Development of Y2O3 Dispersion-Strengthened Copper Alloy by Sol-Gel Method.

In this study, oxide dispersion-strengthened Cu alloy with a Y2O3 content of 1 wt.% was fabricated through citric acid sol-gel synthesis and spark plasma sintering (SPS). The citric acid sol-gel method provides molecular mixing for the preparation of precursor powders, which produces nanoscale and uniformly distributed Y2O3 particles in an ultrafine-grained Cu matrix. The effects of nanoscale Y2O3 particles on the microstructure, mechanical properties and thermal conductivity of the Cu-1wt.%Y2O3 alloy were investigated. The average grain size of the Cu-1wt.%Y2O3 alloy is 0.42 µm, while the average particle size of Y2O3 is 16.4 nm. The unique microstructure provides excellent mechanical properties with a tensile strength of 572 MPa and a total elongation of 6.4%. After annealing at 800 °C for 1 h, the strength of the alloy does not decrease obviously, showing excellent thermal stability. The thermal conductivity of Cu-1wt.%Y2O3 alloy is about 308 Wm-1K-1 at room temperature and it decreases with increasing temperature. The refined grain size, high strength and excellent thermal stability of Cu-1wt.%Y2O3 alloys can be ascribed to the pinning effects of nanoscale Y2O3 particles dispersed in the Cu matrix. The Cu-Y2O3 alloys with high strength and high thermal conductivity have potential applications in high thermal load components of fusion reactors.

Influence of Alloy Atoms on Substitution Properties of Hydrogen by Helium in ZrCoH3.

Intermetallic alloy ZrCo is a good material for storing tritium (T). However, ZrCo is prone to disproportionation reactions during the process of charging and discharging T. Alloying atoms are often added in ZrCo, occupying the Zr or Co site, in order to restrain disproportionation reactions. Meanwhile, T often decays into helium (He), and the purity of T seriously decreases once He escapes from ZrCo. Therefore, it is necessary to understand the influence of alloying atoms on the basic stability property of He. In this work, we perform systematical ab initio calculations to study the stability property of He in ZrCoH3 (ZrCo adsorbs the H isotope, forming ZrCoH3). The results suggest that the He atom will undergo displacements of 0.31 and 0.12 Å when it substitutes for Co and Zr, respectively. In contrast, the displacements are very large, at 0.67-1.09 Å, for He replacing H. Then, we introduce more than 20 alloying atoms in ZrCo to replace Co and Zr in order to examine the influence of alloying atoms on the stability of He at H sites. It is found that Ti, V, Cr, Mn, Fe, Zn, Nb, Mo, Tc, Ru, Ta, W, Re, and Os replacing Co can increase the substitution energy of H by the He closest to the alloying atom, whereas only Cr, Mn, Fe, Mo, Tc, Ru, Ta, W, Re, and Os replacing Co can increase the substitution energy of H by the He next closest to the alloying atom. The influence of the alloying atom substituting Zr site on the substitution energies is inconspicuous, and only Nb, Mo, Ru, Ta, and W increase the substitution energies of H by the He closest to the alloying atom. The increase in the substitution energy may suggest that these alloy atoms are conducive to fix the He atom in ZrCo and avoid the reduction in tritium purity.

Effect of Nano-Y2O3 Content on Microstructure and Mechanical Properties of Fe18Cr Films Fabricated by RF Magnetron Sputtering.

In this work, FeCr-based films with different Y2O3 contents were fabricated using radio frequency (RF) magnetron sputtering. The effects of Y2O3 content on their microstructure and mechanical properties were investigated through scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), inductive coupled plasma emission spectrometer (ICP) and a nanoindenter. It was found that the Y2O3-doped FeCr films exhibited a nanocomposite structure with nanosized Y2O3 particles uniformly distributed into a FeCr matrix. With the increase of Y2O3 content from 0 to 1.97 wt.%, the average grain size of the FeCr films decreased from 12.65 nm to 7.34 nm, demonstrating a grain refining effect of Y2O3. Furthermore, the hardness of the Y2O3-doped FeCr films showed an increasing trend with Y2O3 concentration, owing to the synergetic effect of dispersion strengthening and grain refinement strengthening. This work provides a beneficial guidance on the development and research of composite materials of nanocrystalline metal with a rare earth oxide dispersion phase.

