The aluminum industry is in need of high-speed in-situ elemental identification technology for molten metals. wTe Corporation of Bedford, MA was granted funds to research this technology for aluminum through the Advanced Technology Program (ATP) of the National Institute of Standards and Technology (NIST). As a secondary metal scrap processor, wTe Corporation is interested in increasing the value of scrap and better identification technology is one way of doing this. With better identification technology, foundries and smelters will be more confident in the melt chemistry and more apt to use secondary aluminum which decreases the energy required for processing by approximately 85%. wTe Corporation is exploring two avenues for in-situ molten metal identification: Laser Induced Breakdown Spectroscopy (LIBS) and X-Ray Fluorescence (XRF). The objectives of this work were to contribute to developing XRF technology for in-situ identification of molten metal by establishing a method of data instrumentation and analysis for XRF to determine aluminum melt composition, investigate the major alloying elements in the Al380 alloy series and determine the relationship between intensity and concentration, and to determine the effect of temperature on XRF Spectra. The XRF instrumentation development and the technical challenges associated with high temperature measurements are presented. The relationship between intensity and concentration is presented for three alloys within the 380 alloy series, and lastly it is observed that there are significant differences between liquid and solid spectra and that a calibration curve for liquid data is necessary. Several hypotheses are given as to why this difference between liquid and solid state spectra may occur.

Manufacturers of cast metal parts are interested in the development of a feedback control system for use with the Precision Sand-Casting (PSC) process. As industry demands the ability to cast more complex geometries, there are a variety of challenges that engineers have to address. Certain characteristics of the mold, such as thick-to-thin transitions, extensive horizontal or flat surfaces, and sharp corners increase the likelihood of generating defective casts due to the turbulent metal-flow during fills. Consequently, it is critical that turbulent flow behavior within the mold be minimized as much as possible. One way to enhance the quality of the fill process is to adjust the flow rate of the molten metal as it fills these critical regions of the mold. Existing systems attempt to predict the position of the metal level based on elapsed time from the beginning of the fill stage. Unfortunately, variability in several aspects of the fill process makes it very difficult to consistently predict the position of the metal front. A better approach would be to embed a sensor that can detect the melt through a lift-off distance and determine the position of the metal-front. The information from this sensor can then be used to adjust the flow rate of the aluminum as the mold is filled. This thesis presents the design of a novel non-invasive sensor monitoring system. When deployed on the factory floor, the sensing system will provide all necessary information to allow process engineers to adjust the metal flow-rate within the mold and thereby reduce the amount of scrap being produced. Moreover, the system will exhibit additional value in the research and development of future mold designs.

The PhD thesis provides detailed description of a successful development of MgO and TiO2 particle reinforced Steel Ceramic Composites (SCC) for molten aluminum alloy applications. For this purpose, the influence of MgO and TiO2 addition and subsequent pre-oxidation surface treatment on the structure of SCCs and their corrosion resistance against long-term contact with liquid aluminum alloys was investigated. The initiation and progression of corrosion processes were thoroughly analyzed by means of newly developed DSC-aided corrosion tests, high temperature electrochemical studies and adapted wettability measurements. The gained insights led to the recognition of most important factors contributing to the corrosion, including both the electrochemical and the chemical driving forces arising between the SCCs and aluminum alloy. The evaluation of long-term corrosion resistance was performed with the help of finger immersion tests, crucible corrosion tests and subsequent SEM/EDS/EBSD and XRD analyses aiming at the determination of elements most prone to the dissolution in the liquid aluminum alloy and formation of corrosion phases. The pre-oxidized MgO reinforced SCC revealed superior corrosion