Nanocrystalline Research Articles

FUNCTIONAL OPTICAL MATERIALS BASED ON AEROGELS

Sol-chemistry is an efficient physico-chemical method for the preparation of porous glassy or nanocrystalline materials with tailored electrical, thermal or optical properties. This paper focuses on the dependence preparation–structure-properties of hydrophobic silica aerogel granules, powders and composites with a potential application as optical materials. Using the technique of subcritical preparation of silica aerogel powders, multicolour emitting composites containing Eu(phen)2(NO3 )3 or Tb(phen)2(NO3 )3 nanocrystals are obtained and characterized with luminescence spectroscopy, quantum yield determination and texture measurements. A dependence of the luminescence quantum yield on the degree of hydrophobicity α of the silica aerogel powders is described.

Effects of residual stress on the isothermal tensile behavior of nanocrystalline superelastic NiTi shape memory alloy

The residual stress greatly affects the mechanical behavior of a material. In this work, the effect of residual stress on the isothermal tensile behavior of a NiTi shape memory alloy is studied. The focused ion beam and digital image correlation are combined to measure the two-dimensional residual stress in nanocrystalline NiTi plates processed with prestrain laser shock peening. A four-point bending experiment verified the accuracy of this measurement method. The FIB-DIC method is an attractive tool for measuring the two-dimensional residual stress in phase transition nanocrystalline materials. The internal residual stress significantly decreases the phase transition stress, and the mechanism is studied via finite element and theoretical analyses. This work implies that the mechanical behavior of NiTi shape memory alloys can be tailored via residual stress engineering.

Dysprosium-Doped Glass-Ceramics From the System Na2O-Al2O3-SiO2-B2O3-Dy2O3.

Glasses from the system Na2O-Al2O3-SiO2-B2O3-Dy2O3 are prepared with three different concentrations of the Dy3+ ion-0.5, 1, and 2 at%. Glass-ceramics are obtained after thermal treatment of the parent glass at 580°С and 630°С during 2, 5, and 24 h. The crystallizing phases, the crystallinity degree, and the nano crystalline size are determined. The crystallizing phases after thermal treatment are NaAlSiO4 in two different modifications and Na3B3O6. XRD analyses show the presence of third unknown phase in some samples. Emission and excitation spectra of the glass-ceramics show the characteristic peaks of Dy3+ (4F9/2 → 6H15/2, 4F9/2 → 6H13/2 and 4F9/2 → 6H11/2 at 483, 575, and 668 nm, respectively). The yellow peak is dominating in all samples. The spectra show different intensity depending on the Dy3+ concentration, temperature, and time of the thermal treatment. This result suggests that the emission color can be controlled by these three factors.

In Situ Atomic‐Scale Experiments Reveal the Atomistic Mechanisms of Grain Boundary Plasticity

AbstractGrain boundary (GB) plastic deformation is a critical deformation mode that can significantly affect the microstructure and mechanical properties of metals. Given its importance, numerous studies have been conducted over the past few decades to investigate the atomistic mechanism of GB plasticity, which includes GB migration, GB sliding, and grain rotation. These three deformation modes typically occur simultaneously and interact cooperatively. Despite substantial advancements in understanding the atomic‐scale mechanisms of GB plasticity, there is a scarcity of review papers addressing the in situ atomic‐scale mechanisms of GB plasticity. This work aims to provide a comprehensive overview of the atomistic mechanisms of GB plasticity in metals, detailing modes predicted by theoretical models and molecular dynamics (MD) simulations, as well as discussing mechanisms verified by in situ atomic‐scale experiments. Additionally, it examines the factors influencing GB deformation. The authors intend for this review to serve not only as a valuable resource for researchers in the field of nanocrystalline (NC) metals but also as a textbook for educating graduate students.

