Showing papers by "Alexander M. Korsunsky published in 2020"

Synchrotron X-ray quantitative evaluation of transient deformation and damage phenomena in a single nickel-rich cathode particle

Abstract: The performance and durability of Ni-rich cathode materials are controlled in no small part by their mechanical durability, as chemomechanical breakdown at the nano-scale leads to increased internal resistance and decreased storage capacity. The mechanical degradation is caused by the transient lithium diffusion processes during charge and discharge of layered oxide spherical cathode micro-particles, leading to highly anisotropic incompatible strain fields. Experimental characterisation of the transient mechanisms underlying crack and void formation requires the combination of very high resolution in space (sub-micron) and time (sub-second) domains without charge interruption. The present study is focused on sub-micron focused operando synchrotron X-ray diffraction and in situ Ptycho-Tomographic nano-scale imaging of a single nano-structured LiNi0.8Co0.1Mn0.1O2 core–shell particle during charge to obtain a thorough understanding of the anisotropic deformation and damage phenomena at a particle level. Preferential grain orientation within the shell of a spherical secondary cathode particle provides improved lithium transport but is also associated with spatially varying anisotropic expansion of the hexagonal unit cell in the c-axis and contraction in the a-axis. These effects were resolved in relation to the grain orientation, and the link established with the nucleation and growth of intergranular cracks and voids that causes electrical isolation of active cathode material. Coupled multi-physics Finite Element Modelling of diffusion and deformation inside a single cathode particle during charge and discharge was validated by comparison with experimental evidence and allowed unequivocal identification of key mechanical drivers underlying Li-ion battery degradation.

Design and mechanical properties of 3D-printed auxetic honeycomb structure

Abstract: The combination of theoretical calculations, computer simulations, and experimental evaluation of Poisson's ratio was carried out for re-entrant honeycomb auxetic structure. Optimal honeycomb cell parameters were determined for 3D-printed samples made from thermoplastic polyurethane (TPU). The low-cycle compression tests of 3D-printed re-entrant honeycomb auxetic samples showed that the structure based on auxetic hexagonal cell can withstand almost 1.75 times more very low cycle fatigue cycles than the similar non-auxetic structure. Neither failure nor layer delamination in 3D structures were detected in the auxetic sample after 500 compression cycles. 3D-printed auxetic structures offer a promising candidate for applications in medicine and sports.

Fast Mass-Production of Medical Safety Shields under COVID-19 Quarantine: Optimizing the Use of University Fabrication Facilities and Volunteer Labor.

Abstract: COVID-19 pandemic provoked a number of restrictive measures, such as the closure or severe restriction of border transit for international trading traffic, quarantines and self-isolation. This caused a series of interrelated consequences that not only prevent or slow down the spread of disease, but also impact the medical systems’ capability to treat the patients and help their recovery. In particular, steeply growing demand for medical safety goods cannot be satisfied by regular suppliers due to the shortage of raw materials originating from other countries or remotely located national sources, under conditions of quarantined manpower. The current context inevitably brings back memories (and records!) of the situation 80 years ago, when WWII necessitated major effort directed at the rapid build-up of low-cost mass production to satisfy all aspects of war-time need. In the present short report we document a successful case of fast mass-production of light transparent medical safety face shields (thousands per day) realized in Skolkovo Institute of Science and Technology (Skoltech) at Fablab and Machine Shop Shared Facility (Skoltech FabLab). The demand for safety face shields by tens of hospitals in Moscow and other cities rapidly ramped up due to the need to protect medical staff during patient collection and transportation to hospitals, and within both the infected (“red”) and uninfected (“green”) zones. Materials selection for sterilizable transparent materials was conducted based on the analysis of merit indices, namely, minimal weight at given stiffness and minimal cost at given stiffness. Due to the need for permanent wear, design was motivated by low weight and comfortable head fixation, along with high production efficiency. The selection of minimal tooling in University fabrication workshops and the use of distributed volunteer labor are discussed.

Nano-scale residual stress depth profiling in Cu/W nano-multilayers as a function of magnetron sputtering pressure

Abstract: Residual stresses in thin films and multi-layered coatings fabricated by physical vapour deposition largely affect their mechanical and thermal reliability during operation in numerous fields of applications. By changing the argon working pressure in between each multilayer planar DC magnetron sputter deposition step, it is possible to control the residual stress distribution within coatings. A combination of FIB-DIC ring-core strain analysis, synchrotron XRD analysis based on the sin2(Ψ) method and micro-cantilever deflection analysis is used to reconstruct the in-plane stress state of multilayer coatings at different deposition pressures, with a residual stress depth profile resolution of 50 nm. A clear transition from compressive to tensile residual stresses is observed with an increase of working pressure, with pronounced stress peaks near the substrate-coating interface. These peak stresses resolved by FIB-DIC ring-core analysis exceed the average XRD stress measurements significantly, thus providing a reasonable explanation for multilayer failure. Experimental results are presented and comprehensively discussed in the context of deposition conditions for different thin film applications.

