Boundary Relaxation Research Articles

Relative Hardening Contributions and Ductility of As-prepared and Annealed Nanocrystalline Co-P Electrodeposits

The effect of annealing up to 538 °C (1000 °F) on the hardness and ductility of two electrodeposited bulk nanocrystalline cobalt-phosphorus alloys (L-nCoP, 0.14 at%P and H-nCoP, 2.17 at%P) was investigated. Through a combination of electron microscopy and X-ray/synchrotron diffraction characterization, hardness and bend ductility measurements as well as density functional theory calculations, it is shown that hardness is controlled by four additive contributions. At 0.14 at%P, grain size strengthening and likely grain boundary relaxation are the dominant strengthening mechanisms. In the 2.17 at%P alloy, the contributions from solute strengthening and cobalt phosphide precursors and precipitates are much more significant and typical age strengthening behavior is observed with a peak hardness temperature of 371 °C (700 °F). The bend ductility at 0.14 at%P was in the 12 – 17% range up to 482 °C (900 °F). In contrast, the ductility at 2.17 at%P decreased rapidly with increasing annealing temperatures approaching values less than 1% at 427 °C (800 °F) due to excessive cobalt phosphide precursor and precipitate formation. The dominant deformation mechanism in both alloys was found to be basal dislocation slip.

Role of nanostructured surface layers in enhancing pure titanium diffusion bonding above their destabilization temperatures

The benefits of the nanostructured materials are believed to be probably absent if they are used at high temperatures. In this study, enhanced diffusion bonding of pure Ti was investigated by introducing a nanostructured surface layer through the surface mechanical attrition treatment (SMAT) technique. Complete recrystallization and remarkable grain growth have taken place in the original nanostructured surface layer due to the diffusion bonding conditions far beyond the nanostructured Ti destabilization temperatures. However, they still played a significant role in enhancing the Ti/Ti interfacial bonding. The consistency analysis of relative grain boundary energy, relaxation time, and microstrain reveals that although the original nanocrystalline has disappeared, the newly formed grain boundaries (GBs) during recrystallization probably inherit part of non-equilibrium state of the corresponding GBs in the as-SMATed surface layer, where the atomic diffusivity may increase greatly compared to the general relaxed GBs in their coarse-grained polycrystalline counterparts. The presence of these high-energy non-equilibrium GBs retains ultrafast atomic diffusion paths, leading to a diffusion bonding temperature of at least 100 °C lower than the traditional approach. The joint achieved at a low temperature of 750 °C exhibited a shear strength approximately 2 times higher than that prepared using raw substrates.

Structural properties, dielectric relaxation, and impedance spectroscopy of NASICON type Na3+xZr2−xPrxSi2PO12${\rm Na}_{3+x} {\rm Zr}_{2-x} {\rm Pr}_{x} {\rm Si}_2 {\rm PO}_{12}$ ceramics

AbstractWe investigate the dielectric and impedance spectroscopic investigation of Pr‐doped NASICON type () samples as a function of temperature and frequency. The Rietveld refinement of X‐ray diffraction patterns confirms the monoclinic phase having C2/c space groups for all the samples. The scanning electron microscopy shows the granular‐like structure and energy dispersive X‐ray analysis confirms the desired compositions. The temperature (90–400 K) and frequency (20 Hz–2 MHz) dependence of electric permittivity are explained using Maxwell–Wagner–Sillars (MWS) polarization and space charge polarization mechanisms. The dielectric relaxation shows nearly equal activation energy for all the samples with a non‐Debye type of relaxation in the measured temperature range. The complex impedance analysis shows the presence of broad grain and grain boundary relaxation peaks. The stretched exponent analysis of electric modulus using the Kohlrausch–Williams–Watts (KWW) function further confirms the non‐Debye type of relaxation. Moreover, scaling analysis of the electric modulus shows a similar type of relaxation for all the samples. The ac conductivity data are fitted using modified power law, where the temperature dependence of exponent () confirms the correlated barrier hopping (CBH) type conduction for all the samples. Our results indicate that the Pr‐doped NASICON samples are potential candidates for charge storage devices due to their large electric permittivity.