resistance, being capable of withstanding more than 168 h of contact with liquid aluminum alloy.:Table of content 1 Introduction 1 2 Theoretical background 5 2.1 Wettability measurements 5 2.2 Electrochemical behavior of SCC/molten aluminum alloy material pair 8 2.3 Steel-based materials/molten aluminum alloy reaction 13 2.4 Long-term corrosion mechanisms 16 2.5 Differential Scanning Calorimetry for corrosion precipitation analysis 18 2.6 Corrosion of steel and SCCs during long-term contact with aluminum alloys 19 2.7 Protective coatings and surface treatment of steel and Steel Ceramic Composites 21 2.7.1 Protective coatings against molten aluminum alloys 21 2.7.2 Oxidation kinetics 22 3 Materials and Methods 25 3.1 Materials and Composites Manufacturing 26 3.2 Investigation of corrosion phase formation via DSC-aided corrosion tests 29 3.3 High temperature electrochemical studies 30 3.4 Elaboration of suitable surface pre oxidation for SCCs 33 3.5 Wettability Tests 34 3.6 Finger immersion tests 35 3.7 Crucible Corrosion Tests 36 4 Results and Discussion 41 4.1 Investigation of corrosion phase formation using DSC-aided corrosion tests 41 4.1.1 Determination of reference information for DSC-aided corrosion test 41 4.1.2 Influence of the sample/melt contact duration on the alteration of DSC signal – elaboration of suitable corrosion test conditions. 44 4.1.3 Investigation of 120 min contact time between 316L40TiO2 and 316L40MgO Steel Ceramic Composites with aluminum alloy on the formation of corrosion phases in the melt 47 4.1.4 SEM/EDS microscopical analysis of 316L sample after DSC-aided corrosion test with AlSi7Mg0.3 aluminum alloy for 120 min 51 4.1.5 SEM/EDS microscopical analysis of 316L40TiO2 sample after DSC-aided corrosion test with AlSi7Mg0.3 aluminum alloy for 120 min 53 4.1.6 SEM/EDS microscopical analysis of 316L40MgO sample after DSC-aided corrosion test with AlSi7Mg0.3 aluminum alloy for 120 min 55 4.2 High temperature electrochemical studies of SCCs 60 4.2.1 Evaluation of thermal and chemical stability of selected three-electrode cell materials 60 4.2.2 Differential Potential 61 4.2.3 Impedance Spectroscopy and Potentiodynamic Polarization 64 4.2.4 Microscopical analysis of WE after the electrochemical experiment 68 4.3 Surface treatment of SCCs 79 4.3.1 Dilatometry and Thermogravimetry of SCCs during pre-oxidation 79 4.3.2 Preliminary evaluation of morphology of the SCCs cross-section after pre oxidation at different temperatures and for different durations 83 4.3.3 Detailed SEM/EDS/XRD structure analysis of selected pre-oxidized SCCs 87 4.4 Wettability of aluminum alloy on SCCs 102 4.4.1 Characterization of substrates surface 102 4.4.2 Wetting angle at the drop release 102 4.4.3 Wetting angle 30 min after reaching 850 °C 104 4.4.4 Evaluation of the droplet/substrate cross-section 105 4.5 Finger Immersion Tests 107 4.5.1 Preliminary evaluation of peroxidized SCCs after immersion test 107 4.5.2 Analysis of 316L40TiO2 immersion sample pre oxidized at 850 °C for 24 h 111 4.5.3 Analysis of 316L40TiO2 immersion sample pre-oxidized at 1000 °C for 24 h 112 4.5.4 Analysis of 316L40MgO immersion sample pre oxidized at 850 °C for 24 h 113 4.5.5 Analysis of 316L40MgO immersion sample pre-oxidized at 1000 C for 24 h 114 4.6 Crucible Corrosion Tests 115 4.6.1 Preliminary evaluation of crucible corrosion test results 115 4.6.2 Analysis of 316L40TiO2 sample pre oxidized at 850 °C for 24 h after the crucible corrosion test for 24 h 119 4.6.3 Analysis of 316L40TiO2 sample pre-oxidized at 1000 °C for 24 h after the crucible corrosion test for 168 h 120 4.6.4 Analysis of 316L40MgO sample pre-oxidized at 850 °C for 24 h after the crucible corrosion test for 24 h 122 4.6.5 Analysis of 316L40MgO sample pre-oxidized at 1000 °C for 24 h after the crucible corrosion test for 168 h 125 4.6.6 Analysis of the microstructure of aluminum alloy after crucible corrosion tests 128 4.6.7 Evaluation of contamination of aluminum alloy after crucible corrosion tests 133 Conclusions 137 References 145 Appendixes 161 Appendix A: Preliminary Investigations 161 A.1: Preparation of SCC granulates 161 A.2: Evaluation of properties of composites pressed from granulates 162 Appendix B: Constructions and Designs 169 B.1. Three-Electrode Cell – for high temperature electrochemical measurements with molten aluminum alloys as reference electrode 169 B.2. Capillary System – for capillary purification technique wettability measurements with aluminum alloys 177 Appendix C: Auxiliary Investigations 184 C.1 Detailed SEM/EDS analysis of pre-oxidized SCCs 184 C.2 SEM/EDS analysis of SCCs after 96 h Finger Immersion Tests in aluminum alloy 207