Shape memory polymer blends and composites for 3D and 4D printing applications

Abstract: 4D Printing (4DP) is a term used to denote the ability to control the geometric (shape, dimensions), structural (strength, stiffness), or functional properties of additively manufactured objects via postprocessing. The concept emerged in the 3D printing (3DP) community in the beginning of 2010s. Perhaps the most straightforward manifestation of conferring 4DP capability on a 3D print is via the use of Shape memory effect (SME) in polymers, extensively studied since the 1970s. Using this effect allows expanding the functionality and applications of 3D printed components by triggering specific physical, chemical, and nanostructural phenomena within them. The present Chapter overviews relevant publications focusing on the core mechanisms relating to the SME in additive manufacturing: the nature of polymers suitable for 4DP, the influence of thermal history on polymer supramolecular structure, and the key characteristics of the SME, such as the recovery stress and strain, temperature of activation, reproducibility, etc. The overview also touches upon the diversity of mechanisms of self-healing, self-assembly, self-deployment, etc. that open up the possibilities for use in a range of promising applications, such as sensors and actuators, biomedical implants, mechanical fastening, etc.

Nano-Scale Residual Stress Profiling in Thin Multilayer Films with Non-Equibiaxial Stress State

Abstract: Silver-based low-emissivity (low-E) coatings are applied on architectural glazing to cost-effectively reduce heat losses, as they generally consist of dielectric/Ag/dielectric multilayer stacks, where the thin Ag layer reflects long wavelength infrared (IR), while the dielectric layers both protect the Ag and act as an anti-reflective barrier. The architecture of the multilayer stack influences its mechanical properties and it is strongly dependent on the residual stress distribution in the stack. Residual stress evaluation by combining focused ion beam (FIB) milling and digital image correlation (DIC), using the micro-ring core configuration (FIB-DIC), offers micron-scale lateral resolution and provides information about the residual stress variation with depth, i.e., it allows depth profiling for both equibiaxial and non-equibiaxial stress distributions and hence can be effectively used to characterize low-E coatings. In this work, we propose an innovative approach to improve the depth resolution and surface sensitivity for residual stress depth profiling in the case of ultra-thin as-deposited and post-deposition annealed Si3N4/Ag/ZnO low-E coatings, by considering different fractions of area for DIC strain analysis and accordingly developing a unique influence function to maintain the sensitivity of the technique at is maximum during the calculation. Residual stress measurements performed using this novel FIB-DIC approach revealed that the individual Si3N4/ZnO layers in the multilayer stack are under different amounts of compressive stresses. The magnitude and orientation of these stresses changes significantly after heat treatment and provides a clear explanation for the observed differences in terms of scratch critical load. The results show that the proposed FIB-DIC combined-areas approach is a unique method for accurately probing non-equibiaxial residual stresses with nano-scale resolution in thin films, including multilayers.

The fabrication and characterization of bioengineered ultra-high molecular weight polyethylene-collagen-hap hybrid bone-cartilage patch

Abstract: A layered hybrid implant was designed and fabricated for the surgical replacement of worn cartilage to meet the complex requirements of biocompatibility and mechanics. The natural hierarchical structure was purposefully mimicked to improve the implant performance and integration. The hybrid was fabricated using three components: processed collagen gel, hydroxyapatite (HAp) powder and ultra-high molecular weight polyethylene (UHMWPE) in bulk and sponge form. The fabrication included hot molding, sacrificial templating, infusion, and freeze-casting stages. The hybrid had a porous transition layer made of porous UHMWPE impregnated with collagen by means of infusion. SEM and FTIR analyses confirmed successful collagen impregnation of porous UHMWPE. The morphology of transition layer was selected and produced to provide the UHMWPE pore size distribution in a range ∼50–150 μm that is favorable for the osseointegration by osteoblast proliferation. Biocompatibility tests were carried out in vitro. The index of red blood cells hemolysis showed 0.6 % after 4 h of co-incubation that proved excellent biocompatibility of the fabricated UHMWPE-Collagen-HAp hybrid.

