Chemical Fluctuations Research Articles

Mechanical properties and energy evolution law of marble under the coupled effects of chemical corrosion and dry-wet cycles.

The main factors affecting the safety of underground structures are groundwater chemical corrosion and water level fluctuations. To investigate the mechanical properties of marble and the energy evolution pattern during the failure process under the coupled effects of chemical corrosion and dry-wet cycling, samples were subjected to 5, 10 and 20 cycles of dry-wet ageing in chemical solutions with pH values of 4, 7 and 10, respectively, followed by mechanical property testing. The energy evolution pattern during the failure process of the specimens was also studied. It was found that there is a strong correlation between number of dry-wet cycles and pH value of chemical solution. Chemical corrosion at the early stage of dry-wet cycling has the greatest effect on the deterioration of the rock. As the number of dry-wet cycles increases, the degree of corrosion in acidic solutions is most evident, with the uniaxial compressive strength and elastic modulus decreasing by 27.88% and 33.52% respectively, followed by alkaline solutions, and the degree of corrosion in neutral solutions is the lowest. In addition, dry-wet cycling and chemical corrosion lead to an increase in the internal pores of the rock samples and a decrease in the energy storage capacity. Nevertheless, the proportion of energy loss increases with the number of dry and wet cycles, with the proportion of energy loss in acidic media increasing from 35.61% to 41.63%, indicating that the plastic deformability of marble increases under the action of chemical corrosion and dry and wet cycles. The research results have certain guiding significance for the design, construction and maintenance reinforcement of underground structures under the conditions of chemical corrosion and dry-wet cycling.

Correlations between local chemical fluctuations and grain boundary strength in Ti-Zr-Nb-Ta-Mo refractory multi-principal element alloys

Ti-Zr-Nb-Ta-Mo refractory multi-principal element alloys typically exhibit high yield strength while tensile ductility tends to be poor. In this study, we found that even after solid solution treatment of Ti-Zr-Nb-Ta-Mo alloys, significant change in ductility occur due to the local chemical fluctuations. Ta's dramatic chemical fluctuations cause variations in atomic-scale strain fields, leading to reduced grain boundary strength and brittle fracture. First-principles calculations show that (Ti, Zr)-rich at the grain boundaries increases the delocalization of valence electrons, leading to longer bond lengths and reduced crystal orbital bond index values, thereby causing grain boundary embrittlement. Our findings explore the root causes of brittleness in Ti-Zr-Nb-Ta-Mo alloys at the atomic and electronic scales, providing not only a method to analyze grain boundary embrittlement using bond length, electronic localization function and crystal orbital bond index, but also a theoretical guidance for improving the mechanical properties via grain boundary structure optimization.

Correlation of microstructure and magnetic softness of Si-microalloying FeNiBCuSi nanocrystalline alloy revealed by nanoindentation

Abstract Compared to the commercial soft-magnetic alloys, the high saturation magnetic flux density (B s) and low coercivity (H c) of post-developed novel nanocrystalline alloys tend to realize the miniaturization and lightweight of electronic products, thus attracting great attention. In this work, we designed a new FeNiBCuSi formulation with a novel atomic ratio, and the microstructure evolution and magnetic softness were investigated. Microstructure analysis revealed that the amount of Si prompted the differential chemical fluctuations of Cu element, favoring the different nucleation and growth processes of α-Fe nanocrystals. Furthermore, microstructural defects associated with chemical heterogeneities were unveiled using the Maxwell–Voigt model with two Kelvin units and one Maxwell unit based on creeping analysis by nanoindentation. The defect, with a long relaxation time in relaxation spectra, was more likely to induce the formation of crystal nuclei that ultimately evolved into the α-Fe nanocrystals. As a result, Fe84Ni2B12.5Cu1Si0.5 alloy with refined uniform nanocrystalline microstructure exhibited excellent magnetic softness, including a high B s of 1.79 T and very low H c of 2.8 A/m. Our finding offers new insight into the influence of activated defects associated with chemical heterogeneities on the microstructures of nanocrystalline alloy with excellent magnetic softness.