Partially Crystallized Ultrathin Interfaces between GaN and SiNx Grown by Low-Pressure Chemical Vapor Deposition and Interface Editing.

The formation mechanism of the partially crystallized ultrathin layer at the interface between GaN and SiNx grown by low-pressure chemical vapor deposition was analyzed based on the chemical components of reactants and products detected by high-resolution sputter depth profile analysis by X-ray photoelectron spectroscopy. A reasonable mass action equation for the formation of Si2N2O was proposed from the feasibility analysis of the Gibbs free energy changes of the reaction. The high-energy-activated Ga2O on the surface likely assists in the synthesis of the crystallized components. A well-defined 1ML θ-Ga2O3 transition interface was inserted into Si2N2O/GaN pure interface supercell slabs to edit the unsaturated state of the bonds. Low-density states can be achieved when the effective charges of the unsaturated atoms are adjusted to a certain interval.

Investigation of the dissolution and diffusion properties of interstitial oxygen at grain boundaries in body-centered-cubic iron by the first-principles study.

Oxidation corrosion of steel is a universal problem in various industries and severely accelerated in nuclear reactors. First-principles calculations are performed to explore the dissolution and diffusion properties of interstitial oxygen in the body-centered-cubic iron grain boundaries Σ3〈110〉(111) and Σ5〈001〉(310). Solution energies indicate that interstitial oxygen atoms prefer to dissolve in body-centered-cubic iron, and energetically segregate to grain boundaries. Energy barriers show that oxygen atoms would segregate towards Σ3〈110〉(111) with a low energy barrier. However, they concentrate to the transition region of Σ5〈001〉(310) due to the high-energy barrier in the transition zone. When O atoms arrive at grain boundaries, they would stay there due to the larger solution energy and diffusion energy barrier in grain boundaries compared to that in the defect-free Fe bulk. These results indicate that O atoms would prefer to diffuse through the bulk, and oxidize grain boundaries. This study provides insight into oxidation phenomena in experiments and necessary parameters for future studies on the oxidation of steel under irradiation in nuclear reactors.

Application of Machine Learning to Predict Grain Boundary Embrittlement in Metals by Combining Bonding-Breaking and Atomic Size Effects.

The strengthening energy or embrittling potency of an alloying element is a fundamental energetics of the grain boundary (GB) embrittlement that control the mechanical properties of metallic materials. A data-driven machine learning approach has recently been used to develop prediction models to uncover the physical mechanisms and design novel materials with enhanced properties. In this work, to accurately predict and uncover the key features in determining the strengthening energies, three machine learning methods were used to model and predict strengthening energies of solutes in different metallic GBs. In addition, 142 strengthening energies from previous density functional theory calculations served as our dataset to train three machine learning models: support vector machine (SVM) with linear kernel, SVM with radial basis function (RBF) kernel, and artificial neural network (ANN). Considering both the bond-breaking effect and atomic size effect, the nonlinear kernel based SVR model was found to perform the best with a correlation of r2 ~ 0.889. The size effect feature shows a significant improvement to prediction performance with respect to using bond-breaking effect only. Moreover, the mean impact value analysis was conducted to quantitatively explore the relative significance of each input feature for improving the effective prediction.

Predictive model of hydrogen trapping and bubbling in nanovoids in bcc metals.

The interplay between hydrogen and nanovoids, despite long being recognized as a central factor in hydrogen-induced damage in structural materials, remains poorly understood. Here, focusing on tungsten as a model body-centred cubic system, we explicitly demonstrate sequential adsorption of hydrogen adatoms on Wigner-Seitz squares of nanovoids with distinct energy levels. Interaction between hydrogen adatoms on nanovoid surfaces is shown to be dominated by pairwise power-law repulsion. We establish a predictive model for quantitative determination of the configurations and energetics of hydrogen adatoms in nanovoids. This model, combined with the equation of states of hydrogen gas, enables the prediction of hydrogen molecule formation in nanovoids. Multiscale simulations, performed based on our model, show good agreement with recent thermal desorption experiments. This work clarifies fundamental physics and provides a full-scale predictive model for hydrogen trapping and bubbling in nanovoids, offering long-sought mechanistic insights that are crucial for understanding hydrogen-induced damage in structural materials.

