Si Segregation Research Articles

The microstructure of high manganese TWIP steels produced via simulated direct strip casting

Three TWIP steels based on the composition Fe-23Mn-3Si-3.3Al with different carbon concentrations were examined. The alloys were produced by rapid solidification in an experimental apparatus designed to simulate direct strip casting conditions. Examination of the driving force for solidification for this alloy showed the preference for BCC and FCC solidification were very close for this composition, within 10% of one another. This factor combined with the high undercooling resulted in the change in the primary solidified phase. Chemical analysis of the as-cast strip showed inter-dendritic segregation of Si and Al, but negligible segregation of Mn. A simple heat treatment was sufficient to chemically homogenise all alloys and produce microstructures comprising a fully austenitic structure, consistent with thermodynamic predictions.

Role of Si Segregation in the Structural, Mechanical, and Compositional Evolution of High-Temperature Oxidation Resistant Cr-Si-B2±Z Thin Films

Role of Si Segregation in the Structural, Mechanical, and Compositional Evolution of High-Temperature Oxidation Resistant Cr-Si-B2±Z Thin Films

Segregation of Ni and Si to coherent bcc Fe-Cu interfaces from density functional theory

The formation of Cu rich precipitates (CRPs) is known to substantially contribute to the embrittlement of reactor pressure vessel steels with high Cu contents. CRPs are commonly observed to possess a Cu core surrounded by a shell of other segregating solute species like Mn, Ni and Si. Here we calculate the segregation energies of substitutional Ni and Si to {100}, {110} and {111} orientated coherent Fe-Cu interfaces. We find Ni is strongly attracted to all orientations of coherent bcc Fe-Cu interfaces whilst Si interacts in a more complex manner, with strong attraction only to the {100} orientation. In calculating these segregation energies we also explore different methods, concluding that for this system using an external reference bulk (ERB) is optimal. By performing additional calculations we were able to decouple the elastic and chemical contributions to segregation energy finding that for Ni the chemical contributions dominate whilst for Si the two contributions are more balanced. In conjunction with previous work we conclude that should Cu nanoprecipitate sizes influence segregation behaviours it is likely this will not be due to the strain state surrounding the Cu nanoprecipitate. It is more probable that this size dependence would originate from variation in the proportions of the specific orientations of coherent Fe-Cu interface that make up the Cu nanoprecipitate’s surface at different sizes.

Dynamic strain aging in the intermediate temperature regime of near-[formula omitted] titanium alloy, IMI 834: Experimental and modeling

A dynamic strain aging (DSA) regime is established for a near-α titanium alloy with a microstructure consisting of 80% equiaxed α, 15% lamellar α and 5% β with silicon in solid solution through a series of constant strain rate tests carried out in tension from 5 × 10−2 to 5 × 10−6 s−1 in the temperature range of 623–823 K. Transmission electron microscopy shows jogged screw dislocations within slip bands dominating the dislocation structure in this domain. Strain accumulation occurs by conservative jog glide along the length of screw dislocations due to line tension forces. We estimate the solute concentration accumulating at these edge jogs on arrest during their thermally activated glide over static solute obstacles. The domain of DSA is then predicted using Friedel's model to obtain the stress required to break the jogs free from the solute atmosphere. There is a good agreement between model and experimental data showing a DSA peak in the temperature range of 673–723 K. The solute species responsible for DSA from the model are C and Si, but dominated by C in this temperature and strain rate regime. Atom probe tomography demonstrates C and Si segregation at the dislocations, strongly supporting the model.

Gradient magnetron co-sputtered μ m-thick Al–Si films on dielectric substrates for operation in the millimeter-wave band

Ongoing active development of modern radio frequency electronic devices operating in the millimeter (V) band, such as fifth-generation wireless communications, demands new materials to control electromagnetic interference, compatibility, and reliability of such systems. This work investigates feasibility absorptive non-reflective thin coatings deposition on dielectric substrates using simultaneous magnetron co-deposition. For this, electromagnetic waves propagation in the millimeter band through in micrometer-thick Al–Si films of varied composition was studied. The co-deposition process was controlled by the ratio of sputtered atoms fluxes. Graded segregation was observed under certain parameters of the co-deposition process, resulting in a depth gradient of an aluminum content, as confirmed by the secondary ion mass spectrometry study. A qualitative model was proposed involving aluminum-induced silicon recrystallization happening in the course of a known aluminum interlayer exchange process. The observed Al–Si segregation effect in micrometer-thick films allows for preparation of the non-reflective and absorptive material for operation in the V-band with reflection losses more than 10 dB and transmission losses around 5 dB in the bandwidth of up to 20 GHz.

