Bulk Material Properties Research Articles

Structural, mechanical, optoelectronic and thermodynamic properties of bulk and film materials in Ti–Nb–C system: First-principles and experimental investigations

Both first-principles study of the random TiC–NbC solid solutions and experimental investigation of the films in Ti–Nb–C system were carried out. The mixing energy, electronic and phonon structures, elastic constants and moduli, hardness, Debye temperature, fracture toughness, dielectric function, electron energy-loss spectra and heat capacity of the random Ti1-xNbxC solid solutions were calculated and analyzed depending on composition. The Ti–C, Nb–C and Ti–Nb–C films were deposited by magnetron sputtering. The deposited films were comprehensively studied with XRD, XPS, AFM, EDS, Raman spectroscopy, indentation and tribological tests. The Ti–Nb–C films with equi-atomic composition are found to exhibit the highest Knoop hardness and lowest friction coefficient as compared to those of the parent TiC and NbC carbides. The results obtained were used to establish the mechanism of the stabilization of the TiC–NbC solid solutions, and to predict their structural, mechanical, optical and thermodynamic properties.

Relating the kinetics of grain-boundary complexion transitions and abnormal grain growth: A Monte Carlo time-temperature-transformation approach

Grain boundaries undergo thermally-activated, first-order transitions that result in discontinuous changes of interfacial properties. Importantly, grain boundary transitions lead to changes in bulk material properties (e.g., embrittlement) and/or behavior (e.g., abnormal grain growth). Numerous studies have been completed on the equilibrium states of grain boundaries and their transitions (i.e., complexion transitions), but there have been far fewer investigations of complexion transition kinetics; complexion transitions occur on the atomic-scale and are therefore challenging to detect experimentally. In this work, a 3D Potts grain growth model with stochastic complexion transitions was employed to investigate complexion transition kinetics. A Johnson-Mehl-Avrami-Kolmogorov (i.e., JMAK) approach was used to extract nucleation and growth rates (i.e., transformation rates), while point process analyses and correlation functions were used to infer complex interrelated nucleation and growth events. Time-temperature-transformation (TTT) diagrams, in particular grain-boundary complexion, transformed grain, and abnormal grain TTT diagrams, were constructed to summarize the progress of complexion-related transformations. Such diagrams relate complexion-induced grain growth to the underlying complexion transitions and, in the case of abnormal grain growth (AGG), permit one to assess the role of AGG as a temperature-dependent, time-displaced indicator of complexion transitions. Overall, this work details a theoretical framework that can be used to better understand complexion transition kinetics as well as to develop tools for the design of bulk microstructures.

Surface modification of recycled polymers in comparison to virgin polymers using Ar/O2 plasma etching

AbstractLow‐pressure plasma etching of a recycled polyethylene terephthalate (PET) film is studied in comparison to virgin PET and polypropylene (PP) using a capacitively coupled radio frequency (RF) plasma reactor. Recycled polymers are distinguished by increased impurity content and weakened mechanical properties, both affecting plasma etching and adhesion processes. Mild plasma conditions have been selected to maintain the material bulk properties of the polymers. The etch rates and the morphology of the polymer samples were thus determined at floating potential compared with etching at the RF electrode for varying argon/oxygen gas mixtures, etching duration, and sample size. Thermoanalytical and X‐ray techniques were used to characterize the polymer before and after the plasma etching treatment. Finally, adhesive‐tape peel tests proved that excellent adhesion of silver coatings can also be achieved on a plasma‐treated recycled PET film.

Investigating the relationship of hardness and flow stress in metal forming

Hardness is routinely utilised to link the bulk material properties to surface contact mechanics. Besides possible differences in the material properties between bulk and surface, there is no established relation between hardness and the thermo-viscoplastic flow stress of materials used in the context of metal forming processes. The purpose of this study is to investigate such relationship using 6061 and 6016 aluminium alloys manufactured by hot rolling. Optical microscopy and Vickers hardness tests at different loads and temperatures ranging from 22°C up to 450°C were carried out. A time-dependent Finite Element model of an indentation using thermo-viscoplastic material model based on bulk samples was developed and compared with experiments. Overall, no significant difference between bulk and surface for neither alloy was experimentally identified. The hardness decrease with temperature of the alloys is quantified and ready-to-use constraint factor maps associating the thermo-viscoplastic flow stress with hardness of the materials are presented. The numerical model allowed visualisation of viscoplastic effects, whereas comparisons to the experiments in terms of hardness and topography validated the model and constitutive equations. Constitutive equations derived from compression tests of bulk samples can confidently describe deformation at the surface level and so, be used to develop a contact model in the tribological context of metal forming.

