einfluss der starken Schmelzkonvektion wurden auf ein weiteres peritektisch erstarrendes System ausgedehnt, um eine generalisierte Aussage zum Einfluss der Konvektion auf Gefüge und Eigenschaften peritektisch erstarrender Legierungen zu erhalten. Die ausgewählte Ti45Al55 - Legierung erstarrte unter starker Schmelzkonvektion ebenfalls globulitisch, wobei Reste dendritisch erstarrter properitektischer Phase gefunden wurden. Der Volumenanteil der properitektischen Phase steigt dabei mit zunehmender Rührwirkung an. Der Wechsel der Morphologie von dendritisch zu globular/dendritisch kann mit sphärischem Wachstum oder Fragmentierung der Dendritenarme erklärt werden. Die mechanischen Eigenschaften unter unterschiedlicher Schmelzkonvektion erstarrter Ti45Al55 – Legierung wurden bei Druckversuchen untersucht. Es wurde eine signifikant höhere plastische Verformbarkeit an der unter starker Schmelzkonvektion erstarrten Ti45Al55 – Legierung gefunden. Dies wird der isotropen spherischen Morphologie der lamellaren a2/g-Phase zugeordnet, während die anisotrope Orientierung der dendritisch- lamellaren Phase unerwünschte plastische Eigenschaften zeigt. Die Untersuchungen des Einflusses der Schmelzkonvektion auf das Gefüge peritektisch erstarrender Legierungen zeigten, dass ein maßgeschneidertes Gefüge durch optimale Wahl der Schmelzkonvektion möglich ist und damit magnetische bzw. mechanische Eigenschaften verbessert werden können. Die Kontrolle der Schmelzkonvektion ist daher ein geeignetes Mittel gewünschte Gefüge und Eigenschaften in Abhängigkeit von den Prozessabläufen einzustellen
In this work, the effect of melt convection on the microstructure evolution of peritectic Nd-Fe-B and Ti-Al alloy systems was studied using novel techniques. The microstructural formation including the change in volume fraction and morphology of the properitectic phase influences the magnetic and mechanical properties for the Nd-Fe-B and Ti-Al alloy systems, respectively. On the basis of numerical simulations by the research group of Dr. Gunter Gerbeth from Department of Magnetohydrodynamics, Forschungszentrum Dresden-Rossendorf, two types of specially designed facilities were developed where melt convection can be altered by changing a number of parameters. These are: forced rotation facility and modified floating zone facility. According to the numerical simulation, an additional crucible rotation suppresses the internal melt motion significantly during forced rotation experiments, where the molten alloy is rotated at a well-defined frequency. This method was applied during the solidification of Nd-Fe-B alloys with the aim to suppress the volume fraction of undesired soft magnetic a-Fe phase. As a result, the volume fraction of properitectic phase with this method can be reduced up to 38 %. A detailed statistical analysis of secondary dendritic arm spacing (SDAS) measurements of a-Fe showed that the SDAS decreases as the rotational frequency increases and melt convection decreases. The reduction in the phase fraction and SDAS of properitectic phase is attributed to the reduced convective mass transfer under reduced melt motion. At high fluid velocity and low rotational frequency, the stronger interdendritic flow reduces the solute boundary layer and increases the transfer of solute through the interface. The smaller dendrite arms dissolve into the melt and thus the SDAS becomes higher than that of the samples solidified at higher rotational frequencies with reduced melt convection. Floating zone facility, which allows contactless heating without any contamination for highly reactive melts, was modified with a double coil system so that an additional electromagnetic force is introduced inside the melt. This induces either very intensive (two-phase stirrer in parallel connection coil system) or very reduced flow (series connection coil system) inside the melt The experimental results of series connection coil system showed that a reduced melt convection state is achieved near 5.1 mm coil distance where a-Fe volume fraction becomes minimum. On the contrary, the parallel coil system experiments showed that a-Fe volume fraction becomes maximum when the phase shift between the coils is close to 90°. The morphology of the a-Fe becomes globular due to spherical growth under strong convection. The study on the effect of strong stirring was extended to another alloy to get a generalized idea about the influence of melt convection on the microstructure development and resulting properties of peritectic alloys. Peritectic Ti45Al55 alloys were investigated by the two-phase stirrer using the coils connected in parallel to study the effect of enhanced melt convection. The increase in the properitectic phase fraction together with a strong change in the morphology from dendritic to spherical were observed in the stirred samples. The increase in the properitectic phase fraction occurs due to the enhanced effective mass transfer under strong melt convection. The change in morphology of the properitectic