Local Structural Defects Research Articles

Correlative Raman spectroscopy and electron microscopy identifies glycogen rich deposits correlated with local structural defects in long bones of type IV osteogenesis imperfecta patients

Osteogenesis imperfecta (OI) is a genetic bone disease occurring in approximately 1 in 10,000 births, usually as a result of genetic mutation. OI patients suffer from increased fracture risk and – depending on the severity of the disease – deformation of the limbs, which can even lead to perinatal death.Despite extensive studies, the way in which the genetic mutation is translated into structural and compositional anomalies of the tissue is still an open question. Different observations have been reported, ranging from no structural (or chemical) differences to completely chaotic bone structure and composition.Here, we investigated bone samples from two adolescent OI-IV patients, focusing on the bone structure and chemistry in naturally occurring fractures. The exposed fracture plane allows the investigation of the structure and composition of the weakest bone plane. We do so by combining scanning electron microscopy (SEM) imaging with chemical information from Raman microscopy.The exposed fracture planes show different regions within the same tissue, displaying normal osteonal structures next to disorganized osteons and totally disordered structures, while the collagen mineralization in all cases is similar to that of a healthy bone.In addition, we also detected significant amounts of depositions of glycogen-rich, organic, globules of 250–1000 nm in size. These depositions point to a role of cellular disfunction in the disorganization of the collagen in qualitative OI.Overall, our results unite multiple, sometimes contradicting views from the literature on qualitative OI.

Local defect structure design enhanced energy storage performance in lead-free antiferroelectric ceramics

Antiferroelectrics (AFEs) are ideal candidates in dielectric, electromechanical, and electrothermal applications. NaNbO3 (NN), as a lead-free antiferroelectric (AFE) material under extensive investigation, exhibits ferroelectric (FE)-like polarization–electric field (P-E) hysteresis loops, characterized by high remnant polarization and large hysteresis. Herein, the local defect structure design is proposed to achieve high energy storage (ES) density in NN-based AFE ceramics. The pinning effect of defect dipoles and the enhancement of local structural disorder stabilize the AFE phase and reduce hysteresis losses. Consequently, an excellent ES performance of large recoverable energy density (Wrec) of 9.70 J/cm3 and high efficiency (η) of 88.75 % is concurrently obtained in NN-based relaxor AFE ceramics, with outstanding charge–discharge performance (PD∼413.2 MW/cm3, WD∼4.47 J/cm3), which are significantly improved compared to other reported values in lead-free ES ceramics. This indicates that NN-based ceramics are candidates for advanced ES capacitors and provides a feasible modulation approach for the development of new lead-free high-performance dielectric materials.

Evolution of magnetization of Bi1-ySmyFe1-xTixO3 ceramics at the morphotropic phase boundary attested by multistep magnetization measurements, time aging and electric field

Bi1-ySmyFe1-xTixO3 ceramics with compositions at the rhombohedral- orthorhombic morphotropic phase boundary (y = 0.1, 0.12, 0 ≤ x ≤ 0.1) were prepared by solid state reaction method. Analysis of the crystal structure of the compounds based on the results of laboratory and synchrotron X-ray diffraction measurements as well as Raman spectroscopy experiments revealed a coexistence of the rhombohedral phase (SG R3c) and the anti-polar orthorhombic phase (SG Pbam) in the compounds Bi0.88Sm0.12Fe1-xTixO3 with 0 ≤ x ≤ 0.1; the compounds Bi0.9Sm0.10Fe1-xTixO3 are characterized by the mixed structural state for the concentration range 0 ≤ x ≤ 0.06 and by the single phase rhombohedral state within 0.06 < x ≤ 0.1. Room temperature magnetization measurements demonstrate a gradual increase of remanent magnetization with Ti content in the compounds of both systems up to the maximal value of MR ∼0.28 emu/g for compounds with x = 0.06 which is followed by a decrease in magnetization with further titanium doping. Temperature decrease leads to a reduction of remanent magnetization which is mainly caused by a partial recovery of spatially modulated spin structure occurred in the compounds of both systems. Time aging of the compounds for about ∼1 year leads to a drastic increase of MR, which is caused by a change in the structural phase ratio, homogeneity of the structural state and a contribution of unbounded spins demonstrated by low field measurements. Subjecting of the annealed compounds to external electric field of E ∼40 kV/cm leads to a decrease of magnetization associated with backward structural transformations and redistribution of the local structural defects in the compounds.