Role of severe plastic deformation on mechanical behavior of irradiated materials: A case study with Nb-1Zr alloy

In this investigation, the effect of 5.6 MeV proton irradiation on the microstructure and mechanical properties of coarse grained (CG) and nanocrystalline (NC) Nb-1wt.%Zr (NZ) has been analysed. Bulk nanocrystalline microstructure was obtained by subjecting the alloy to room temperature high pressure torsion under 6 GPa hydrostatic pressure and 5 rotations. The CG and NC samples were irradiated at doses of 1.9 × 1017 p/cm2 and 1.8 × 1017 p/cm2, respectively. Microstructural parameters like crystallite size, dislocation density, and dislocation arrangements were studied in detail using X-ray line profile analysis (XLPA) by Convolutional Multiple Whole Profile (CMWP) fitting. Microscopic observations were made with electron microscopy techniques in the scanning and transmission modes. Differential Scanning Calorimetry (DSC) was performed to estimate the concentration of vacancies after HPT processing and irradiation. Tensile tests of irradiated CG and NC irradiated samples were performed and compared to those in unirradiated conditions. In the NC condition, not only did the irradiated sample show higher ultimate tensile strength but also twice the amount of uniform elongation as compared to the irradiated CG sample. The fracture surface clearly exhibited this higher plasticity post-irradiation in the NC samples. The change in deformation mechanisms due to nano-structuring of the microstructure has been anticipated to be a reason for the increase in ductility in a single-phase alloy has been explained thereafter.

Grain rotation mechanisms in nanocrystalline materials: Multiscale observations in Pt thin films.

Near-rigid-body grain rotation is commonly observed during grain growth, recrystallization, and plastic deformation in nanocrystalline materials. Despite decades of research, the dominant mechanisms underlying grain rotation remain enigmatic. We present direct evidence that grain rotation occurs through the motion of disconnections (line defects with step and dislocation character) along grain boundaries in platinum thin films. State-of-the-art in situ four-dimensional scanning transmission electron microscopy (4D-STEM) observations reveal the statistical correlation between grain rotation and grain growth or shrinkage. This correlation arises from shear-coupled grain boundary migration, which occurs through the motion of disconnections, as demonstrated by in situ high-angle annular dark-field STEM observations and the atomistic simulation-aided analysis. These findings provide quantitative insights into the structural dynamics of nanocrystalline materials.

Insights into the Illuminating World of Nanocrystalline Materials: Structure–Property Relationships in Precise Nanocrystals to Ensembles

Insights into the Illuminating World of Nanocrystalline Materials: Structure–Property Relationships in Precise Nanocrystals to Ensembles

A model of thermodynamic stabilization of nanocrystalline grain boundaries in alloy systems

Nanocrystalline (NC) materials are intrinsically unstable against grain growth. Significant research efforts have been dedicated to suppressing the grain growth by solute segregation, including the pursuit of a special NC structure that minimizes the total free energy and completely eliminates the driving force for grain growth. This fully stabilized state has been predicted theoretically and by simulations but is yet to be confirmed experimentally. To better understand the nature of the full stabilization, we propose a simple two-dimensional model capturing the coupled processes of grain boundary (GB) migration and solute diffusion. Kinetic Monte Carlo simulations based on this model reproduce the fully stabilized polycrystalline state and link it to the condition of zero GB free energy. The simulations demonstrate the emergence of a fully stabilized state by the divergence of capillary wave amplitudes on planar GBs and by fragmentation of a large grain into a stable ensemble of smaller grains. The role of solute diffusion in the full stabilization is examined. Possible extensions of the model are discussed.