Planar and three-dimensional damage-free etching of β-Ga2O3 using atomic gallium flux

In situ etching using Ga flux in an ultra-high vacuum environment like molecular beam epitaxy is introduced as a method to make high aspect ratio three-dimensional (3D) structures in β-Ga2O3. Etching of β-Ga2O3 due to excess Ga adatoms on the epilayer surface had been viewed as non-ideal for epitaxial growth especially since it results in plateauing and lowering of the growth rate. In this study, we use this well-known reaction from epitaxial growth to intentionally etch β-Ga2O3. We demonstrate etch rate ranging from 2.9 to 30 nm/min with the highest reported etch rate being only limited by the highest Ga flux used. Patterned in situ etching is also demonstrated and used to study the effect of fin orientation on the sidewall profiles and dopant (Si) segregation on the etched surface. Using in situ Ga etching, we also demonstrate 150 nm wide fins and 200 nm wide nanopillars with high aspect ratio. This etching method could enable future development of highly scaled vertical and lateral 3D devices in β-Ga2O3.

Effect of scan pattern on Hastelloy-X wall structures built by laser-directed energy deposition-based additive manufacturing

This article systematically analyzes the effect of scan pattern on the geometry and material properties of wall structures built using laser-directed energy deposition (LDED)-based additive manufacturing. Hastelloy-X (Hast-X), a nickel superalloy, is deposited using an indigenously developed 2-kW fiber laser–based LDED system. The wall structures are built using unidirectional and bidirectional scan patterns with the same LDED process parameters and effect of scan pattern on the geometry, microstructural and mechanical characteristics of Hast-X wall structures built using LDED. The wall width is higher for samples deposited with the bidirectional pattern at the starting and ending points as compared to walls built with the unidirectional pattern. Further, the range of width value is higher for walls built with bidirectional strategy as compared to walls built with unidirectional strategy. Wall height is more uniform with unidirectional deposition at the central region, with the range and standard deviation for walls built using bidirectional deposition at 3 and 2.5 times more than unidirectional deposition, respectively. The deposition rate for bidirectional deposition is two times that of unidirectional deposition. The microstructure of the built walls is cellular/dendritic, with bidirectional deposition showing a finer grain structure. Elemental mapping shows the presence of elemental segregation of Mo, C and Si, confirming the formation of Mo-rich carbides. Micro-hardness and ball indentation studies reveal higher mechanical strength for samples built using the bidirectional pattern, with unidirectional samples showing strength lower than the conventional wrought Hast-X samples (197 HV). This study paves a way to understand the effect of scan pattern on LDED built wall structures for building intricate thin-walled components.

Interface analysis and diffusion behavior of YAG/Nd:LuAG heterojunction structure

YAG/Nd:LuAG heterojunction structure materials combined with crystals and ceramics were fabricated using a diffusion bonding method in which thermal bonding is applied before HIP treatment. The interface morphologies, microstructures, and optical properties of the samples were investigated. The results indicated that the YAG crystal was mixed and solid solutions were formed with the Nd:LuAG ceramic at the bonding interface for the existence of Si ions derived from the ceramic fabrication process. The diffusion process was investigated based on Fick’s law. The diffusion coefficients of Lu and Y were fitted using theoretical calculations. In addition, Si and Nd ion segregation occurred at the grain boundaries. Finally, pore-free heterojunction structure materials were successfully fabricated with the transmittance of the sample reaching 83.26% at 1064 nm. This study reveals the migration and diffusion of ions in the crystal-ceramic heterojunction structure, which is an effective method for achieving low scattering loss and restraining active ion diffusion for the design of planar waveguides.