Binder-jetting of TiCN-based cermets

ABSTRACT Additive Manufacturing is experiencing an upswing in many sectors of industry for a broad variety of materials. Processes are mainly developed for polymers and metals. For ceramics, hardmetals and especially cermets there are only a few additive processes suitable. The powder-based technique Binder-Jetting is one of these suitable processes with high productivity and relatively low green density. Within this study, TiCN-based cermets are printed by Binder-Jetting for the first time. The complexity of influences of the morphology and composition of cermet powders are discussed in regard to bulk density and material properties of printed and sintered parts. Studied TiCN-based cermet compositions represent different Ni and Mo2C contents. Main points of this investigation are further the adjustment of ratio of the raw materials for good sintering behaviour and their influence on the microstructures and as a function of varied sintering temperatures.

Numerical modelling of the growth of polygonal fault systems

Despite over three-decades of active research and wide debate in the published literature, the mechanisms that govern the growth of polygonal faults are poorly understood. Here we investigate the growth of polygonal faults using a suite of geomechanical finite element forward models that couple dynamic fault propagation, sedimentation, and the mechanical compaction of unconsolidated granular sediment. We undertook a suite of numerical model simulations to explore the relationships between varying fault plane dip, residual friction of the fault, and the bulk material properties of the sedimentary sequence hosting the polygonal fault system. We find that the growth of polygonal faults within laterally-pinned sedimentary tiers can be explained by gravity-driven differential compaction and does not require additional causative elements to explain the gross pattern of strain accumulation. We also find that the magnitude of fault throw is influenced by the material properties and the original fault plane dip, but is most sensitive to the residual friction angle. Our models yield values for maximum throw versus height for the faults that fall within the range of global values compiled for polygonal faults, and throw rates are comparable to those recently measured in naturally occurring polygonal faults.

Flow properties of powdery or granular filling substances of dangerous goods packagings—Comparison of the measurement of the angle of repose and the determination of the Hausner ratio

To ensure safety when transporting dangerous goods, it is important to specify the flow properties of the respective solid filling substance of the packagings. For this purpose, the angle of repose is currently used for the UN approvals in Germany. Measurements were carried out on 12 powdery or granular substances applying the angle of repose measuring methods customary in the test centres. The results of the methods differ significantly from each other. In addition, some of the techniques cannot be applied for very cohesive or coarse‐grained materials. The results for the angle of repose show a strong scatter for some constellations (coefficient of variation more than 20%). Safety during transport of dangerous goods cannot be guaranteed with this currently practised system of measuring the angle of repose. As a consequence, an alternative parameter to characterize the flow properties of bulk materials should be used in the recognized test centers for dangerous goods packagings, such as the Hausner ratio. This approach leads to more precise test results for the substances examined (maximum coefficient of variation 2.8%). It also has advantages in terms of applicability and occupational safety. Since the flow properties are safety‐relevant, both in terms of mechanical safety and safety against the release of dangerous substances, the testing practice in the recognized test labs should be improved and standardized.

Invisible assassin coated on dental appliances for on-demand capturing and killing of cariogenic bacteria

The accumulation of microbes on long-wear artificial dental materials creates a great risk for oral diseases and causes deterioration of material properties. Therefore, smart antibacterial materials capable of resisting the colonization of microorganisms and simultaneously eliminating pathogenic bacteria as needed show outstanding superiority for the recovery of dental health, which are scarcely reported until now. Here, we present a responsive hydrogel coating as invisible assassin on clear overlay appliances target for dental caries. Taking advantage of pH-responsive carboxybetaine methacrylate-dimethylaminoethyl methacrylate copolymer P(CBMA-co-DMAEMA) and antibacterial peptides, the surface potential of hydrogel shifts positively, accompanied with the release of antibacterial peptides when pH gets lower. The hybrid hydrogel layer hence exerts antifouling property and resists bacterial adhesion in normal physiological, while captures and kills cariogenic bacteria in acidic condition. This biocompatible, transparent and stable hydrogel coating has little influence for the aesthetics and mechanical properties of bulk materials. The strategy developed here can provide reference for the design of biomedical devices in other areas.

