Numerical Simulation and Optimization of Directional Solidification Process of Single Crystal Superalloy Casting

The rapid development of numerical modeling techniques has led to more accurate results in modeling metal solidification processes. In this study, the cellular automaton-finite difference (CA-FD) method was used to simulate the directional solidification (DS) process of single crystal (SX) superalloy blade samples. Experiments were carried out to validate the simulation results. Meanwhile, an intelligent model based on fuzzy control theory was built to optimize the complicate DS process. Several key parameters, such as mushy zone width and temperature difference at the cast-mold interface, were recognized as the input variables. The input variables were functioned with the multivariable fuzzy rule to get the output adjustment of withdrawal rate (v) (a key technological parameter). The multivariable fuzzy rule was built, based on the structure feature of casting, such as the relationship between section area, and the delay time of the temperature change response by changing v, and the professional experience of the operator as well. Then, the fuzzy controlling model coupled with CA-FD method could be used to optimize v in real-time during the manufacturing process. The optimized process was proven to be more flexible and adaptive for a steady and stray-grain free DS process.     

Impact of Mechanical Stress and Nitrogen Doping on the Defect Distribution in the Initial Stage of the 4H-SiC PVT Growth Process

Nitrogen incorporation changes the lattice spacing of SiC and can therefore lead to stress during physical vapor transport (PVT). The impact of the nitrogen-doping concentration during the initial phase of PVT growth of 4H-SiC was investigated using molten potassium hydroxide (KOH) etching, and the doping concentration and stress was detected by Raman spectroscopy. The change in the coefficient of thermal expansion (CTE) caused by the variation of nitrogen doping was implemented into a numerical model to quantitatively determine the stress induced during and after the crystal growth. Furthermore, the influence of mechanical stress related to the seed-mounting method was studied. To achieve this, four 100 mm diameter 4H-SiC crystals were grown with different nitrogen-doping distributions and seed-mounting strategies. It was found that the altered CTE plays a major role in the types and density of defect present in the grown crystal. While the mounting method led to increased stress in the initial seeding phase, the overall stress induced by inhomogeneous nitrogen doping is orders of magnitude higher.     

Influence of Different Heater Structures on the Temperature Field of AlN Crystal Growth by Resistance Heating

Based on the actual hot zone structure of an AlN crystal growth resistance furnace, the global numerical simulation on the heat transfer process in the AlN crystal growth was performed. The influence of different heater structures on the growth of AlN crystals was investigated. It was found that the top heater can effectively reduce the axial temperature gradient, and the side heater 2 has a similar effect on the axial gradient, but the effect feedback is slightly weaker. The axial temperature gradient tends to increase when the bottom heater is added to the furnace, and the adjustable range of the axial temperature gradient of the side 1 heater + bottom heater mode is the largest. Our work will provide important reference values for AlN crystal growth by the resistance method.     

Study on Purification Technology of Silicon Carbide Crystal Growth Powder

Silicon carbide (SiC) is a wide-bandgap (WBG) semiconductor material, and its preparation process has strict requirements on the purity of raw materials. A self-developed medium-frequency induction heating furnace was used to carry out powder heat treatment and purification experiments on SiC powder to improve the purity of the powder. Samples with 3.5N purity were analyzed using XRD and GDMS characterization methods. It was found that under conditions of high-temperature (2200 °C) and long-time (50 h) processing, the impurity removal effect was quite good, but the powder loss was as high as 53.42%. The powder loss during the low-temperature (less than 2050 °C) and short-time process was less than 1.5%, but the purification effect was not substantial. After a prolonged processing time, the purification effect of low-temperature heat treatment conditions was improved, but the powder loss was also increased to 30%. In contrast, segmented purification processing at a low temperature in the early stage and a high temperature in the later stage achieved a good purification effect. On the premise of maintaining the utilization rate of raw materials, a 5N-purity SiC source was successfully prepared. The test results show that the contents of free Si, free C and free oxygen impurities were reduced to less than 0.01%, and the contents of Al, B, Fe, Mg, Na, Ti and other impurities were less than 1.15 ppm, which is close to the ppb level.     

