Bulk Material Response Research Articles

Variable Mechanical Properties in Layered Copper Bromide Hybrid Solids Based on Configuration of Organic Cations.

Organic-inorganic organohalide hybrid solids have garnered significant attention due to their unique structural diversity, desirable electronic structures, and excellent optoelectronic properties. Here, we investigate the mechanical properties of a homologous series of 2D copper bromide hybrids (A2CuBr4, ACuBr4) through nanoindentation to analyze the contribution of organic interlayer interactions to bulk mechanical response. We identify a direct correlation between the identity of the organic spacer and the bulk mechanical response, where stronger bonding interactions in the organic interlayer resulted in increased hardness and elasticity. Additionally, we uncover a unique conformational dependence within the series of arylammonium spacers which was found to periodically modulate pi-pi interactions between neighboring molecules, leading to an alternating even-odd bulk material response.

Systematic Calibration and Validation Approach for Discrete Element Method (DEM) Modeling of Corn Under Varying Moisture Contents (MC)

Abstract. Discrete Element Method (DEM) based simulation of grain threshing and conveyance processing at relatively dry to wet grain moisture content range has been limited. A comprehensive five-step framework of a DEM grain model calibration and validation of flow and grain impacts on equipment was investigated. The framework was examined by developing DEM models for corn grain moisture conditions sampled during crop harvesting, and simulated hopper discharge corn flow, and corn impact forces on a grain paddle elevator of a crop harvesting machine. Five bulk material response parameters were obtained from two calibration experiments of the angle of repose and direct shear test at the MC levels of 11%, 16%, and 26%. Latin hypercube sampling statistical design of experiment points, Gaussian Process Regression surrogate model, and optimization algorithms were successfully implemented to generate Hertz-Mindlin (HM) with Johnson-Kendall-Roberts (JKR) cohesive model of corn at three moisture content levels. The DEM simulation results predict the corn mass flow rate of hopper discharge with relative errors of -5%, -4%, and 1% for corn at 11%, 16%, and 26% MC levels, respectively. The DEM also predicts corn impact forces on a paddle elevator with a relative error of less than 11%. The established DEM calibration methodology, used for simulation of crop threshing, and harvested grain handling processes at extreme grain moisture content, can accelerate the simulation-based design of crop harvesting equipment. Keywords: Calibration, Corn, Discrete Element Method, Moisture Content, Sensitivity analysis, Validation.

Effect of Fractal Topology on the Resistivity Response of Thin Film Sensors.

We discuss the effect of topological inhomogeneity of very thin metallic conductometric sensors on their response to external stimuli, such as pressure, intercalation, or gas absorption, that modify the material's bulk conductivity. The classical percolation model was extended to the case in which several independent scattering mechanisms contribute to resistivity. The magnitude of each scattering term was predicted to grow with the total resistivity and diverge at the percolation threshold. We tested the model experimentally using thin films of hydrogenated palladium and CoPd alloys where absorbed hydrogen atoms occupying the interstitial lattice sites enhance the electron scattering. The hydrogen scattering resistivity was found to grow linearly with the total resistivity in the fractal topology range in agreement with the model. Enhancement of the absolute magnitude of the resistivity response in the fractal range thin film sensors can be particularly useful when the respective bulk material response is too small for reliable detection.

Finite-size and quantum effects in plasmonics: manifestations and theoretical modelling [Invited

The tremendous growth of the field of plasmonics in the past twenty years owes much to the pre-existence of solid theoretical foundations. Rather than calling for the introduction of radically new theory and computational techniques, plasmonics required, to a large extent, application of some of the most fundamental laws in physics, namely Maxwell’s equations, albeit adjusted to the nanoscale. The success of this description, which was triggered by the rapid advances in nanofabrication, makes a striking example of new effects and novel applications emerging by applying known physics to a different context. Nevertheless, the prosperous recipe of treating nanostructures within the framework of classical electrodynamics and with use of macroscopic, bulk material response functions (known as the local-response approximation, LRA) has its own limitations, and inevitably fails once the relevant length scales approach the few- to sub-nm regime, dominated by characteristic length scales such as the electron mean free path and the Fermi wavelength. Here we provide a review of the main non-classical effects that emerge when crossing the border between the macroscopic and atomistic worlds. We study the physical mechanisms involved, highlight experimental manifestations thereof and focus on the theoretical efforts developed in the quest for models that implement atomistic descriptions into otherwise classical-electrodynamic calculations for mesoscopic plasmonic nanostructures.