Traps and transport resistance are the next frontiers for stable non-fullerene acceptor solar cells

Stability is one of the most important challenges facing material research for organic solar cells (OSC) on their path to further commercialization. In the high-performance material system PM6:Y6 studied here, we investigate degradation mechanisms of inverted photovoltaic devices. We have identified two distinct degradation pathways: one requires the presence of both illumination and oxygen and features a short-circuit current reduction, the other one is induced thermally and marked by severe losses of open-circuit voltage and fill factor. We focus our investigation on the thermally accelerated degradation. Our findings show that bulk material properties and interfaces remain remarkably stable, however, aging-induced defect state formation in the active layer remains the primary cause of thermal degradation. The increased trap density leads to higher non-radiative recombination, which limits the open-circuit voltage and lowers the charge carrier mobility in the photoactive layer. Furthermore, we find the trap-induced transport resistance to be the major reason for the drop in fill factor. Our results suggest that device lifetimes could be significantly increased by marginally suppressing trap formation, leading to a bright future for OSC.

The ω3 scaling of the vibrational density of states in quasi-2D nanoconfined solids

The vibrational properties of crystalline bulk materials are well described by Debye theory, which successfully predicts the quadratic ω2 low-frequency scaling of the vibrational density of states. However, the analogous framework for nanoconfined materials with fewer degrees of freedom has been far less well explored. Using inelastic neutron scattering, we characterize the vibrational density of states of amorphous ice confined inside graphene oxide membranes and we observe a crossover from the Debye ω2 scaling to an anomalous ω3 behaviour upon reducing the confinement size L. Additionally, using molecular dynamics simulations, we confirm the experimental findings and prove that such a scaling appears in both crystalline and amorphous solids under slab-confinement. We theoretically demonstrate that this low-frequency ω3 law results from the geometric constraints on the momentum phase space induced by confinement along one spatial direction. Finally, we predict that the Debye scaling reappears at a characteristic frequency ω× = vL/2π, with v the speed of sound of the material, and we confirm this quantitative estimate with simulations.

Programmable gear-based mechanical metamaterials

Elastic properties of classical bulk materials can hardly be changed or adjusted in operando, while such tunable elasticity is highly desired for robots and smart machinery. Although possible in reconfigurable metamaterials, continuous tunability in existing designs is plagued by issues such as structural instability, weak robustness, plastic failure and slow response. Here we report a metamaterial design paradigm using gears with encoded stiffness gradients as the constituent elements and organizing gear clusters for versatile functionalities. The design enables continuously tunable elastic properties while preserving stability and robust manoeuvrability, even under a heavy load. Such gear-based metamaterials enable excellent properties such as continuous modulation of Young’s modulus by two orders of magnitude, shape morphing between ultrasoft and solid states, and fast response. This allows for metamaterial customization and brings fully programmable materials and adaptive robots within reach.

Tight-binding band structure of β- and α-phase Ga2O3 and Al2O3

Rapid design and development of the emergent ultrawide-bandgap semiconductors Ga2O3 and Al2O3 require a compact model of their electronic structures, accurate over the broad energy range accessed in future high-field, high-frequency, and high-temperature electronics and visible and ultraviolet photonics. A minimal tight-binding model is developed to reproduce the first-principles electronic structures of the β- and α-phases of Ga2O3 and Al2O3 throughout their reciprocal spaces. Application of this model to α-Ga2O3/α-Al2O3 superlattices reveals that intersubband transitions can be engineered to the 1.55μm telecommunications wavelength, opening new directions in oxide photonics. Furthermore, by accurately reproducing the bandgap, orbital character, effective mass, and high-energy features of the conduction band, this compact model will assist in the investigation and design of the electrical and optical properties of bulk materials, devices, and quantum confined heterostructures.

Temperature and Electron concentration dependent Thermoelectric Power in Wide Band Gap semiconductor GaN Nanowire

Abstract: Nanostructures have a significant promise as potential building blocks for the next generation thermoelectric devices. While the thermal transport properties of bulk materials have been intensely studied, the understanding of nanostructure thermoelectric properties and their interrelation is still incomplete. In the calculated temperature range, the thermoelectric power (TEP) was found to be linearly dependent on temperature, suggesting the degenerate nature of the GaN semiconductor nanowire similar to that of ZnO semiconductor nanowire. Observed negative values of TEP indicating that, majority charge carriers are electrons in GaN semiconductor. Linear dependence of TEP with temperature shows that TEP is only due to electron diffusion and not due to phonon-drag effect. Also observed the calculated TEP values are in good agreement with the experimental results in the overall temperature range 10 – 300 K. Keywords: Semiconductor nanowire, GaN, Mott relation, Thermoelectric power, wide band gap semiconductor

Comparison of Geometric Properties of Regular and Irregular Mineral Grains by Dynamic Image Analysis (2D) and Optoelectronic Analysis (3D) Methods