A 3D Analysis of Dendritic Solidification and Mosaicity in Ni-Based Single Crystal Superalloys

Ni-based single crystal superalloys contain microstructural regions that are separated by low-angle grain boundaries. This gives rise to the phenomenon of mosaicity. In the literature, this type of defect has been associated with the deformation of dendrites during Bridgman solidification. The present study introduces a novel serial sectioning method that allows to rationalize mosaicity on the basis of spatial dendrite growth. Optical wide-field micrographs were taken from a series of cross sections and evaluated using quantitative image analysis. This allowed to explore the growth directions of close to 2500 dendrites in a large specimen volume of approximately 450 mm³. The application of tomography in combination with the rotation vector base-line electron back-scatter diffraction method allowed to analyze how small angular differences evolve in the early stages of solidification. It was found that the microstructure consists of dendrites with individual growth directions that deviate up to ≈4° from the average growth direction of all dendrites. Generally, individual dendrite growth directions coincide with crystallographic <001> directions. The quantitative evaluation of the rich data sets obtained with the present method aims at contributing to a better understanding of elementary processes that govern competitive dendrite growth and crystal mosaicity.     

High-Energy Computed Tomography as a Prospective Tool for In Situ Monitoring of Mass Transfer Processes inside High-Pressure Reactors—A Case Study on Ammonothermal Bulk Crystal Growth of Nitrides including GaN

For the fundamental understanding and the technological development of the ammonothermal method for the synthesis and crystal growth of nitrides, an in situ monitoring technique for tracking mass transport of the nitride throughout the entire autoclave volume is desirable. The feasibility of using high-energy computed tomography for this purpose was therefore evaluated using ex situ measurements. Acceleration voltages of 600 kV were estimated to yield suitable transparency in a lab-scale ammonothermal setup for GaN crystal growth designed for up to 300 MPa operating pressure. The total scan duration was estimated to be in the order of 20 to 40 min, which was sufficient given the comparatively slow crystal growth speed in ammonothermal growth. Even shorter scan durations or, alternatively, lower acceleration voltages for improved contrast or reduced X-ray shielding requirements, were estimated to be feasible in the case of ammonoacidic growth, as the lower pressure requirements for this process variant allow for thinned autoclave walls in an adapted setup designed for improved X-ray transparency. Promising nickel-base and cobalt-base alloys for applications in ammonothermal reactors with reduced X-ray absorption in relation to the maximum operating pressure were identified. The applicability for the validation of numerical simulations of the growth process of GaN, in addition to the applicability of the technique to further nitride materials, as well as larger reactors and bulk crystals, were evaluated.     

Crystal Evolution of Calcium Silicate Minerals Synthesized by Calcium Silicon Slag and Silica Fume with Increase of Hydrothermal Synthesis Temperature

In order to realize high-value utilization of calcium silicon slag (CSS) and silica fume (SF), the dynamic hydrothermal synthesis experiments of CSS and SF were carried out under different hydrothermal synthesis temperatures. In addition, phase category, microstructure, and micropore parameters of the synthesis product were analyzed through testing methods of XRD, SEM, EDS and micropore analysis. The results show that the main mechanism of synthesis reaction is that firstly β-Dicalcium silicate, the main mineral in CSS, hydrates to produce amorphous C–S–H and Ca(OH)₂, and the environment of system is induced to strong alkaline. Therefore, the highly polymerized Si-O bond of SF is broken under the polarization of OH⁻ to form (SiO₄) of Q⁰. Next, amorphous C–S–H, Ca(OH)₂ and (SiO₄) of Q⁰ react each other to gradually produce various of calcium silicate minerals. With an increase of synthesis temperature, the crystal evolution order for calcium silicate minerals is cocoon-like C–S–H, mesh-like C–S–H, large flake-like gyrolite, small flake-like gyrolite, petal-like gyrolite, square flake-like calcium silicate hydroxide hydrate, and strip-like tobermorite. In addition, petal-like calcium silicate with high average pore volume (APV), specific surface area (SSA) and low average pore diameter (APD) can be prepared under the 230 °C synthesis condition.     