Investigation of microstructural and thermal stability of Ni-Y-Zr ternary nanocrystalline alloy

This investigation focused on the thermal stability of nanocrystalline (NC) binary and ternary Ni-Y-Zr alloys synthesized through ball-milling. The microstructural changes following annealing, conducted up to 1200 °C, were studied using various techniques, including X-ray-line-broadening, micro-hardness, and transmission electron microscopy. The results revealed that the rate of grain growth observed in the Ni-Y-Zr ternary alloy at 600 °C resembled that in pure NC-Ni at 100 °C. Moreover, the Ni-1.4Y-1.1Zr ternary system exhibited a maximum hardness of 753 HV (average) at 600 °C, which was approximately 60 HV higher than the Ni-1.2Y/1.9Y and Ni-1.5Zr/2.7Zr binary alloys and more than double that of pure NC-Ni for similar grain sizes. These characteristics were linked to the formation of nano-sized oxides and nitrides of Y and Zr within the microstructure. In summary, this study emphasizes the notable high-temperature microstructure stability of Ni-based ternary alloys, attributed to the additive effects of Y and Zr. Due to this extended stability, this ternary system could find potential applications at elevated temperatures in areas such as jet engine turbine blades and power plants.

Hydrogen permeation in iron-chromium-aluminum (FeCrAl) alloys and the effects of microstructure and surface oxide

Iron–chromium–aluminum (FeCrAl) class alloys are candidates for use as cladding for accident-tolerant fuels and moderators. In this context, hydrogen isotope permeation in FeCrAl alloys is an important material property. In the present work, the apparent permeability, effective diffusivity, and apparent solubility of hydrogen in the FeCrAl alloys C26M and Kanthal D (KD) were measured with gas-driven hydrogen permeation. Permeation measurements were conducted at temperatures of 400 to 700 °C and at gas-driven pressures from 1 to 100 kPa. In particular, the effect of grain size on hydrogen transport was studied with KD samples with three different microstructures: nanocrystalline (NC), ultra-fine grained (UFG), and coarse-grained (CG). The UFG and NC specimens had higher apparent activation energies (73.4 kJ mol-1 and 65.2 kJ mol-l, respectively) for hydrogen permeability than the CG sample (46.9 kJ mol-1). An aluminum oxide layer formed on the primary- and secondary-side surfaces of all samples subjected to permeation experiments which demonstrated the propensity of FeCrAl alloys to form these innate oxide permeation barriers.

Real-Space Tilting Method for Atomic Resolution STEM Imaging of Nanocrystalline Materials.

Atomic-resolution scanning transmission electron microscopy (STEM) characterization requires precise tilting of the specimen to a high symmetric zone axis, which is usually processed in reciprocal space by following the diffraction patterns. However, for small-sized nanocrystalline materials, their diffraction patterns are often too faint to guide the tilting process. Here, a simple and effective tilting method is developed based on the diffraction contrast change of the shadow image in the Ronchigram. The misorientation angle of the specimen can be calculated and tilted to the zone axis based on the position of the shadow image with lowest intensity. This method requires no prior knowledge of the sample and the maximum misorientation angle that can be corrected is >±6.9° with sub-mrad accuracy. It operates in real space, without recording the diffraction patterns of the specimens, making it particularly effective for nanocrystalline materials. Combined with the scripting to control the microscope, the sample can be automatically tilted to the zone axis under low dose conditions (<0.17 e-Å- 2s-1), facilitating the imaging of beam sensitive materials such as zeolites or metal-organic frameworks. This automated tilting method can significantly contribute to the atomic-scale characterization of the nanocrystalline materials by STEM imaging.

Extraction, and characterization of CNC from waste sugarcane leaf sheath as a reinforcement of multifunctional bio-nanocomposite material: A waste to wealth approach

