Superior mechanical properties of multilayer covalent-organic frameworks enabled by rationally tuning molecular interlayer interactions.

Two-dimensional (2D) covalent-organic frameworks (COFs) with a well-defined and tunable periodic porous skeleton are emerging candidates for lightweight and strong 2D polymeric materials. It remains challenging, however, to retain the superior mechanical properties of monolayer COFs in a multilayer stack. Here, we successfully demonstrated a precise layer control in synthesizing atomically thin COFs, enabling a systematic study of layer-dependent mechanical properties of 2D COFs with two different interlayer interactions. It was shown that the methoxy groups in COFTAPB-DMTP provided enhanced interlayer interactions, leading to layer-independent mechanical properties. In sharp contrast, mechanical properties of COFTAPB-PDA decreased significantly as the layer number increased. We attributed these results to higher energy barriers against interlayer sliding due to the presence of interlayer hydrogen bonds and possible mechanical interlocking in COFTAPB-DMTP, as revealed by density functional theory calculations.

Evolution of dislocation substructures in metals via high-strain-rate nanoindentation.

Deformation at high strain rates often results in high stresses on many engineering materials, potentially leading to catastrophic failure without proper design. High-strain-rate mechanical testing is thus needed to improve the design of future structural materials for a wide range of applications. Although several high-strain-rate mechanical testing techniques have been developed to provide a fundamental understanding of material responses and microstructural evolution under high-strain-rate deformation conditions, these tests are often very time consuming and costly. In this work, we utilize a high-strain-rate nanoindentation testing technique and system in combination with transmission electron microscopy to reveal the deformation mechanisms and dislocation substructures that evolve in pure metals from low (10-2 s-1) to very high indentation strain rates (104 s-1), using face-centered cubic aluminum and body-centered cubic molybdenum as model materials. The results help to establish the conditions under which micro- and macro-scale tests can be compared with validity and also provide a promising pathway that could lead to accelerated high-strain-rate testing at substantially reduced costs.

Anelasticity in thin-shell nanolattices.

In this work, we investigate the anelastic deformation behavior of periodic three-dimensional (3D) nanolattices with extremely thin shell thicknesses using nanoindentation. The results show that the nanolattice continues to deform with time under a constant load. In the case of 30-nm-thick aluminum oxide nanolattices, the anelastic deformation accounts for up to 18.1% of the elastic deformation for a constant load of 500 µN. The nanolattices also exhibit up to 15.7% recovery after unloading. Finite element analysis (FEA) coupled with diffusion of point defects is conducted, which is in qualitative agreement with the experimental results. The anelastic behavior can be attributed to the diffusion of point defects in the presence of a stress gradient and is reversible when the deformation is removed. The FEA model quantifies the evolution of the stress gradient and defect concentration and demonstrates the important role of a wavy tube profile in the diffusion of point defects. The reported anelastic deformation behavior can shed light on time-dependent response of nanolattice materials with implication for energy dissipation applications.

Lattice Distortion Promotes Incipient Plasticity in Multiprincipal Element Alloys.

Multiprincipal element alloys usually exhibit earlier pop-in events than pure metals and dilute solid solutions during nanoindentation experiments. To understand the origin of this phenomenon, large-scale atomic simulations of nanoindentation were performed on a series of metallic materials to investigate the underlying physics of incipient plasticity at the nanoscale. Statistical result shows that lattice distortion δ and normalized critical pressure pc/Es follow a power-law relationship. Via quantitative analysis on the relative positions of the atoms within the nearest neighbor shell, the physical origin of premature incipient plasticity is revealed as severe lattice distortion induces large relative atomic displacement, so only a small indentation strain is required to meet the critical displacement threshold that triggers incipient plasticity. Therefore, for perfect crystals, lattice distortion is an intrinsic and determinative factor that affects the first pop-in event.

Nanorheology and Nanoindentation Revealed a Softening and an Increased Viscous Fluidity of Adherent Mammalian Cells upon Increasing the Frequency.