X-ray Imaging of Alloy Solidification: Crystal Formation,Growth, Instability and Defects

Synchrotron and laboratory-based X-ray imaging techniques have been increasingly used for in situ investigations of alloy solidification and other metal processes. Several reviews have been published in recent years that have focused on the development of in situ X-ray imaging techniques for metal solidification studies. Instead, this work provides a comprehensive review of knowledge provided by in situ X-ray imaging for improved understanding of solidification theories and emerging metal processing technologies. We first review insights related to crystal nucleation and growth mechanisms gained by in situ X-ray imaging, including solute suppressed nucleation theory of α-Al and intermetallic compound crystals, dendritic growth of α-Al and the twin plane re-entrant growth mechanism of faceted Fe-rich intermetallics. Second, we discuss the contribution of in situ X-ray studies in understanding microstructural instability, including dendrite fragmentation induced by solute-driven, dendrite root re-melting, instability of a planar solid/liquid interface, the cellular-to-dendritic transition and the columnar-to-equiaxed transition. Third, we review investigations of defect formation mechanisms during near-equilibrium solidification, including porosity and hot tear formation, and the associated liquid metal flow. Then, we discuss how X-ray imaging is being applied to the understanding and development of emerging metal processes that operate further from equilibrium, such as additive manufacturing. Finally, the outlook for future research opportunities and challenges is presented.     

Homogenization of Radial Temperature by a Tungsten Sink in Sublimation Growth of 45 mm AlN Single Crystal

To reduce the thermal stress during the sublimation growth of 45 mm AlN single crystal, a tungsten sink was put on the top of the crucible lid. Numerical experiments showed that the radial temperature gradient was reduced due to the homogenization effect on temperature as a result of the sink. Therefore, this simple tungsten sink method has the potential to grow large-size AlN ingots with fewer cracks. It also reveals that enhancing the heat exchange of the crucible lid is an effective way to improve the quality of crystal growth.     

Study of Effect of Coil Movement on Growth Conditions of SiC Crystal

SiC substrates have outstanding advantages over traditional materials in power device application, and are mainly prepared by a physical vapor transport method (PVT). Whether the PVT furnace works by resistance heating or induction heating, both face the problem of the deterioration of growth conditions during a long-term process. The relative position of the thermal field directly affects the crystal growth conditions, but the law of specific influence and the change in physical environment inside the thermal field have not been made sufficiently clear and lack systematic research. Therefore, SiC single crystal growth, with different directions and rates in the direction of movement of the heating module, was modeled using a simulation method, and the law of variation of the physical field, including heat flux, temperature, powder porosity and growth rate parameters under different schemes, was analyzed. The study indicates that the decay of raw materials is the primary reason why growth conditions cannot be maintained. The results verified that different coils’ modes of movement have different effects on the improvement or adjustment of SiC crystals’ growth conditions. Under the same temperature control conditions, the coils’ movement rates of 200 μm/h, 0, −200 μm/h and −400 μm/h correspond to the average growth rates of 140, 152, 165 and 172 μm/h, respectively. The results show that downward displacement of the coils is beneficial in compensating for the deterioration of growth conditions, but it is easier to form convex surfaces and is not conducive to expanding diameter growth. This also verifies that the desired crystal growth state can be obtained by adjusting the position of the thermal field.     

Surface Morphology and Microstructure Evolution of Single Crystal Diamond during Different Homoepitaxial Growth Stages

Homoepitaxial growth of step-flow single crystal diamond was performed by microwave plasma chemical vapor deposition system on high-pressure high-temperature diamond substrate. A coarse surface morphology with isolated particles was firstly deposited on diamond substrate as an interlayer under hillock growth model. Then, the growth model was changed to step-flow growth model for growing step-flow single crystal diamond layer on this hillock interlayer. Furthermore, the surface morphology evolution, cross-section and surface microstructure, and crystal quality of grown diamond were evaluated by scanning electron microscopy, high-resolution transmission electron microcopy, and Raman and photoluminescence spectroscopy. It was found that the surface morphology varied with deposition time under step-flow growth parameters. The cross-section topography exhibited obvious inhomogeneity in crystal structure. Additionally, the diamond growth mechanism from the microscopic point of view was revealed to illustrate the morphological and structural evolution.     

