High melting point materials such as ceramics and metal carbides are in general difficult to manufacture due to their physical properties, which imposes the need for new manufacturing methods where electron beam powder bed fusion (EB-PBF) seems promising. Most materials that have been successfully printed with EB-PBF are metals and metal alloys with good electrical conductivity, whereas dielectric materials such as ceramics are generally difficult to print. Catastrophic problems such as smoking and spattering can occur during the EB-PBF processing owing to inappropriate physical properties such as lack of electrical, and thermal conductivity and high melting point, which are challenging to overcome by process optimization. Due to these difficulties, a limited level of understanding has been achieved regarding melting ceramics and refractory alloys. Herein, three different substrates of niobium carbide (NbC) are melted using EB-PBF. The established process parameter window shows a good correlation between EB-PBF process parameters, surface, and melt characteristics, which can be used as a baseline for a printing process. Melting NbC is proven feasible using EB-PBF; the work also points out challenges related to arc trips and spattering, as well as future investigations necessary to create a stable printing process. Additive manufacturing offer new ways of manufacturing ceramics and metal carbides otherwise hard to produce. This study presents one of the first attempts at melting niobium carbide using electron beam powder bed fusion by identifying process window and investigating how the different process parameters affect the melt characteristics, as well as identifying potential issues regarding printing metal carbides.image (c) 2024 WILEY-VCH GmbH

Currently, huge undertakings to develop concepts for fossil free aviation are being made. For instance,hydrogen gas can be used in fuel cells generating electricity for motors or in fossil free combustion engines.To minimize the volume, the hydrogen must be stored in liquid form in tanks at very low temperature (-253°C).These tanks should preferably have as low weight as possible, which may be obtained by using carbon fiberreinforced polymer composites. However, pressure and temperature changes during fueling can causemicrocracks between the fibers, which then causes gas leakage. By using thin composite plies of differentorientations, the formation of microcracks can be suppressed. However, the damage development due tocryogenic cycling and its effect on long term performance is not well understood. This work aims at reducingthis knowledge gap by characterizing thin ply composites under cryogenic thermo-mechanical fatigue. In thiswork, the materials (carbon fiber and matrix) were selected and cross ply [90/0] 4s composite laminates weremanufactured using wet filament winding. The laminates were inspected for damage, and samples preparedfor testing. Quasi-static, mechanical fatigue and thermal fatigue tests were performed. Only a few matrix crackswere observed at a very high load and high number of cycles. Those cracks were initiated but not propagatedalong the width of the specimens. The results show that they have potential for being used in ultralight tanksfor liquid hydrogen.

SiC multilayer coatings were deposited via thermal chemical vapor deposition (CVD) using silicon tetrachloride (SiCl₄) and various hydrocarbons under identical growth conditions, i.e. at 1100 °C and 10 kPa. The coatings consisted of layers whose preferred growth orientation alternated between random and highly 〈111〉-oriented. The randomly oriented layers were prepared with either methane (CH₄) or ethylene (C₂H₄) as carbon precursor, whereas the highly 〈111〉-oriented layers were grown utilizing toluene (C₇H₈) as carbon precursor. In this work, we demonstrated how to fabricate multilayer coatings with different growth orientations by merely switching between hydrocarbons. Moreover, the success in depositing multilayer coatings on both flat and structured graphite substrates has strengthened the assumption proposed in our previous study that the growth of highly 〈111〉-oriented SiC coatings using C₇H₈ was primarily driven by chemical surface reactions.