Mechanical behavior of 17-4 PH stainless steel processed by atomic diffusion additive manufacturing

This work explores the multiscale mechanical behavior of 17-4 PH stainless steel structures processed through the atomic diffusion additive manufacturing technique (ADAM). 17-4 PH stainless steel parts were fabricated with a Markforged Metal X 3D printer and characterized with respect to variable printing orientations for samples loaded in tension, shear, and bending. Sections of material were taken from each face of a bending test sample and prepared for microscopy to quantify porosity, grain size, and local stiffness and hardness. Microscale evaluation showed a porosity content of 3.3% on average across all faces. The yz face specifically showed the same sort of packing limitations often seen in other extrusion-based methods leading to greater porosity. An electron backscatter diffraction investigation showed a mean grain size of 6.5 μm with some grain alignment in the z-direction in the xz plane. Bulk material response in tension was dependent upon the print orientation of the sample. Cases where material was extruded entirely in the direction of loading saw a stiffness, strength, and strain to failure improvement of greater that 10% compared with other infill schemes. Shear testing revealed similar increases in strain to failure for samples with material extruded in only one direction compared with cross hatching at alternating orthogonal angles. Bend test results were similar in tension and compression regardless of orientation. For a sample printed with primary loading in the print plane (xy), the tensile modulus was 130–140 GPa, the tensile yield and ultimate strength were 600 MPa and 800 MPa, and the shear strength was 40.6 MPa on average.

A microstructure-based constitutive model of anisotropic cellulose nanopaper with aligned nanofibers

Endowed with excellent mechanical properties, cellulose nanopaper provides a promising design strategy for addressing the dilemma between the strength and toughness of engineering materials. Anisotropic nanopaper with highly aligned nanofibers can achieve high mechanical properties. In this paper, we develop a multiscale tension-shear model that correlates both the strength and toughness with the microstructure to quantitatively understand the exceptional properties of anisotropic cellulose nanopaper. By formulating a relationship between the interfacial macroscopic performance and nanoscale parameters involving the self-healing of hydrogen bonds, we establish a microstructure-based constitutive model of cellulose nanopaper to describe its nonlinear mechanical behavior. It is theoretically suggested that engineering the nanofiber size enables cellulose nanopaper to realize strengthening and toughening. Meanwhile, multiple mechanical properties of the nanopaper can be simultaneously enhanced by increasing the hydrogen bond density. A scaling relation is proposed to correlate the mechanical properties of cellulose nanopaper with the microstructure parameters. The developed model predictions agree well with the relevant experimental data. The constitutive model can also be extended to describe the mechanical response of cellulose bulk materials. This work can not only help understand the fundamental deformation mechanisms of cellulose nanopaper, but also help design high-performance nanocellulose structural materials.

Anisotropic mechanical response of layered disordered fibrous materials.

Mechanically bonded fabrics account for a significant portion of nonwoven products, and serve many niche areas of nonwoven manufacturing. Such fabrics are characterized by layers of disordered fibrous webs, but we lack an understanding of how such microstructures determine bulk material response. Here we numerically determine the linear shear response of needle-punched fabrics modeled as cross-linked sheets of two-dimensional (2D) Mikado networks. We systematically vary the intra-sheet fiber density, inter-sheet separation distance, and direction of shear, and quantify the macroscopic shear modulus alongside the degree of affinity and energy partition. For shear parallel to the sheets, the response is dominated by intrasheet fibers and follows known trends for 2D Mikado networks. By contrast, shears perpendicular to the sheets induce a softer response dominated by either intrasheet or intersheet fibers depending on a quadratic relation between sheet separation and fiber density. These basic trends are reproduced and elucidated by a simple scaling argument that we provide. We discuss the implications of our findings in the context of real nonwoven fabrics.

Giant Single-Crystal Shape Transformation with Wide Thermal Hysteresis Actuated by Synergistic Motions of Molecular Cations and Anions.

Manipulating the collective molecular movements to implement macroscopic mechanical response of bulk material is attractive and challenging. Here, an organic-inorganic hybrid single crystal is synthesized, which exhibits a giant macroscopic shape transformation with a remarkable thermal hysteretic feature. The colossal anisotropic shape change, which manifests as an abrupt elongation of ca. 9 % along the crystallographic c-axis and a concomitant contraction of ca. 9 % in a perpendicular direction, is induced by a significant reorientation of imidazolium, accompanied with a substantial configurational variation in CuBr4 2- complex anions. The synergistic motions of both the molecular cations and anions engender a remarkable large thermal hysteresis (>30 K) in the shape transformation of the single crystal, implying that this material may play a role in alternating memory media. Furthermore, due to the stable crystal lattice, a single crystal that demonstrates naked-eye detectable large shape transformation was used as a thermal actuator to spontaneously control an electric circuit by temperature variation.

