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Efficient and cost-effective soft magnetic materials (SMMs) are essential for accelerating the adoption of electric vehicles and the sustainable growth of renewable electricity. While amorphous and nanocrystalline SMMs offer remarkably low magnetic losses, their poor mechanical properties, limited availability in size and shape (particularly ribbon widths), and high cost prevent them from widespread industrial application. Here, we show that ductile Fe-6.5%Si 2-D flakes could be used as building blocks for making high performance bulk SMMs. This approach bypasses the brittleness problem and creates a new morphology and a new fabrication method for the SMMs with improved energy efficiency and lower processing cost. Ductile Fe-6.5%Si flakes are mass-produced by melt spinning and are then consolidated to bulk SMMs with a brick-wall type of structure. The novel process introduces anisotropic electrical and magnetic properties and enables near net shape processing. Resulting Fe-6.5%Si thin sheets display low iron loss (W10/400 = 6.1 W/kg) and high permeability (µr = 28,000), which are comparable to the current state of the art high silicon steel. CaF2 coating reduces the iron losses for thick Fe-6.5%Si parts. Polymer coated Fe-6.5%Si flake cores show potential for high power inductors with greater permeability and lower losses than traditional powder cores.

Severe plastic deformation leads to cementite decomposition in pearlitic and martensitic alloys, resulting in high-strength nanocrystalline ferrite. This effect can be employed to strengthen pearlitic wires but it can also be associated with material failure by white etching cracks (WECs) that are primarily known to concern bearings or rails. We investigate the decomposition of spheroidal cementite in the martensitic bearing steel 100Cr6 with 62 Rockwell hardness during high pressure torsion at 9.5 GPa applied pressure. The hard martensitic matrix and the even harder spheroidal cementite precipitates behave plastically very differently. The enforced macroscopic plastic deformation is almost entirely carried by the matrix. Plastic material flow of the matrix around the spheroidal cementite leads to wear of the spheroidal cementite as indicated by continuously increasing levels of chromium in the matrix. Plastic deformation of spheroidal cementite via dislocation gliding supposedly accelerates this process as slip steps generated thereby are preferential sites of wear at the matrix/cementite interface. Larger spheroidal cementite precipitates are more prone to plastic deformation and to decomposition than smaller ones. The mechanism likely holds true in general for multiphase materials with large strain difference between phases subjected to high pressure torsion. Although the formation of WECs in 100Cr6 bearings might be slowed down by reducing the size of the spheroidal cementite precipitates, it is unlikely that this could entirely prevent this failure mechanism.

Nanoprecipitates or grain refinement can effectively enhance the mechanical strength of Al alloys, but the room-temperature strengths of precipitation hardened and nanocrystalline Al alloys often fall below 1 GPa. Furthermore, they are largely plagued by precipitous mechanical softening at elevated temperature below 300°C, mostly due to degraded microstructural stability. Here, we report a mechanism of coupled solute effect in nanotwinned Al-Fe-Ti alloys that enables stability of nanograins up to 400°C and an unprecedented high-temperature flow stress of ~ 1.7 GPa at 300°C. The supersaturated Fe solutes in Al act as effective grain refiner, forming superstrong solid solution alloys. More importantly, empirical evidence combined with first principle calculations indicate that the Ti solutes delay the agglomeration of Fe solutes, thereby remarkably extending the temperature window for the stability of nanograins in nanotwinned Al alloys. This study highlights the opportunity to design ultrastrong and stable nanostructured alloys for potential high temperature applications via a coupled solute effect.

Non-metallic contamination is a practically unavoidable byproduct of commercial synthesis processes; however, non-metallic impurities are often overlooked when considering material design and performance of nanostructured materials. Importantly, there is disputing evidence as to whether non-metallic contamination stabilize or destabilize nanocrystalline materials against grain growth. Furthermore, it is unclear if non-metallic contamination has a significant impact on hardness of nanocrystalline systems. In this work, two nanocrystalline Ni-28at%W alloys with different impurity concentrations were produced via mechanical alloying to directly evaluate the effect of contamination on thermal stability and hardness of nanostructured materials. The alloys were isothermally annealed at several temperatures, and the microstructures were compared by applying atom probe tomography and aberration-corrected scanning transmission electron microscopy. It was determined that impurity concentrations can be substantially reduced by using specific milling media and pre-milling reduction processes. Furthermore, the clean and contaminated alloys exhibited similar thermal stabilities against grain growth, but the clean alloy displayed a 100% improvement in hardness despite a similar grain size and distribution of second phases. Impurity phases including CrOx, Ni6W6C, and trapped Ar pores were also identified and likely contributed to the thermal stability and mechanical properties observed in this study. Overall, this work suggests that impurities my not always be detrimental to thermomechanical behavior of nanocrystalline systems.