Rotating Directional Solidification of Ternary Eutectic Microstructures in Bi-In-Sn: A Phase-Field Study

For the first time, the experimental processing condition of a rotating directional solidification is simulated in this work, by means of a grand-potential-based phase-field model. To simulate the rotating directional solidification, a new simulation setup with a rotating temperature field is introduced. The newly developed configuration can be beneficent for a more precise study of the ongoing adjustment mechanisms during temperature gradient controlled solidification processes. Ad hoc, the solidification of the ternary eutectic system Bi-In-Sn with three distinct solid phases α,β,δ is studied in this paper. For this system, accurate in situ observations of both directional and rotating directional solidification experiments exist, which makes the system favorable for the investigation. The two-dimensional simulation studies are performed for both solidification processes, considering the reported 2D patterns in the steady state growth of the bulk samples. The desired αβαδ phase ordering repeat unit is obtained within both simulation types. By considering anisotropy of the interfacial energies, experimentally reported tilted lamellae with respect to normal vectors of the solidification front, as well as predominant role of αβ anisotropy in tilting phenomenon, are observed. The results are validated by using the Jackson–Hunt analysis and by comparing with the existing experimental data. The convincing agreements indicate the applicability of the introduced method.     

Crystal Growth and Spectroscopic Investigations of Tm3+:Li3Ba2Gd3(MoO4)8 Crystal

Tm³⁺:Li₃Ba₂Gd₃(MoO₄)₈ crystal has been grown by the top seeded solution growth (TSSG) method from a Li₂MoO₄ flux. The room temperature polarized absorption spectra, fluorescence spectra, and fluorescence decay curves of the crystal were measured. Based on the Judd-Ofelt (J-O) theory, the main spectroscopic parameters of the crystal, including the spontaneous emission probabilities, fluorescence branching ratios, and radiative lifetimes were calculated and analyzed. The broad and strong absorption bands of the crystal show that it can be efficiently pumped by the diode laser, while the large emission cross-sections of the ³F₄ → ³H₆ transition indicate that the crystal is a promising candidate for tunable and short pulse lasers.     

Growth of High-Density Zinc Oxide Nanorods on Porous Silicon by Thermal Evaporation

The formation of high-density zinc oxide (ZnO) nanorods on porous silicon (PS) substrates at growth temperatures of 600–1000 °C by a simple thermal evaporation of zinc (Zn) powder in the presence of oxygen (O₂) gas was systematically investigated. The high-density growth of ZnO nanorods with (0002) orientation over a large area was attributed to the rough surface of PS, which provides appropriate planes to promote deposition of Zn or ZnO_x seeds as nucleation sites for the subsequent growth of ZnO nanorods. The geometrical morphologies of ZnO nanorods are determined by the ZnO_x seed structures, i.e., cluster or layer structures. The flower-like hexagonal-faceted ZnO nanorods grown at 600 °C seem to be generated from the sparsely distributed ZnO_x nanoclusters. Vertically aligned hexagonal-faceted ZnO nanorods grown at 800 °C may be inferred from the formation of dense arrays of ZnO_x clusters. The formation of disordered ZnO nanorods formed at 1000 °C may due to the formation of a ZnO_x seed layer. The growth mechanism involved has been described by a combination of self-catalyzed vapor-liquid-solid (VLS) and vapor-solid (VS) mechanism. The results suggest that for a more precise study on the growth of ZnO nanostructures involving the introduction of seeds, the initial seed structures must be taken into account given their significant effects.     

Growth,Structure and Optical Characterization of Rb3Ti3P5O20 Single Crystal

Phosphate crystals attract much attention on account of their rich crystal structures and excellent physical and chemical properties. Herein, Rb₃Ti₃P₅O₂₀ single crystals were grown by the high temperature solution method using Rb₂CO₃ and NH₄H₂PO₄ as the fluxes. This crystal, with non-centrosymmetric Pca2₁ space group, presents a three-dimensional framework structure composed of [TiO₆] octahedron, [PO₄] tetrahedra, and [P₂O₇] dimers. The electronic structure was measured via X-ray photoelectron spectroscopy. The measurements found that Rb₃Ti₃P₅O₂₀ has stronger Ti–O ionic bonding properties and weaker P–O covalent bonding properties compared to RbTiOPO₄. Optical measurements indicated that Rb₃Ti₃P₅O₂₀ has a 3.54 eV band gap and a wide transmission range (0.33–4.5 μm). Theoretical calculations showed that Rb₃Ti₃P₅O₂₀ crystals have a moderate birefringence of 0.079 at 1064 nm. In addition, the relationship of the structure–property was studied using first-principles method. The results demonstrated that TiO₆ octahedron played a significant role for the optical properties.     