The nanomechanical response of a cell depends on the frequency at which the cell is probed. The components of the cell that contribute to this property and their interplay are not well understood. Here, two force microscopy methods are integrated to characterize the frequency and/or the velocity-dependent properties of living cells. It is shown on HeLa and fibroblasts, that cells soften and fluidize upon increasing the frequency or the velocity of the deformation. This property was independent of the type and values (25 or 1000 nm) of the deformation. At low frequencies (2-10 Hz) or velocities (1-10 µm s-1 ), the response is dominated by the mechanical properties of the cell surface. At higher frequencies (>10 Hz) or velocities (>10 µm s-1 ), the response is dominated by the hydrodynamic drag of the cytosol. Softening and fluidization does not seem to involve any structural remodeling. It reflects a redistribution of the applied stress between the solid and liquid-like elements of the cell as the frequency or the velocity is changed. The data indicates that the quasistatic mechanical properties of a cell featuring a cytoskeleton pathology might be mimicked by the response of a non-pathological cell which is probed at a high frequency.

Superlubric Sliding of Graphene Auto-Kirigami with Interfaces Containing Self-Assembled Stripe-Pattern Adsorbates.

Van der Waals heterostructures formed by stacked 2D materials show exceptional electronic, mechanical, and optical properties. Superlubricity, a condition where atomically flat, incommensurate planes of atoms result in ultra-low friction, is a prime example enabling, for example, self-assembly of optically visible graphene nanostructures in air via a sliding auto-kirigami process. Here, it is demonstrated that a subtle but ubiquitous adsorbate stripe structure found on graphene and graphitic surfaces in ambient conditions remains stable within the interface between twisted graphene layers as they slide over each other. Despite this contamination, the interface retains an exceptional superlubricious state with an estimated upper bound frictional shear strength of 10 kPa, indicating that direct atomic incommensurate contact is not required to achieve ambient superlubricity for 2D materials. The results suggest that any phenomena depending on 2D heterostructure interfaces such as exotic electronic behavior may need to consider the presence of stripe adsorbate structures that remain intercalated.

In situ characterization of stresses, deformation and fracture of thin films using transmission X-ray nanodiffraction microscopy.

The use of hard X-ray transmission nano- and microdiffraction to perform in situ stress and strain measurements during deformation has recently been demonstrated and used to investigate many thin film systems. Here a newly commissioned sample environment based on a commercially available nanoindenter is presented, which is available at the NanoMAX beamline at the MAX IV synchrotron. Using X-ray nanoprobes of around 60-70 nm at 14-16 keV and a scanning step size of 100 nm, we map the strains, stresses, plastic deformation and fracture during nanoindentation of industrial coatings with thicknesses in the range of several micrometres, relatively strong texture and large grains. The successful measurements of such challenging samples illustrate broad applicability. The sample environment is openly accessible for NanoMAX beamline users through the MAX IV sample environment pool, and its capability can be further extended for specific purposes through additional available modules.

In situ characterization of stresses, deformation and fracture of thin films using transmission X-ray nanodiffraction microscopy. Corrigendum.

Errors in variable subscripts, equations and Fig. 8 in Section 3.2 of the article by Lotze et al. [(2024). J. Synchrotron Rad. 31, 42-52] are corrected.

Correlation between plant cell wall stiffening and root extension arrest phenotype in the combined abiotic stress of Fe and Al.

The plasticity and growth of plant cell walls (CWs) remain poorly understood at the molecular level. In this work, we used atomic force microscopy (AFM) to observe elastic responses of the root transition zone of 4-day-old Arabidopsis thaliana wild-type and almt1-mutant seedlings grown under Fe or Al stresses. Elastic parameters were deduced from force-distance curve measurements using the trimechanic-3PCS framework. The presence of single metal species Fe2+ or Al3+ at 10 µM exerts no noticeable effect on the root growth compared with the control conditions. On the contrary, a mix of both the metal ions produced a strong root-extension arrest concomitant with significant increase of CW stiffness. Raising the concentration of either Fe2+ or Al3+ to 20 µM, no root-extension arrest was observed; nevertheless, an increase in root stiffness occurred. In the presence of both the metal ions at 10 µM, root-extension arrest was not observed in the almt1 mutant, which substantially abolishes the ability to exude malate. Our results indicate that the combination of Fe2+ and Al3+ with exuded malate is crucial for both CW stiffening and root-extension arrest. However, stiffness increase induced by single Fe2+ or Al3+ is not sufficient for arresting root growth in our experimental conditions.