phase is attributed to spherical growth or fragmentation of dendrite arms under strong convection. The mechanical properties of Ti45Al55 alloys, which are solidified at different convection states, were studied. There was a significantly higher plastic deformability of stirred samples compared to unstirred samples. The coarse anisotropic orientation of the dendritic lamellar phase is detrimental for the plastic deformability, which is absent in the stirred samples due to the spherical and discrete morphology of the properitectic phase. This study indicates that tailored microstructure can be obtained either by decreasing (e.g. for Nd-Fe-B alloy) or increasing (e.g. for Ti-Al alloy) the convection state using effective techniques inside the melt to improve the magnetic and mechanical properties, respectively. Thus, controlling convection is a useful way to get favorable microstructure according to the process need

In dieser Arbeit wurde der Einfluss der Schmelzkonvektion auf das erstarrende Gefüge von peritektischen Nd-Fe-B – und TiAl-Legierungen mit Hilfe neuartiger Methoden untersucht. Da die magnetischen und mechanischen Eigenschaften dieser technisch relevanten Legierungen stark vom Gefüge und insbesondere vom Volumenanteil der properitektischen Phase abhängen, sind diese Untersuchungen von großem Interesse. Auf der Basis der numerischen Simulationen der Schmelzkonvektionsmoden und des elektromagnetischen Problems in einer induktiv beheizten Schmelze, die am Forschungszentrum Dresden-Rossendorf durchgeführt wurden, wurden am IFW Dresden neuartige Versuchsaufbauten entwickelt, die die Modifizierung der Konvektion in einer Metallschmelze ermöglichen. Dies sind ein Aufbau zur erzwungenen Schmelzrotation in einem Tiegel und eine modifizierte Floating-Zone-Anlage. Die erzwungene Schmelzrotation, bei der der Schmelztiegel mit einer definierten Frequenz rotiert, führt in Übereinstimmung mit der Simulation zu einer starken Reduzierung der Konvektion in Abhängigkeit von der Frequenz. Diese Methode wurde auf Nd-Fe-B-Legierungen angewendet mit dem Ziel, die Bildung der unerwünschten weichmagnetischen Eisenphase zu unterdrücken bzw. deren Volumenanteil zu reduzieren. Im Ergebnis konnte der Volumenanteil der properitektischen Phase mit diesem Verfahren um 38.5 % reduziert werden. Das dendritische Gefüge wurde einer ausführlichen statistischen Analyse unterzogen, bei der die Abstände der sekundären Dendritenarme (SDAS) gemessen wurden. Es konnte gezeigt werden, dass die SDAS sich mit steigender Frequenz der Tiegelrotation, was einer reduzierten Schmelzkonvektion entspricht, verringern. Die Verringerung des Volumenanteils der properitektischen Eisenphase und der SDAS wird mit dem reduzierten konvektiven Massentransport unter reduzierter Schmelzkonvektion erklärt. Starke interdendritische Strömung reduziert die Dicke der Diffusionsgrenzschicht um die properitektische Phase. Dadurch wird der Stofftransport durch die Grenzschicht erleichtert. Kleinere Dendritenarme werden in die Schmelze zurückgeschmolzen, wodurch sich der Abstand zwischen den verbleibenden Dendritenarmen vergrößert. Eine Floating-Zone-Anlage, die das tiegelfreie Prozessieren von Metallschmelzen erlaubt wurde so modifiziert, dass mit Hilfe eines Doppelspulensystems eine zusätzliche wohl definierte elektromagnetische Kraft eingebracht wird, über die eine sehr intensive (Zweiphasenrührer in Parallelschaltung) bzw. stark verringerte Strömung (Doppelspule in Reihenschaltung) in der Schmelze eingestellt werden kann. Die experimentellen Ergebnisse der Untersuchungen am Nd-Fe-B-System mit der Doppelspule in Reihenschaltung zeigten, dass sich bei einem optimalen Spulenabstand von 5,1 mm die geringste Schmelzkonvektion ergab, wobei der Anteil des a-Eisen-Volumenanteils weiter verringert werden konnte. Im Gegensatz dazu wurde mit dem Zweiphasenrührer in Parallelschaltung eine sehr starke Schmelzkonvektion mit einem maximalen Volumenanteil der a-Eisen-Phase eingestellt, wobei durch die starke Rührung ein Wechsel der Morphologie von dendritisch zu globular zu beobachten war. Die Untersuchungen zum Einfluss der starken Schmelzkonvektion wurden auf ein weiteres peritektisch erstarrendes System ausgedehnt, um eine generalisierte Aussage zum Einfluss der Konvektion auf Gefüge und Eigenschaften peritektisch erstarrender Legierungen zu erhalten. Die ausgewählte Ti45Al55 - Legierung erstarrte unter starker Schmelzkonvektion ebenfalls globulitisch, wobei Reste dendritisch erstarrter properitektischer Phase gefunden wurden. Der Volumenanteil der properitektischen Phase steigt dabei mit zunehmender Rührwirkung an. Der Wechsel der Morphologie von dendritisch zu globular/dendritisch kann mit sphärischem Wachstum oder Fragmentierung der Dendritenarme erklärt werden. Die mechanischen Eigenschaften unter unterschiedlicher Schmelzkonvektion erstarrter Ti45Al55 – Legierung wurden bei Druckversuchen untersucht. Es wurde eine signifikant höhere plastische Verformbarkeit an der unter starker Schmelzkonvektion erstarrten Ti45Al55 – Legierung gefunden. Dies wird der isotropen spherischen Morphologie der lamellaren a2/g-Phase zugeordnet, während die anisotrope Orientierung der dendritisch- lamellaren Phase unerwünschte plastische Eigenschaften zeigt. Die Untersuchungen des Einflusses der Schmelzkonvektion auf das Gefüge peritektisch erstarrender Legierungen zeigten, dass ein maßgeschneidertes Gefüge durch optimale Wahl der Schmelzkonvektion möglich ist und damit magnetische bzw. mechanische Eigenschaften verbessert werden können. Die Kontrolle der Schmelzkonvektion ist daher ein geeignetes Mittel gewünschte Gefüge und Eigenschaften in Abhängigkeit von den Prozessabläufen einzustellen.