Nowadays we are extremely dependent on various synthetic plastic materials to maintain the massive demand, therefore, both the industries and mankind have been generating a massive amount of plastic waste which is so hazardous for the total environment due to their nonbiodegradable nature. To solve this problem by replacing the fossil-based plastic materials with ecofriendly biopolymers in this current study we will be described a novel method for producing Crystalline Nano Cellulose (CNC) from the waste sugarcane leaf sheaths (SLSF) fibers as a green reinforcing agent. The waste-to-wealth approach aims to elevate agricultural residues, particularly SLSF, by transforming them into high-quality CNCs for use in a variety of sectors. SLSF was initially washed with detergent to remove impurities, followed by alkali treatment and bleaching operation before CNC manufacture using acid hydrolysis (60% H2SO4). The resulting materials were characterized using Fourier transform infrared (FTIR) spectroscopy, Scanning electron microscopy (SEM), X-ray diffraction (XRD), Thermogravimetric analysis (TGA), Differential thermogravimetry (DTG), and Differential thermal analysis (DTA). FTIR indicates the newly produced CNCs is very much rich with active sites like –OH, -NH, -COOH, -C-O-C-, etc., while SEM revealed the raw fiber surface was rough, whereas the surface of CNCs became smooth even after the removal of lignin, fatty, and waxy compounds. Overall, acid hydrolysis was shown to increase the crystallinity of bleached SLSF while reducing cellulose dimensions to the nanoscale. After analysis it was revealed that most CNC particle size was around 100 nm. The outstanding properties of CNCs, including as high strength, biodegradability, and low environmental impact, make them ideal candidates for reinforcing composites, improving medicine delivery systems, and aiding new electronics. Ongoing research and technology advancements in integrating CNCs into many applications have the potential to alter industries looking for sustainable and high-performance materials.

Clustering characteristic diffraction vectors in 4-D STEM data sets from overlapping structures in nanocrystalline and amorphous materials

We describe a method for identifying and clustering diffraction vectors in four-dimensional (4-D) scanning transmission electron microscopy data to determine characteristic diffraction patterns from overlapping structures in projection. First, the data is convolved with a 4-D kernel, then diffraction vectors are identified and clustered using both density-based clustering and a metric that emphasizes rotational symmetries. The method works well for both crystalline and amorphous samples and in high- and low-dose experiments. A simulated dataset of overlapping aluminum nanocrystals provides performance metrics as a function of Poisson noise and the number of overlapping structures. Experimental data from an aluminum nanocrystal sample shows similar performance. For an amorphous Pd77.5Cu6Si16.5 thin film, experiments measuring glassy structure show strong evidence of 4- and 6-fold symmetry structures. A significant background arises from the diffraction of overlapping structures. Quantifying this background helps to separate contributions from single, rotationally symmetric structures vs. apparent symmetries arising from overlapping structures in projection.

Enhancing heat transfer performance in forced convective systems using experimental study with crystalline nano cellulose-dispersed H2O/C2H6O2 nanofluids

This work examines the heat transfer properties of a forced convection circular tube heat exchange system employing a nanofluid made of crystalline nano cellulose (CNC) diluted in a 60:40 ratio of distilled water (H2O) and ethylene glycol (C2H6O2). The objective is to measure the generated nano-fluid's thermal characteristics and analyze its potential for usage as a cooling agent in thermal systems, with a focus on encouraging the use of this biodegradable green coolant. A single pipe forced convection system was used for the experimental experiments, which were focused on a temperature range of 30 °C to 100 °C and nanoparticle volume concentrations of 0.1% to 0.9%. The investigation looks at the density, heat conductivity, and viscosity of the nanofluid, among other important thermo-physical characteristics. The findings show that the coolant's density exhibits an inverse relationship with temperature, increasing as nanoparticle dispersion occurs. At a concentration of 0.9% and room temperature, the dynamic viscosity was 0.0096 kg m−1.sec. A 0.9% concentration of nanoparticle dispersion resulted in a significant increase in thermal conductivity of 27.8%. The effectiveness of the nanofluid is demonstrated by the measurement of pressure drop and convective heat transfer coefficients across the flow channel. The maximum convective heat transfer coefficient of 262.2 W m−2K−1 was recorded at a discharge rate of 17.5LPM and a concentration of 0.9% of nanoparticles. A temperature of 70 °C was found to yield the best heat transfer coefficient and the least amount of pressure loss when the nanoparticle volume percentage was 0.65%.