Opposite Effects of SiO2 Nanoparticles on the Local α and Larger-Scale α' Segmental Relaxation Dynamics of PMMA Nanocomposites.

The segmental relaxation dynamics of poly(methyl methacrylate)/silica (PMMA/SiO2) nanocomposites with different compositions ( ϕ SiO 2 ) near and above the glass transition temperature were investigated by mechanical spectroscopy. At ϕ SiO 2 ≤ 0.5%, the α peak temperature hardly changes with ϕ SiO 2 , but that of α' relaxation composed of Rouse and sub-Rouse modes decreases by 15 °C due to the increase of free volume. At ϕ SiO 2 ≥ 0.7%, both α and α' relaxations shift to high temperatures because of the steric hindrance introduced by nanoparticle agglomeration. On the other hand, with increasing ϕ SiO 2 , the peak height for α relaxation increases at ϕ SiO 2 ≤ 0.5% and then decreases at ϕ SiO 2 ≥ 0.7%, but that for α' relaxation shows an opposite behavior. This is because at low ϕ SiO 2 , the short-chain segments related to α relaxation can easily bypass the particles, but the longer-chain segments related to α' relaxation cannot. At high ϕ SiO 2 , the polymer chains were bound to the nanoparticles due to the physical adsorption effect, leading to the decrease of relaxation unit concentration involved in α relaxation. However, the dissociation of those bonds with heating and the concentration heterogeneity of polymer chains result in the increase of peak height for α' relaxation.

Insight into the Near-Conduction Band States at the Crystallized Interface between GaN and SiN x Grown by Low-Pressure Chemical Vapor Deposition.

Constant-capacitance deep-level transient Fourier spectroscopy is utilized to characterize the interface between a GaN epitaxial layer and a SiN x passivation layer grown by low-pressure chemical vapor deposition (LPCVD). A near-conduction band (NCB) state ELP ( EC - ET = 60 meV) featuring a very small capture cross section of 1.5 × 10-20 cm-2 was detected at 70 K at the LPCVD-SiN x/GaN interface. A partially crystallized Si2N2O thin layer was detected at the interface by high-resolution transmission electron microscopy. Based on first-principles calculations of crystallized Si2N2O/GaN slabs, it was confirmed that the NCB state ELP mainly originates from the strong interactions between the dangling bonds of gallium and its vicinal atoms near the interface. The partially crystallized Si2N2O interfacial layer might also give rise to the very small capture cross section of the ELP owing to the smaller lattice mismatch between the Si2N2O and GaN epitaxial layer and a larger mean free path of the electron in the crystallized portion compared with an amorphous interfacial layer.

Multiple pathways in pressure-induced phase transition of coesite.

High-pressure single-crystal X-ray diffraction method with precise control of hydrostatic conditions, typically with helium or neon as the pressure-transmitting medium, has significantly changed our view on what happens with low-density silica phases under pressure. Coesite is a prototype material for pressure-induced amorphization. However, it was found to transform into a high-pressure octahedral (HPO) phase, or coesite-II and coesite-III. Given that the pressure is believed to be hydrostatic in two recent experiments, the different transformation pathways are striking. Based on molecular dynamic simulations with an ab initio parameterized potential, we reproduced all of the above experiments in three transformation pathways, including the one leading to an HPO phase. This octahedral phase has an oxygen hcp sublattice featuring 2 × 2 zigzag octahedral edge-sharing chains, however with some broken points (i.e., point defects). It transforms into α-PbO2 phase when it is relaxed under further compression. We show that the HPO phase forms through a continuous rearrangement of the oxygen sublattice toward hcp arrangement. The high-pressure amorphous phases can be described by an fcc and hcp sublattice mixture.

Origin of the crossover in dynamics of the sub-Rouse modes at the same temperature as the structural α-relaxation in polymers.