Influence of Ho, Gd, La Doping on Grain-Grain Boundary Characteristics and Minimization of Leakage Current in Nickel Ferrites

This study explores the impact of doping with Ho, Gd, and La on sol-gel-derived nickel ferrites through a comprehensive analysis using various analytical techniques. The combination of X-ray diffraction (XRD) analysis, X-ray fluorescence (XRF) spectra analysis, impedance spectroscopy, and I-V analysis enables a detailed exploration of the structural, compositional, and electrical characteristics of the samples. Williamson-Hall plots in XRD analysis reveal crucial insights into grain and grain boundary impacts, revealing a shift in trends for doped samples indicative of tensile strain and underscores the influence of dopant ions on lattice distortion. XRF study confirms the elemental composition of the samples, validating the experimental approach. Impedance spectroscopy sheds light on conduction mechanisms and charge transfer processes, while the modulus study identifies distinct relaxation peaks corresponding to grain and grain boundary relaxation mechanisms. IV analysis demonstrates a significant reduction in leakage current with rare Earth element doping, suggesting promising applications.

Achieving high fatigue endurance of nanocrystalline Ni/Ni-W layered composites through thermally and mechanically-induced relaxations

Stabilizing non-equilibrium nanograin boundaries has been shown to enhance the strength of nanocrystalline metals. Nevertheless, a thorough comprehension of how these stable grain boundaries impact the fatigue behavior in nanocrystalline metallic layered composites with heterogeneous interfaces is currently lacking. Here, aiming to develop high-performance small components in microelectromechanical systems, we prepared nanocrystalline Ni/Ni-W layered composites that underwent various degrees of annealing treatment. Our results reveal that the Ni/Ni-W layered composites annealed at 200 °C exhibit significantly higher fatigue strength, surpassing that of the as-prepared composites by 40 % and the Pt-10 at.% Au alloy by 17 % which is one of the best candidates for the microelectromechanical systems switches at present. The enhanced fatigue strength is primarily attributed to the annealing-induced grain boundary relaxation and mechanically-induced structural relaxation. Grain boundary relaxation enhances the strength by improving GB stability, while the mechanically-induced structural relaxation results in the coarsening and expansion of triangular columnar grains towards the Ni-W layer during fatigue loading. As a result, the dispersive strain localized regions triggered by the triangular columnar grains undertook cyclic strain accumulation and weakened localized damage accumulation in Ni layers, and thus further improved the fatigue resistance. The finding of the underlying mechanisms may offer a promising approach for designing high-performance materials for microelectromechanical systems switches operating at elevated temperatures.

Anelasticity of Mg-Mn and Mg-Gd alloys

Anelastic relaxation at sub-resonance frequency (from 0.01 to 100 Hz), temperature (from 0 to 450°C) and amplitude (ε0 from 5×10−5 to 10−3) range in binary Mg-0.8 wt%Mn (0.36 at%) and Mg-2 wt%Gd (0.31 at%) in as-extruded and annealed states was experimentally studied and analyzed, to characterize acting thermally activated and structural relaxation effects. Activation parameters for thermally activated anelastic effect and structural studies suggest that it is the grain boundary relaxation with dominating large angle boundaries, while the high-temperature background is mainly controlled by dislocations sliding. Pseudo peak at ∼290 °C (Mg-Mn) and ∼410 °C (Mg-Gd) is the result of the recrystallization process in the as-extruded samples, which indicates that the addition of Gd restricts the recrystallization of Mg compared with the addition of Mn. Analysis of amplitude dependencies of internal friction in the frames of Granato and Lücke approach suggests higher density of movable dislocations in as-extruded Mg-Mn alloy.