Stereochemically Active Lone Pairs Stabilizing Intrinsic Vacancy Defects in Thermoelectric InTe.

Harvesting waste heat efficiently with thermoelectric energy conversion requires materials with low thermal conductivity. Recently, it was demonstrated how dynamic lone pair expression in thermoelectric InTe is responsible for giant anharmonicity leading to a very low lattice thermal conductivity. InTe also contains correlated disorder of intrinsic defects due to vacancies, and this contributes to additional lowering of the thermal conductivity. Here we use the three-dimensional difference pair distribution function (3D-ΔPDF) to analyze 25 K single crystal diffuse X-ray scattering from InTe to unravel the local defect structure, and propose a microscopic structural model. Extended off-centering of In+ ions induced by vacancies allows for the local expression of stereochemically active lone pairs. The associated electronic stabilization is proposed to be a driving force for the formation of In+ vacancy defects in InTe.

Enhanced activity and durability of Pt nanoclusters catalyst by using nitrogen-doped carbon layer coated carbon nanotubes as anchors and nanowires for ORR

Platinum-based catalysts remain the top choice for oxygen reduction reaction (ORR) in fuel cells. However, their activity and durability in the acidic medium are still under improvement. In this work, the Pt nanoclusters anchored the nitrogen-doped carbon nanotubes (Pt-NCNTs) have been synthesized by using a series process of pyrrole coating on the CNTs and subsequent pyrolysis to the chemical immersion reduction of Pt ions. The inner CNTs of Pt-NCNTs function as the nanowires offering a high-speed pathway for electron transport, and the Pt nanoclusters increases the active sites. The theoretical calculation demonstrates that the local structural defects and the uneven charge distribution induced by nitrogen-containing functional groups and porous structure are favorable to capture Pt ions for the nucleation of Pt nanoclusters. Compared with the commercial 40 wt% Pt/C (0.94 and 0.80 V), the Pt-NCNTs-1000 with Pt loading amount of 33.0 wt% owns the more positive onset potential and half-wave potential of 0.97 and 0.81 V in the sulfuric acid medium. Meanwhile, the strong attachment of Pt nanoclusters on the nitrogen-doped porous carbon layer results in a stable interface to effectively prevent the metallic species from migration and agglomeration during the electrode reactions. Therefore, the ORR current of Pt-NCNTs-1000 retained 84.3% of the initial value after 50000 s operation superior to the commercial Pt/C (64.6%).

EPR parameters and optical spectrum of α-Al2O3:Ti3+ with dynamic Jahn-Teller effect

The quenching phenomenon of trigonal crystal field (CF), spin–orbit (SO) coupling operators, and orbital operators reflected in electron paramagnetic resonance (EPR) parameters and energy splitting intervals observed in experiments of α-Al2O3:Ti3+ is theoretically investigated by the calculation of EPR g factors and the energy differences of the lowest three levers E3/2, 1E1/2 and 2E1/2 with the formulas derived with high-order perturbation method. In the calculation, the coupling of 2T2g and 2Eg with e vibrational model of dynamic Jahn-Teller effect are considered. The calculated results are in agreement with the experimental values. The local defect structure around Ti3+ ions (bond lengths and angles of [TiO6]9-) and trigonal CF parameters ν and v′ are determinedand the covalence effects on SO coupling parameters ζ, ζ’ and orbital reduction parameters k、k’ are determined also.

Resonant Raman scattering on graphene: SERS and gap-mode TERS.