In this work, the effect of melt convection on the microstructure evolution of peritectic Nd-Fe-B and Ti-Al alloy systems was studied using novel techniques. The microstructural formation including the change in volume fraction and morphology of the properitectic phase influences the magnetic and mechanical properties for the Nd-Fe-B and Ti-Al alloy systems, respectively. On the basis of numerical simulations by the research group of Dr. Gunter Gerbeth from Department of Magnetohydrodynamics, Forschungszentrum Dresden-Rossendorf, two types of specially designed facilities were developed where melt convection can be altered by changing a number of parameters. These are: forced rotation facility and modified floating zone facility. According to the numerical simulation, an additional crucible rotation suppresses the internal melt motion significantly during forced rotation experiments, where the molten alloy is rotated at a well-defined frequency. This method was applied during the solidification of Nd-Fe-B alloys with the aim to suppress the volume fraction of undesired soft magnetic a-Fe phase. As a result, the volume fraction of properitectic phase with this method can be reduced up to 38 %. A detailed statistical analysis of secondary dendritic arm spacing (SDAS) measurements of a-Fe showed that the SDAS decreases as the rotational frequency increases and melt convection decreases. The reduction in the phase fraction and SDAS of properitectic phase is attributed to the reduced convective mass transfer under reduced melt motion. At high fluid velocity and low rotational frequency, the stronger interdendritic flow reduces the solute boundary layer and increases the transfer of solute through the interface. The smaller dendrite arms dissolve into the melt and thus the SDAS becomes higher than that of the samples solidified at higher rotational frequencies with reduced melt convection. Floating zone facility, which allows contactless heating without any contamination for highly reactive melts, was modified with a double coil system so that an additional electromagnetic force is introduced inside the melt. This induces either very intensive (two-phase stirrer in parallel connection coil system) or very reduced flow (series connection coil system) inside the melt The experimental results of series connection coil system showed that a reduced melt convection state is achieved near 5.1 mm coil distance where a-Fe volume fraction becomes minimum. On the contrary, the parallel coil system experiments showed that a-Fe volume fraction becomes maximum when the phase shift between the coils is close to 90°. The morphology of the a-Fe becomes globular due to spherical growth under strong convection. The study on the effect of strong stirring was extended to another alloy to get a generalized idea about the influence of melt convection on the microstructure development and resulting properties of peritectic alloys. Peritectic Ti45Al55 alloys were investigated by the two-phase stirrer using the coils connected in parallel to study the effect of enhanced melt convection. The increase in the properitectic phase fraction together with a strong change in the morphology from dendritic to spherical were observed in the stirred samples. The increase in the properitectic phase fraction occurs due to the enhanced effective mass transfer under strong melt convection. The change in morphology of the properitectic phase is attributed to spherical growth or fragmentation of dendrite arms under strong convection. The mechanical properties of Ti45Al55 alloys, which are solidified at different convection states, were studied. There was a significantly higher plastic deformability of stirred samples compared to unstirred samples. The coarse anisotropic orientation of the dendritic lamellar phase is detrimental for the plastic deformability, which is absent in the stirred samples due to the spherical and discrete morphology of the properitectic phase. This study indicates that tailored microstructure can be obtained either by decreasing (e.g. for Nd-Fe-B alloy) or increasing (e.g. for Ti-Al alloy) the convection state using effective techniques inside the melt to improve the magnetic and mechanical properties, respectively. Thus, controlling convection is a useful way to get favorable microstructure according to the process need.