Recently 1:12 magnets of Sm-(Fe,V) have shown promising coercivities and the potential to be alternative rare-earth-lean permanent magnets. In this work, we investigated the effects of partial substitution of Cu, Mo and Ti for V in the magnets prepared by hot compaction and hot deformation of mechanically milled powders. The microstructure of the Sm-Fe-(V,Cu) and Sm-Fe-(V,Ti) hot-deformed magnets consisted in fine grains with sizes between 50 and 150 nm. The Sm-Fe-(V,Cu) magnet showed the best performance with μ0H c = 0.96 T, μ0M r = 0.49 T, (BH) max = 42 kJ m − 3 and T C = 362 ∘ C. Atom probe tomography of this magnet revealed the presence of a thin Sm17.5Fe71.5V8Cu3intergranular phase of 3-6 nm surrounding the 1:12 nanograins. The addition of a small amount of Cu, not only improved the magnetic properties but also hindered the grain growth during hot deformation. Micromagnetic simulations of the magnetization reversal agreed with the experimental values of coercivity. The presence of the intergranular phase reduces the number of grains that switch simultaneously.

Shock induced plasticity, structural phase transitions, as well as dynamic failure in nanocrystalline SiC ceramics, with grain sizes varying from ~2 to ~32 nm, are investigated systematically using large scale molecular dynamics simulations. Shock particle velocities are varied from 1 to 5 km/s in order to study elastic and plastic behavior. Multiple non-monotonic grain-size dependent mechanical properties of nanocrystalline SiC are elucidated. Deformation twinning identified at Up = 2 km/s is reduced with decreasing grain size with a breakdown between dG = 6 to 10 nm. Statistics from grain size effects on the phase transformation from Zinc-Blend to Rock-Salt structure at different particle velocities are obtained. The characteristics of failure shift from classical spall to micro-spall as Up is increased from 1 to 5 km/s. Spall strengths are evaluated by an indirect free-surface method, akin to experimental measurements, and a direct method evaluating the atomic stress tensor at the point of spallation. Differences between the two methods at high strain rates are discussed in detail. The direct method provides a measure of ultimate spall strength, while the indirect method shows pronounced agreement with the nucleation stress. An unexpected grain size dependence of the tensile strengths is also identified, which is similar to a theoretically predicted trend in nanoscale systems. Our results provide new support to the grain size dependence of mechanical properties of nanocrystalline system at high strain rates, which could benefit the design of nanocrystalline ceramics.

Wear and friction of nanocrystalline (NC) aluminum were investigated via molecular dynamics simulations and the effects of dopants were considered. Zr-doped NC Al was found to have a better wear resistance and a smaller friction force, which is consistent with a higher hardness and a higher strength of the doped sample. The underlying mechanisms are suppressed emission of dislocations from grain boundaries (GBs), suppressed GB migration, and suppressed GB sliding. After multiple sliding cycles, the trend in mechanical response was reversed, with the pure NC Al showing a better wear resistance and a lower friction force than the doped sample. One reason is that the higher dislocation density introduced during wear into the pure sample leads to more strain hardening. Another reason is that the pure NC Al has undergone more significant grain growth than the doped sample. Since the grain size of our samples is in the inverse Hall-Petch regime, here grain growth leads to strengthening of the pure sample. Mechanisms of grain growth in the pure NC Al and its suppression in the doped NC Al are analyzed and discussed.

Being lightweight, energy-efficient and environmentally benign, magnesium alloys present great potential for various industrial applications. However, they possess relatively low mechanical properties and need to be strengthened. During the last decade, significant effort has been directed towards preparation of strong nanocrystalline (NC) Mg alloys, although because of the limited plasticity inherent to HCP metals, the grain size of Mg was rarely refined below 1000 nm and the yield strength seldom exceeded 500 MPa. Here, by means of a conventional industrial method of rotary swaging, we prepared bulk NC Mg–Gd–Y–Zr alloys with an average grain size of 80 nm and a dimension of ∅3 mm × 1000 mm. The further-aged NC Mg alloy exhibits the yield strength of 650 MPa and the ultimate tensile strength of 710 MPa, the highest such values published for bulk Mg alloys. Fracture surface observation suggested a ductile inter-granular fracture in the NC Mg alloys. The high strength are attributed to nano-grain, intra-granular Gd rich clustering, inter-granular solutes segregation, β′ precipitation, dislocation and solution strengthening contributions, among which the nano-grain strengthening is dominant. The nano-grain formation results from the large number of mechanical twins, deformation bands and stacking faults induced by the high strain rate of swaging. Our work advances the industrial-scale production of bulk NC Mg alloys by exploring a simple and low-cost fabrication technique.

The kinetic evolution of a multiplicity of metastable grain boundaries (GBs) under fast driving conditions are studied by atomistic modeling. Assisted with an enhanced statistical analysis, the energetic evolution of GBs over a broad metastability-temperature space is mapped out, wherein two distinct regimes—an ageing regime and a rejuvenating regime—are retrieved with high fidelity. By comparing the results under various conditions (e.g. random perturbations, isothermal annealing, and fast heating/cooling), it is shown that such ageing/rejuvenating mechanism map is universal, irrespective of the actual stimuli used to elicit the metastable GBs. The ageing/rejuvenating phenomena are demonstrated to stem from the energy imbalance of uphill climbing and downhill dropping during sequential transitions in the system's potential energy landscape. Without the necessity of introducing free parameters, such model can reconcile experimentally measured hardness variation of nanocrystalline metals subjected to femto-second laser irradiation, and it therefore provides a novel perspective on achieving a plurality of interfacial states and facilitating previously inaccessible property regimes.