Measurements of heat flow from surface defects in lithium triborate.

We present what is, to our knowledge, the first measurement of temperature distributions in a nonlinear optic resulting from absorption in a localized surface defect. These measurements were performed on principal cut samples of lithium triborate with damage spots centered on their front surfaces, pumped by a kW-scale continuous-wave laser. The changes in optical-path length associated with this heating were measured with a Mach-Zehnder interferometer, from which the temperature distribution could be inferred. These distributions have sharper features with larger magnitudes than would be expected with bulk-absorption heating. Comparison with both numerical and analytical models is used to qualify the measurements and to estimate the total power absorbed at a given site using this bulk material response. While sensitivity is dependent on the properties of the material of study, we demonstrate measurements of absorption levels of one part in 105.

Nanomechanics Modeling of Interface Interactions in Asphalt Concrete: Traction and Shearing Failure Study

The interface bonding strength is critical for asphalt concrete performance under external load applications. A thorough understanding of the load transfer mechanism bridging the nanoscale interfacial details and the macroscale properties is required to accurately predict the performance of asphalt concrete. This research presents a multiscale analysis procedure for the modeling of interface behaviors, in which material properties are evaluated by atomic scale interactions, emphasizing the complex shearing and separation mechanisms under various loading modes. The representative model system was established based on multiscale experimental characterization of the tight-bonding interface between asphalt and aggregate. Interfacial load transfer and failure studies were conducted for investigating the effect of tension and compression on shearing mode separation. The cohesive zone model parameters, such as peak traction and energy of separation were evaluated for each loading mode. Different boundary conditions were applied to obtain the representative volume element (RVE) and connection to continuum level properties. Results indicated that depending on the various loading modes, the failure of the nanoscale interface system may occur within the asphalt phase or at the interface. These results set the basis for continuum length-scale micromechanical models which may be used to determine the bulk material response, incorporating interfacial phenomena. The findings presented in this paper are consistent with observations reported in previous studies and expand on the understanding of the relationship between molecular structures and combined shearing separation failure properties of asphalt concrete interfaces.

Oscillatory nanoindentation of highly compliant hydrogels: A critical comparative analysis with rheometry

We present a method for measuring the shear complex modulus of hydrogels by oscillatory nanoindentation, with unprecedented attention to procedure and uncertainty analysis. The method is verified by testing a typical low-molecular-weight gelator formed from the controlled hydrolysis of glucono-δ-lactone. Nanoindentation results are compared with those obtained by rheometry using both vane-in-cup and parallel-plate fixtures. At 10 Hz, the properties measured by oscillatory nanoindentation were G′ = 38.1 ± 2.8 kPa, tan δ = 0.22 ± 0.02. At the same frequency, the properties measured by rheometry were G′ = 15.3 ± 2.9 kPa, tan δ = 0.11 ± 0.016 (vane-in-cup) and G′ = 7.9 ± 1.1 kPa, tan δ = 0.05 ± 0.004 (parallel-plate). The larger shear modulus measured by nanoindentation is due to the scale of testing. Whereas rheometry characterizes the bulk material response, nanoindentation probes the fibrous network of the gel. The procedure and analysis presented here are valuable for nanoindentation testing of other compliant materials such as hydrogels, soft biological tissue, and food products.

Photon‐Pair Generation with a 100 nm Thick Carbon Nanotube Film

Nonlinear optics based on bulk materials is the current technique of choice for quantum-state generation and information processing. Scaling of nonlinear optical quantum devices is of significant interest to enable quantum devices with high performance. However, it is challenging to scale the nonlinear optical devices down to the nanoscale dimension due to relatively small nonlinear optical response of traditional bulk materials. Here, correlated photon pairs are generated in the nanometer scale using a nonlinear optical device for the first time. The approach uses spontaneous four-wave mixing in a carbon nanotube film with extremely large Kerr-nonlinearity (≈100 000 times larger than that of the widely used silica), which is achieved through careful control of the tube diameter during the carbon nanotube growth. Photon pairs with a coincidence to accidental ratio of 18 at the telecom wavelength of 1.5 µm are generated at room temperature in a ≈100 nm thick carbon nanotube film device, i.e., 1000 times thinner than the smallest existing devices. These results are promising for future integrated nonlinear quantum devices (e.g., quantum emission and processing devices).

