Tan Sui

Nano-structural changes in Li-ion battery cathodes during cycling revealed by FIB-SEM serial sectioning tomography

The growing demand for reliable, durable electrical energy systems to power electric and hybrid vehicles motivates worldwide efforts aimed at developing high-energy, high-power density batteries. One of the obstacles to widespread industry adoption is the lack of profound understanding and the ability to monitor and control the long-term degradation and capacity fading observed in these systems. Focused Ion Beam-Scanning Electron Microscopy (FIB-SEM) serial sectioning is used to reconstruct the evolution of the three-dimensional structure of Li-ion battery electrodes during extended cycling. High resolution imaging reveals microstructural information at the level of the composite framework consisting of the spheroidal micro-particles of the active material held together by the polymer matrix. The evolution of damage within the micro-particles of the active material can be seen in the form of voiding, cracking and ultimate fragmentation. In particular, when spherical micro-particles of Li-rich layered oxides are used as the cathode, it is found that the extent of fragmentation varied in the direction of Li+ diffusion current from the particle surface inwards. We use a simple model of the strain and strain gradient effects of Li+ transient diffusion within the electrode to identify the driving force for particle fragmentation, and discuss the implication of these results.

A state-of-the-art review of micron-scale spatially resolved residual stress analysis by FIB-DIC ring-core milling and other techniques

Quantification of residual stress gradients can provide great improvements in understanding the complex interactions between microstructure, mechanical state, mode(s) of failure and structural integrity. Highly focused local probe non-destructive techniques such as X-ray diffraction, electron diffraction or Raman spectroscopy have an established track record in determining spatial variations in the relative changes in residual stress with respect to a reference state for many structural materials. However, the interpretation of these measurements in terms of absolute stress values requires a strain-free sample often difficult to obtain due to the influence of chemistry, microstructure or processing route. With the increasing availability of focused ion beam instruments, a new approach has been developed which is known as the micro-scale ring-core focused ion beam-digital image correlation technique. This technique is becoming the principal tool for quantifying absolute in-plane residual stresses. It can be applied to a broad range of materials: crystalline and amorphous metallic alloys and ceramics, polymers, composites and biomaterials. The precise nano-scale positioning and well-defined gauge volume of this experimental technique make it eminently suitable for spatially resolved analysis, that is, residual stress profiling and mapping. Following a summary of micro-stress evaluation approaches, we focus our attention on focused ion beam-digital image correlation methods and assess the application of micro-scale ring-core methods for spatially resolved residual stress profiling. The sequential ring-core milling focused ion beam-digital image correlation method allows micro- to macro-scale mapping at the step of 10–1000 μm, while the parallel focused ion beam-digital image correlation approach exploits simultaneous milling operation to quantify stress profiles at the micron scale (1–10 μm). Cross-validation against X-ray diffraction results confirms that these approaches represent accurate, reliable and effective residual stress mapping methods.

Multiple-length-scale deformation analysis in a thermoplastic polyurethane

Thermoplastic polyurethane elastomers enjoy an exceptionally wide range of applications due to their remarkable versatility. These block co-polymers are used here as an example of a structurally inhomogeneous composite containing nano-scale gradients, whose internal strain differs depending on the length scale of consideration. Here we present a combined experimental and modelling approach to the hierarchical characterization of block co-polymer deformation. Synchrotron-based small- and wide-angle X-ray scattering and radiography are used for strain evaluation across the scales. Transmission electron microscopy image-based finite element modelling and fast Fourier transform analysis are used to develop a multi-phase numerical model that achieves agreement with the combined experimental data using a minimal number of adjustable structural parameters. The results highlight the importance of fuzzy interfaces, that is, regions of nanometre-scale structure and property gradients, in determining the mechanical properties of hierarchical composites across the scales.

In situ X-ray scattering evaluation of heat-induced ultrastructural changes in dental tissues and synthetic hydroxyapatite.