Solute segregation to individual grain boundaries is used by design to produce strong and stable nanocrystalline metallic alloys. Grain-boundary segregation, however, is known to cause adverse embrittlement effects from a strain-localization failure mechanism that imposes significant material limitations for structural applications. Here, using atomistic simulations, it is discovered that heterogeneous Ni segregation in nanocrystalline Ni-mixed Ag alloys dramatically shuts down localized shear bands during plastic deformation, while simultaneously increasing the tensile strength. Nanocrystalline Cu-mixed Ag metals are predicted to exhibit standard homogeneous Cu segregation and a tensile strength that saturates above a solute concentration of 8 at.% due to glass-like shear localization induced by grain boundaries. By contrast, it is found that heterogeneous Ni segregation in nanocrystalline Ag-Ni alloys forms solute-rich clusters along interfaces leading to strain delocalization at high strain and continuous strengthening at high solute concentrations up to 15 at.%. This study reveals the importance of heterogeneous versus homogeneous segregation behaviors on strain localization and points to a fundamentally new strategy to design failure-resistant nanostructured materials through grain boundary segregation engineering.

As the numbers of medium- to high-entropy alloys being studied and impressive structural properties they exhibit increase rapidly, questions regarding the role played by their complex chemical fluctuations rise concomitantly. Here, using a combination of large-scale molecular dynamics (MD), a hybrid MD and Monte-Carlo simulation method, and crystal defect analysis, we investigate the role lattice distortion (LD) and chemical short-range order (CSRO) play in the nucleation and evolution of dislocations and nanotwins with straining in single crystal and nanocrystalline CoCrNi, a medium entropy alloy (MEA). LD and CSRO effects are elucidated by comparisons with responses from a hypothetical pure A-atom alloy, which bears the same bulk properties of the nominal MEA but no LD and no CSRO. The analysis reveals that yield strengths are determined by the strain to nucleate Shockley partial dislocations, and LD lowers this strain, while higher degrees of CSRO increase it. We show that while these partials prefer to nucleate in the CoCr clusters, regardless of their size, they find it increasingly difficult to propagate away from these sites as the level of CSRO increases. After yield, nanotwin nucleation occurs via reactions of mobile Shockley partials and is promoted in MEAs, due to the enhanced glide resistance resulting from LD and CSRO.

Nanocrystalline (NC) materials possess excellent room temperature properties, such as high strength, wear resistance, and toughness as compared to their coarse-grained counterparts. However, due to the excess free energy, NC microstructures are unstable at higher temperatures. Significant grain growth is observed already at moderately low temperatures, limiting the broader applicability of NC materials. Here, we present a design approach that leads to a significant improvement in the high temperature tensile creep resistance (up to 0.64 of the melting temperature) of a NC Cu-Ta alloy. The design approach involves alloying of pure elements to create a distribution of nanometer sized solute clusters within the grains and along the grain boundaries. We demonstrate that the addition of Ta nanoclusters inhibits the migration of grain boundaries at high temperatures and reduces the dislocation motion. This leads to a highly unusual tensile creep behavior, including the absence of any appreciable steady-state creep deformation normally observed in almost all materials. This design strategy can be readily scaled-up for bulk manufacturing of creep-resistant NC parts and transferred to other multicomponent systems such as Ni-based alloys.

Metallic materials with a gradient microstructure usually exhibit excellent mechanical properties. However, the radiation response of gradient structural materials is less well understood. Here, room-temperature He ion irradiation up to ~4.5 dpa with ~10 at% He injection was performed on a gradient T91 steel processed by surface severe plastic deformation. In comparison to the coarse-grained ferritic T91, the gradient T91 with the nanocrystalline layers shows improved radiation tolerance in terms of less bubble swelling and radiation hardening. Additionally, bubble distribution along grain boundaries depends on misorientation angle suggesting a strong capacity of non-equilibrium grain boundaries in storing He atoms. The present study provides insight into the design of radiation tolerant gradient steels for nuclear industry applications.

The composition Au49Ag5.5Pd2.3Cu26.9Si16.3 (at.%) is of interest as the basis for the development of gold-based bulk metallic glasses for application in jewellery. In-situ heating in transmission electron microscopy (TEM) and differential scanning calorimetry (DSC, both conventional and fast) are used to obtain a comprehensive characterization of the decomposition on heating a melt-spun glass of this composition. Linking TEM with DSC over a range of heating rates 0.083‒2000 K s‒1, allows the sample temperature in the TEM heating stage to be calibrated. On heating up to melting, the glass decomposes in up to four stages: (1) complete transformation to single-phase nanocrystalline (Au,Cu)7Si; (2) grain growth of this phase; (3) precipitation of (Pd,Ag)Si, reducing the supersaturation of silicon in the (Au,Cu)7Si matrix; (4) with the precipitate phase remaining stable, decomposition of the matrix to a mixture of (Au,Ag)8Cu2, AuCu and Cu3Au phases. At all stages, grain diameters remain sub-micrometre; some of the stable nanocrystalline microstructures may themselves be of interest for applications. The characterization of the decomposition can assist in the optimization of the glass composition to improve tarnish-resistance, while retaining adequate glass-forming ability, formability in thermoplastic processing, and resistance to crystallization. For materials in general, the close correlation of in-situ TEM and DSC results should find wide use in characterizing complex transformation sequences.