Polymorphism-driven Distinct Nanomechanical, Optical, Photophysical, and Conducting Properties in a Benzothiophene-quinoline.

Polymorphic forms of organic conjugated small molecules, with their unique molecular shapes, packing arrangements, and interaction patterns, provide an excellent opportunity to uncover how their microstructures influence their observable properties. Ethyl-2-(1-benzothiophene-2-yl)quinoline-4-carboxylate (BZQ) exists as dimorphs with distinct crystal habits - blocks (BZB) and needles (BZN). The crystal forms differ in their molecular arrangements - BZB has a slip-stacked column-like structure in contrast to a zig-zag crystal packing with limited π-overlap in BZN. The BZB crystals characterized by extended π-stacking along [100] demonstrated semiconductor behavior, whereas the BZN, with its zig-zag crystal packing and limited stacking characteristics, was reckoned as an insulator. Monotropically related crystal forms also differ in their nanomechanical properties, with BZB crystals being considerably softer than BZN crystals. This discrepancy in mechanical behavior can be attributed to the distinct molecular arrangements adopted by each crystal form, resulting in unique mechanisms to relieve the strain generated during nanoindentation experiments. Waveguiding experiments on the acicular crystals of BZN revealed the passive waveguiding properties. Excitation of these crystals using a 532 nm laser confirmed the propagation of elastically scattered photons (green) and the subsequent generation of inelastically scattered (orange) photons by the crystals. Further, the dimorphs display dissimilar photoluminescence properties; they are both blue-emissive, but BZN displays twice the quantum yield of BZB. The study underscores the integral role of polymorphism in modulating the mechanical, photophysical, and conducting properties of functional molecular materials. Importantly, our findings reveal the existence of light-emitting crystal polymorphs with varying electric conductivity, a relatively scarce phenomenon in the literature.

Surface Engineering of the Mechanical Properties of Molecular Crystals via an Atomistic Model for Computing the Facet Stress Response of Solids.

Dynamic molecular crystals are an emerging class of crystalline materials that can respond to mechanical stress by dissipating internal strain in a number of ways. Given the serendipitous nature of the discovery of such crystals, progress in the field requires advances in computational methods for the accurate and high-throughput computation of the nanomechanical properties of crystals on specific facets which are exposed to mechanical stress. Here, we develop and apply a new atomistic model for computing the surface elastic moduli of crystals on any set of facets of interest using dispersion-corrected density functional theory (DFT-D) methods. The model was benchmarked against a total of 24 reported nanoindentation measurements from a diverse set of molecular crystals and was found to be generally reliable. Using only the experimental crystal structure of the dietary supplement, L-aspartic acid, the model was subsequently applied under blind test conditions, to correctly predict the growth morphology, facet and nanomechanical properties of L-aspartic acid to within the accuracy of the measured elastic stiffness of the crystal, 24.53±0.56 GPa. This work paves the way for the computational design and experimental realization of other functional molecular crystals with tailor-made mechanical properties.

Fracture Mechanism of Nanocomposite of Metal and Graphene with Defect Pores.

Molecular dynamics simulations were performed to investigate the fracture mechanism and mechanical response of Ni/Graphene nanocomposites under nanoindentation. The effects of size and location of defect pores were explored by examining the pore structure transition, microstructure transition, variation of HCP atomic fraction and dislocation density with indentation depth, load-displacement relationship, and stress distribution. It was found that when the long edges of the pore are located along the longer dimension, the pores are fractured by indentation forces from the short edges. The closer the pore is to the indent, the smaller loading force is required for the pores to reach its fracture limit. For the long edges located along the transverse direction, the maximum indentation depth increases with the distance of the pore away from the indenter. The density of HCP atoms and dislocations in the composite gradually increases with the indentation depth. To understand the physical mechanism of the fracture behavior, we also evaluated the stress distribution in graphene at the fracture point.