Ultrabroad distribution of multiple anelasticities in O-doped refractory multiprincipal element alloys

The Snoek anelastic internal friction (IF) peak due to stress-induced dipole ordering associated with interstitial atoms was well observed in IF curves of single-principal element alloys (SPEAs) as early as in the 1950s, however, its behavior remains elusive in multi-principal element alloys (MPEAs) to date. Here the temperature-dependent IF spectra of NbTiV0.5Zr refractory MPEAs with varying O contents were presented, and the analysis of these data indicates that for O-doped NbTiV0.5Zr MPEAs, the O addition triggers two anelastic IF peaks (the PO1 and PO2), corresponding to the O-Snoek-type relaxation in random solid solution (RSS) and local chemical ordering (LCO) structures, respectively. The half-peak width of the PO1 is 2–3 times broader than that for SPEAs, associated with the wide O migration energy barrier distribution in MPEAs. These phenomena show a striking contrast to the single and narrow Snoek-type peak observed for SPEAs. Our analysis further reveals an approximate linear correlation between the half-peak width of the Snoek-type peak and the mixing entropy. The introduction of O also shifts grain boundary relaxation peaks (PG) towards higher temperatures. Interestingly, high-temperature anomalous modulus changes were observed for the first time in TiV-based lightweight refractory MPEAs, which is suggested to be originated from the order reduction of the body-centered cubic (bcc) structure at elevated temperatures. Moreover, the 1 at.%O doped NbTiV0.5Zr MPEA with a favorable balance between the peak heights of the PO2 and PG, exhibits outstanding specific yield stress (SYS) among refractory MPEAs while maintaining an elongation as high as 20 %. This work provides not only a bridge between the anelastic behavior of SPEAs and MPEAs for upcoming studies and theories concerning bcc MPEAs with interstitial atoms, but contributes to the holistic design of bcc MPEAs with high strength and excellent ductility.

Dielectric Properties and Carrier Transport Mechanism in Annealed HfOx‐Based Resistive Random Access Memory Devices

The diversity of the carrier transport mechanism in the resistive switching process remains a significant obstacle for the design and application of resistive random access memory (RRAM) devices. In this study, the influence of annealing on the dielectric properties of the Ti/HfOx/Pt RRAM device and its associated carrier transport mechanism is investigated. The results reveal that the current conduction in both annealed and unannealed devices is primarily attributed to grain boundary (GB) relaxation, with only the GB acting as a depletion layer that induces dielectric relaxation. Furthermore, annealing decreases the interfacial polarization and changes the relaxation time at the GB. In addition, the charge carriers exhibit nearest‐neighbor hopping conduction at a higher temperature in Ti/HfOx/Pt RRAM devices, whereas variable‐range‐hopping conduction occurs at lower temperatures. Long‐range charge carrier transport also plays a significant role in the conduction process. To offer a deeper understanding of the conduction processes in the Ti/HfOx/Pt RRAM device, a carrier transport model is proposed, which provides valuable insights into the intricate mechanisms governing conduction in these devices.

Thermal stability of electrodeposited nanostructured high-entropy alloys

Over the past decade, the study of nanostructured high-entropy alloys (HEAs) has attracted great attention due to their high strength (grain boundary hardening) and improved thermal stability over conventional nanostructured metals and alloys. However, a lingering issue yet to be resolved by these studies is that of commercial viability; the synthesis processes used to date are costly, not easily scalable, and energy intensive. This work examines the thermal stability and mechanical properties of electrodeposited nanostructured HEAs, towards establishing a cost-effective and versatile synthesis route to commercialize this underutilized material class. Nanocrystalline, amorphous, and nanoglass alloys of NiFeCoW, NiFeCoMo, and NiFeCoMoW were systematically characterized to assess the stability of their structure and mechanical properties, compared against conventional nanocrystalline materials and HEA counterparts. The structural stability of these electrodeposited HEAs was shown to improve with increasing number of elements, from a peak temperature for grain growth of ∼270 °C in pure nanocrystalline Ni, to ∼500 °C in electrodeposited HEAs, corresponding to a near doubling of the activation energy for grain growth from 1.3 eV (Ni) to a maximum of 3.1 eV (NiFeCoW). This improved stability was matched with a 60 % increase in hardness after annealing to the point of nanograin nucleation (∼500 °C), to a maximum hardness of ∼8.4 GPa. Such hardening trends followed an extrinsic inverse-to-regular Hall-Petch relationship, where the inverse regime was largely dominated by grain boundary relaxation and nanoglass structural breakdown. With these results, we have established electrodeposition as a promising candidate route for fabricating nanostructured HEAs for applications at elevated temperatures.