Metallic materials produced by additive manufacturing experience complex stress and thermal gyrations along the build direction. This has the potential to produce complicated heterogeneous microstructures that may exhibit a wide variety of mechanical properties. There remains a paucity of studies on the nature and the formation mechanisms of the microstructural heterogeneity and this limits our capability for microstructural design in additively manufactured metallic materials. Here, we present an electron microscopy-based investigation of a CrMnFeCoNi high-entropy alloy produced by selective laser melting. We have focussed on a systematic investigation of the microstructural evolution along the build direction. Our results reveal a remarkable hierarchy of microstructures, including the formation of nanocrystalline grains, elemental segregation and precipitation, cellular dislocation structures, deformation twinning, and deformation-induced phase transformation. Our research clarifies the relationships amongst different features, and provides guidance for future structural manipulation of materials produced by additive manufacturing.

This study investigated the mechanisms and temperature dependence of the R phase variant reorientation deformation in a nanocrystalline NiTi wire by means of in-situ synchrotron high-energy X-ray diffraction technique during tensile deformation. The NiTi wire exhibited a single stage B2 → R transformation upon cooling with the R → B19′ martensitic transformation completely suppressed down to the liquid nitrogen temperature. The R phase variant reorientation deformation in tension was revealed to proceed in a Luders-manner, as evidenced by sudden changes of diffraction peak intensity and increases of lattice elastic strains of the R phase during the deformation. The variant reorientation obeys the principles to yield maximum crystallographic strain in the direction of the applied load. Thus, the variants with larger d-spacing values aligned to the axis of tension grew at the expense of those of lower d-spacing values. The increases of lattice elastic strains are attributed to the internal load transfer among the different crystallographic variants during the R phase reorientation. The crystallographic strain of R phase reorientation was found to increase with decreasing the deformation temperature. This corresponds directly to the continued evolution of the structure of the R phase of increased structural distortion relative the B2 phase with decreasing the temperature. This reflects the second order nature of the R phase.

This work explores the development of a heterogeneous nanostructured material through leveraging abnormal recrystallization, which is a prominent phenomenon in coarse-grained Ni-based superalloys. Through synthesis of a sputtered Inconel 725 film with a heterogeneous distribution of stored energy and subsequent aging treatments at 730°C, a unique combination of grain sizes and morphologies was observed throughout the thickness of the material. Three distinct domains are formed in the aged microstructure, where abnormally large grains are observed in-between a nanocrystalline and a nanotwinned region. In order to investigate the transitions towards a heterogeneous structure, crystallographic orientation and elemental mapping at interval aging times up to 8 h revealed the microstructural evolution and precipitation behavior. From the experimental observations and the detailed analysis of this study, the current methodology can be utilized to further expand the design space of current heterogeneous nanostructured materials.

The grain size (GS) dependence of fatigue crack growth in nanocrystalline superelastic NiTi shape memory alloys (SMAs) with the average GS of 10, 30, 60 and 235 nm is investigated. Synchronized measurements of the fatigue crack growth, load-displacement response and temperature field of the compact tension specimens are performed. It is found that the fatigue crack growth rate (da/dN) is monotonically decreased by 10 times when the GS is increased from 10 to 235 nm. The significant GS effect on the fatigue crack growth is also confirmed by the direct observation of fatigue striation spacing on the postmortem fracture surface. It is shown that the increase of the GS significantly enhances the phase transition and plasticity of the material and therefore enhances the crack-tip shielding (Ksh) which reduces the effective driving force (ΔKeff) of the fatigue crack growth. Subtracting Ksh due to phase transition and plastic deformation from the external applied Kapp, the effective crack-tip fatigue driving force ΔKeff is obtained. The da/dN-ΔKeff curves for different GS specimens then almost collapse onto a single curve which may represent an intrinsic fatigue property of the NiTi in the absence of the shielding effects. Therefore the observed apparent GS dependence of the fatigue crack growth resistance in the superelastic NiTi SMAs is mainly caused by the shielding effect from the GS dependent phase transition and plastic deformation.

Nanocrystalline materials are known to possess excellent radiation resistance due to high fraction of grain boundaries that act as defect sinks, provided they are microstructurally stable at such extreme conditions. In this work, radiation response of a stable nanocrystalline Cu-Ta alloy is studied by irradiating with 4 MeV copper ions to doses (close to the surface) of 1 displacements per atom (dpa) at room temperature (RT); 10 dpa at RT, 573 and 723 K; 100 and 200 dpa at RT and 573 K. Nanoindentation results carried out for samples irradiated till 100 dpa at RT and 573 K show exceptionally low radiation hardening behavior compared to various candidate materials from literature. Results from microstructural characterization, using atom probe analysis and transmission electron microscopy, show a stable nanocrystalline microstructure with minimal grain growth and a meagre swelling in samples irradiated to 100 dpa (~0.2%) and 200 dpa at RT, while no voids in those at 573 K. This radiation tolerance is partly attributed to the stability of Ta nanoclusters due to phase separating nature of the alloy. Additionally, the larger tantalum particles are observed to undergo ballistic dissolution at doses greater than 100 dpa and are eventually precipitated as nanoclusters, replenishing the sink strength, which enhanced material's radiation tolerance when exposed to high irradiation doses and elevated temperatures.