Hard X-ray ptychography for optics characterization using a partially coherent synchrotron source

Abstract: Ptychography is a scanning coherent diffraction imaging technique which provides high resolution imaging and complete spatial information of the complex electric field probe and sample transmission function. Its ability to accurately determine the illumination probe has led to its use at modern synchrotrons and free-electron lasers as a wavefront-sensing technique for optics alignment, monitoring and correction. Recent developments in the ptychography reconstruction process now incorporate a modal decomposition of the illuminating probe and relax the restriction of using sources with high spatial coherence. In this article a practical implementation of hard X-ray ptychography from a partially coherent X-ray source with a large number of modes is demonstrated experimentally. A strongly diffracting Siemens star test sample is imaged using the focused beam produced by either a Fresnel zone plate or beryllium compound refractive lens. The recovered probe from each optic is back propagated in order to plot the beam caustic and determine the precise focal size and position. The power distribution of the reconstructed probe modes also allows the quantification of the beams coherence and is compared with the values predicted by a Gaussian–Schell model and the optics exit intensity.

In Situ Formation of Nanoporous Silicon on a Silicon Wafer via the Magnesiothermic Reduction Reaction (MRR) of Diatomaceous Earth.

Abstract: Successful direct route production of silicon nanostructures from diatomaceous earth (DE) on a single crystalline silicon wafer via the magnesiothermic reduction reaction is reported. The formed porous coating of 6 µm overall thickness contains silicon as the majority phase along with minor traces of Mg, as evident from SEM-EDS and the Focused Ion Beam (FIB) analysis. Raman peaks of silicon at 519 cm−1 and 925 cm−1 were found in both the film and wafer substrate, and significant intensity variation was observed, consistent with the SEM observation of the directly formed silicon nanoflake layer. Microstructural analysis of the flakes reveals the presence of pores and cavities partially retained from the precursor diatomite powder. A considerable reduction in surface reflectivity was observed for the silicon nanoflakes, from 45% for silicon wafer to below 15%. The results open possibilities for producing nanostructured silicon with a vast range of functionalities.

Synchrotron X-ray Scattering Analysis of Nylon-12 Crystallisation Variation Depending on 3D Printing Conditions

Abstract: Nylon-12 is an important structural polymer in wide use in the form of fibres and bulk structures. Fused filament fabrication (FFF) is an extrusion-based additive manufacturing (AM) method for rapid prototyping and final product manufacturing of thermoplastic polymer objects. The resultant microstructure of FFF-produced samples is strongly affected by the cooling rates and thermal gradients experienced across the part. The crystallisation behaviour during cooling and solidification influences the micro- and nano-structure, and deserves detailed investigation. A commercial Nylon-12 filament and FFF-produced Nylon-12 parts were studied by differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS) to examine the effect of cooling rates under non-isothermal crystallisation conditions on the microstructure and properties. Slower cooling rates caused more perfect crystallite formation, as well as alteration to the thermal properties.

Photo induced self-diffusion and viscosity in amorphous chalcogenide films

Abstract: Acceleration of themass transport in amorphous chalcogenidefilms under band gap light illumination is usually attributed to thedecrease of thefilm viscosity.However, our directmeasurements of thefilm viscosity at various temperatures and light intensities,madebyflatteningof surface relief gratings, have shown that the viscosity did not varyunder illumination and the accelerationof themass transferwas causedby the contribution of photo-induced (PI) self-diffusion. ThePIdiffusion coefficient is not related to the viscosity coefficient by the Stokes-Einstein relation andPIdiffusion shouldbe considered as an additionalmechanismof theoverallmass transport. In this paper, usingwell-knownmodels of self-trapped excitons,wepresent thefirst atomic interpretationof PI diffusion coefficients, explain their dependence on temperature and light intensity, and comparewith our experimental data. For characterization ofPI accelerationof themass transferwe introduce the term ‘diffusional viscosity’, like it is used for description of diffusion creep in crystalline solids.We estimate the temperature dependence of diffusional viscosity and show that it noticeably depends on the distance overwhich thematerial is redistributed. Taking into account the diffusional viscosity allows an adequate general interpretationof many photo-inducedphenomenaobserved in the literature.