Nanoscale deformations and corrugations occur in graphene-like two-dimensional materials during their incorporation into hybrid structures and real devices, such as sensors based on surface-enhanced Raman scattering (SERS-based sensors). The structural features mentioned above are known to affect the electronic properties of graphene, thus highly sensitive and high-resolution techniques are required to reveal and characterize arising local defects, mechanical deformations, and phase transformations. In this study, we demonstrate that gap-mode tip-enhanced Raman Scattering (gm-TERS), which offers the benefits of structural and chemical analytical methods, allows variations in the structure and mechanical state of a two-dimensional material to be probed with nanoscale spatial resolution. In this work, we demonstrate locally enhanced gm-TERS on a monolayer graphene film placed on a plasmonic substrate with specific diameter gold nanodisks. SERS measurements are employed to determine the optimal disk diameter and excitation wavelength for further realization of gm-TERS. A significant local plasmonic enhancement of the main vibrational modes in graphene by a factor of 100 and a high spatial resolution of 10 nm are achieved in the gm-TERS experiment, making gm-TERS chemical mapping possible. By analyzing the gm-TERS spectra of the graphene film in the local area of a nanodisk, the local tensile mechanical strain in graphene was detected, resulting in a split of the G mode into two components, G+ and G-. Using the frequency split in the positions of G+ and G- modes in the TERS spectra, the stress was estimated to be up to 1.5%. The results demonstrate that gap-mode TERS mapping allows rapid and precise characterization of local structural defects in two-dimensional materials on the nanoscale.

Study on Strengthening and Reforming Scheme of Door Frame Signs with Local Structural Defects of Expressway in Service

Study on Strengthening and Reforming Scheme of Door Frame Signs with Local Structural Defects of Expressway in Service

Defect induced ferromagnetism in Mn3Ga

Ni-substituted Mn3Ga displays a weak ferromagnetism embedded in an antiferromagnetic (AF) phase. Upon field cooling, the alloy exhibits exchange bias and an open hysteresis loop, signifying kinetic arrest at room temperature. For the first time, a kinetic arrest is seen in a compound due to the first order transition of an embedded defect phase. A systematic study of crystal structure, local structure, and magnetic properties of Mn 3−x Ni x Ga (x = 0, 0.25) alloys reveal the origin of ferromagnetism in Mn2.75Ni0.25Ga is due to the segregation of a Heusler-type environment around Ni in the cubic Mn3Ga matrix. Upon temper annealing at 400 ∘C, these local structural defects around the Ni phase separate into a modulated ferromagnetic (FM) Ni-Mn-Ga Heusler phase. A strong interaction between the AF host and the FM defect phase gives rise to exchange bias. The first-order transition of the defect phase seems to be responsible for the observed kinetic arrest in Mn2.75Ni0.25Ga.

Influence of brine leakage on frozen wall development in offshore sand layer when active freezing: A numerical study

Brine leakage after freezing pipe fracture when active freezing will cause local structural defects or even failure of frozen wall. A water-heat-solute coupled model that includes a modified Michalowski model considering both temperature and salt concentration was proposed to simulate the freezing construction in offshore sand layer. It was verified by the artificial freezing model tests of saturated saline sand under seepage. The structural defects of frozen wall were observed at the boundary between straight and arch walls on the upstream. The range of the structural defect and the closing time of frozen wall both rise with larger pressure head. The brine leakage was then simulated to evaluate the effects of both pressure head and fracture range of freezing pipe on the structural defect of frozen wall. As indicated by the normalized unfrozen water content contour, there are obvious flaws in determining whether the frozen wall is closed only by the average temperature when brine leakage. A characteristic index, the area ratio of structural defect of frozen wall, was derived from the normalized unfrozen water content contour. The structural defect results from brine leakage when the pressure head is below 2.0 m, otherwise from both brine leakage and groundwater seepage. It is recommended that in addition to monitoring temperature during active freezing, additional moisture monitoring devices should be installed to prevent brine leakage hazards.

Crystal Lattice Defects in Deuterated Zr in Presence of O and C Impurities Studied by PAS and XRD for Electron Screening Effect.