Interfacial solute segregation behavior of P in nanocrystalline (NC) Ni alloys is investigated at the atomic scale using cross-correlative PED-APT measurements and atomistic simulations. Inhomogeneous P-segregation in grain boundaries (GBs) of NC Ni is observed from both experimental measurements and simulation calculations. Interfacial excess (IE) of the solute within GBs is further studied as function of GB misorientation. Significant scatter is detected in the IE of boundaries with similar misorientation angles and even within special boundaries with identical Σ values. From atomistic simulations, a general trend of increasing IE with initial GB energy and volume is observed but with poor correlation, indicating that the segregation behavior cannot be captured with a single average measure of the entire GB character. Rather the results suggest that the extent of interfacial solute segregation correlates better with fraction of high energy atomic sites in the boundary. By comparing IE values with thermodynamic model predictions, it is shown that the interfacial segregation behavior is strongly influenced by the energy distribution of atomic sites in the GBs. However, in order to predict the extent of solute segregation, the evolution of the atomic energy landscape in the GB with continuous solute segregation must be considered.

Shear localization in nanocrystalline metals is a severely limiting factor precluding their use as practical engineering materials. While several strategies exist to enhance the thermal and mechanical behavior of these materials, there are still many outstanding questions regarding the effects of chemical segregation on shear localization of FCC nanocrystalline materials. In this paper we investigate the mechanical response of a ternary aluminum alloy with a sub-10 nm nanocrystalline microstructure subject to various thermal treatments. Contrary to previous observations, our results suggest that annealing up to 0.7 Tm reduces the propensity for shear localization and increases strength, as demonstrated by a transition in deformation morphology from pronounced strain localization to more homogeneous deformation during indentation. This behavior coincides with the formation of an amorphous intergranular film during annealing, causing intragranular dislocation plasticity to be favored over other grain boundary dominated deformation mechanisms, in turn resulting in a lower propensity for long range plastic localization.

Nanocrystalline metals are promising radiation tolerant materials due to their large interfacial volume fraction, but irradiation-induced grain growth can eventually degrade any improvement in radiation tolerance. Therefore, methods to limit grain growth and simultaneously improve the radiation tolerance of nanocrystalline metals are needed. Amorphous intergranular films are unique grain boundary structures that are predicted to have improved sink efficiencies due to their increased thickness and amorphous structure, while also improving grain size stability. In this study, ball milled nanocrystalline Cu-Zr alloys are heat treated to either have only ordered grain boundaries or to contain amorphous intergranular films distributed within the grain boundary network, and are then subjected to in situ transmission electron microscopy irradiation and ex situ irradiation. Differences in defect density and grain growth due to grain boundary complexion type are then investigated. When amorphous intergranular films are incorporated within the material, fewer and smaller defect clusters are observed while grain growth is also limited, leading to nanocrystalline alloys with improved radiation tolerance.

Nanostructured materials with amorphous intergranular films (AIFs) have demonstrated superior strength and ductility. Their radiation tolerance is expected to be high as the large fraction of interfacial volume efficiently sinks radiation-induced defects. Here we demonstrate how a crystalline-amorphous system (nanocrystalline Cu with Zr-doped AIFs) responds to continuous irradiation with molecular dynamics simulations. We propose a diffusion model that well characterizes the cascade-driven mixing process, and reveal that the spread of Zr distribution scales linearly with the damage level. The exceptional radiation resistance is attributed to the interfaces acting as sustainable defect sinks, Zr mixing into the bulk to enhance local defect annihilation due to solute-interstitial dragging, and Zr impeding radiation-enhanced grain growth by restraining AIFs from migration and maintaining interface stiffness. These findings suggest that AIF-engineered systems hold promise as highly radiation-tolerant materials with strong structural stability and self-healing capability under radiation damage.

Contrary to the characteristic strengthening of polycrystalline ceramics with a decrease in grain size, extremely fine nanocrystalline ceramics exhibit softening, increased plasticity and an inverse Hall-Petch relation. Despite experimental evidence, questions remain regarding the underlying deformation mechanisms governing this abnormal mechanical behavior. In the present study, an in-depth microstructural examination was performed on nanostructured transparent magnesium aluminate spinel (MgAl2O4) subjected to microhardness tests. Microstructural observations revealed regions strained to various degrees below the point of indentation, containing varying amounts of dislocations and nano-cavities. Furthermore, the residual strain in different areas was estimated by local electron diffraction. These observations and analysis provided evidence for grain boundary (GB) mediated mechanisms (e.g., GB sliding and rotation). Moreover, shear bands formed and were found to be associated with micro-cracking. By combining the microstructural analysis with suitable models, it was concluded that these mechanisms govern plastic deformation. By elucidating how strain is accommodated within nanocrystalline ceramics, a deeper understanding of their unique mechanical behavior is gained.