The properties of bulk materials are influenced by geometrical features of grains such as size, size distribution and shape. However, size is an ambiguous parameter for non-spherical particles. Therefore, the influence of the shape of a particle on its size, as described by various measuring methods and estimators using the main particle dimensions, was studied here. Granulometric analyses of mineral raw material samples containing regular and irregular grains were performed as part of the research. The measurements were made using two methods: the dynamic image analysis and the optoelectronic analysis. The main dimensions of the particles in 2D and 3D space were measured. Particle shape descriptors were determined based on the measurements: circularity and sphericity. Particle size distributions were also determined as a function of the minimum and maximum Feret diameters (for the 2D method) and the shortest and longest dimensions of particles recorded by the 3D method. The distribution of grain shapes according to Zingg classification was used for the 3D method. The results of the study were discussed in the context of comparing both of the measuring methods and selecting the most appropriate one to assess particle (ir)regularity.

Dynamic fracture behavior of hygrothermally degraded carbon epoxy composites

Composite structures used in aerospace, automotive, and military applications are often subjected to aggressive marine or water environments during their service life that can cause material degradation over time. Many composites absorb moisture when exposed to wet environments which may affect their microstructure, consequently influencing their bulk material properties and performance. Additionally, certain applications may require them to be subjected to seawater environments where the addition of saline can further degrade the material over time. This experimental investigation examines the effects of moisture absorption and saline on the dynamic fracture behavior of unidirectional carbon epoxy composites. To accelerate mass absorption, samples were soaked in elevated temperature baths (70°C) of either ASTM standard seawater or distilled water. To explore the role of absorption duration on the dynamic fracture behavior, soaking time varied between 3.5 hours and longer than 4 months. Pre-cracked specimens were impacted using a long-bar striker device at 4 m/s, to instigate a dominantly Mode-I (opening) fracture response. Digital image correlation was used in conjunction with ultra-high-speed imaging to track the crack tip surface displacements and an elastodynamic solution for an orthotropic material leveraged to extract the stress intensity factor (SIF) up to and at initiation. The critical SIF of the soaked samples is compared with results from a group of ambient condition, unsoaked samples. Results suggest that moisture absorption causes the matrix to expand and introduce microcracks or delamination between plies as the composite swells to accommodate the additional water, inversely affecting the material resistance to fracture.

Complex Material Properties of Gel-Amin: A Transparent and Ionically Conductive Hydrogel for Neural Tissue Engineering

The field of tissue engineering has benefited greatly from the broad development of natural and synthetic polymers. Extensive work in neural engineering has demonstrated the value of conductive materials to improve spontaneous neuron activity as well as lowering the necessary field parameters for exogenous electrical stimulation. Further, cell fate is directly coupled to the mechanical properties of the cell culture substrate. Increasing the conductivity of hydrogel materials often necessitates the addition of dopant materials that facilitate electron mobility. However, very little electron transfer is observed in native cell signaling and most of these materials are opaque, severely limiting microscopy applications commonly employed to assess cell culture morphology and function. To overcome these shortcomings, the inclusion of an ionic liquid, choline acrylate, into the backbone of a modified collagen polymer increases the bulk conductivity 5-fold at a 1:1 ratio while maintaining optical transmission of visible light. Here, we explore how the inclusion of choline acrylate influences bulk material properties including the mechanical, swelling, and optical properties of our hydrogels, referred to as Gel-Amin hydrogels, as a material for tissue culture. Despite an increase in swelling over traditional GelMA materials, the conductive hydrogels support whole dorsal root ganglia encapsulation and outgrowth. Our results indicate that our Gel-Amin system holds potential for neural engineering applications and lowering the required charge injection for the application of exogenous electrical stimulation. This is this first time an ionic liquid-hydrogel system has been used to culture and support primary neurons in vitro.

Insights on Shear Transfer Efficiency in "Brick-and-Mortar" Composites Made of 2D Carbon Nanoparticles.

Achieving high mechanical performances in nanocomposites reinforced with lamellar fillers has been a great challenge in the last decade. Many efforts have been made to fabricate synthetic materials whose properties resemble those of the reinforcement. To achieve this, special architectures have been considered mimicking existing materials, such as nacre. However, achieving the desired performances is challenging since the mechanical response of the material is influenced by many factors, such as the filler content, the matrix molecular mobility and the compatibility between the two phases. Most importantly, the properties of a macroscopic bulk material strongly depend on the interaction at atomic levels and on their synergetic effect. In particular, the formation of highly-ordered brick-and-mortar structures depends on the interaction forces between the two phases. Consequently, poor mechanical performances of the material are associated with interface issues and low stress transfer from the matrix to the nanoparticles. Therefore, improvement of the interface at the chemical level enhances the mechanical response of the material. The purpose of this review is to give insight into the stress transfer mechanism in high filler content composites reinforced with 2D carbon nanoparticles and to describe the parameters that influence the efficiency of stress transfer and the strategies to improve it.