Precipitation in reactor pressure vessel steels under ion and neutron irradiation: On the role of segregated network dislocations

The ultrahigh density of Mn-Ni-Si-Cu precipitates that form in irradiated reactor pressure vessels (RPV) result in hardening and embrittlement, which may limit the service life of aging nuclear reactors. Here, we quantitatively analyze solute segregation to, and precipitation on, network dislocations in irradiated low alloy RPV steels. The analysis is based on a broad thermodynamic framework, which allows proper identification of possible non-equilibrium perturbative effects of irradiation, like radiation induced segregation (RIS). For the first time, we quantify the segregation of Cu, Mn, Ni and Si to ≈ 5–10 nm network dislocation segments, typically separated by a string-of-pearl type array of MnNiSi precipitates (MNSPs); the MNSPs are appended to Cu rich co-precipitates (CRPs) in steels bearing this element. Detailed atom probe tomography (APT) data are reported for 16 RPV steels, with a wide matrix of tailored compositions, irradiated by both neutrons and 6.4 MeV Fe3+ ions at 320 and 290 °C, respectively. A key aspect of this study is that the very high displacement per atom (dpa) doses and radiation enhanced diffusion (RED) result in nearly full phase separation, allowing isolation of thermodynamic (equilibrium or non-equilibrium) effects. We characterize segregation and precipitates with a comprehensive set of descriptors under both ion and neutron irradiation, including: a) solute enrichment factors (EFs) at dislocations, as a function of alloy composition; and, b) matrix versus dislocation precipitates and their respective characteristics. Formation of these dislocation features can be due to RIS, or thermodynamic in origin, or both. Coupled with simple models, we show that the nucleation MNSP features in low Cu steels is enhanced by segregation. However, in typical supersaturated RPV steels, rapid growth of the precipitates is thermodynamically driven to a quantitatively predictable, nearly full phase separation mole fraction.

MBE growth and donor doping of coherent ultrawide bandgap AlGaN alloy layers on single-crystal AlN substrates

Single-crystal Aluminum Nitride (AlN) crystals enable the epitaxial growth of ultrawide bandgap Al(Ga)N alloys with drastically lower extended defect densities. Here, we report the plasma-MBE growth conditions for high Al-composition AlGaN alloys on single-crystal AlN substrates. An AlGaN growth guideline map is developed, leading to pseudomorphic AlxGa1−xN epitaxial layers with x ∼0.6–1.0 Al contents at a growth rate of ∼0.3 μm/h. These epitaxial layers exhibit atomic steps, indicating step flow epitaxial growth, and room-temperature band edge emission from ∼4.5 to 5.9 eV. Growth conditions are identified in which the background impurity concentrations of O, C, Si, and H in the MBE layers are found to be very near or below detection limits. An interesting Si segregation and gettering behavior is observed at the epitaxial AlGaN/AlN heterojunction with significant implications for the formation and transport of 2D electron or hole gases. Well-controlled intentional Si doping ranging from ∼2 × 1017 to 3 × 1019 atoms/cm3 is obtained, with sharp dopant density transition profiles. In Si-doped Al0.6Ga0.4N epilayers, a room-temperature free electron concentration of ∼3 × 1019/cm3, an electron mobility of ∼27 cm2/V s, and an n-type resistivity of ∼7.5 m Ω cm are obtained. The implications of these findings on electronic and photonic devices on single-crystal AlN substrates are discussed.

Yttrium's Effect on the Hot Cracking and Creep Properties of a Ni-Based Superalloy Built Up by Additive Manufacturing.

We studied the effects of the rare earth element yttrium (Y) on the hot cracking and creep properties of Hastelloy-X processed by selective laser melting. We used two different alloys to study hot cracking in Hastelloy-X: one with 0.12 mass% yttrium added and one with no yttrium. Y-free Hastelloy-X exhibited less cracks, mainly due to the segregation of Si, W, and C resulting in SiC- and W6C-type carbides at the grain boundary and interdendritic regions. On the other hand, more cracks formed in the Y-added Hastelloy-X specimen because of segregation of Y, resulting in the formation of yttrium-rich carbide (YC). Post-heat treatment was conducted at 1177 °C for 2 h, followed by air cooling, to obtain good creep properties. We carried out a creep test along the vertical and horizontal directions. Despite having more cracks, the Y-added as-built Hastelloy-X specimen showed longer creep life and ductility than the Hastelloy-X specimen. This was mainly because of the formation of Y2O3 and SiO2 inside the grains. After solution treatment, the Y-added specimen’s creep life was eight times longer than that of the Y-free solution-treated specimen. This was mainly because of the maintenance of the columnar grain morphology even after solution treatment. In addition, the formation of M6C carbides, Y2O3, and SiO2 improved creep life. To summarize the effect of Y, Y addition promoted the formation of cracks, which brought about creep anisotropy; however, it improved creep properties through the stabilization of oxygen and the promotion of discrete carbide precipitation, which prohibited the migration and sliding of grain boundary.