Bulk nanoporous tungsten as an extremely strong and low density nanocrystalline material was for the first time created to satisfy the need for advanced high performance materials that can endure harsh environments. Synthesis of nanoporous tungsten was achieved by a unique procedure involving severe plastic deformation of a coarse-grained tungsten-copper composite followed by selective dissolution of the nobler copper phase. The used ammonium persulfate etching solution, in which the less noble tungsten is chemically stable, is proved to be effective in removing the nobler copper phase. A nanoporous microstructure characterized by a network of interconnected nanocrystalline tungsten ligaments and interconnected nanopores was obtained. Based on a high-resolution interface analysis, the underlined mechanisms for formation of the nanoporous tungsten structure were elucidated. Moreover, using nanoindentation we demonstrate that, due to the nanoscale microstructure, the created nanoporous tungsten possesses outstanding strength, making it an attractive material for applications in radiation shielding.

Irradiation induced creep (IIC) compliance in NiCoFeCrMn high entropy alloys is measured as a function of grain size (30

Solute segregation at grain boundaries (GBs) is emerging as an alloy design tool, uses of which include the stabilization of nanocrystalline alloys. To predict the equilibrium segregation state in a given alloy, most thermodynamic models treat the full network of GBs as a single “entity”, and thus use an “effective” segregation energy to describe it. This simplification ignores the spectral nature of available GB segregation energies in a polycrystal, which we elucidate here computationally for a Mg solute in an Al polycrystal; the distribution is found to be captured accurately with a skew-normal function. A thermodynamic segregation isotherm that incorporates this spectrum is outlined and employed to study the effect of such a spectrum on predictions of the equilibrium GB segregation state. The ramifications for experimentally-extracted GB segregation energies are shown to be potentially significant, and nanocrystalline stability criteria are extended to account for this spectral nature of GB segregation.

Nickel carbonyl vapor deposition (CVD) is a high-efficiency process used to produce nickel shell molds with high yield strength, reasonable ductility, and strong corrosion resistance. Such advantageous properties arise from the nanocrystals and nanotwins inside CVD nickel. However, the nanotwins do not persist at high temperatures, transforming into dislocation cells after 40-min annealing at 800 °C . Using experimental examinations and computational simulations, we investigated the kinetics of the annealing-induced detwinning in CVD nickel. TEM examinations showed that detwinning is realized by incoherent twin boundary (ITB) migration; meanwhile, plentiful dislocations are generated from coherent twin boundaries (CTBs). Our theoretical analysis revealed that these dislocations are necessary for the formation of the ITBs. Next, using molecular dynamics simulations, we found that the dislocations nucleated from CTBs during annealing are intrinsic grain boundary dislocations (IGBDs). Driven by the internal stress intensified by grain growth in the nanocrystalline regime, the IGBDs can separate from CTBs due to creep at 800 °C , resulting in a higher dislocation density inside the twin lamella than that of the outside. These dislocations can trigger the formation of ITBs. Overall, unlike grain growth, stress is necessary for detwinning, so a monolithic nanotwin structure should be more stable than the nanotwins inside a nanocrystalline matrix.

We report a novel mechanism for explosive crystallization in amorphous germanium (a-Ge), which operates through liquid-mediated nucleation occurring under extreme thermal gradient conditions. The crystallization kinetics of sputter-deposited films with thicknesses ranging from 30 to 150 nm were characterized using in situ movie-mode dynamic transmission electron microscopy (MM-DTEM). After localized heating from a short laser pulse, explosive liquid phase nucleation (LPN) was observed to occur during the early stage ( 50 nm) films deposited on silicon nitride substrates. The crystallization front propagated at ∼12–15 m/s and produced nanocrystalline microstructure with ∼50 nm grains. A mechanism involving the existence of a relatively thick (>100 nm) transient liquid layer and a high nucleation rate is proposed to explain the behavior. The key thermodynamic and kinetic features as well as the feasibility of the mechanism are further explored by employing parametric and systematic phase-field modeling and simulations.

Ti–Ni based shape memory alloys are promising elastocaloric materials for solid-state refrigeration. In this paper, we made a comprehensive study on elastocaloric effect of a nanocrystalline Ti–44Ni–5Cu–1Al (at%) alloy exhibiting successive B2–B19–B19′ transformation. The maximum adiabatic temperature decrease by stress removal from 600 MPa is ΔTadi∼25 K with a small temperature distribution of ∼0.5 K. The value of ΔTadi is consistent with that calculated from strain-temperature relation. The effective working temperature window is ∼55 K, resulting in a high refrigeration capacity of RC = 4.2 kJ/kg. Material coefficient of performance reaches COP ∼9.6 when an Otto cycle is considered. The middle eigenvalue of the transformation matrix is λ2 ∼ 0.99, implying high lattice compatibility between the parent and martensite phases. These properties are related to the diffuse nature of successive B2–B19–B19’ martensitic transformation of this alloy.