要旨ファイルのタイトルは"Peritectic reactions in Mg-O-H and Fe-S-H systems in the primordial solar nebula
Kyoto University (京都大学)
0048
新制・課程博士
博士(理学)
甲第5617号
理博第1546号
新制||理||859(附属図書館)
UT51-94-J49
京都大学大学院理学研究科地質学鉱物学専攻
(主査)教授 坂野 昇平, 教授 西村 進, 教授 鎮西 清高
学位規則第4条第1項該当

Surface transverse cracking is still one of the main problems in the continuous casting of steel. The cooling rate at the corners of the slab and strand is usually the highest. Therefore, depending on the cooling regime, the initial temperature drop (primary cooling to the Tmin values) in the corner regions can result in temperatures that fall into the low-temperature range of the austenite region or the α+γ transformation zone. This can cause ferrite formation or promote the precipitation of non-metallic inclusion particles at the grain boundaries and in ferrite due to the lower solubility of these particles in ferrite than in austenite. The objective of this study was to simulate the effect of the initial austenite conditioning, the extent of primary cooling, the magnitude of the temperature rebound and the unbending temperature on the ductility properties of a plain carbon peritectic steel grade under conditions resembling the commercial continuous casting process. The austenite grain conditioning was studied using two methods, the 1350 °C treatment and the simulated in-situ melting conditionings. Both of these conditionings were utilised to accomplish the initial austenite grain sizes similar to the as-cast microstructure in the magnitudes of ± 500 μm to ± 1000 μm. Bähr DIL805 Dilatometer equipment was used to simulate the heat treatments which allowed the study of the initial austenite grain size distributions. The Gleeble 1500D thermomechanical simulator was used to study the hot ductility behavior of the plain carbon peritectic steel grade. During the hot ductility test, the tensile specimens are usually solution treated at high temperatures, followed by cooling to the unbending temperatures and then fractured isothermally. However, in this study, instead of cooling the specimens directly to the unbending temperatures after the austenite treatment, the specimens were subjected to simulated primary cooling, followed by temperature rebound (i.e. ΔTr) of either 200 °C or 300 °C as well as a simulated secondary slow cooling process (at a cooling rate of 0.1 °C/s) and then isothermally deformed to fracture in the temperature range of 630–1060 °C. In both cases of the austenite conditioning, the ductility was observed to be high when the hot deformation specimens were subjected to Tmin (830 °C), this temperature being the minimum temperature reached after primary cooling and was very close to the equilibrium austenite start transformation temperature, 840 °C. In both cases of Tmin values closer to the equilibrium austenite start transformation temperature, the coarse-grained (± 500 μm) specimens showed better ductility results, compared to the abnormally large grained (±1000 μm) specimens. This was attributed to the differences in the microstructure such as the initial austenite grain sizes, the segregation effects and high fraction of non-metallic inclusion particles at the austenite grain boundaries. The influence of the magnitude of the rebound steps (i.e. ΔTr) was also studied. The result showed that for the specimens subjected to the Tmin (830 °C), ductility increased as the ΔTr increased from 200 °C to 300 °C. Moreover, with the rebound step of 300 °C ductility values increased further with an increase in the unbending temperatures (TU) and this was observed for the specimens heated to 1350 °C. In contrast to this observation for the specimens treated at 1350 °C, small ΔTr (200 °C) showed better hot ductility values than large ΔTr (300 °C) for the specimens molten in-situ condition and this was observed in the unbending temperature range of 830-940 °C. However, the hot ductility values of these specimens were observed to increase with an increase in unbending temperature range of 980-1040 °C. In both cases of the austenite conditionings, the relatively good ductility results were attributed to the beneficial effect of Tmin values. These temperatures were 10 °C and 30 °C below the equilibrium austenite start transformation temperature, Ae3 for the specimens treated at 1350 °C and molten in-situ conditions, respectively. After quenching the specimens from these temperatures (Tmin), no grain boundary films of ferrite were observed. Due to the absence of ferrite, a smaller density of inclusion particles at the grain boundaries was expected. Furthermore, the effect of Tmax values (e.g. 1030 °C and 1130 °C) and high unbending temperatures (830-1060 °C and 830-960 °C) were also thought to have contributed towards good ductility results. The hot ductility values only decreased when the unbending temperatures fell below the Ar3S (~788 °C) temperature and this was observed for both austenite conditionings.