Correlative STEM-APT characterization of radiation-induced segregation and precipitation of in-service BWR 304 stainless steel

Radiation induced segregation and precipitation phenomena in an in-service boiling water reactor 304 stainless steel component were investigated using directly correlated 3D-atom probe tomography and scanning transmission electron microscopy. Significant quantitative differences in measured segregation at grain boundaries were found between the atom probe and energy dispersive spectroscopy measurements of the exact same locations. In particular, a much stronger Si segregation (~10 atomic% via atom probe versus ~4 atomic% via electron microscopy) and different Cr profile shapes were detected that are critical to models of radiation induced segregation and stress corrosion cracking behavior. These quantitative differences highlight the need for comparative microscopy and critical evaluation of limitations in each analytical method. Elemental segregation to dislocations and conjoined-clusters were also highlighted by atom probe; confirming and expanding upon what has been observed in test reactor neutron and accelerator-based ion irradiations.

Composition-dependent solidification cracking of aluminum-silicon alloys during laser powder bed fusion

Consistent manufacturing of volumetrically dense engineering components, free of solidification cracks by laser powder bed fusion (LPBF), has been demonstrated for Al-Si alloys such as AlSi10Mg and Al12Si. The success in LPBF of these alloys is attributed to the near eutectic composition with a small freezing range. To illuminate this observation, cracking susceptibility was examined from Scheil-Gulliver solidification modeling by calculating the hot cracking susceptibility, |dT/dfS1/2|. To validate the findings from hot cracking susceptibility calculations, six binary Al-Si alloys, whose compositions were strategically chosen at hypo-, near-, and hyper-eutectic compositions, were gas atomized into alloy powders, and processed by LPBF. Only Al-Si alloys with 1.0 and 2.0 wt.% Si were found to exhibit cracking, which was predicted by relatively large magnitudes of |dT/dfS1/2|. Either as particles or with a eutectic structure, Si segregation at the intercellular boundaries was observed to define the sub-grain cellular structure. For selected compositions, measurement of the cellular structure allowed for estimation of the cooling rate to be 106 to 107 K•s−1. Excluding the alloys with solidification cracking, an increase in tensile strength and the corresponding decrease in ductility were observed with an increase in Si concentration, which were attributed to the formation of a cellular structure and the amount of Al-Si eutectic found at the intercellular boundaries.

Modified microstructures in proton irradiated dual phase 308L weldment filler material

The effect of proton irradiation on the microstructure of δ ferrite—γ austenite mixed phase 308L filler material in a 508–304 dissimilar metal weldment was investigated over a depth of 0 to 10 µm. Ni–Si–Mn G-phase precipitates were observed with SEM and TEM in δ ferrite but not in γ austenite. Our density functional theory based calculations show that the G/Fe interface energy in δ-Fe is significantly lower than that in γ-Fe (0.35 versus 1.25 J/m2), which provides a thermodynamics-based explanation for our experimental observations of preferential formation of G-phase in δ ferrite. STEM-EDS, TEM dark field imaging, and diffraction patterns confirmed the Ni–Si–Mn enriched precipitates were G-phase precipitates with a stoichiometry of Mn6Ni16Si7. Intragranular voids and Ni–Si enriched clusters were observed in irradiated γ austenite. Additionally, Ni and Si segregation was observed along the void interfaces. In both cases, Ni–Si clusters and segregation to voids, selected area diffraction patterns did not reveal the existence of a second phase. Proton irradiation induced Cr depletion and Si and Ni enrichment at γ−γ austenite grain boundaries that was characterized with STEM/EDS.