Recent advances in polycrystalline ceramic synthesis have established fabrication routes for producing dense ceramics with grain size on the order of few nanometers. Light transmission properties and, specifically, the high transparency of birefringent nanocrystalline ceramics cannot be captured by classical geometrical optics theory. In this investigation, we combine the Raman-Viswanathan wave-retardation theory with finite element method (FEM) based numerical simulations to develop an approach for predicting the refractive index variation within and real in-line transmission through relevant optical materials. This approach is validated on non-cubic (and, therefore birefringent) Al2O3 and MgF2 polycrystalline ceramics, by comparing the computed light transmission to experimental transmission measurements. For both of the considered ceramics systems, the developed numerical model effectively reproduces the experimentally measured transmission as a function of average grain size and incident light wavelength, showing improvement over the original approach of Raman and Viswanathan and a recent particle-scattering based adaptation of geometrical optics theory by Apetz and van Bruggen. The same modeling framework can also simulate the effects of applied elastic and electric fields, allowing for the design and predictive evaluation of functional optical properties in piezoelectric ceramics.

In order to find a promising trade-off permanent magnet material regarding a performance/cost-ratio, the Ce 1 − x Sm x Fe 11 − y Ti 1 V y -phase (x = 0–1; y = 0, 1) is analyzed in detail. In the first part, its existence range is studied (1000 °C) and the intrinsic magnetic properties are comprehensively determined. Diffraction experiments localize both structure-stabilizing transition metals on 8i-sites, explaining the measured reduction in saturation polarization as V is added. Curie temperatures increase upon Sm-substitution with a negligible dependence on V. Annealings of nanocrystalline material produced via intensive milling and melt-spinning show that V especially raises the obtainable maximum coercivities for Sm-rich phases (924 kA/m). In the second part, the promising magnetic properties of the nanocrystalline material are successfully transferred to the bulk state via hot-pressing. The isotropic Ce 0 . 5 Sm 0 . 5 Fe 10 Ti 1 V 1 -magnet (coercivity = 425 kA/m) is characterized by various means. Magnetic measurements, structural investigations and calculations of the elastic constants consider necessary factors for a successful texturing by die-upsetting (as accepted for Nd - Fe -B). The results are fundamental for further considerations in this active field of research.

Control of the crystallization process at the microscopic level makes it possible to generate the nanocrystalline samples with the desired structural and morphological properties, that is of great importance for modern industry. In the present work, we study the influence of supercooling on the structure and morphology of the crystalline nuclei arising and growing within a liquid metallic film. The cluster analysis allows us to compute the diffraction patterns and to evaluate the morphological characteristics (the linear sizes of the homogeneous part and the thickness of the surface layer) of the crystalline nuclei emergent in the system at different levels of supercooling. We find that the liquid metallic film at the temperatures corresponded to low supercooling levels crystallizes into a monocrystal, whereas a polycrystalline structure forms at deep supercooling levels. We find that the temperature dependence of critical size of the crystalline nuclei contains two distinguishable regimes with the crossover temperature $T/T_{g}\approx1.15$ ($T_{g}$ is the glass transition temperature), which appears due to the specific geometry of the system., Comment: 12 pages, 7 figures

This paper reports a new type of unique gradient microstructure (i.e., fine-grained core and coarse-grained surface regions) fabricated using a continuous severe plastic deformation process for metallic sheets, called single-roll angular-rolling (SRAR). The gradient-structured Cu sheet produced by SRAR has a reverse microstructure that is distinctly different from conventional gradient materials (i.e., fine-grained surface and coarse-grained core regions) created by surface nanocrystalline processes. Finite element analysis demonstrated that the evolution of the gradient microstructure in SRAR is attributable to the heterogeneity of its shear deformation history along the thickness direction due to the combined effect of circumferential shear deformation, equal-channel angular pressing, and frictional effects. The resultant gradient-structured Cu sheet exhibited simultaneous enhancements of strength and ductility. By systematic comparison to homogeneous counterparts, it was confirmed that the extraordinary combination of strength and ductility came from the gradient structural effect. Using the micro-scale digital image correlation method, clear strain partitioning and its corresponding strain gradients were observed. This high plastic-incompatibility was compensated by the pile-ups of geometrically necessary dislocations (GNDs) at the interface between the fine- and coarse-grained layers. The large amount of GNDs resulted in corresponding high back-stress evolution, contributing to the extraordinary strain hardening of the gradient-structured Cu sheet. The SRAR process sheds lights on developing new type of heterogeneous materials applicable to industry.

Most research on nanocrystalline alloys has been focused on planned doping of metals with other metallic elements, but nonmetallic impurities are also prevalent in the real world. In this work, we report on the combined effects of metallic dopants and nonmetallic impurities on grain boundary energy and strength using first-principles calculations, with a Σ5 (310) grain boundary in Cu chosen as a model system. We find a clear correlation between the grain boundary energy and the change in excess free volume of doped grain boundaries. A combination of a larger substitutional dopant and an interstitial impurity can fill the excess free volume more efficiently and further reduce the grain boundary energy. We also find that the strengthening effects of dopants and impurities are dominated by the electronic interactions between the host Cu atoms and the two types of dopant elements. For example, the significant competing effects of metal dopants such as Zr, Nb, and Mo with impurities on the grain boundary strength are uncovered from the density of states of the d electrons. As a whole, this work deepens the field's understanding of the interaction between metallic dopants and nonmetallic impurities on grain boundary properties, providing a guide for improving the thermal stability of materials while avoiding embrittling effects.