Dissertation (MSc)--University of Pretoria, 2020.
Materials Science and Metallurgical Engineering
MSc
Unrestricted

This thesis work concerns about the importance of the cast surfaces, surface phenomenon such as the formation of the oscillation marks and exudation and related defects including cracks and segregation that happened during the continuous casting. All of the investigated materials were collected during the plant trials while an in-depth analysis on these materials was performed at the laboratory scale with certain explanations supported by the schematic and theoretical models. The work consists on different material classes such as steels and phosphor bronzes with a focus on the surface defects and their improvements. In order to facilitate the theoretical analysis which could be capable of explaining the suggested phenomenon in the thesis, a reduced model is developed which required lesser computational resources with lesser convergence problems.

QC 20160527

Oscilation mark formation during continous casting of steel

Thesis (PhD (Earth Sciences))--University of Stellenbosch, 2010.
ENGLISH SUMMARY: S-type granite intrusions are extremely common in the continental crust and form from the partial melting of metasediments. Compositions of S-type granite range from leucogranite to granodiorite and have trace element contents that globally increase with increasing maficity (Fe + Mg). Models proposed for the formation of S-type granite do not answer satisfactorily all petrological and compositional requirements. In this study, S-type granite of the Cape Granite Suite (CGS), South Africa is used to discriminate between potential sources of compositional variation. Experimental studies show that melt produced from the partial melting of sediment is exclusively leucocratic. On this basis, the entrainment of up to 20 wt.% of peritectic garnet within S-type melt can be established to produce the observed major element variations. S-type CGS locally contains garnet. This garnet is in equilibrium with granite composition at P-T conditions (5kb and 750 C for the core of the garnet and 3kb and 720 C for the rim) well below conditions recorded by xenoliths from the same granite (10 kb and 850 C from a metabasite). From this result it seems that the originally entrained garnet no longer exists in the Stype CGS and it have been replaced by newly formed minerals (garnet, cordierite and biotite). Considering the short time necessary to emplace granites (about 100 000 years), it appears that garnet has been compositionnally re-equilibrated through a dissolution-precipitation process. The study of trace element variations in S-type CGS shows that most leucocratic compositions are undersaturated in Zr and Ce compared to predictions from experimental models for dissolution of accessory zircon and monazite in their source regions. Thus, S-type melts are likely to be formed in disequilibrium with respect to accessory phase stability. As a result the observed increase in trace element content with increasing maficity indicates that accessory minerals such as zircon and monazite are co-entrained with peritectic garnet in melt to produce the observed trace element variation in S-type granite. Trace element disequilibrium in the CGS S-type granitoids requires particularly short times of residence of melt within the source region. Together, these results provide for the first time, a fully comprehensive model for major and trace elements variations. Compositional variation in CGS S-type granite results from source processes by a selective entrainment of peritectic and accessory minerals. After entrainment, these minerals are likely to be re-equilibrated within the magma, through a dissolution-reprecipitation process. In addition, it appears that the construction of large S-type granitic bodies occurs through successive addition of magma batches of different composition that originates directly from the source region.