Microscopic Cracks Modulate Nucleation and Solid-State Crystallization Tendency of Amorphous Celecoxib.

Drugs have been classified as fast, moderate, and poor crystallizers based on their inherent solid-state crystallization tendency. Differential scanning calorimetry-based heat-cool-heat protocol serves as a valuable tool to define the solid-state crystallization tendency. This classification helps in the development of strategies for stabilizing amorphous drugs. However, microscopic characteristics of the samples were generally overlooked during these experiments. In the present study, we evaluated the influence of microscopic cracks on the crystallization tendency of a poorly water-soluble model drug, celecoxib. Cracks developed in the temperature range of 0-10 °C during the cooling cycle triggered the subsequent crystallization of the amorphous phase. Nanoindentation study suggested minimal differences in mechanical properties between samples, although the cracked sample showed relatively inhomogeneous mechanical properties. Nuclei nourishment experiments suggested crack-assisted nucleation, which was supported by Raman data that revealed subtle changes in intermolecular interactions between cracked and uncracked samples. Celecoxib has been generally classified as class II, i.e., a drug with moderate crystallization tendency. Interestingly, classification of amorphous celecoxib may change depending on the presence or absence of cracks in the amorphous sample. Hence, subtle events such as microscopic cracks should be given due consideration while defining the solid-state crystallization tendency of drugs.

Material composition and mechanical properties of the venom-injecting forcipules in centipedes.

BACKGROUND: Centipedes are terrestrial and predatory arthropods that possess an evolutionary transformed pair of appendages used for venom injection-the forcipules. Many arthropods incorporate reinforcing elements into the cuticle of their piercing or biting structures to enhance hardness, elasticity or resistance to wear and structural failure. Given their frequent exposure to high mechanical stress, we hypothesise that the cuticle of the centipede forcipule might be mechanically reinforced. With a combination of imaging, analytical techniques and mechanical testing, we explore the centipede forcipule in detail to shed light on its morphology and performance. Additionally, we compare these data to characteristics of the locomotory leg to infer evolutionary processes. RESULTS: We examined sclerotization patterns using confocal laser-scanning microscopy based on autofluorescence properties of the cuticle (forcipule and leg) and elemental composition by energy-dispersive X-ray spectroscopy in representative species from all five centipede lineages. These experiments revealed gradually increasing sclerotization towards the forcipular tarsungulum and a stronger sclerotization of joints in taxa with condensed podomeres. Depending on the species, calcium, zinc or chlorine are present with a higher concentration towards the distal tarsungulum. Interestingly, these characteristics are more or less mirrored in the locomotory leg's pretarsal claw in Epimorpha. To understand how incorporated elements affect mechanical properties, we tested resistance to structural failure, hardness (H) and Young's modulus (E) in two representative species, one with high zinc and one with high calcium content. Both species, however, exhibit similar properties and no differences in mechanical stress the forcipule can withstand. CONCLUSIONS: Our study reveals similarities in the material composition and properties of the forcipules in centipedes. The forcipules transformed from an elongated leg-like appearance into rigid piercing structures. Our data supports their serial homology to the locomotory leg and that the forcipule's tarsungulum is a fusion of tarsus and pretarsal claw. Calcium or zinc incorporation leads to comparable mechanical properties like in piercing structures of chelicerates and insects, but the elemental incorporation does not increase H and E in centipedes, suggesting that centipedes followed their own pathways in the evolutionary transformation of piercing tools.

Frictional resistance and delamination mechanisms in 2D tungsten diselenide revealed by multi-scale scratch andin-situobservations.