Effects of vanadium content on the microstructure and tensile properties of NbTiVxZr high-entropy alloys

Vanadium boasts a relatively small atomic radius among numerous refractory alloying elements, yet its effects on the microstructure and mechanical behavior of refractory alloys remain enigmatic. In this work, a series of NbTiVxZr high-entropy alloys (HEAs) with low density were formulated to explore the evolution of microstructures and mechanical properties with varying vanadium content. When the vanadium content was low, the matrix exhibited the single-phase body-centered cubic structure. Excessive vanadium contents (NbTiV0.75Zr, NbTiVZr) disrupted phase stability and tended to aggregate at grain boundaries, forming V-rich and Zr-rich phases. These precipitated phases pinned grain boundaries, impeding grain growth and resulting in both grain boundary strengthening and precipitation strengthening, albeit at the expense of grain boundary cohesion, ultimately leading to brittleness. However, these deleterious phases were redissolved, and fracture elongation increased more than 2 times after water quenching at 1200 °C. The microstructural changes induced by heat treatment were corroborated by alterations in grain boundary relaxation behavior, where the redissolution of precipitated phases after water quenching caused a shift of the grain boundary relaxation internal friction peak to a lower temperature and an increase in peak height. This study elucidates the intrinsic relationship between mechanical properties and microstructures with vanadium content in NbTiVxZr alloys, offering insights for the design of TiV-based lightweight refractory HEAs with high strength and excellent ductility.

Dissipation estimation for the impedance tube measurement using Bayesian inference

Although air dissipation is usually neglected in the impedance tube measurement, it affects the accuracy of the measurement results. Multiple effects contribute to the sound dissipation in an impedance tube, like the boundary layer effect or relaxation effect. This work formulates a transfer function model incorporating different dissipation. Bayesian inference is applied to estimate the acoustic dissipation in an impedance tube. Critical parameters in dissipation models are estimated based on the transfer function measured from an empty impedance tube. Nested sampling is applied to get an accurate approximation of parameters. The results of the analysis demonstrate that the critical parameters estimated by the Bayesian method are accurate. The accurate estimated dissipation helps improve the accuracy of impedance measurement with the material under test.

Grain-Boundary Structural Relaxation in Sb2Se3 Thin-Film Photovoltaics

Grain boundaries play an important role in the efficiency of thin-film photovoltaics, where the absorber layer is invariably polycrystalline. Density-functional-theory simulations have previously identified a “self-healing” mechanism in Sb2Se3 that passivates the grain boundaries. During “self-healing,” extensive structural relaxation at the grain boundary removes the band-gap electronic defect states that give rise to high carrier recombination rates. In this work, lattice imaging in a transmission electron microscope is used to uncover evidence for the theoretically proposed structural relaxation in Sb2Se3. The strain measured along the [010] crystal direction is found to be dependent on the nature of the grain-boundary plane. For a (010) grain boundary, the strain and structural relaxation is minimal, since no covalent bonds are broken by termination of the grain. On the other hand, strains of up to approximately 4% extending approximately 2 nm into the grain interior are observed for a (041) grain boundary, where grain termination results in significant structural relaxation due to the ideal atomic coordination being disrupted. These results are consistent with theory and suggest that Sb2Se3 may have a high level of grain-boundary-defect tolerance. Published by the American Physical Society 2024

Re-dissolution of precipitates in reactor pressure vessel steels evaluated by internal friction technique

The re-dissolution process of Mn-Si-rich precipitates in Fe-1.0 %Mn-0.4 %Ni-0.2 %Si (wt.%) reactor pressure vessel (RPV) model steel was assessed using the internal friction (IF) technique. A relaxation IF peak (P1), corresponding to grain boundary relaxation, was observed near 600 °C in the temperature-dependent IF curve of the as-received sample. After long-term aging at 600 °C, a significant suppression of the P1 was observed due to the extensive precipitation of Mn-Si-rich precipitates. Upon further annealing at 700–800 °C, the P1 gradually recovered with increasing annealing temperature, indicating the gradual dissolution of Mn-Si-rich precipitates along the grain boundaries. This phenomenon was consistent with transmission electron microscopy experimental results.