AFRIKAANSE OPSOMMING: S-tipe granietinstrusies is baie algemeen in die kontinentale kors en vorm deur die gedeeltelike smelting van metasedimente. Samestellings van S-tipe graniete strek vanaf leukograniet tot granodioriet en het spoorelementsamestellings wat global toeneem met ’n toenemende mafiese component (Fe + Mg). Modelle wat voorgestel is vir die formasie van S-tipe graniete beantwoord nie bevredigend al die petrologiese en komposisionele benodigdhede nie. In hierdie studie word S-tipe graniete van die Kaapse Graniet Suite (CGS), Suid Afrika, gebruik om te diskrimineer tussen potensiele bronne van komposisionele variasie. Eksperimentele studies wys dat smelt, geproduseer van die gedeeltelike smelting van sedimente, uitsluitlik leukokraties is. Op hierdie basis kan bewys word, dat die optel-en-meevoering van tot 20 wt% van peritektiese granaat in S-tipe smelt, die waargeneemde hoofelement variasies kan produseer. S-tipe CGS bevat lokale granaat. Hierdie granaat is in ekwilibrium met die graniet samestelling by P-T kondisies (5kb en 750circC vir die kern van die granaat en 3kb en 720circC vir die rand) ver onder kondisies waargeneem by xenoliete van dieselfde granite (10kb en 850circC van ’n metabasiet). Van hierdie resultaat kan afgelei word dat die oorspronklike opgetel-en-meegevoerde graniet bestaan nie meer in die S-tipe CGS en dat dit vervang is deur nuutgevormde minerale (granaat, kordieriet en biotiet). As in ag geneem word die kort tyd wat nodig is om graniete in te plaas (omtrent 100 000 jaar), wil dit voorkom dat granaat se samestelling geherekwilibreer word deur ’n oplossings-presipitasie proses. Die studie van spoorelement variasies in S-tipe CGS wys dat meeste leukokratiese samestellings is onderversadig in Zr en Ce in vergelyking met voorspellings deur eksperimentele modelle vir die oplossing van bykomstige zircon en monasiet in hulle brongebiede. Dus is S-tipe smelte meer geneig om gevorm te word in disekwilibrium in verhouding tot bykomstige mineraalstabilileit. Met die gevolg is dat die waargenome toename in spoorelementinhoud met toename in mafiese component wys dat bykomstige minerale, soos zirkoon en monasiet, word saam opgetel-enmeegevoer met peritektiese granaat in smelt om die waargenome spoorelement variasie in S-tipe graniete te verklaar. Spoorelement disekwilibrium in die CGS S-tipe granitoide benodig veral kort tye van residensie van die smelt binne die brongebied. Saam gee hierdie resultate vir die eerste keer ’n algehele antwoord vir hoof- en spoorelement variasies. Variasie in samestelling in CGS S-tipe graniete is die resultaat van bronprosesse deur ’n selektiewe optel-en-meevoer van peritektiese en bykomstige minerale. Na die optel-en-meevoer van hierdie minerale word hulle geherekwilibreer binne die magma deur ’n oplossings-presipitasie proses. Addisioneel wil dit voorkom of die konstruksie van groot S-tipe granietliggame plaasvind deur opeenvolgende toevoegings van magma lotte van verskillende samestellings wat direk uit die brongebied kom.

Cette thèse est le volet expérimental d’un projet de recherche qui vise à développer un code de calcul qui prédit finement la micro ségrégation des aciers présentant une réaction péritectique. La caractérisation expérimentale de la micro ségrégation a été menée grâce à des essais de solidification dirigée et des essais de trempe en cours de solidification dirigée ainsi que sur des échantillons de lingots industriels. Les alliages sélectionnés font partie des systèmes Fe-C-Ni et Fe-C-Cr. Nous avons d’abord étudié sur des aciers solidifiés l’effet de la composition chimique et l’effet du premier solide ferrite / austénite sur la micro ségrégation. Par la suite nous avons caractérisé la formation de la micro ségrégation avec et sans réaction péritectique. On a montré aussi les effets de la taille de la structure, de la microstructure (dendritique / cellulaire)et de la texture du grain sur la micro ségrégation (colonnaire / équiaxe) sur la micro ségrégation. Enfin, nous avons comparé les résultats expérimentaux avec les résultats de la modélisation
This PhD work is an experimental part of a global R&D project witech aim to study the microsegregation in peritectic steels. The experimental investigations were made by a Directional Solidification device (DS), Quenched Directional Solidification (QDS) and from parts of industrials ingots. The alloys selected were taken from the Fe-C-Ni and Fe-C-Cr systems. On the solidified steels we investigate the effect of the chemical composition and the first solid (ferrite/austenite) on the microsegregation. The next step was the characterization of the microsegregation during the solidification with and without a peritectic reaction. Afterwards we study the effects of the length of the structure, the microstructure (dendritic/cellular) and the texture of the grains (columnar/equiaxed) on the microsegregation. At the end we have do a comparison bethween the experimental results and those from the numerical simulations

Climate change is no longer imminent but eminent. To combat climate change, effective, efficient and smart energy use is imperative. Thermal energy storage (TES) with phase change materials (PCMs) is one attractive choice to realize this. Besides suitable phase change temperatures and enthalpies, the PCMs should also be robust, non-toxic, environmental-friendly and cost-effective. Cost-effective PCMs can be realized in bulk blends. Blends however do not have robust phase change unless chosen articulately. This thesis links bulk blends and robust, cost-effective PCMs via the systematic design of blends as PCMs involving phase equilibrium evaluations. The key fundamental phase equilibrium knowledge vital to accurately select robust PCMs within blends is established here. A congruent melting composition is the most PCM-ideal among blends. Eutectics are nearly ideal if supercooling is absent. Any incongruent melting composition, including peritectics, are unsuitable as PCMs. A comprehensive state-of-the-art evaluation of the phase equilibrium-based PCM design exposed the underinvestigated categories: congruent melting compositions, metal alloys, polyols and fats. Here the methods and conditions essential for a comprehensive and transparent phase equilibrium assessment for designing PCMs in blends are specified. The phase diagrams of the systems erythritol-xylitol and dodecane-tridecane with PCM potential are comprehensively evaluated. The erythritol-xylitol system contains a eutectic in a partially isomorphous system unlike in a non-isomorphous system as previous literature proposed. The dodecane-tridecane system forms a probable congruent minimum-melting solid solution, but not a maximum-melting liquidus or a eutectic as was previously proposed. The sustainability aspects of a PCM-based TES system are also investigated. Erythritol becomes cost-effective if produced using glycerol from bio-diesel production. Olive oil is cost-effective and has potential PCM compositions for cold storage. A critical need exists in the standardization of methods and transparent results reporting of the phase equilibrium investigations in the PCM-context. This can be achieved e.g. through international TES collaboration platforms.