Synthesis of nanoscale spinel aluminates powder and studies of their optical and structural properties

In this research, Manganese aluminate (MA), Nickel aluminate (NA), and Zinc aluminate (ZA) nanocrystallites were synthesized using the combustion method at a temperature of 1173 K. This technique was selected for its effectiveness in producing nanocrystalline materials with high purity and precise compositional control. The synthesized nanocrystallites underwent extensive characterization to understand their structural and optical properties. Techniques such as UV–visible spectrophotometry (UV–vis), Fourier-transform infrared spectroscopy (FT-IR), and x-ray diffraction (XRD) were utilized to examine the impact of different cations (Mn2+, Ni2+, Zn2+) on the optical bandgap, binding energy, and crystallographic parameters of the materials. The optical bandgap values (Eg), determined using Tauc’s formula, were 4.121 eV for manganese aluminate, 3.819 eV for nickel aluminate, and 3.771 eV for zinc aluminate. FT-IR spectroscopy identified fundamental absorption peaks within the range of 450 to 750 cm−1, confirming the formation of aluminate spinel structures. XRD analysis confirmed the presence of a cubic spinel-type structure in all three prepared samples. The results revealed that the average crystallite sizes ranged from 23.890 nm to 45.100 nm, cell volumes varied between 521.47 Å3 and 548.68 Å3, lattice constants spanned from 8.258 Å to 8.049 Å, and inter-planar spacing ranged from 2.4268 nm to 2.4532 nm. These variations were observed as the cation transitioned from nickel to manganese passing through zinc element. Additionally, Rietveld refinements were performed to further analyze and refine the crystal structures based on XRD data. This comprehensive study aimed to elucidate the relationship between the synthesis conditions and the resultant properties of the nanocrystallites, providing insights into their potential applications in fields such as optoelectronics and photocatalysis.

Retraction Note: Arsenic album 30C exhibits crystalline nano structure of arsenic trioxide and modulates innate immune markers in murine macrophage cell lines

Retraction Note: Arsenic album 30C exhibits crystalline nano structure of arsenic trioxide and modulates innate immune markers in murine macrophage cell lines

Nanocrystalline copper for direct copper-to-copper bonding with improved cross-interface formation at low thermal budget

Direct copper-to-copper (Cu-Cu) bonding is a promising technology for advanced electronic packaging. Nanocrystalline (NC) Cu receives increasing attention due to its unique ability to promote grain growth across the bonding interface. However, achieving sufficient grain growth still requires a high thermal budget. This study explores how reducing grain size and controlling impurity concentration in NC Cu leads to substantial grain growth at low temperatures. The fabricated NC Cu has a uniform nanograin size of around 50 nm and a low impurity level of 300 ppm. To prevent ungrown NC and void formation caused by impurity aggregation, we propose a double-layer (DL) structure comprising a normal coarse-grained (CG) layer underneath the NC layer. The CG layer, with a grain size of 1 μm and an impurity level of 3 ppm, acts as a sink, facilitating impurity diffusion from the NC layer to the CG layer. Thanks to sufficient grain growth throughout the entire NC layer, cross-interface Cu-Cu bonding becomes possible under a low thermal budget, either at 100 °C for 60 min or at 200 °C for only 5 min.

Effect of grain size, temperature, and tensile strain rate on mechanical response of CoCrNi medium-entropy alloys