Additive manufacturing (AM), e.g., laser powder bed fusion (LPBF) technique, has become a powerful manufacturing process for producing metallic components with the advantages of design freedom, net-shape-forming flexibility, product customization, and reduced lead time to market. Nickel-based superalloys is one of the most significant alloy families used at elevated temperatures. Nickel-based superalloys commonly contain up to 10 more alloying elements like chromium, aluminum, cobalt, tungsten, molybdenum, titanium, and so on. The great capacity of the nickel-based superalloys for high-temperature operation is ensured by the well-tailored microstructures with the assistance of carefully doped alloying elements, and the intently developed corresponding manufacturing processes. However, high-performance nickel-based superalloys generally suffer from structural integrity issues during AM process, i.e., this class of superalloys is highly susceptible to crack. Therefore, new nickel-based superalloys adapted to AM process with tailored chemical composition are under the urgent call. Meanwhile, high-temperature performance is another prioritized target for the new superalloys.The first topic is the chemical composition-dependent cracking mechanisms. The interdendritic region formed at the last-stage solidification has been found as the cracked spaces. Owing to the suppression of precipitate formation, the cracking mechanism is generalized as (1) the large mismatch of the solidification steps accounting for the crack initiation, and (2) the large mismatch of load-bearing capacity accounting for the crack propagation, between the dendritic and interdendritic regions. To quantitatively formulate the additive manufacturability of nickel-based superalloys, herein a two-parameter-based, heat resistance, and deformation resistance (HR-DR) model, has been successfully proposed to predict the printability on accounting for the relation between chemical composition (both major and minor elements) and cracking susceptibility. The concept of this model is formulated as that if the interdendritic region obtains both higher heat and deformation resistances than the rest dendritic region, this alloy is expected to be crack resistant. Validated by the experimental results and hitherto reported literature data, the HR-DR model provides an excellent sound prediction on the crack susceptibility of nickel-based superalloy during AM process. By considering the combination of additive manufacturability and high-temperature performance, a novel high-strength nickel-based superalloy, MAD542 has been developed based on the materials selection procedure from 921,600 candidate compositions. In addition, another precipitation-strengthened nickel-based superalloy, Alloy738+ has been developed based on the modification of the composition of heritage superalloy IN738LC, aiming for improving the additive manufacturability, creep, and oxidation resistance.

The second topic is the post-processing treatments related to microstructural evolution and mechanical properties. Owing to the thermal history during the LPBF process, the as-built microstructure commonly consists of columnar grains nearly parallel to the building direction with strong crystallographic texture. Subjected to the post-processing treatments, the solution treatment is the key to controlling the grain evolution. It has been shown for both LPBF MAD542 and heritage LPBF CM247 superalloys, the high crystallographic texture is maintained at the sub-γ′-solvus temperatures because of the grain boundary pinning effect from grain boundary precipitates. Whilst the crystal anisotropy is highly reduced by the treatment at super-γ′-solvus temperatures driven by the means of recrystallization. However, fully recrystallized microstructure with low texture largely reduced the mechanical properties by the embrittlement manner at elevated temperatures accordingly.

The third topic is the examination of creep and oxidation performance of various LPBF superalloys. A strong building direction-dependent creep performance is found for an LPBF IN738LC superalloy fabricated by the vertical and horizontal build. Vertically built samples show 7-40 times longer rupture life and approximately 2 times longer elongation at fracture than the horizontally produced samples, for the creep at 150-300 MPa at 850 °C. To evaluate the short-term creep performance, constant displacement rate-controlled slow strain rate tensile (SSRT) testing was carried out. The constant load-controlled creep and SSRT are correlated by deformation rate-based power-law type analysis. The new superalloy LPBF MAD542 generally displays a 5 times slower deformation rate than the LPBF IN738LC superalloy at 850 °C. The new superalloy Alloy738+ shows a comparable creep performance to LPBF IN738LC. Oxidation tests were conducted at 850/950/1050 °C. The new superalloy Alloy738+ presents an excellent oxidation resistance at 850 and 950 °C. By comparison, for example, Alloy738+ has 3 times slower oxidation kinetics than IN738LC at 950 °C.

The several investigations associated with the composition/processing/property in multiple precipitation-strengthened nickel-based superalloys fabricated by AM in this thesis have proven that the materials development requires comprehensive in-depth considerations. The presented results can contribute to the fundamental understanding and/or serve as the reference data for other superalloys by AM from the properties perspective.