High-temperature mechanical behavior and microstructural destabilization evolution of the lightweight refractory high-entropy alloy prepared by laser additive manufacturing

Lightweight refractory high-entropy alloy (LRHEA) has lower density and higher specific strength, which makes it very promising for future applications in rocket engine components. Their high-temperature resistance to softening and high microstructure stability in a wide temperature range are also essential to sustaining their performance due to being used in harsh, high-temperature situations. In this work, the high-temperature tensile behavior of Al0.3NbTi3VZr1.5 LRHEA fabricated by laser additive manufacturing has been systematically investigated from 400 °C to 800 °C, and the relationship between the deformed microstructure and the mechanical behavior was revealed, and analyzing the reasons for the thermodynamic instability of the solid solution in LRHEA are discussed in detail. It is found that the weakening of the high entropy effect at intermediate temperatures reduces the stability of the solid solution, and the accelerated diffusion between elements further promotes the solid solution destabilization, mainly manifested as the Laves phase and the local chemical fluctuation (LCFs). The high dislocation density introduced by the additive manufacturing technology leads to the irregular connection of the Laves phases within the grains, and it can be improved by grain growth. The high negative mixing enthalpy competes with the high-entropy effect, and temperature is the decisive factor. In this situation, the atomic clusters were promoted and induced spinodal decomposition for generating LCFs. The formation of LCFs exhibits solute competition with the emergence of the C14 Laves phase, and the phase proportions fluctuate at different temperatures. This work provides new thinking and attention for developing lightweight, heat-resistant materials.

Origins of strength stabilities at elevated temperatures in additively manufactured refractory high entropy alloy

While refractory high-entropy alloys (RHEAs) show promising potential for extreme applications, those directly fabricated via additive manufacturing methods have been hindered by their inferior mechanical properties, particularly at high temperatures. In this study, we successfully produced a Hf-Nb-Ti-V RHEA using directed energy deposition (DED) technique, achieving satisfactory tensile properties across a wide temperature range. This was accomplished by inducing severe lattice distortions in the fabricated RHEA, which can be traced back to the local chemical fluctuations present in the newly fabricated RHEA and the significant atomic radius mismatch. Due to strong solute pinning, these factors contribute to the superior yield strength of the DED-fabricated RHEA across a wide temperature range. Furthermore, the elastic constants in the fabricated RHEA show a negligible temperature dependence, revealed by first-principles calculations, ensuring satisfactory strengths even at high temperatures. This alloy design strategy, which involves introducing significant lattice distortion and maintaining the temperature-low sensitivity of the elastic moduli, opens up new possibilities for directly fabricating RHEAs with superior high-temperature properties.

Lightweight single-phase Al-based complex concentrated alloy with high specific strength

Developing light yet strong aluminum (Al)-based alloys has been attracting unremitting efforts due to the soaring demand for energy-efficient structural materials. However, this endeavor is impeded by the limited solubility of other lighter components in Al. Here, we propose to surmount this challenge by converting multiple brittle phases into a ductile solid solution in Al-based complex concentrated alloys (CCA) by applying high pressure and temperature. We successfully develop a face-centered cubic single-phase Al-based CCA, Al55Mg35Li5Zn5, with a low density of 2.40 g/cm3 and a high specific yield strength of 344×103 N·m/kg (typically ~ 200×103 N·m/kg in conventional Al-based alloys). Our analysis reveals that formation of the single-phase CCA can be attributed to the decreased difference in atomic size and electronegativity between the solute elements and Al under high pressure, as well as the synergistic high entropy effect caused by high temperature and high pressure. The increase in strength originates mainly from high solid solution and nanoscale chemical fluctuations. Our findings could offer a viable route to explore lightweight single-phase CCAs in a vast composition-temperature-pressure space with enhanced mechanical properties.

The microcrack inhibition and mechanical properties of an in-situ synthesized refractory high-entropy alloy fabricated by additive manufacturing

A crack-free refractory high-entropy alloy (RHEA), composed of (Cr25Mo25Nb25V25)99C1 was synthesized in-situ from blended elemental powders using laser directed energy deposition (DED). This study revealed that a minor addition of carbon effectively enhances the grain-boundary cohesion of the DEDed RHEA, thereby mitigating microcrack propagation along the grain boundaries during the additive manufacturing process. Notably, the DEDed RHEA exhibited exceptional high-temperature mechanical properties, highlighted by a yield strength of 787 MPa at 1000 °C along with sustained strain-hardening capacity, surpassing other additively manufactured high-entropy alloys reported to date. The remarkable high-temperature strength of the DEDed RHEA can be attributed to the potent pinning effect exerted on dislocations within both dendritic and interdendritic regions at elevated temperature. This effect stems from severe lattice distortion, local chemical fluctuations (LCFs), solute atom pinning, and dislocation interactions. The method employed to inhibit microcrack formation, along with the elucidation of the high-temperature strengthening mechanism, opens avenues for the fabrication of RHEAs tailored for high-temperature structural applications.