Energi är en integrerad del av samhället men energiprocesser leder till miljöbelastning, och klimatförändringar. Därför är effektiv energianvändning, ökad energieffektivitet och smart energihantering nödvändigt. Värmeenergilagring (TES) är ett attraktivt val för att bemöta detta behov, där ett lagringsalternativ med hög densitet är s.k. fasomvandlingsmaterial (PCM). Ett exempel på ett billigt, vanligt förekommande PCM är systemet vatten-is, vilket har använts av människor i tusentals år. För att tillgodose de många värme- och kylbehov som idag uppstår inom ett brett temperaturintervall, är det viktigt med innovativ design av PCM. Förutom lämplig fasförändringstemperaturer, entalpi och andra termofysikaliska egenskaper, bör PCM också ha robust fasändring, vara miljövänlig och kostnadseffektiv. För att förverkliga storskaliga TES system med PCM, är måste kostnadseffektivitet och robust funktion under många cykler bland de viktigaste utmaningarna. Kostnadseffektiva PCM kan bäst erhållas från naturliga eller industriella material i bulkskala, vilket i huvudsak leder till materialblandningar, snarare än rena ämnen. Blandningar uppvisar dock komplexa fasförändringsförlopp, underkylning och/eller inkongruent smältprocess som leder till fasseparation. Denna doktorsavhandling ger ny kunskap som möjliggör att bulkblandningar kan bli kostnadseffektiva och robusta PCM-material, med hjälp av den systematiskutvärdering av fasjämvikt och fasdiagram. Arbetet visar att detta kräver förståelse av relevanta grundläggande fasjämviktsteorier, omfattande termiska och fysikalisk-kemiska karakteriseringar, och allmänt tillämpliga teoretiska utvärderingar. Denna avhandling specificerar befintlig fasjämviktsteori för PCM-sammanhang, men sikte på att kunna välja robusta PCM blandningar med specifika egenskaper, beroende på tillämpning. Analysen visar att blandningar med en sammansättning som leder till kongruent smältande, där faser i jämvikt har samma sammansättning, är ideala bland PCM-blandningar. Kongruent smältande fasta faser som utgör föreningar eller fasta lösningar av ingående komponenter är därför ideala. Eutektiska blandningar är nästan lika bra som PCM, så länge underkylning inte förekommer. Därmed finns en stor potential för att finna och karakterisera PCM-ideala blandningar som bildar kongruent smältande föreningar eller fasta lösningar. Därigenom kan blandningar med en skarp, reversibel fasändring och utan fasseparation erhållas – egenskaper som liknar rena materialens fasändringsprocess. Vidare kan man, via fasdiagram, påvisa de blandningar som är inkongruent smältande, inklusive peritektiska blandningar, som är direkt olämpliga som PCM. Denna avhandling ger grundläggande kunskap som är en förutsättning för att designa PCM i blandningar. Genom en omfattande state-of-the-art utvärdering av fas-jämviktsbaserad PCM-design lyfter arbetet de PCM-idealiska blandningarna som hittills inte fått någon uppmärksamhet, såsom kongruenta smältande blandningar, och materialkategorierna metallegeringar, polyoler och fetter. Resultatet av arbetet visar dessutom att vissa PCM-material som ibland föreslås är direkt olämpliga då fasdiagram undersöks, bl a pga underkylning och även peritektiska system med fasseparation och degradering av kapaciteten (t ex Glauber-salt och natriumacetat-trihydrat). Denna avhandling specificerar och upprättar grundläggande teori samt tekniker, tillvägagångssätt och förhållanden som är nödvändiga för en omfattande och genomsynlig fasjämviktsbedömning, för utformning av PCM från blandningar för energilagering. Med detta som bas har följande fasdiagramtagits fram fullständigt: för erytritol-xylitol och för dodekan-tridekan, med PCM-potential för låg temperaturuppvärmning (60-120 °C) respektive frysning (-10 °C till -20 °C) utvärderas fullständigt. Erytritol-xylitol