Computational modeling of interfacial behaviors in nanocomposite materials

Towards understanding the bulk material response in nanocomposites, an interfacial zone model was proposed to define a variety of material interface behaviors (e.g. brittle, ductile, rubber-like, elastic-perfectly plastic behavior etc.). It also has the capability to predict bulk material response though independently control of the interface properties (e.g. stiffness, strength, toughness). The mechanical response of granular nanocomposite (i.e. nacre) was investigated through modeling the “relatively soft” organic interface as an interfacial zone among “hard” mineral tablets and simulation results were compared with experimental measurements of stress-strain curves in tension and compression tests. Through modeling varies material interfaces, we found out that the bulk material response of granular nanocomposite was regulated by the interfacial behaviors. This interfacial zone model provides a possible numerical tool for qualitatively understanding of structure-property relationships through material interface design.

Impact-induced compaction of primitive solar system solids: The need for mesoscale modelling and experiments

Primitive solar system solids were accreted as highly porous bimodal mixtures of mm-sized chondrules and sub-μm matrix grains. To understand the compaction and lithification of these materials by shock, it is necessary to investigate the process at the mesoscale; i.e., the scale of individual chondrules. Here we document simulations of hypervelocity compaction of primitive materials using the iSALE shock physics model. We compare the numerical methods employed here with shock compaction experiments involving bimodal mixtures of glass beads and silica powder and find good agreement in bulk material response between the experiments and models. The heterogeneous response to shock of bimodal porous mixtures with a composition more appropriate for primitive solids was subsequently investigated: strong temperature dichotomies between the chondrules and matrix were observed (non-porous chondrules remained largely cold, while the porous matrix saw temperature increases of 100’s K). Matrix compaction was heterogeneous, and post-shock porosity was found to be lower on the lee-side of chondrules. The strain in the matrix was shown to be higher near the chondrule rims, in agreement with observations from meteorites. Chondrule flattening in the direction of the shock increases with increasing impact velocity, with flattened chondrules oriented with their semi-minor axis parallel to the shock direction.

Two-Step Phase Transition in SnSe and the Origins of its High Power Factor from First Principles.

The interest in improving the thermoelectric response of bulk materials has received a boost after it has been recognized that layered materials, in particular SnSe, show a very large thermoelectric figure of merit. This result has received great attention while it is now possible to conceive other similar materials or experimental methods to improve this value. Before we can now think of engineering this material it is important we understand the basic mechanism that explains this unusual behavior, where very low thermal conductivity and a high thermopower result from a delicate balance between the crystal and electronic structure. In this Letter, we present a complete temperature evolution of the Seebeck coefficient as the material undergoes a soft crystal transformation and its consequences on other properties within SnSe by means of first-principles calculations. Our results are able to explain the full range of considered experimental temperatures.

The significance of grain morphology, moisture, and strain rate on the rapid compaction of silica sands

There is considerable interest in the high-rate compaction of brittle granular materials such as sand. However, the vast majority of studies focus on a single granular system, limiting our ability to make comparisons between materials to discern how granular structure manifests as bulk material response. Here, three different silica sands with similar grain size and shape are studied: we compare a rough quarry sand, a smoother-grained sand, and a sandy loam. Quasi-static compaction and planar shock loading responses are compared, and recovered samples analyzed. The combination provides information regarding the interplay between granular properties, loading conditions, and material response. We show that the fundamental grain-scale behaviour depends on loading conditions: At low strain rates compaction behaviour is dominated by grain morphology, and in particular, smoothness and particle size distribution. Under shock loading, grain rearrangement and force chain effects are suppressed, and the nature of inter-granular contact points, modified by the presence of moisture or fines, is most important. Furthermore, grain fracture under shock loading is substantially reduced with increasing moisture content.

Nonaffine deformation under compression and decompression of a flow-stabilized solid

Understanding the particle-scale transition from elastic deformation to plastic flow is central to making predictions about the bulk material properties and response of disordered materials. To address this issue, we perform experiments on flow-stabilized solids composed of micron-scale spheres within a microfluidic channel, in a regime where particle inertia is negligible. Each solid heap exists within a stress field imposed by the flow, and we track the positions of particles in response to single impulses of fluid-driven compression or decompression. We find that the resulting deformation field is well-decomposed into an affine field, with a constant strain profile throughout the solid, and a non-affine field. The magnitude of this non-affine response decays with the distance from the free surface in the long-time limit, suggesting that the distance from jamming plays a significant role in controlling the length scale of plastic flow. Finally, we observe that compressive pulses create more rearrangements than decompressive pulses, an effect that we quantify using the statistic for non-affine motion. Unexpectedly, the time scale for the compression response is shorter than for decompression at the same strain (but unequal pressure), providing insight into the coupling between deformation and cage-breaking.