Exploring high corrosion-resistant refractory high-entropy alloy via a combined experimental and simulation study

Refractory high-entropy alloys (HEAs) have attracted considerable attention due to their stable phase structure and excellent high-temperature properties. In this work, we performed first-principles calculations, coupled with experiments, to explore HEAs with high corrosion resistance. The results revealed that TiNbTa-based HEAs exhibited a lower tendency for corrosion. However, the appearance of local chemical fluctuations (LCFs) increased the corrosion tendency of TiNbTa-based HEAs. Comprehensive SHapley Additive exPlanations analyses uncovered that in a sample with configurational LCFs, the atomic order near the surface was altered. Therefore, corrosion behavior was affected. Based on experiments, the annealed samples exhibited typical chemical segregation and declined corrosion resistance.

Periodic spinodal decomposition in double–strengthened medium–entropy alloy

Achieving an optimal balance between strength and ductility in advanced engineering materials has long been a challenge for researchers. In the field of material strengthening, most approaches that prevent or impede the motion of dislocations involve ductility reduction. In the present study, we propose a strengthening approach based on spinodal decomposition in which Cu and Al are introduced into a ferrous medium–entropy alloy. The matrix undergoes nanoscale periodic spinodal decomposition via a simple one-step aging procedure. Chemical fluctuations within periodic spinodal decomposed structures induce spinodal hardening, leading to a doubled strengthening effect that surpasses the conventional precipitation strengthening mechanism. Notably, the periodic spinodal decomposed structures effectively overcome strain localization issues, preserving elongation and doubling their mechanical strength. Spinodal decomposition offers high versatility because it can be implemented with minimal elemental addition, making it a promising candidate for enhancing the mechanical properties of various alloy systems.

Tailoring local chemical fluctuation of high-entropy structures in thermoelectric materials.

In high-entropy materials, local chemical fluctuation from multiple elements inhabiting the same crystallographic site plays a crucial role in their unique properties. Using atomic-resolution chemical mapping, we identified the respective contributions of different element characteristics on the local chemical fluctuation of high-entropy structures in thermoelectric materials. Electronegativity and mass had a comparable influence on the fluctuations of constituent elements, while the radius made a slight contribution. The local chemical fluctuation was further tailored by selecting specific elements to induce large lattice distortion and strong strain fluctuation to lower lattice thermal conductivity independent of increased entropy. The chemical bond fluctuation induced by the electronegativity difference had a noticeable contribution to the composition-dependent lattice thermal conductivity in addition to the known fluctuations of mass and strain field. Our findings provide a fundamental principle for tuning local chemical fluctuation and lattice thermal conductivity in high-entropy thermoelectric materials.

Quantification and chemical fluctuation in NMC Li-ion battery cathode materials analyzed using APT

Quantification and chemical fluctuation in NMC Li-ion battery cathode materials analyzed using APT

Interactions between methyl octabromo ether flame retardant and expanded polystyrene microplastics in the photoaging process

Expanded polystyrene (EPS) plastic is widely used because of its low density and lightweight properties, enabling it to float on water and increase its exposure to sunlight. In this study, we simulated the photoaging process of flame retardant-added EPS (FR-EPS) and common original EPS (OR-EPS) microplastic (MP) particles with and without methyl octabromoether flame retardant (MOBE) in the laboratory to explore the effect of MOBE on the photodegradation of EPS. Results showed that MOBE accelerated size reduction and surface hole formation on the particles, hastening the shedding and replacement of particle surfaces. FR-EPS particles exhibited a weight loss exceeding that of OR-EPS, reaching 40.85 ± 3.72% after 36 days of irradiation. Moreover, rapid physical peeling of the FR-EPS surface was accompanied by continuous chemical oxidation and fluctuations of the carbonyl index and O/C ratio. A diffusion model based on Fick's second law fitted well for the concentration of MOBE remaining in FR-EPS particles. MOBE's sensitivity to direct photochemical reactions inhibited the early-stage photoaging of EPS MP particles by competing for photons. However, MOBE as chromophores could absorb photons and produce •OH to promote the aging of EPS. Moreover, the capacity of EPS to absorb light energy also accelerated MOBE degradation. These findings suggested that the photoaging behavior of commercial EPS products containing flame retardants in the environment is quite different from that of pure EPS, indicating that additive-plastic interactions significantly alter MP fate and environmental risks.