Friction phenomena in two-dimensional (2D) materials are conventionally studied at atomic length scales in a few layers using low-load techniques. However, the advancement of 2D materials for semiconductor and electronic applications requires an understanding of friction and delamination at a few micrometers length scale and hundreds of layers. To bridge this gap, the present study investigates frictional resistance and delamination mechanisms in 2D tungsten diselenide (WSe2) at 10µm length and 100-500 nm depths using an integrated atomic force microscopy (AFM), high-load nanoscratch, andin-situscanning electron microscopic (SEM) observations. AFM revealed a heterogenous distribution of frictional resistance in a single WSe2layer originating from surface ripples, with the mean increasing from 8.7 to 79.1 nN as the imposed force increased from 20 to 80 nN. High-loadin-situnano-scratch tests delineated the role of the individual layers in the mechanism of multi-layer delamination under an SEM. Delamination during scratch consists of stick-slip motion with friction force increasing in each successive slip, manifested as increasing slope of lateral force curves with scratch depth from 10.9 to 13.0 (× 103) Nm-1. Delamination is followed by cyclic fracture of WSe2layers where the puckering effect results in adherence of layers to the nanoscratch probe, increasing the local maximum of lateral force from 89.3 to 205.6µN. This establishment of the interconnectedness between friction in single-layer and delamination at hundreds of layers harbors the potential for utilizing these materials in semiconductor devices with reduced energy losses and enhanced performance.

Effects of two types of surface treatments on the structural elasticity of human fingernails.

BACKGROUND: The human nail has a three-layered structure. Although it would be useful to quantitatively evaluate the changes in deformability of the nail due to various surface treatments, few studies have been conducted. METHODS: The effects of two types of surface treatment-a chemically acting nail softener and a physically acting nail strengthener-on the deformability of human fingernails were investigated. The Young's modulus of each plate of the nail samples before and after softening treatment was determined by nanoindentation. The Young's modulus of the strengthener was determined by conducting a three-point bending test on a polyethylene sheet coated with the strengthener. RESULTS: Young's modulus decreased in order from the top plate against the softening treatment time, and the structural elasticity for bending deformation (SEB) of the nail sample, which expresses the deformability against bending deformation independent of its external dimensions, decreased to 60% after 6 h of treatment. The Young's modulus of the nail strengthener was 244.5 MPa, which is less than 10% of the SEB of the nail. When the nail strengthener was applied to the nail surface, the SEB decreased to 73%, whereas the flexural rigidity increased to 117%. CONCLUSION: Changes in nail deformability caused by various surface treatments for softening and hardening were quantitatively evaluated successfully.

Interfacial Nanoblisters Formed in Water Serving as Freestanding Platforms for Measuring Elastic Moduli of Polymeric Nanofilms.

Polymeric nanofilms have been widely utilized in diverse cutting-edge technologies, yet accurately determining their elastic moduli remains challenging. Here we demonstrate that interfacial nanoblisters, which are produced by simply immersing substrate-supported nanofilms in water, represent natural platforms for assessing the mechanical properties of polymeric nanofilms using the sophisticated nanoindentation method. Nevertheless, high-resolution, quantitative force spectroscopy studies reveal that the indentation test must be performed on an effective freestanding region around the nanoblister apex and meanwhile under an appropriate loading force, to obtain load-independent, linear elastic deformations. The nanoblister stiffness increases with either decreasing its size or increasing its covering film thickness, and such size effects can be adequately rationalized by an energy-based theoretical model. The proposed model also enables an exceptional determination of the film elastic modulus. Given that interfacial blistering is a frequently occurring phenomenon for polymeric nanofilms, we envision that the presented methodology would stimulate broad applications in relevant fields.

Local Nanostrain Engineering of Monolayer MoS2 Using Atomic Force Microscopy-Based Thermomechanical Nanoindentation.