Ovine Bone Morphology and Deformation Analysis Using Synchrotron X-ray Imaging and Scattering

Abstract: Bone is a natural hierarchical composite tissue incorporating hard mineral nano-crystals of hydroxyapatite (HAp) and organic binding material containing elastic collagen fibers. In the study, we investigated the structure and deformation of ovine bone by the combination of high-energy synchrotron X-ray tomographic imaging and scattering. X-ray experiments were performed prior to and under three-point bending loading by using a specially developed in situ load cell constructed from aluminium alloy frame, fast-drying epoxy resin for sample fixation, and a titanium bolt for contact loading. Firstly, multiple radiographic projection images were acquired and tomographic reconstruction was performed using SAVU software, following segmentation using Avizo. Secondly, Wide Angle X-ray Scattering (WAXS) and Small Angle X-ray Scattering (SAXS) 2D scattering patterns were collected from HAp and collagen. Both sample shape and deformation affect the observed scattering. Novel combined tomographic and diffraction analysis presented below paves the way for advanced characterization of complex shape samples using the Dual Imaging and Diffraction (DIAD) paradigm.

Mode I fracture toughness determination in Cu/W nano-multilayers on polymer substrate by SEM - Digital Image Correlation

Abstract: Nanostructured metallic multilayers with carefully designed mechanical and functional properties are omnipresent in cutting edge technological applications. To ensure the mechanical integrity of such coatings, the Mode I critical Stress Intensity Factor KIC is used to quantify their fracture toughness in order to avoid material failure by appropriate design. In this article, we present a novel approach for the KIC determination of thin and ultrathin films on compliant substrate, based on micro-displacement field analysis using Digital Image Correlation within SEM. Using this method, KIC of a Cu/W nano-multilayer with a total coating thickness of 240 nm was determined as K IC = 4.8 ± 0.05 MPa m , showing excellent agreement with the values published for comparable systems in the literature. To verify the validity of the chosen approach, two independent finite element simulations were employed, thus revealing the role and effect of the compliant substrate on the stress and displacement fields arising around the crack tip in thin films.

Multi-Scale Digital Image Correlation Analysis of In Situ Deformation of Open-Cell Porous Ultra-High Molecular Weight Polyethylene Foam

Abstract: Porous ultra-high molecular weight polyethylene (UHMWPE) is a high-performance bioinert polymer used in cranio-facial reconstructive surgery in procedures where relatively low mechanical stresses arise. As an alternative to much stiffer and more costly polyether-ether-ketone (PEEK) polymer, UHMWPE is finding further wide applications in hierarchically structured hybrids for advanced implants mimicking cartilage, cortical and trabecular bone tissues within a single component. The mechanical behaviour of open-cell UHMWPE sponges obtained through sacrificial desalination of hot compression-moulded UHMWPE-NaCl powder mixtures shows a complex dependence on the fabrication parameters and microstructural features. In particular, similarly to other porous media, it displays significant inhomogeneity of strain that readily localises within deformation bands that govern the overall response. In this article, we report advances in the development of accurate experimental techniques for operando studies of the structure-performance relationship applied to the porous UHMWPE medium with pore sizes of about 250 µm that are most well-suited for live cell proliferation and fast vascularization of implants. Samples of UHMWPE sponges were subjected to in situ compression using a micromechanical testing device within Scanning Electron Microscope (SEM) chamber, allowing the acquisition of high-resolution image sequences for Digital Image Correlation (DIC) analysis. Special masking and image processing algorithms were developed and applied to reveal the evolution of pore size and aspect ratio. Key structural evolution and deformation localisation phenomena were identified at both macro- and micro-structural levels in the elastic and plastic regimes. The motion of pore walls was quantitatively described, and the presence and influence of strain localisation zones were revealed and analysed using DIC technique.

FEM exploration of the potential of silica diatom frustules for vibrational MEMS applications

Abstract: Numerical simulations were carried out using the Finite Element Method (FEM) to determine the frequency characteristics of mechanical vibration of diatom silica frustules under the conditions and at frequencies that are not readily accessible to experimental measurement. The results revealed the influence of the frustule morphology on the natural frequency spectra. The effect of frustule density, stiffness, dimensions, pore size, and wall thickness on the eigenfrequencies and the corresponding modal shapes were studied in detail. Diatom frustules have natural frequencies in the range between several MHz and tens of MHz that make them a promising candidate for future MEMS applications. Eigenfrequencies depend linearly on the speed of sound in the frustule wall and decrease parabolically with the diameter and the pore size to diameter ratio. Dimensional analysis allowed obtaining functional correlations that encapsulate the various dependencies in compact analytical form. The satisfactory nature of our calculations and correlations derived from them is confirmed through an agreement with the analytical solutions from the literature.