Validation of a Long-Wavelength, Near-Field Scattering Simulator Based on Boundary Relaxation

Validation of a Long-Wavelength, Near-Field Scattering Simulator Based on Boundary Relaxation

Complex dielectric and impedance analysis in Dy1-XPrXMnO3 compounds: Partial substitution effects

Synthesis and characterization of single phasic Dy1-xPrxMnO3 (DPMO) ceramic samples through solid-state reaction (SSR) method are reported in present study. XRD analysis confirmed the structural formation of DPMO and revealed lattice changes induced by Pr substitution that affect JT-distortion and tilting of MnO6 octahedra. Fine-grained microstructures with a micrometre-sized grain size were observed using FESEM images, which increased with increasing Pr concentration. The variation of activation energy in DPMO was found to be induced by modification in Mn–O bond distances. The dielectric behaviour of DPMO was significantly enhanced, which was explained using the UDR model fitting. Impedance analysis confirmed the existence of non-Debye type relaxation and negligible electronic polarization mechanisms in all DPMO samples. With the increase in temperature, a reduction in the magnitude of Z' was observed, indicating a decrease in the resistance of contributing electroactive components such as grains, grain boundaries, and electrode interfaces. Electric modulus studies revealed the existence of grain and grain boundary relaxation processes throughout the studied frequency and temperature range in DPMO compounds. Overall, the study provides deep insights into the effect of Pr substitution on the structural, electrical, and dielectric properties of DPMO and highlights the potential of DPMO for future electronic and energy device applications.

Thermally-triggered grain boundary relaxation in a nanograined Ni-Mo-W alloy

Thermally-triggered grain boundary relaxation in a nanograined Ni-Mo-W alloy

A new look at imines and their mixture with PC71BM for organic, flexible photovoltaics

Due to its high electron affinity and electron mobility in a wide absorption range of the visible solar spectrum, [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) is often used as an efficient acceptor in organic photovoltaics. In turn, imines are additives to the active layer of organic solar cells, mainly due to the free electron pair of the imine nitrogen atom and the presence of various chemical groups affecting the polarity and conformations of molecules. However, the attainable efficiency is not as high as expected. Therefore, we have systematically investigated two imines and their mixtures with PC71BM by spectroscopic (the high pressure UV–Vis and frequency domain dielectric), thermoelectric, and mechanical methods for organic, flexible photovoltaics. Both the imines, (N,NʹE,N,NʹE)-N,Nʹ-([2,2ʹ:5ʹ,2ʺ-terthiophene]-5,5ʺ-diylbis(methanylylidene))bis(benzo[d]thiazol-2-imine) (SC3) and (6E)-N-((5-(5-(5-((E)-(4-(4-(4-fluorophenyl)thiazol-2-yl)phenylimino)methyl)thiophen-2-yl)thiophen-2-yl)thiophen-2-yl)methylene)-4-(4-(4-fluorophenyl)thiazol-2-yl)benzenamine (SC13), have the same core composed of three thiophene rings but different terminal chains of the molecules. In the imine SC3, the imine bond is followed by benzothiazole rings on both sides of the core, while in SC13, a thiazole ring separates two benzene rings, the terminal one F-substituted. The difference in molecular structure affects the electric properties of the neat imine and its mixed layers. An addition of PC71BM to the imines improves their electric conductivity. The mechanical studies focused on the stress at break and elongation showed superior behaviour compared to fullerene derivative. High pressure systematically reduces the band gap energy, Eg, from 1.68 eV at 0.16 GPa to 1.51 eV at 2.69 GPa for PC71BM, from 1.77 eV at 0.1 MPa to 1.53 eV at 4.15 GPa for SC3, and from 1.99 eV at 0.11 GPa to 1.8 eV at 3.10 GPa for SC13, as determined by the UV–Vis absorbance measurements in a diamond-anvil cell. These Eg reductions reflect the compressed intermolecular interactions that can be used to monitor the structural stability of these compounds. Based on the dielectric studies it was found that the relaxation processes registered for both imines are probably the grain boundary relaxation. Two processes also appear in the systems with PC71BM, but none of them is the one characteristic of imines. The high-frequency process has a dipole character while the low-frequency one is probably the grain boundary relaxation of these systems. The mechanism of quasi-DC conduction in various temperature ranges in the studied systems was also determined.