Effect of Si content on the uniaxial tensile behavior of Mo-Si solid solution alloys

Recrystallized binary Mo-0.2 wt.% Si (Mo-0.68 at.% Si) and Mo-0.3 wt.% Si (Mo-1.0 at.% Si) alloys and a ternary Mo-0.75 wt.% Si-0.14 wt.% B (Mo-2.5 at.% Si-1.2 at.% B) alloy were tested in uniaxial tension as a function of temperature in vacuum and the results are compared to previous results on recrystallized commercial purity (CP) Mo and a binary Mo-0.1 wt.% Si (Mo-0.34 at.% Si) solid solution alloy. Yield strength increases with increasing Si content at all temperatures examined except at room temperature where the 0.1 wt.% Si alloy demonstrates softening; atomistic simulation confirms this behavior to be associated with Si segregation to the core and the associated ease of kink nucleation. Tensile ductility at room temperature rapidly deteriorates with increasing Si content in solid solution but in the Mo-0.3 wt.% Si solid solution alloy, tensile ductility of ~10% was measured at 300°C and thereafter, it increases rapidly at higher temperatures. Serrated flow occurs in the temperature range 600°C~800°C with the serration amplitude increasing with increasing Si content; atomistic simulation illustrates O trapping by Si in solid solution and subsequent de-trapping/release at higher temperatures that can account for the onset temperature delay of serrated flow in these Mo-Si solid solution alloys relative to commercial purity Mo. The serrated flow phenomenon is accompanied by significant work hardening; the presence of dislocation tangles, dipoles and prismatic loops in specimens fractured above ≥ 700°C accounts for the observed work hardening.

M23C6 precipitation and Si segregation promoted by deep cryogenic treatment aggravating pitting corrosion of supermartensitic stainless steel

M23C6 precipitation and Si segregation promoted by deep cryogenic treatment aggravating pitting corrosion of supermartensitic stainless steel

Solidification microstructure and tensile deformation mechanisms of selective electron beam melted Ni3Al-based alloy at room and elevated temperatures

Selective electron beam melting (SEBM) was used to process crack-free Ni3Al-based IC21 alloy (low density superalloy) containing ~85% γ′-volume fraction. There are distinct differences between dendrites and inter-dendritic regions with the presence of coarse γ+γ′ eutectic and secondary solidification microconstituents (Cr and Mo-rich) in the latter. The pronounced inter-dendritic eutectic regions suggest that a significant elemental partitioning between the liquid and solid occurred during the SEBM. The terminal liquid is trapped at boundaries between dendrites and grains, as evidenced by the liquid films on cracked surfaces. In contrast to extensive studies indicating the segregation of Zr and B, we show unambiguously the segregation of Si to low melting point liquid films and thereby enhancing the susceptibility to solidification cracking in IC21 produced by SEBM. The tensile specimens extracted from the crack-free IC21 samples exhibit superior properties at room temperature (RT) and 1000 °C. The RT deformation mechanism is characterised by cutting γ′-phase with two paired dislocations and antiphase boundaries in between. At 1000 °C tensile deformation, the well-developed γ/γ′ interfacial dislocation networks are in good agreement with their promising high-temperature performance (σy = 518 ± 10 MPa, σUTS = 560 ± 16 MPa, 20.5% for ductility).

Use of combined linear and nonlinear ultrasound to examine microstructural and microchemical variations in highly irradiated 304 stainless steel