Low-energy nuclear reactions are known to be extremely dependent on the local crystal structure and crystal defects of the deuterated samples. This has a strong influence on both hydrogen diffusion and the effective electron mass. The latter determines the strength of the local electron-screening effect and can change the deuteron-deuteron reaction rates at very low energies by many orders of magnitude. In the present study, zirconium samples were exposed to various conditions and energies of deuteron beams using the unique accelerator system with ultra-high vacuum, installed in the eLBRUS laboratory at the University of Szczecin. Irradiated and virgin samples were investigated by means of the X-ray diffraction (XRD) and positron annihilation spectroscopy (PAS). While the first method delivers information about changes of crystal lattice parameters and possible production of hydrides accompanying the formation of dislocations that are produced during irradiation of the samples, the second one can determine the depth distribution of crystal defects, being especially sensitive to vacancies. The studied Zr samples were also implanted by carbon and oxygen ions in order to simulate the real situation taking place in nuclear reaction experiments and to investigate their influence on the kinetic of produced vacancies. The observed enhancement of the electron-screening effect in the deuteron fusion reaction at very low energies could be explained by formation of a high number of vacancies during the deuteron irradiation of samples. Possible carbon and oxygen impurities can affect this process in various ways by changing the depth distribution of vacancies and their diffusion, but they play only a minor role in the strength of the electron-screening effect.

Investigating Partial Factors for the Assessment of Existing Reinforced Concrete Bridges

There is great interest in developing an adequate partial factor format for the assessment of existing structures, and in particular bridges, that should be able to take various aspects into account linked to the fact that the structure already exists. As the structure is existing, additional information related to material parameters, loading conditions, local structural defects, etc. can be accounted for. In addition, the degree of conservatism needs to be well balanced to avoid unnecessary investment of resources in replacement or retrofitting. This contribution considers the experience gained in recent years in parallel with some ongoing standardisation work in relation to Eurocodes and the next edition of the fib Model Code for new and existing concrete structures. The current state of the art of partial factors for the assessment of existing structures is explored and the differences are assessed based on a comparison between (i) the use of recommended fixed partial factors as provided in many national and international codes, (ii) adjusted (flexible) partial factors derived for the individual case under consideration, and (ii) reliability-based verification. In order to assess the adequacy of proposals and identify some differences, the available partial factor formats are applied to two case studies of reinforced concrete bridges and they are critically assessed.

Ni‐rich Cathode Materials for High‐performance Li‐ion Batteries: Challenges, Progress and Perspectives

AbstractNi‐rich layered ternary oxides are considered as one of optimal cathode materials for lithium‐ion batteries because of high energy density and low raw material cost. However, their local structural defect, microstructural destruction and poor interfacial stability deteriorate the specific energy density, lifespan and safety of batteries. Therefore, understanding the root cause of failure and clarifying their relationship in depth can pave the way to promoting the modification and application of Ni‐rich cathode materials (NRCM). In this review, the chain‐like failure of NRCM triggered by multiple‐scaled structure variations are systematically analyzed based on their fundamental characteristic. Subsequently, current tailoring strategies of NRCM at different size scales are especially discussed. Finally, along with the concluding remarks and remaining challenges, the future development possibilities are discussed to stimulate the commercialization of NRCM.

Microdynamics of active particles in defect-rich colloidal crystals

Hypothesis. Because they are self-propulsive, active colloidal particles can interact with their environment in ways that differ from passive, Brownian particles. Here, we explore how interactions in different microstructural regions may contribute to colloidal crystal annealing.Experiments. We investigate active particles propagating in a quasi-2D colloidal crystal monolayer produced by alternating current electric fields (active-to-passive particle ratio ∼ 1:720). The active particle is a platinum Janus sphere propelled by asymmetric decomposition of hydrogen peroxide. Crystals are characterized for changes in void properties. The mean-squared-displacement of Janus particles are measured to determine how active microdynamics depend on the local microstructure, which is comprised of void regions, void-adjacent regions (defined as within three particle diameters of a void), and interstitial regions.Findings. At active particle energy EA = 2.55 kBT, the average void size increases as much as three times and the average void anisotropy increases about 40% relative to the passive case. The average microdynamical enhancement, <δ(t)>, of Janus particles in the crystal relative to an equivalent passive Janus particle is reduced compared to that of a free, active particle (<δ(t) > is 1.88 ± 0.04 and 2.66 ± 0.08, respectively). The concentration of active particles is enriched in void and void-adjacent regions. Active particles exhibit the greatest change in dynamics relative to the passive control in void-adjacent regions (<δ(t)> = 2.58 ± 0.06). The results support the conjecture that active particle microdynamical enhancement in crystal lattices is affected by local defect structure.