Stabilizing nanograined austenitic stainless steel with grain boundary relaxation

Grain boundary (GB) relaxation can be triggered by interaction of GB with partial dislocations during plastic deformation, which is effective to stabilize nanograined structures in a number of face-centered cubic (FCC) metals and alloys. But this mechanism is interfered by deformation-induced martensitic transformation in 304 stainless steels with a metastable FCC structure. In this work, gradient FCC nanograined structures were prepared in a 304 stainless steel by using warm surface mechanical grinding treatment. GB relaxation was triggered in the samples with grains below 60 nm in size, in which partial dislocation dominates the plastic deformation. With the GB relaxation, thermal stability increases with decreasing grain sizes, contradictory to the conventional “smaller less stable” trend. The onset temperature for coarsening of nanograins of ∼30 nm in size is as high as ∼896 °C (0.7 Tm), about 250 °C above the reported value of the steel. The GB relaxation was not detected in martensitic nanograins of the same composition, of which the instability temperatures is around 650 °C (0.54 Tm), independent of grain size from 26 nm to the submicron scale, as it is controlled by the reverse martensitic transformation.

Anneal Hardening in Single Phase Nanostructured Metals

Recovery of cold worked metals is associated with a loss of strength due to the reduction of the defect density. However, already in the 1960s analytical models and few experiments suggested that this may not generally be the case and even a hardening rather than a softening might occur. With the availability of severe plastic deformation and deposition techniques this anneal hardening phenomenon has been observed frequently. In this overview we summarize early findings on this topic before focusing on general observations and potential origins, with a special focus to show the similarities for nanostructures across different grain size scales (i.e., structures prepared by deposition and severe plastic deformation techniques, respectively). Comparison of different results indicate a grain size dependent hardening increment that could be additionally affected by segregation or the processing variables. Considering the agreement of the peak hardening temperatures with that for dislocation annihilation at grain boundaries, anneal hardening can be rationalized by the loss of intragranular defects and grain boundary relaxation. Grain boundary diffusivity hence plays a crucial role and particular solutes could amplify the hardening process even further. As anneal hardening already occurs for grain sizes at the micron scale, its effect on properties is even of technological relevance. Beneficial effects on the fatigue strength are evident, but the strain softening of anneal hardened specimens drastically shortens ductility. Nevertheless, some strategies to overcome this adverse effect seem promising to create metallic structures with exceptional combinations of strength and ductility.

Effects of annealing on the structure and microhardness of nanocrystalline Ni–Mn electrodeposits

Nanocrystalline pure nickel and Ni-Mn alloy with 1.2 at% Mn deposits were obtained via pulse current electrodeposition. To understand the effects of annealing on their structure and microhardness, the surface morphology, crystal structure, grain size, microhardness and microstructure of the obtained Ni-Mn and pure Ni deposits were investigated. The results indicated that Ni-Mn alloy exhibited a similar face-centered cubic structure with a strong (111) preferred orientation to that of Ni deposits, but as-deposited Ni–Mn had a smaller crystallite size and substantially higher microhardness compared to as-deposited Ni deposit. During annealing, the crystal grains of Ni deposits grew sharply, resulting in a great decrease in their microhardness, while Ni-Mn deposits showed good thermal stability and annealing induced hardening at 300 °C and 350 °C. Neither precipitate nor clear segregation of Mn was observed on annealed deposits; however, a number of twin boundaries were found. It is suggested that the thermal stability of Ni-Mn was mainly derived from the formation of twin boundaries and the annealing-induced hardening could be ascribed to grain boundary relaxation and annealing twin strengthening.