Human dental tissues consist of inorganic constituents (mainly crystallites of hydroxyapatite, HAp) and organic matrix. In addition, synthetic HAp powders are frequently used in medical and chemical applications. Insights into the ultrastructural alterations of skeletal hard tissues exposed to thermal treatment are crucial for the estimation of temperature of exposure in forensic and archaeological studies. However, at present, only limited data exist on the heat-induced structural alterations of human dental tissues. In this paper, advanced non-destructive small- and wide angle X-ray scattering (SAXS/WAXS) synchrotron techniques were used to investigate the in situ ultrastructural alterations in thermally treated human dental tissues and synthetic HAp powders. The crystallographic properties were probed by WAXS, whereas HAp grain size distribution changes were evaluated by SAXS. The results demonstrate the important role of the organic matrix that binds together the HAp crystallites in responding to heat exposure. This is highlighted by the difference in the thermal behaviour between human dental tissues and synthetic HAp powders. The X-ray analysis results are supported by thermogravimetric analysis. The results concerning the HAp crystalline architecture in natural and synthetic HAp powders provide a reliable basis for deducing the heating history for dental tissues in the forensic and archaeological context, and the foundation for further development and optimization of biomimetic material design.

X-ray scattering evaluation of ultrastructural changes in human dental tissues with thermal treatment.

Micro‐ and ultrastructural analysis of burned skeletal remains is crucial for obtaining a reliable estimation of cremation temperature. Earlier studies mainly focused on heat‐induced changes in bone tissue, while this study extends this research to human dental tissues using a novel quantitative analytical approach. Twelve tooth sections were burned at 400–900°C (30‐min exposure, increments of 100°C). Subsequent combined small‐ and wide‐angle X‐ray scattering (SAXS/WAXS) experiments were performed at the Diamond Light Source synchrotron facility, where 28 scattering patterns were collected within each tooth section. In comparison with the control sample, an increase in mean crystal thickness was found in burned dentine (2.8‐fold) and enamel (1.4‐fold), however at a smaller rate than reported earlier for bone tissue (5–10.7‐fold). The results provide a structural reference for traditional X‐ray scattering methods and emphasize the need to investigate bone and dental tissues separately to obtain a reliable estimation of cremation temperature.

Hierarchical modelling of in situ elastic deformation of human enamel based on photoelastic and diffraction analysis of stresses and strains

Human enamel is a typical hierarchical mineralized tissue with a two-level composite structure. To date, few studies have focused on how the mechanical behaviour of this tissue is affected by both the rod orientation at the microscale and the preferred orientation of mineral crystallites at the nanoscale. In this study, wide-angle X-ray scattering was used to determine the internal lattice strain response of human enamel samples (with differing rod directions) as a function of in situ uniaxial compressive loading. Quantitative stress distribution evaluation in the birefringent mounting epoxy was performed in parallel using photoelastic techniques. The resulting experimental data was analysed using an advanced multiscale Eshelby inclusion model that takes into account the two-level hierarchical structure of human enamel, and reflects the differing rod directions and orientation distributions of hydroxyapatite crystals. The achieved satisfactory agreement between the model and the experimental data, in terms of the values of multidirectional strain components under the action of differently orientated loads, suggests that the multiscale approach captures reasonably successfully the structure-property relationship between the hierarchical architecture of human enamel and its response to the applied forces. This novel and systematic approach can be used to improve the interpretation of the mechanical properties of enamel, as well as of the textured hierarchical biomaterials in general.

Structure-mechanical function relations at nano-scale in heat-affected human dental tissue