Nickel-based superalloys, an alloy system bases on nickel as the matrix element with the addition of up to 10 more alloying elements including chromium, aluminum, cobalt, tungsten, molybdenum, titanium, and so on. Through the development and improvement of nickel-based superalloys in the past century, they are well proved to show excellent performance at the elevated service temperature. Owing to the combination of extraordinary high-temperature mechanical properties, such as monotonic and cyclic deformation resistance, fatigue crack propagation resistance; and high-temperature chemical properties, such as corrosion and oxidation resistance, phase stability, nickel-based superalloys are widely used in the critical hot-section components in aerospace and energy generation industries.

The success of nickel-based superalloy systems attributes to both the well-tailored microstructures with the assistance of carefully doped alloying elements, and the intently developed manufacturing processes. The microstructure of the modern nickel-based superalloys consists of a two-phase configuration: the intermetallic precipitates (Ni,Co)3(Al,Ti,Ta) known as γ′ phase dispersed into the austenite γ matrix, which is firstly introduced in the 1940s.  The recently developed additive manufacturing (AM) techniques, acting as the disruptive manufacturing process, offers a new avenue for producing the nickel-based superalloy components with complicated geometries. However, γ′ strengthened nickel-based superalloys always suffer from the micro-cracking during the AM process, which is barely eliminated by the process optimization.

On this basis, the new compositions of γ′ strengthened nickel-based superalloy adapted to the AM process are of great interest and significance. This study sought to design novel γ′ strengthened nickel-based superalloys readily for AM process with limited cracking susceptibility, based on the understanding of the cracking mechanisms. A two-parameter model is developed to predict the additive manufacturability for any given composition of a nickel-based superalloy. One materials index is derived from the comparison of the deformation-resistant capacity between dendritic and interdendritic regions, while another index is derived from the difference of heat resistant capacity of these two spaces. By plotting the additive manufacturability diagram, the superalloys family can be categorized into the easy-to-weld, fairly-weldable, and non-weldable regime with the good agreement of the existed knowledge. To design a novel superalloy, a Cr-Co-Mo-W-Al-Ti-Ta-Nb-Fe-Ni alloy family is proposed containing 921,600 composition recipes in total. Through the examination of additive manufacturability, undesired phase formation propensity, and the precipitation fraction, one composition of superalloy, MAD542, out of the 921,600 candidates is selected.

Validation of additive manufacturability of MAD542 is carried out by laser powder bed fusion (LPBF). By optimizing the LPBF process parameters, the crack-free MAD542 part is achieved. In addition, the MAD542 superalloy shows great resistance to the post-processing treatment-induced cracking. During the post-processing treatment, extensive annealing twins are promoted to achieve the recrystallization microstructure, ensuring the rapid reduction of stored energy. After ageing treatment, up to 60-65% volume fraction of γ′ precipitates are developed, indicating the huge potential of γ′ formation. Examined by the high-temperature slow strain rate tensile and constant loading creep testing, the MAD542 superalloy shows superior strength than the LPBF processed and hot isostatic pressed plus heat-treated IN738LC superalloy. While the low ductility of MAD542 is existed, which is expected to be improved by modifying the post-processing treatment scenarios and by the adjusting building direction in the following stages of the Ph.D. research.

MAD542 superalloy so far shows both good additive manufacturability and mechanical potentials. Additionally, the results in this study will contribute to a novel paradigm for alloy design and encourage more γ′-strengthened nickel-based superalloys tailored for AM processes in the future.