systemet har funnits vara eutektiskt i ett delvis isomorft system, snarare än ett icke-isomorft system vilket har föreslagits tidigare litteratur. Dodekan-tridekan systemet bildar ett system med kongruent smältande fast lösning (idealisk som en PCM) vid en minimumtemperatur, till skillnad från tidigare litteratur som föreslagt en maximumtemperatur, eller ett eutektiskt system. Teoretisk modellering av fasjämvikt har också genomförts för att komplettera det experimentella fasdiagrammet för systemet erytritol-xylitol. Efter granskning av de metoder som använts tidigare i PCM-litteraturen har här valts ett generiskt tillvägagångssätt (CALPHAD-metoden). Denna generiska metod kan bedöma vilken typ av material och fasändring som helst, till skillnad från en tidigare använda metoder som är specifika för materialtyper eller kemiska egenskaper. Denna teoretiska studie bekräftar termodynamiskt solvus, solidus, eutektisk punkt och erytritol-xylitol fasdiagrammet i sin helhet. Vad gäller hållbarhetsaspekter med PCM-baserad TES, lyfter denna avhandling fokus på förnybara och kostnadseffektiva material (t.ex. polyoler och fetter) som PCM. Som exempel har här undersökts erytritol och olivolja, med förnybart ursprung. Erytritol skulle kunna bli ett kostnadseffektivt PCM (163 USD/kWh), om det produceras av glycerol vilket är en biprodukt från biodiesel/bioetanolframställning. Olivolja är ännu ett kostnadseffektivt material (144 USD/kWh), och som här har påvisats innehålla potentiella PCM sammansättningar med lämpliga fasändringsegenskaper för kylatillämpningar. En övergripande slutsats från denna avhandling är att det finns ett behov av att standardisera tekniker, metoder och transparent resultatrapportering när det gäller undersökningar av fasjämvikt och fasdiagram i PCM-sammanhang. Internationella samarbetsplattformar för TES är en väg att koordinera arbetet.

QC 20170830

High-energy ball milling and powder metallurgy methods were used to produce a partially alloyed nickel and molybdenum of γ-Ni₃Mo composition (Ni-25at.%Mo). Milled powders were cold-compacted, sintered/solutionized at 1300°C for 100h sintering followed by quenching. Three transformation studies were performed. First, the intermetallic γ-Ni₃Mo was formed from the supersaturated solution at temperatures ranging between 600°C and 900°C for up to 100h. The 100% stable γ-Ni₃Mo phase was formed at 600°C after 100h, while aging at temperatures ranging between 650°C and 850°C for 25h was not sufficient to complete the transformation. The δ-NiMo phase was observed only at 900°C as cellular and basket strands precipitates. Second, the reversed peritectoid transformation from γ-Ni₃Mo to α-Ni and δ-NiMo was performed. Supersaturated solid solution samples were first aged at 600C for 100h followed by quenching to form the equilibrium γ-Ni₃Mo phase. After that, the samples were heat treated between 910°C and 1050°C for up to 10h followed by quenching. Regardless of heat-treatment temperature, samples heat-treated for shorter times exhibited small precipitates of δ-NiMo along and within grain boundaries of α-Ni phase, and it coarsened with time. Third, the transformation from the supersaturated solution α-Ni to the peritectoid two-phase region was performed. The samples were aged between 910°C and 1050°C for up to 10h followed by quenching. Precipitates of δ-NiMo were observed in the α-Ni matrix as small particles and then coarsened with aging time. In all three cases, hardness values increased and peaked in a way similar to that of traditional aging, except that the peak occurred much rapidly in the second and third cases. In the first case, hardness increased by about 113.6% due to the development of the new phases, while the hardness increased by 90.5% and 77.2% in the second and third cases, respectively.
Master of Science