Grain boundary (GB) strengthening of metallic materials faces limitations as grain sizes are reduced to the nanoscale, primarily due to the transition from the strengthening to the softening effects. Understanding the intrinsic mechanisms behind such pronounced transitions is essential for optimizing the mechanical properties of nanocrystalline (NC) alloys. In this work, the critical grain size responsible for this transition is determined for NC CoCrNi medium-entropy alloys using molecular dynamics simulation, and the underlying mechanisms concerning varying temperatures and strain rates are systematically investigated for the samples with the critical grain size. The transition from Hall-Petch (HP) strengthening to Inverse Hall-Petch (IHP) softening is established by decreasing the average grain sizes from 21 nm to 3 nm. The critical grain size for the current alloys is estimated to be 12 nm, and the underlying deformation mechanisms are illustrated as follows: In the IHP regime, GB-mediated deformation becomes dominant, leading to softening. Conversely, in the HP regime, dislocation slip dominates the deformation mode, contributing to strengthening. It is found that an increase in temperature from 77 K to 1100 K leads to a decrease in the average flow stress and Young's modulus. Meanwhile, the deformation mechanisms change from dislocation slip (77K–700K) to GB-mediated deformation (700 K–1100 K). Furthermore, the underlying mechanisms correlating to the critical strain rate are uncovered. It can be attributed to the shift in deformation mechanisms from dislocation slip at relatively low strain rate regimes (5 × 107 s−1-2 × 109 s−1) to dislocation drag at relatively high strain rate regimes (2 × 109 s−1-5 × 109 s−1). Our atomistic insights into the tensile response of NC CoCrNi may provide a crucial basis for designing superior properties to meet the growing demands of advanced engineering fields.

Synthesis of Highly Oriented Nanocrystal Thin-Films and Their Applications to Electrochemical Devices

The precisely defined particle assembly at the nanoscale with simultaneously scalable patterning at the microscale is indispensable for enabling functionality and improving the performance of devices. While synthetic advances in the past decades now allow precise control of their size, shape, and composition, they must be processed from dispersion into functional films for many applications, which presents additional challenges. In this work, we introduce the self-assembly of inorganic nanoubes (Co3O4 NCs) and we also describe the fabrication of centimeter-scale NC superlattice thin-films on silicone substrate with anisotropic NC building blocks, thin-film patterning, and the supercrystal formation of superlattice structures. As a result, the Raman spectra of Co3O4 NC thin-films clearly exhibits the distinct feature of vibration modes of Co3O4 and synchrotron-based X-ray diffraction techniques showed the Co3O4 NCs order into [100] aligned arrays. Also, the uniformly prepared Co3O4 NC building blocks and thin-films were examined by field-emission scanning electron microscopy analysis and it shows well-defined nanostructures with ~13nm-side of NCs and ~3nm space between self-assembled NCs. To investigate the distinct feature of functional films, we prepared various type of device structures (memory, electrode, gas sensor) and examined the performances. In case of memristor, the device exhibits excellent bipolar resistance switching characteristics with better reliability and stability over various polycrystalline metal oxide nanostructures. Utilizing our approach enables the creation of miniaturized devices, followed by the transfer of NC thin-films onto TEM grids. Subsequent in-situ TEM analysis offers the potential to observe unique phenomena at the nano-scale, unveiling phase transitions in nanocrystalline materials or electrochemical reaction mechanisms previously unexplored by researchers.

Water dynamics in calcium silicate hydrates probed by inelastic neutron scattering and molecular dynamics simulations

Calcium-silicate-hydrate (C-S-H) is a disordered, nanocrystalline material, acting as a primary binding phase in Portland cement. C-S-H and C-A-S-H (an Al-bearing substitute present in low-CO2 cement) contain thin films of water on solid surfaces and inside nanopores. Water controls multiple chemical and mechanical properties of C-S-H, including drying shrinkage, ion transport, creep, and thermal behavior. Therefore, obtaining a fundamental understanding of its properties is essential. We applied a combination of inelastic incoherent neutron scattering and molecular dynamics simulations to unravel water dynamics in synthetic C-(A)-S-H conditioned at five hydration states (from drier to more hydrated) and with three Ca/Si ratios (0.9, 1, and 1.3). Our results converge towards a picture where the evolution from thin layers of interfacial water to bulk-like capillary water is dampened by the structure of C-(A)-S-H. In particular, the hydrophilic Ca2+ sites organize the distribution of interfacial C-(A)-S-H water.