Tailored thermal expansion alloys

Current approaches to tailoring the thermal expansion coefficient of materials or finding materials with negative thermal expansion rely on careful manipulation of either the material's composition and/or the complex fabrication of composites. Here, by contrast, we report a new principle that enables the precise control of macroscopic thermal expansion response of bulk materials via crystallographic texture manipulation and by taking advantage of anisotropic Coefficients of Thermal Expansion (CTE) in a large class of martensitically transforming materials. Through simple thermo-mechanical processing, it is possible to tailor the thermal expansion response of a single material––without manipulating its composition––over a wide range of positive and negative values. We demonstrate this principle by gradually tuning the macroscopic CTE in a model NiTiPd alloy between a positive (+14.90 × 10−6 K−1) and a negative (−3.06 × 10−6 K−1) value, simply by incrementally increasing tensile plastic deformation in the martensite phase. This surprising response is linked to the large positive, +51.33 × 10−6 K−1, and negative, −34.51 × 10−6 K−1, CTE anisotropy, at the lattice level, along the different crystal directions in martensite. Similar CTE anisotropy is also shown experimentally in CoNiGa and TiNb alloys. In a model TiNb alloy, giant macroscopic CTEs of +181 × 10−6 K−1 and −142 × 10−6 K−1 are measured. A connection between the CTE anisotropy and the martensitic transformation in these and other materials systems such as NiTi, pure uranium, and PbTiO3 is later made. It is shown that negative or positive thermal expansion crystallographic directions are connected to the crystallographic relationship between the austenite and martensite lattices, and can easily be predicted using the lattice parameters of austenite and martensite phases. Our current observations and analyses suggest that the tunability of the macroscopic CTE through thermo-mechanical processing is universal in materials––both ceramic and metals––that undergo martensitic transformations.

Response of thin-skinned sandwich panels to contact loading with flat-ended cylindrical punches: Experiments, numerical simulations and neutron diffraction measurements

The response of aluminium foam-cored sandwich panels to localised contact loading was investigated experimentally and numerically using flat-ended cylindrical punch of four varying sizes. ALPORAS and ALULIGHT closed-cell foams of 15 mm thickness with 0.3 mm thick aluminium face sheets (of 236 MPa yield strength) were used to manufacture the sandwich panels. Face sheet fracturing at the perimeter of the indenter, in addition to foam cells collapse beneath the indenter and tearing of the cell walls at the perimeter of the indenter were the major failure mechanisms of the sandwich panels, irrespective of the strength and density of the underlying foam core. The authors employed a 3D model in ABAQUS/Explicit to evaluate the indentation event, the skin failure of the face sheets and carry out a sensitivity study of the panel's response. Using the foam model of Deshpande and Fleck combined with the forming limit diagram (FLD) of the aluminium face sheet, good quantitative and qualitative correlations between experiments and simulations were achieved. The higher plastic compliance of the ALPORAS led to increased bending of the sheet metal and delayed the onset of sheet necking and failure. ALULIGHT-cored panels exhibited higher load bearing and energy absorption capacity, compared with ALPORAS cores, due to their higher foam and cell densities and higher yield strength of the cell walls. Additionally, they exhibited greater propensity for strain hardening as evidenced by mechanical testing and the neutron diffraction measurements, which demonstrated the development of macroscopically measurable stresses at higher strains. At these conditions the ALULIGHT response upon compaction becomes akin to the response of bulk material with measurable elastic modulus and evident Poisson effect.

Boundary conditions for quadrupolar metamaterials

One of the long-standing problems in effective medium theories is using the knowledge of the bulk material response to predict the behavior of the electromagnetic fields at the material boundaries. Here, using a first principles approach, we derive the boundary conditions satisfied by the macroscopic fields at interfaces between reciprocal metamaterials with a quadrupolar-type response. Our analysis reveals that in addition to the usual Maxwellian-type boundary conditions for the tangential fields, in general—to ensure the conservation of the power flow and Lorentz reciprocity—it is necessary to enforce an additional boundary condition (ABC) at an interface between a quadrupolar material and a standard dielectric. It is shown that the ABC is related to the emergence of an additional wave in the bulk quadrupolar medium.