The influence of structure and local structural defects on the magnetic properties of cobalt nanofilms.

The present paper considers a mathematical model describing the time evolution of spin states and magnetic properties of a nanomaterial. We present the results of two variants of nanosystem simulations. In the first variant, cobalt with a structure close to the hexagonal close-packed crystal lattice was considered. In the second case, a cobalt nanofilm formed in the previously obtained numerical experiment of multilayer niobium-cobalt nanocomposite deposition was investigated. The sizes of the systems were the same in both cases. For both simulations, after pre-correction in the initial time stages, the value of spin temperature stabilized and tended to the average value. Also, the change in spin temperature occurred near the average value. The system with a real structure had a variable spin temperature compared to that of a system with an ideal structure. In all cases of calculations for cobalt, the ferromagnetic behavior was preserved. Defects in the structure and local arrangement of the atoms cause a deterioration in the magnetic macroscopic parameters, such as a decrease in the magnetization modulus.

Conductivity in sulfur doped gallium selenide crystals measured by terahertz time-domain spectroscopy

In this work, the conductivity of intrinsic GaSe, S doped 2.5 mass% GaSe (GaSe: S(2.5%)), and S doped 7 mass% GaSe (GaSe: S(7%)) crystals, in a frequency range of 0.3–2.5 THz, is measured by transmission terahertz time-domain spectroscopy, and fitted with Drude-Smith-Lorentz model which is introduced by lattice vibration effect. It is found that the real part of conductivity decreases with the augment of S doping, which is caused by the gradual shift of the Fermi energy level of GaSe crystals to the charge neutrality level due to the generation of substitution impurities and gap impurities by S doping, resulting in the reduction of carrier concentration. The intrinsic GaSe and GaSe: S(2.5%) have a clear lattice vibration peak at about 0.56 THz, while GaSe: S(7%) has no lattice vibration peak near 0.56 THz, which is mainly due to the S doping increasing the structural hardness of the crystal and reducing the interlayer rigidity vibration of the crystal. All three samples have the obvious narrow lattice vibration peaks at about 1.81 THz, and the intensities that first decrease and then increase with the augment of S doping, which is mainly due to the fact that a small amount of S doping can reduce the local structural defects of GaSe and weaken the intensity of the narrow lattice vibration peak, while excessive S doping can generate the β-type GaS crystal, increase the local structural defects of the crystals and the intensity of the narrow lattice vibration peak. With the increase of S doping, the intensity of the broad lattice vibration peak of GaSe crystal weakens or even disappears at about 1.07 THz and 2.28 THz, mainly due to the S doping resulting in the substitution of S for impurities and GaS gap impurities, which reduces the fundamental frequency phonon vibration intensity, thereby weakening the lattice vibration caused by the second-order phonon difference mode of the crystal. The results show that the appropriate concentration of S doping can effectively suppress the lattice vibration of GaSe crystal and reduce the conductivity and power loss in the THz band. This study provides important data support and theoretical basis for the design and fabrication of low loss THz devices.

Advanced Mapping of Optically-Blind and Optically-Active Nitrogen Chemical Impurities in Natural Diamonds

Natural diamonds with a rich variety of optically blind and optically active nitrogen impurity centers were explored at a nano/microscale on the surface and in bulk by a number of advanced chemical and structural analytical tools in order to achieve a comprehensive characterization by establishing enlightening links between their analysis results. First, novel compositional relationships were established between high-energy X-ray photoelectron spectroscopy (XPS) and low-energy Fourier-transform infrared vibrational spectroscopy (FT-IR) signals of nitrogen impurity defects acquired in the microscopy mode at the same positions of the diamond surface, indicating the verification XPS modality for qualitative and quantitative FT-IR analysis of high concentrations of nitrogen and other chemical impurity defects in diamond. Second, depth-dependent spatial distributions of diverse photoluminescence (PL)-active nitrogen defects were acquired in the confocal scanning mode in an octahedral diamond and then for the first time corrected to the related Raman signals of the carbon lattice to rule out artefacts of the confocal parameter and to reveal different micron-scale ontogenetic layers in the impurity distributions on its surface. Third, intriguing connections between local structural micro-scale defects (dislocation slip bands of plastic deformation zones) visualized by optical microscopy and Raman microspectroscopy, and related distributions of stress-sensitive PL-active nitrogen impurity defects in the proximity of these planes inside bulk diamonds were revealed. These findings demonstrate the broad instrumental opportunities for comprehensive in situ studies of the chemical, structural, and mechanical micro-features in diamonds, from the surface into bulk.