Directional Growth of cm-Long PLGA Nanofibers by a Simple and Fast Wet-Processing Method

The development of aligned nanofibers as useful scaffolds for tissue engineering is an actively sought-for research objective. Here, we propose a novel improvement of an existing self-assembly-based nanofabrication technique (ASB-SANS). This improvement, which we termed Directional ASB-SANS, allows one to produce cm²-large domains of highly aligned poly(lactic-co-glycolic acid) (PLGA) nanofibers in a rapid, inexpensive, and easy way. The so-grown aligned PLGA nanofibers exhibited remarkable adhesion to different substrates (glass, polyimide, and Si/SiOx), even when immersed in PBS solution and kept at physiological temperature (37 °C) for up to two weeks. Finally, the Directional ASB-SANS technique allowed us to grow PLGA fibers also on highly heterogeneous substrates such as polyimide-based, gold-coated flexible electrodes. These results suggest the viability of Directional ASB-SANS method for realizing biocompatible/bioresorbable, nanostructured coatings, potentially suitable for neural interface systems.     

Kinetics of Holographic Recording and Spontaneous Erasure Processes in Light-Sensitive Liquid Crystal Elastomers

The optical mechanism for imprinting one-dimensional grating structures into thin films of a light-sensitive monodomain liquid crystal elastomer is investigated by analyzing the time dependence of optical diffraction properties. The recording kinetics shows an irregular oscillatory behavior, which is most expressed at small grating spacings and at temperatures close to the nematic-isotropic phase transition. The oscillations are attributed to the opto-mechanical response of the film, i.e., to contraction of the film during the recording process. At temperatures far below the nematic-isotropic phase transition, the spontaneous erasure kinetics exhibits exponential relaxation with relaxation time following the Arrhenius activation law. However, at temperatures close to the nematic-isotropic phase transition, the erasure process shows an interesting nonmonotonic behavior that we attribute to the non-linear relation between the concentration of the photo-transformed chemical groups and the nematic order parameter.     

Environment-Friendly Preparation of Reaction-Bonded Silicon Carbide by Addition of Boron in the Silicon Melt

Reaction-bonded silicon carbide ceramics were sintered by infiltration of Si and B–Si alloy under an argon atmosphere at different temperatures. The element boron was added to the silicon melt to form a B–Si alloy first. The mechanical properties of samples were improved by infiltration of the B–Si melt. The samples infiltrated with the Si-only melt were found to be very sensitive to experimental temperature. The bending strengths of 58.6 and 317.0 MPa were achieved at 1530 and 1570 °C, respectively. The sample made by infiltration of B–Si alloy was successfully sintered at 1530 °C. The relative density of the sample was more than 90%. The infiltration of B–Si alloy reduced the sintering temperature and the bending strength reached 326.9 MPa. The infiltration mechanism of B–Si alloy is discussed herein.     

Growth and Characterization of Lead-free Piezoelectric Single Crystals

Lead-free piezoelectric materials attract more and more attention owing to the environmental toxicity of lead-containing materials. In this work, we review our first attempts of single crystal grown by the top-seeded solution growth method of BaTiO₃ substituted with zirconium and calcium (BCTZ) and (K_0.5Na_0.5)NbO₃ substituted with lithium, tantalum, and antimony (KNLSTN). The growth methodology is optimized in order to reach the best compositions where enhanced properties are expected. Chemical analysis and electrical characterizations are presented for both kinds of crystals. The compositionally-dependent electrical performance is investigated for a better understanding of the relationship between the composition and electrical properties. A cross-over from relaxor to ferroelectric state in BCTZ solid solution is evidenced similar to the one reported in ceramics. In KNLSTN single crystals, we observed a substantial evolution of the orthorhombic-to-tetragonal phase transition under minute composition changes.     

New Approaches and Understandings in the Growth of Cubic Silicon Carbide

In this review paper, several new approaches about the 3C-SiC growth are been presented. In fact, despite the long research activity on 3C-SiC, no devices with good electrical characteristics have been obtained due to the high defect density and high level of stress. To overcome these problems, two different approaches have been used in the last years. From one side, several compliance substrates have been used to try to reduce both the defects and stress, while from another side, the first bulk growth has been performed to try to improve the quality of this material with respect to the heteroepitaxial one. From all these studies, a new understanding of the material defects has been obtained, as well as regarding all the interactions between defects and several growth parameters. This new knowledge will be the basis to solve the main issue of the 3C-SiC growth and reach the goal to obtain a material with low defects and low stress that would allow for realizing devices with extremely interesting characteristics.