Anomalous magnetization induced by local chemistry fluctuations in Mn-containing α’-martensite

An anomalous increase in magnetization was investigated in a cold-rolled high-Mn TRIP steel (16.8 wt% Mn) annealed at 350°C for times varying from 5 to 120 min, before the start of austenite reversion (α’ → γ). Besides in-situ and ex-situ magnetic measurements, the full characterization of this phenomenon was also performed with the aid of X-ray diffraction (XRD), Mössbauer spectroscopy, and microstructural characterization using electron backscatter diffraction (EBSD) and atom probe tomography (APT). Based on XRD measurements, the volume fraction of austenite and α’-martensite was estimated as a function of annealing time, as well as their lattice strain. Phase quantification confirmed the absence of newly-fresh α’-martensite in the material during annealing at 350°C. Short annealing up to 15 min promoted the increase of Ms (saturation magnetization) due to stress relief in α’-martensite (Villari effect). Further annealing to 30 min promotes the decrease in Ms driven by short-range solute reorganization within the lattice. After 60 min annealing, the creation of long-range solute-depleted zones (i.e. confined zones highly enriched in Fe) causes a new increase in Ms. In comparison, for 120 min of annealing time, Ms tends to remain unaltered. These findings revealed that short- and long-range chemical fluctuations strongly affect the saturation magnetization of the steel and brought new insights on the use of magnetic probing as a tool for phase quantification in Mn-bearing steels.

High‐Entropy Anti‐Perovskites with Enhanced Negative Thermal Expansion Behavior

AbstractThe negative thermal expansion (NTE) materials, which can act as thermal‐expansion compensators to counteract the positive thermal expansion, have great applications merit in precision engineering. However, the exploration of NTE behavior with a wide temperature range has reached its upper ceiling through traditional doping strategies due to composition limitations. In this paper, the unique sluggish characteristics and extended optimization space in empirically screened high‐entropy anti‐perovskite (HEAP) are utilized to broaden the NTE temperature range. Typically, the NTE temperature range in Mn3Cu0.2Zn0.2Ga0.2Ge0.2Mn0.2N is broadened to ΔT = 235 K (5 K ≤ T ≤ 240 K), which is two or three times wider than that of traditional low‐entropy doping systems. The neutron diffraction analysis reveals a unique sluggish characteristic in magnetic phase transition which survives in an ultra‐wide temperature range of 5 K ≤ T ≤ 350 K (ΔT = 345 K). The sluggish characteristic is further experimentally proved to come from disturbed phase transition dynamics due to distortion in atomic spacing and chemical environmental fluctuation observed by the spherical aberration‐corrected electron microscope. The demonstration provides a unique paradigm for broadening the temperature range of NTE materials through entropy engineering.

Atomistic Study on Defect–Grain Boundary Interactions in TiVTa Concentrated Solid–Solution Alloys

The elemental segregation behaviors and interactions between point defects and symmetrical tilt grain boundaries (GBs) in TiVTa concentrated solid–solution alloys (CSAs) have been studied through hybrid Monte Carlo/molecular dynamics (MC/MD) simulations. A pure V model, a random TiVTa CSA with randomly distributed elements, and an equilibrated TiVTa CSA with Ti segregation were constructed to investigate the influence of chemical disorder and local elemental segregation on defect–GB interactions. For defect–GB interactions, GBs interact more strongly with interstitials than with vacancies. Compared with the pure V, the vacancy absorption length scale of GBs is greater, whereas the interstitial absorption length scale of GBs is shorter in TiVTa CSAs due to the chemical fluctuation and local lattice distortion. This means a higher recombination efficiency of point defects in TiVTa CSAs. The elemental (Ti) segregation in TiVTa CSAs can further enhance the sink strength of GBs towards interstitials, while simultaneously reducing their sink strength towards vacancies. Consequently, the preference effects of GBs towards interstitials and vacancies are amplified in the equilibrated CSA due to local ordering, thereby reducing efficient defect annihilation around GBs. These results provide fundamental insights into the irradiation defect dynamics of CSAs with body-centered cubic (bcc) structure.