Local Structure in α-BIMEVOXes (ME = Ge, Sn).

The BIMEVOXes are among the best oxide ion conductors at low and intermediate temperatures. Their high conductivity is associated with local defect structure. In this work, the local structures of two BIMEVOX compositions, Bi2V0.9Ge0.1O5.45 and Bi2V0.95Sn0.05O5.475, are examined using total neutron and X-ray scattering methods, with both compositions exhibiting the ordered α-phase at 25 °C and the disordered γ-phase at 700 °C. While the diffraction data for the α-phase do not allow for the polar (C2) and nonpolar (C2/m) structures to be readily distinguished, measurements of dielectric permittivity suggest the α-phase is weakly ferroelectric in character, consistent with calculations of spontaneous polarization based on a combination of density functional calculations and machine learning methodology. Reverse Monte Carlo (RMC) analysis of total scattering data reveals Ge preferentially adopts tetrahedral geometry at both temperatures, while Sn is found to predominantly adopt octahedral coordination in the α-phase and tetrahedral coordination in the γ-phase. In all cases, V polyhedra are found to consist of tetrahedral, pentacoordinate, and octahedral geometries, as also predicted by the crystallographic analysis and confirmed by 51V solid state NMR spectroscopy. Although similar long-range structures are observed at room temperature, the oxide ion vacancy distributions were found to be quite different between the two studied compositions, with a nonrandom deficiency in vacancy pairs in the second-nearest shell along the ⟨100⟩ tetragonal direction for BIGEVOX10, compared with a long-distance (>8.0 Å) ordering of equatorial vacancies for BISNVOX05. This is attributed to the differences in the preferred coordination geometries of the substituent cations in the two systems. Impedance spectroscopy measurements reveal both compositions show high conductivity in the order of 10-1 S cm-1 at 600 °C.

Direct Evidence on Effect of Oxygen Dissolution on Thermal and Electrical Conductivity of AlN Ceramics Using Al Solid-State NMR Analysis.

Aluminum nitride, with its high thermal conductivity and insulating properties, is a promising candidate as a thermal dissipation material in optoelectronics and high-power logic devices. In this work, we have shown that the thermal conductivity and electrical resistivity of AlN ceramics are primarily governed by ionic defects created by oxygen dissolved in AlN grains, which are directly probed using 27Al NMR spectroscopy. We find that a 4-coordinated AlN3O defect (ON) in the AlN lattice is changed to intermediate AlNO3, and further to 6-coordinated AlO6 with decreasing oxygen concentration. As the aluminum vacancy (VAl) defect, which is detrimental to thermal conductivity, is removed, the overall thermal conductivity is improved from 120 to 160 W/mK because of the relatively minor effect of the AlO6 defect on thermal conductivity. With the same total oxygen content, as the AlN3O defect concentration decreases, thermal conductivity increases. The electrical resistivity of our AlN ceramics also increases with the removal of oxygen because the major ionic carrier is VAl. Our results show that to enhance the thermal conductivity and electrical resistivity of AlN ceramics, the dissolved oxygen in AlN grains should be removed first. This understanding of the local structure of Al-related defects enables us to design new thermal dissipation materials.

Optical Soldering of MoS2 Layers for Defect Structure Formation with Induced Photoluminescence (Advanced Optical Materials 21/2022)

This cover image shows a conceptual schematic of the optical soldering of 2D transition metal dichalcogenides (TMDs). By focused optical beam illumination with energy higher than the bandgap of 2D TMDs, optical heating energy is transferred to the underlying soldering nanoparticles. In turn, the nanoparticles are melted down to the substrate forming local defect structures in 2D TMDs on the focal spots. The optical soldering method provides site-selective and real-time patterning capability of defect structures in 2D TMDs. For further details, see article number 2201583 by Taewan Kim, ChaeHo Shin, Hyunwoo Kim, and co-workers.