The nature of the liquid-glass transition remains an unsolved fundamental problem. One aspect is the striking change in dynamics of the structural α-relaxation generally observed at a temperature T(B) above Tg in all glass-formers. More intriguing in the case of polymers is that the change of dynamics occurs not only in the structural α-relaxation but also in the sub-Rouse modes, i.e. chain modes in between the α-relaxation and the Rouse modes. However, the nature of the dynamic crossover of the sub-Rouse modes remains unclear. In this paper, the dynamics of a series of poly(n-alkyl methacrylates) with different molecular weights and microstructures studied by mechanical spectroscopy are reported. We demonstrate that the sub-Rouse modes exhibit a similar crossover of dynamics at the same T(B) as the α-relaxation. This property shared by the two viscoelastic mechanisms is remarkable. By invoking the results from the studies using positron annihilation spectroscopy and adiabatic calorimetry, we show that both viscoelastic mechanisms are coupled to density, correlated with the change of the configuration entropy, and are intermolecularly cooperative. The time scale of sub-Rouse modes at T(B) of the polymers studied is approximately independent of molecular weight and micro-structure of the polymers studied. The findings enhance the understanding of the sub-Rouse modes and their manifestation in the viscoelasticity of polymers in the glass-rubber transition region.

A universal scaling law of grain chain elasticity under pressure revealed by a simple force vibration method.

The grain contact force, the key player in determining the mechanical properties of grain materials, depends on the elastic modulus and deformation (δ) of grains. However, our knowledge on their relationship in a three-dimensional granular medium is limited mainly owing to the difficulty of realizing direct experimental investigation. Using a simple force vibration technique, we measure the dissipation spectra (the frequency response) of three kinds of grains with different elastic moduli under different pressures (to change the grain deformation). The dissipation spectra exhibit multiple resonant peaks, indicative of the resonance of grain chains with different lengths. This allows us to quantitatively characterize the elastic behaviors of grain chains. A universal correlation of the resonant frequency (f) of a grain chain with deformation is observed for all granular systems with different material properties (Young's modulus E, density ρ and Poisson's coefficient ν): f(2) ∝ δ(1/2)E/ρ(1 - ν). The deformation of the grain chain under pressure follows a p(2/3) pressure dependence. This general behavior suggests that the pressure-induced deformation of the grain chain under low-frequency weak shear vibration is overwhelmed by the nonlinear Hertzian contact elasticity.

Revisit to phase diagram of poly(N-isopropylacrylamide) microgel suspensions by mechanical spectroscopy.

Microgels are soft particles that can be deformed and compressed, which would induce intriguing phase behaviors at high packing fractions. Poly(N-isopropylacrylamide) (PNIPAM) microgels, with a lower critical solution temperature (LCST) of 33 °C, have attracted considerable interests as model colloids, since the volume of them and the interaction between the microgels can be tuned precisely by temperature. In this work, the linear viscoelastic properties of PNIPAM microgel suspensions have been investigated using mechanical spectroscopy. A particular attention is focused on the phase behaviors at high concentrations. With increasing concentration the system undergoes a repulsive glass-to-gel transition below the LCST, while, as temperature is raised across the LCST, the system undergoes a gel-to-attractive glass transition. A mechanism of these transitions for the microgels is proposed based on the directional interaction between the particles. In moderate concentration or de-swelling microgels the interaction is isotropic leading to the glass phase, while in concentrated and deformed microgels the interaction is directional leading to the gel phase. Our results enrich the current understanding of the phase transition in microgel systems and shed new light on the phase diagram of colloidal suspensions in general.

Quantifying changes in the low-frequency dynamics of amorphous polymers by 2D correlation mechanical spectroscopy.

The longer segmental dynamics of sub-Rouse modes in polystyrene with different molecular weights has been investigated by 2D correlation mechanical spectroscopy. The sub-Rouse modes were first separated from the α relaxation and Rouse modes, and their dynamics exhibits a similar change at the same temperature, T(B) ≈ 1.2T(g), as the α relaxation. The relaxation time of sub-Rouse modes at T(B) is independent of molecular weight and has a value of about 0.1 s, indicating that solely the time scale of the relaxation determines the change in dynamics of sub-Rouse modes. According to the coupling model, the change is caused by a strong increase in intermolecular cooperativity. The present work provides direct evidence for the intermolecular coupled nature of the sub-Rouse modes and demonstrates that the properties of the sub-Rouse modes resemble those of α relaxation, which could provide a new perspective for understanding the glass transition of polymers.