The shear softening and dislocation glide competition due to the shear-induced short-range order degeneration in CoCrNi medium-entropy alloy

The short-range order (SRO) in multi-principal element alloys (MPEAs) is an intriguing topic in advanced alloy research. The crucial question related to this topic lies in the effect of the local chemical fluctuations on the deformation behavior of MPEAs. In this study, the large-scale molecular dynamics (MD) simulation is used to investigate the dislocation glide behavior and mechanical performance of CoCrNi medium-entropy alloy (MEA) with respect to the SRO and lattice distortion (LD) effects. The slip plane softening and dislocation glide competition are found in the models with SRO. The change of energy barrier caused by SRO degeneration is the dominant reason for the slip plane softening, while the combination of dislocation pinning and slip plane softening leads to the dislocation glide competition, which is the primary mechanism for the shear localization in the CoCrNi MEA with SRO. Moreover, the dislocation glide competition compensates for the strength loss induced by slip plane softening. The results provide a new proposition for the conflicting simulation and experimental results on the topic of the SRO effect in MPEAs.

Negative mixing enthalpy solid solutions deliver high strength and ductility.

Body-centred cubic refractory multi-principal element alloys (MPEAs), with several refractory metal elements as constituents and featuring a yield strength greater than one gigapascal, are promising materials to meet the demands of aggressive structural applications1-6. Their low-to-no tensile ductility at room temperature, however, limits their processability and scaled-up application7-10. Here we present a HfNbTiVAl10 alloy that shows remarkable tensile ductility (roughly 20%) and ultrahigh yield strength (roughly 1,390 megapascals). Notably, these are among the best synergies compared with other related alloys. Such superb synergies derive from the addition of aluminium to the HfNbTiV alloy, resulting in a negative mixing enthalpy solid solution, which promotes strength and favours the formation of hierarchical chemical fluctuations (HCFs). The HCFs span many length scales, ranging from submicrometre to atomic scale, and create a high density of diffusive boundaries that act as effective barriers for dislocation motion. Consequently, versatile dislocation configurations are sequentially stimulated, enabling the alloy to accommodate plastic deformation while fostering substantial interactions that give rise to two unusual strain-hardening rate upturns. Thus, plastic instability is significantly delayed, which expands the plastic regime as ultralarge tensile ductility. This study provides valuable insights into achieving a synergistic combination of ultrahigh strength and large tensile ductility in MPEAs.

Chemical Fluctuation in Olivine-type LiFe<sub>0.4</sub>Mn<sub>0.6</sub>PO<sub>4</sub> Single Particle as Confirmed by Electron Energy-loss Spectroscopy Mapping

Chemical Fluctuation in Olivine-type LiFe<sub>0.4</sub>Mn<sub>0.6</sub>PO<sub>4</sub> Single Particle as Confirmed by Electron Energy-loss Spectroscopy Mapping

Unusual Precipitation at Grain Boundaries in Non-Equiatomic CoCrFeMnNi High Entropy Alloys

In Cr-rich CoCrFeMnNi alloys, the precipitation of the σ phase at grain boundaries during recrystallization is so fast that ultrafine-grained structure is formed due to the pinning effect of the precipitates. The average grain size of the fcc parent phase is found to be consistent with modified Zener-Smith model. If conventional alloys come to equilibrium, volume fraction of precipitates should approach a saturation value. However, it is interesting to note that the volume fraction of the σ phase in Cr-rich CoCrFeMnNi alloys is inversely proportional to the average grain size of the fcc parent phase. For instance, in Co20Cr25Fe20Ni15Mn20 alloys, the volume fraction changes from 6.5% to 1.2% with increasing average gran size from 14 μm to 210 μm even after annealing at 1273 K for 100 h. It is well known that heterogeneous nucleation of precipitates at grain boundary is energetically favorable and fast diffusion through grain boundary can assist the precipitation. However, they cannot account for the grain size dependence of the volume fraction after reaching equilibrium. Based on stereology, the reciprocal of grain size is proportional to grain boundary area. Thus, chemical fluctuation at grain boundaries (e.g. segregation) is considered to be related to the unusual precipitation at the grain boundaries.

Indoor air quality for heritage objects and human health: just a different interpretation of the same measurements?

The environmental conditions in a conservation-restoration studio for paintings induce an inherent risk to objects of art and to humans working on those objects. They are both subject to (sometimes dangerous) chemical substances and fluctuations in environmental conditions (e.g., temperature, relative humidity). In this paper, we report on a measuring campaign which lasted more than a year collecting data about the air quality within a painting studio of a higher education institute. An existing algorithm assessed the indoor air quality for heritage objects using international air quality standards. This contribution presents a new algorithm to assess indoor air quality for human health relying on thresholds imposed by legislation and recommended by reference institutes. This algorithm has been applied to the same measuring campaign. The assessments illustrate that the same environmental conditions have a different impact on canvas paintings, panel paintings, students, and staff. Air quality is thus a relative concept that depends on the object/subject that is considered in the analysis.Graphical abstract