Probing the role of grain boundaries in single Cu nanoparticle oxidation by in situ plasmonic scattering

Grain boundaries determine physical properties of bulk materials including ductility, diffusivity, and electrical conductivity. However, the role of grain boundaries in nanostructures and nanoparticles is much less understood, despite the wide application of nanoparticles in nanophotonics, nanoelectronics, and heterogeneous catalysis. Here, we investigate the role of high-angle grain boundaries in the oxidation of Cu nanoparticles, using a combination of in situ single particle plasmonic nanoimaging and $postmortem$ transmission electron microscopy image analysis, together with ab initio and classical electromagnetic calculations. We find an initial growth of a 5-nm-thick ${\mathrm{Cu}}_{2}\mathrm{O}$ shell on all nanoparticles, irrespective of different grain morphologies. This insensitivity of the ${\mathrm{Cu}}_{2}\mathrm{O}$ shell on the grain morphology is rationalized by extraction of Cu atoms from the metal lattice being the rate limiting step, as proposed by density functional theory calculations. Furthermore, we find that the change in optical scattering intensity measured from the individual particles can be deconvoluted into one contribution from the oxide layer growth and one contribution that is directly proportional to the grain boundary density. The latter contribution signals accumulation of Cu vacancies at the grain boundaries, which, as corroborated by calculations of the optical scattering, leads to increased absorption losses and thus a decrease of the scattering, thereby manifesting the role of grain boundaries as vacancy sinks and nuclei for Kirkendall void formation at a later stage of the oxidation process.

Grain size analysis in permanent magnets from Kerr microscopy images using machine learning techniques

Understanding the relationships between composition, structure, processing and properties helps in the development of improved materials for known applications as well as for new applications. Materials scientists, chemists and physicists have researched these relationships for many years, until the recent past, by characterizing the bulk properties of functional materials and describing them with theoretical models. Magnets are widly used in electric vehicles (EV), hybrid electric vehicles (HEV), data storage, power generation and transmission, sensors etc. The search for novel magnetic phases requires an efficient quantitative microstructure analysis of microstructural information like phases, grain distribution and micromagnetic structural information like domain patterns, and correlating the information with intrinsic magnetic parameters of magnet samples. The information out of micromagnetic domains helps in obtaining the optimized microstructures in magnets that have good intrinsic magnetic properties. This paper is aimed at introducing the use of a traditional machine learning (ML) model with a higher dimensional feature set and a deep learning (DL) model to classify various regions in sintered NdFeB magnets based on Kerr-microscopy images. The obtained results are compared against reference data, which is generated manually by subject experts. Additionally, the results were compared against the approach for grain analysis, which is based on the electron backscatter diffraction (EBSD) technique. Further, the challenges faced by the traditional machine learning model for classifying microstructures in Kerr micrographs are discussed.

Predicting Young's Modulus of Linear Polyurethane and Polyurethane-Polyurea Elastomers: Bridging Length Scales with Physicochemical Modeling and Machine Learning.

Predicting the properties of complex polymeric materials based on monomer chemistry requires modeling physical interactions that bridge molecular, interchain, microstructure, and bulk length scales. For polyurethanes, a polymer class with global commercial and industrial significance, these multiscale challenges are intrinsic due to the thermodynamic incompatibility of the urethane and polyol-rich domains, resulting in heterogeneities from molecular to microstructural length scales. Machine learning can model patterns in data to establish a relationship between the monomer chemistry and bulk material properties, but this is made difficult by small data sets and a diverse set of monomers. Using a data set of 63 industrially relevant and complex elastomers, we demonstrate that accurate machine learning predictions are possible when monomer chemistry is used to estimate interactions at interchain length scales. Here, these features were used to accurately (r2 = 0.91) predict the Young's modulus of polyurethane and polyurethane-urea elastomers. Furthermore, by a query of the trained model for compositions that yield a target modulus within the range of accessible values, the capabilities of using this methodology as a design tool are demonstrated. The presented methodology could become increasingly useful in building models for materials with small data sets and may guide the interpretation of the underlying physicochemical forces.