Nanocrystalline metals are often postulated as irradiation tolerant materials due to higher grain boundary densities. The efficiency of these materials in mitigating irradiation damage is still under investigation. Here, we present an in-situ transmission electron microscopy with ion irradiation study on equiaxed 35 nm grained tungsten (NCW-35 nm) and compare its radiation tolerance, in terms of dislocation loop damage, to several other grades of tungsten with different grain sizes at two temperatures (RT and 1073 K). The NCW-35 nm was shown to possess significant higher radiation tolerance in terms of loop damage. As demonstrated by Kinetic Monte Carlo simulations, at least part of the higher radiation tolerance of the small grains is due to higher interstitial storage (at the grain boundaries) and defect recombination (in the grain interiors) in the small grain material. In addition, experimental observations reveal rapid and efficient dislocation loop absorption by the grain boundaries and this is considered the dominant factor for mass transport to the boundaries during irradiation, enabling the remarkable radiation tolerance of 35 nm grained tungsten. This study demonstrates the possibility of attaining high radiation tolerant materials, in terms of dislocation loop damage, by minimizing grain sizes in the nanocrystalline regime.

Nanocrystalline materials exhibit various properties or phenomena not common in the conventional grain size regime, including enhanced strain rate sensitivity for FCC metals or strength increase during recovery annealing. These peculiarities are associated with the enhanced confinement of plasticity. Accordingly, the interaction of dislocations with the numerous grain boundaries, the boundary state as well as its local chemistry are of importance for a complete understanding. Due to the various influencing factors, determination of the dominant and rate controlling processes remains challenging. Here, we present a study on selected nanostructured FCC materials where dislocation-grain boundary interactions have been studied earlier for their coarse grained counterparts. High temperature nanoindentation revealed for all materials a pronounced increase of strain rate sensitivity when exceeding a certain temperature, peaking prior to the occurrence of significant grain growth. Static annealing of samples close to these peak temperatures leads, for sufficiently small grain sizes, to a maximum hardness increase. Interestingly, despite the nanocrystalline grain size, these temperatures perfectly agree with those obtained earlier for annihilation of lattice dislocations at grain boundaries in coarse-grained samples. This suggests that at elevated temperatures the dominant mechanism controlling the enhanced rate sensitivities in nanocrystalline metals is the thermally activated annihilation of lattice dislocations at grain boundaries. Measurements of activation energies being close to reported values for grain boundary diffusion further support this concept.

Superelastic shape memory alloys (SMAs) exhibit a reversible elastocaloric effect that originates from a release/absorption of latent heat associated with a stress-induced martensitic phase transformation. In typical SMAs, the conventional elastocaloric effect will vanish when the operating temperature falls below the temperature range in which martensitic phase transformation can be triggered by stress. We report emergence of an unprecedented elastocaloric effect with a decrease of temperature, well below the temperature range of martensitic phase transformation, in a model nanocrystalline NiTi that preserves slim-hysteresis superelasticity at ultra-low temperatures. The new elastocaloric effect emerges at a temperature of ∼ 90 K, exhibits an opposite sign than the conventional elastocaloric effect, and intensifies gradually with a decrease of temperature to 18 K. At 18 K, a large adiabatic temperature change ΔTad of +3.4 K is measured upon rapid release of tensile stress. The measured ΔTad are larger and extend over a wider temperature span than the existing electrocaloric, piezocaloric, and barocaloric cryo-refrigeration materials. We show that such low temperature elastocaloric effect originates from an entropic elasticity associated with large non-linear elastic deformations of the nanocrystalline microstructure at ultra-low temperatures. Our study suggests a new avenue to cool ultra-low temperature ambients.

Uranium-molybdenum (U-Mo) particles dispersed in an aluminum matrix is the most promising candidate fuel to convert high-power research and test reactors in Europe from using high-enriched to using low-enriched fuel. However, chemical interaction between the U-Mo and the Al matrix leads to undesirable fuel behavior. Zirconium nitride (ZrN) is used as a diffusion barrier between the U-Mo fuel particles and the Al matrix. To understand the potential microstructural evolution of ZrN during irradiation, a high-energy heavy ion (84 MeV Xe) irradiation experiment was performed on atomic layer deposited (ALD) nanocrystalline ZrN deposited on an Al plate. A fluence of 1.86 × 1017 ions/cm2, or 90.3 dpa was reached during this experiment. Both analytic transmission electron microscopy (TEM) and synchrotron microbeam X-ray diffraction (μXRD) techniques were utilized to investigate the kinetics of radiation-induced grain growth of ZrN at various radiation doses based on the Williamson-Hall analyses. The grain growth kinetics can be described by a power law expression, D n − D 0 n = K ϕ , with n = 5.1. The Al-ZrN interaction products (Al3Zr and AlN) created by radiation-induced ballistic mixing/radiation-enhanced diffusion and their corresponding formation mechanism were determined from electron diffraction and elemental composition analysis. These experimental results were confirmed by first principle thermodynamic density functional theory (DFT) calculations. The results from this ion irradiation study were also compared to in-pile irradiation data from physical vapor deposited (PVD) ZrN samples for a comprehensive evaluation of the interaction between Al and ZrN and its influence on diffusion barrier performance.