Strain engineering in two-dimensional materials (2DMs) has important application potential for electronic and optoelectronic devices. However, achieving precise spatial control, adjustable sizing, and permanent strain with nanoscale resolution remains challenging. Herein, a thermomechanical nanoindentation method is introduced, inspired by skin edema caused by mosquito bites, which can induce localized nanostrain and bandgap modulation in monolayer molybdenum disulfide (MoS2) transferred onto a poly(methyl methacrylate) film utilizing a heated atomic force microscopy nanotip. Via adjustment of the machining parameters, the strains of MoS2 are manipulated, achieving an average strain of ≤2.6% on the ring-shaped expansion structure. The local bandgap of MoS2 is spatially modulated using three types of nanostructures. Among them, the nanopit has the largest range of bandgap regulation, with a substantial change of 56 meV. These findings demonstrate the capability of the proposed method to create controllable and reproducible nanostrains in 2DMs.

Simulating porcelain firing effect on the structure, corrosion and mechanical properties of Co-Cr-Mo dental alloy fabricated by soft milling.

This study aims at evaluating the effect of simulating porcelain firing on the microstructure, corrosion behavior and mechanical properties of a Co-Cr-Mo alloy fabricated by Metal Soft Milling (MSM). Two groups of Co-28Cr-5Mo specimens (25 × 20 × 3 mm) were prepared by MSM: The as-sintered (AS) specimens and the post-fired (PF) specimens that were subjected to 5 simulating porcelain firing cycles without applying the ceramic mass onto their surface. Phase identification by X-ray Diffraction (XRD), microstructure examination by optical microscopy and Scanning Electron Microscopy combined with Energy-Dispersive X-ray Spectroscopy (SEM/EDX), corrosion testing by cyclic polarization and chronoamperometry in simulated body fluid (SBF), the latter test accompanied by Cr3+ and Cr6+ detection in the electrolyte through the 1.5-diphenylcarbazide (DPC) method and UV/visible spectrophotometry, and mechanical testing by micro-/nano-indentation were conducted to evaluate the effect of the post-firing cycles on the properties of Co-Cr-Mo. The results were statistically analyzed by the t test (p < 0.05: statistically significant). All specimens had a mixed γ-fcc and ε-hcp cobalt-based microstructure with a dispersion of pores filled with SiO2 and a fine M23C6 intergranular presence. PF led to an increase in the ε-Co content and slight grain coarsening. Both AS and PF alloys showed high resistance to general and localized corrosion, whereas neither Cr6+ nor Cr3+ were detected during the passivity-breakdown stage. PF improved the mechanical properties of the AS-alloy, especially the indentation modulus and true hardness (statistically significant differences: p = 0.0009 and 0.006, respectively). MSM and MSM/simulating-porcelain firing have been proven trustworthy fabrication methods of Co-Cr-Mo substrates for metal-ceramic prostheses. Moreover, the post-firing cycles improve the mechanical behavior of Co-Cr-Mo, which is vital under the dynamically changing loads in the oral cavity, whereas they do not degrade the corrosion performance.

An Assessment of the Mechanophysical and Hormonal Impact on Human Endometrial Epithelium Mechanics and Receptivity.

The endometrial epithelium and underlying stroma undergo profound changes to support and limit embryo adhesion and invasion, which occur in the secretory phase of the menstrual cycle during the window of implantation. This coincides with a peak in progesterone and estradiol production. We hypothesized that the interplay between hormone-induced changes in the mechanical properties of the endometrial epithelium and stroma supports this process. To study it, we used hormone-responsive endometrial adenocarcinoma-derived Ishikawa cells growing on substrates of different stiffness. We showed that Ishikawa monolayers on soft substrates are more tightly clustered and uniform than on stiff substrates. Probing for mechanical alterations, we found accelerated stress-relaxation after apical nanoindentation in hormone-stimulated monolayers on stiff substrates. Traction force microscopy furthermore revealed an increased number of foci with high traction in the presence of estradiol and progesterone on soft substrates. The detection of single cells and small cell clusters positive for the intermediate filament protein vimentin and the progesterone receptor further underscored monolayer heterogeneity. Finally, adhesion assays with trophoblast-derived AC-1M-88 spheroids were used to examine the effects of substrate stiffness and steroid hormones on endometrial receptivity. We conclude that the extracellular matrix and hormones act together to determine mechanical properties and, ultimately, embryo implantation.