The post-processing on the additively manufactured component is of huge interest as the key to tailor the microstructure to obtain certain mechanical properties. In this present study, the effects of hot isostatic pressing, as well as heat treatment on the microstructure, phase configuration and mechanical properties of laser powder bed fused (LPBF) IN718 superalloy were systematically investigated. Three different post-processes were studied such as hot isostatic pressing (HIP), heat treatment (HT), and HIP followed by HT (HIP+HT). The HIP process effectively eliminated the Laves phase remained in the as-built microstructure and brought uniformly distributed super fine γ″ precipitates in nano-meter size. In the heat-treated microstructure, larger γ″ precipitates were promoted directly from the as-built material. In comparison the HIP+HT process caused a moderate growth of γ″. In the latter two cases, the developed γ″ significantly strengthened the material. Yield strength of IN718 was increased from 738 MPa in as-built condition to 1015 MPa and 1184 MPa after HT and HIP+HT, respectively. On the contrary the ductility in the as-built IN718 condition was reduced by more than 40% after HT and HIP+HT. This can be compared to an increase in the ductility by almost 30% when subjected the as-built specimens to only HIPping. Finally, the correlation between microstructure evolution and mechanical properties is discussed in detail.

Microstructural evolution related to the mechanical response from isothermal dwell-fatigue testing at 700 °C of two austenitic steels, Esshete 1250 and Sanicro 25, is reported. Coherent Cu-precipitates and incoherent Nb-carbides were found to impede dislocation motion, increase hardening and improving the high temperature properties of Sanicro 25. Sparsely placed intergranular Cr- and Nb-carbides made Esshete 1250 susceptible to creep damage and intergranular crack propagation, mainly from interaction of the carbides and fatigue induced slip bands. Dynamic recrystallization of the plastic zone at the crack tip appeared to affect crack propagation of Sanicro 25 by providing an energetically privileged path.

Relationships between microstructures and hardening nature of laser powder bed fused (L-PBF) 316 L stainless steel have been studied. Using integrated experimental efforts and calculations, the evolution of microstructure entities such as dislocation density, organization, cellular structure and recrystallization behaviors were characterized as a function of heat treatments. Furthermore, the evolution of dislocation-type, namely the geometrically necessary dislocations (GNDs) and statistically stored dislocations (SSDs), and their impacts on the hardness variation during annealing treatments for L-PBF alloy were experimentally investigated. The GND and SSD densities were statistically measured utilizing the Hough-based EBSD method and Taylor's hardening model. With the progress of recovery, the GNDs migrate from cellular walls to more energetically-favourable regions, resulting in the higher concentration of GNDs along subgrain boundaries. The SSD density decreases faster than the GND density during heat treatments, because the SSD density is more sensitive to the release of thermal distortions formed in printing. In all annealing conditions, the dislocations contribute to more than 50% of the hardness, and over 85.8% of the total dislocations are GNDs, while changes of other strengthening mechanism contributions are negligible, which draws a conclusion that the hardness of the present L-PBF alloy is governed predominantly by GNDs.

The γ′ phase strengthened Nickel-base superalloy is one of the most significant dual-phase alloy systems for high-temperature engineering applications. The tensile properties of laser powder-bed-fused IN738LC superalloy in the as-built state have been shown to have both good strength and ductility compared with its post-thermal treated state. A microstructural hierarchy composed of weak texture, sub-micron cellular structures and dislocation cellular walls was promoted in the as-built sample. After post-thermal treatment, the secondary phase γ′ precipitated with various size and fraction depending on heat treatment process. For room-temperature tensile tests, the dominated deformation mechanism is planar slip of dislocations in the as-built sample while dislocations bypassing the precipitates via Orowan looping in the γ′ strengthened samples. The extraordinary strengthening effect due to the dislocation substructure in the as-built sample provides an addition of 372 MPa in yield strength. The results of our calculation are in agreement with experimental yield strength for all the three different conditions investigated. Strikingly, the γ′ strengthened samples have higher work hardening rate than as-built sample but encounter premature failure. Experimental evidence shows that the embrittlement mechanism in the γ′ strengthened samples is caused by the high dislocation hardening of the grain interior region, which reduces the ability to accommodate further plastic strain and leads to premature intergranular cracking. On the basis of these results, the strengthening micromechanism and double-edge effect of strength and ductility of Nickel-base superalloy is discussed in detail.