This research combines linear and nonlinear ultrasound to examine the microstructural and microchemical changes in five large, highly irradiated cold-worked ANSI 304 stainless steel coin specimens cut from two hexagonal cross section blocks with radiation damage levels ranging from ~0.4 to ~33 dpa following irradiation in the EBR-II fast reactor. Both linear (velocity) and nonlinear ultrasonic (β) measurements were conducted in a hot cell using an automated fixture device specially designed to hold the sensor for repeatable measurements in an environment where direct human access is limited, demonstrating their potential to more fully investigate the complex defect ensemble introduced by irradiation. The measurements were performed at the Westinghouse Churchill site hot cell facility.The linear measurements agree very well with previous measurements employing a different sensor application technique. The ultrasonic nonlinearity parameters measured after irradiation increased by more than 100% from the unirradiated state and show a level of random variation below 4.7%. These ultrasonic nonlinearity parameters also show a spatial dependence on measurement location across each of the specimens in agreement with the spatial inhomogeneity of microstructure and microchemical distribution previously observed in adjacent, nominally identical specimens using transmission electron microscopy (TEM) and atom probe tomography (APT). It is proposed that the inhomogeneous distribution of microstructural and microchemical features including Frank loops, and both intragranular and grain boundary precipitates, as well as their different nonlinearity generation efficiencies are responsible for the spatial dependence of the measured ultrasonic nonlinearity parameters. The major and dominant component of the microstructure of these specimens at 20–30 dpa is vacancy agglomerations called voids, previously observed by microscopy and measurable using either linear ultrasonic velocity or linear attenuation, but which are not readily visible using nonlinear ultrasound. Components such as Frank loops, which are one of the other major microstructural components, do not contribute significantly to changing the linear ultrasonic velocity. Using this combination of linear and nonlinear measurements allows for the examination of microstructural/microchemical components whose linear ultrasonic interactions are overshadowed by voids, especially Frank loops and various radiation-induced precipitates.The changes in ultrasonic nonlinearity parameters in these specimens are thought to arise from two major sources. The smaller contribution is due to carbide pinning of dislocations in the grain boundary walls and the few line dislocations present in the grain interior. The largest contribution appears to come from segregation of Ni and Si to the perimeter of the very high density of Frank loops, leading to the formation of Ni3Si precipitates which are thought to be very efficient at pinning the Frank loops. These results on two hex blocks provide an ideal, though not completely realistic, test case to demonstrate the sensitivity of nonlinear ultrasound to two different microstructure sources.

Mechanism for Si Poisoning of Al-Ti-B Grain Refiners in Al Alloys

Al-5Ti-1B is the most widely used grain refiner for Al alloys. However, it is not effective for grain refining Al alloys containing more than 3 wt pct Si. This adverse effect of Si is referred to as Si poisoning. In spite of extensive experimental and theoretical investigations in the past decades, the exact mechanism for Si poisoning is still not clear. In this work, the state-of-the-art electron microscopy was performed to investigate the mechanism for Si poisoning. Our experimental results suggest that Si segregates preferably to the TiB2/Al-Si melt interface and the pre-existing Al3Ti 2-dimensional compound (2DC) layer on TiB2 surface dissolves into the Al-Si melt. Based on the experimental results, we have postulated a new mechanism for Si poisoning: interfacial segregation of Si leads to enrichment of Si at the TiB2/Al-Si melt interface, and this in turn makes the pre-existing Al3Ti 2DC on the TiB2 surface unstable and dissolve gradually in the melt, resulting in a loss of TiB2 nucleation potency and hence a decreased total number of potent TiB2 particles available for heterogeneous nucleation and grain initiation and consequently an increased grain size. This mechanism for Si poisoning can explain consistently the experimentally observed phenomenon reported in the literature.

Influence of copper precipitates on clustering behavior of alloying elements observed in Japanese reactor pressure vessel surveillance materials using atom probe tomography

In a highly irradiated reactor pressure vessel (RPV), solute Mn, Ni, and Si (MNS) atoms gather to form nanometer-sized microstructures, generally called MNS clusters. MNS often gather with Cu-rich precipitates, which can form in RPVs following lower dose irradiation. In this study, surveillance specimens provided from four nuclear power plants in Japan were analyzed using three-dimensional atom probe tomography (APT), and the nature of the solute enrichment was carefully compared. When analyzing the chemical composition of each cluster, a clear negative correlation was found between Si and Cu in all materials, but conversely, Mn was likely present in clusters with a high Cu concentration. Moreover, in a boiling water reactor material with high Cu, the ratio of MNS was shown to be similar to that of the Γ2 phase [Mn (Ni, Si)2]. In pressurized water reactor materials with medium and low Cu, however, Ni and Si enrichment was demonstrated to be higher than the ratio of the expected intermetallic compounds; such as a Γ2 phase and a G phase [Mn6 Ni16 Si7]. Ni and Mn atoms, once enriched in a copper-rich region, may elute out, and form an intermetallic compound with Si atoms within the vicinity. Particularly in highly irradiated RPV materials, such a structure may tend to be decorated by irradiation-induced lattice defects with Si segregation.