Dynamics in N-isopropylacrylamide-acrylic acid copolymer aqueous solution from mechanical spectroscopy.

Gaining control over precise and predictable structures of colloidal systems and understanding the abundant dynamic behaviors remains a formidable challenge. In this study, low-frequency mechanical spectroscopy was applied to investigate the dynamics of aqueous solutions of N-isopropylacrylamide-acrylic acid (NIPAM-AA) copolymers with three different AA contents. A mechanical loss valley was found for the solution with low molar fraction of AA (f(AA)), f(AA) = 25 and 50 mol %, and a loss peak was shown for the solution with f(AA) = 75 mol %. The former is suggested to be due to the particle glass phase of repulsive micelles above the low critical solution temperature, whereas the latter is associated with the α relaxation behavior of NIPAM-AA/water mixture at high concentrations. The relaxation time of the α relaxation seems to follow a simple Arrhenius temperature dependence. The activation energy H is ∼53 kJ/mol, and the larger H value is suggested to be due to multiple strong hydrogen bonds in the copolymer solution. The present work demonstrates that by controlling the proportion of ingredients in the colloidal systems the systems can exhibit distinct dynamic behaviors, which is helpful in the design and fabrication of colloids.

Phase diagram of the Pluronic L64-H2O micellar system from mechanical spectroscopy.

The linear viscoelastic properties of aqueous Pluronic L64 solutions have been investigated at high copolymer concentrations (25-62 wt%) using our modified low-frequency mechanical spectroscopy. The concentration-temperature phase diagram of the L64/H(2)O system was constructed by studying the evolution of the loss modulus and loss tangent as temperature is increased at a fixed frequency. A particular attention was focused on the dynamics approaching the beginning and ending points (39% and 60%) of the fusiform gel region in the phase diagram. The dynamics is found to have a similar viscoelastic behavior at the low and high concentrations, where a frequency scaling expected for a static percolated network is exhibited. Moreover, with increasing temperature, the system above the critical gel concentration undergoes a transition from a viscoelastic liquid to a solid gel through a percolated particle network. Therefore, our results suggest that the formation of the gel is dominated by the percolation of the particle clusters.

Dynamic crossover of alpha' relaxation in poly(vinyl acetate) above glass transition via mechanical spectroscopy.

The molecular relaxation dynamics of poly(vinyl acetate) (PVAc) has been studied by mechanical spectroscopy above the glass transition temperature (T(g)) within a frequency range from 1 mHz to 100 Hz. The temperature-dependent mechanical spectra reveal the existence of two relaxation modes: alpha, ascribed to the glass transition, and alpha', which may be related to the softening dispersion, composed of the sub-Rouse modes and the Rouse modes. The alpha' mode has a weaker temperature dependence than the alpha mode. Furthermore, the alpha' mode from the frequency-domain spectra exhibits a similar dynamic crossover at temperature T(B) approximately 387 K as the alpha mode through the temperature dependence of relaxation time, relaxation strength, and shape parameter. However, the crossover of the alpha' mode occurs at a time of about 0.08 s, longer than 10(-6)-10(-7) s for the alpha mode by dielectric spectroscopy. According to the coupling model, the crossover is suggested to be caused by the strong increase of intermolecular cooperativity below T(B).

Low-frequency mechanical spectroscopy study of conformational transition of polymer chains in concentrated solutions.

A low-frequency mechanical spectroscopy approach for liquids was proposed for studying conformational transition of polymer chains in concentrated solutions. The technique is applied to aqueous solutions of a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymer in order to determine if chain conformation is altered in response to temperature. Two transitions are revealed by mechanical spectra and verified by differential thermal analysis with increasing temperature, which may be related to the unimer-to-micelle transition and the phase separation, respectively. The transitions are also found to be much dependent on the concentration of the solution and the addition of NaCl. Moreover, it reveals that the PEO blocks play a more important role in the micellar crystallization process. This study may be helpful in understanding the dynamics of polymer chains in concentrated solutions.