The knowledge of the mechanical properties of dental materials related to their hierarchical structure is essential for understanding and predicting the effect of microstructural alterations on the performance of dental tissues in the context of forensic and archaeological investigation as well as laser irradiation treatment of caries. So far, few studies have focused on the nano-scale structure-mechanical function relations of human teeth altered by chemical or thermal treatment. The response of dental tissues to thermal treatment is thought to be strongly affected by the mineral crystallite size, their spatial arrangement and preferred orientation. In this study, synchrotron-based small and wide angle X-ray scattering (SAXS/WAXS) techniques were used to investigate the micro-structural alterations (mean crystalline thickness, crystal perfection and degree of alignment) of heat-affected dentine and enamel in human dental teeth. Additionally, nanoindentation mapping was applied to detect the spatial and temperature-dependent nano-mechanical properties variation. The SAXS/WAXS results revealed that the mean crystalline thickness distribution in dentine was more uniform compared with that in enamel. Although in general the mean crystalline thickness increased both in dentine and enamel as the temperature increased, the local structural variations gradually reduced. Meanwhile, the hardness and reduced modulus in enamel decreased as the temperature increased, while for dentine, the tendency reversed at high temperature. The analysis of the correlation between the ultrastructure and mechanical properties coupled with the effect of temperature demonstrates the effect of mean thickness and orientation on the local variation of mechanical property. This structural-mechanical property alteration is likely to be due to changes of HAp crystallites, thus dentine and enamel exhibit different responses at different temperatures. Our results enable an improved understanding of the mechanical properties correlation in hierarchical biological materials, and human dental tissue in particular.

Multiscale modelling and diffraction-based characterization of elastic behaviour of human dentine

Human dentine is a hierarchical mineralized tissue with a two-level composite structure, with tubules being the prominent structural feature at a microlevel, and collagen fibres decorated with hydroxyapatite (HAp) crystallite platelets dominating the nanoscale. Few studies have focused on this two-level structure of human dentine, where the response to mechanical loading is thought to be affected not only by the tubule volume fraction at the microscale, but also by the shape and orientation distribution of mineral crystallites, and their nanoscale spatial arrangement and alignment. In this paper, in situ elastic strain evolution within HAp in dentine subjected to uniaxial compressive loading along both longitudinal and transverse directions was characterized simultaneously by two synchrotron X-ray scattering techniques: small- and wide-angle X-ray scattering (SAXS and WAXS, respectively). WAXS allows the evaluation of the apparent modulus linking the external load to the internal HAp crystallite strain, while the nanoscale HAp distribution and arrangement can be quantified by SAXS. We proposed an improved multiscale Eshelby inclusion model that takes into account the two-level hierarchical structure, and validated it with a multidirectional experimental strain evaluation. The agreement between the simulation and measurement indicates that the multiscale hierarchical model developed here accurately reflects the structural arrangement and mechanical response of human dentine. This study benefits the comprehensive understanding of the mechanical behaviour of hierarchical biomaterials. The knowledge of the mechanical properties related to the hierarchical structure is essential for the understanding and predicting the effects of structural alterations that may occur due to disease or treatment on the performance of dental tissues and their artificial replacements.

Fine-scale tribological performance of zeolitic imidazolate framework (ZIF-8) based polymer nanocomposite membranes

We combined zeolitic imidazolate framework nanoparticles (ZIF-8: ˜150 nm diameter) with Matrimid® 5218 polymer to form permeable mixed matrix membranes, featuring different weight fractions of nanoparticles (up to 30 wt. % loading). We used ball-on-disc micro-tribological method to measure the frictional coefficient of the nanocomposite membranes, as a function of nanoparticle loading and annealing heat treatment. The tribological results reveal that the friction and wear of the unannealed samples rise steadily with greater nanoparticle loading because ZIF-8 is relatively harder than the matrix, thus promoting abrasive wear mechanism. After annealing, however, we discover that the nanocomposites display an appreciably lower friction and wear damage compared with the unannealed counterparts. Evidence shows that the major improvement in tribological performance is associated with the greater amounts of wear debris derived from the annealed nanocomposite membranes. We propose that detached Matrimid-encapsulated ZIF-8 nanoparticles could function as “spacers,” which are capable of not only reducing direct contact between two rubbing surfaces but also enhancing free-rolling under the action of lateral forces.

Hierarchical modelling of elastic behaviour of human enamel based on synchrotron diffraction characterisation

Human enamel is a hierarchical mineralized tissue with a two-level composite structure. Few studies have focused on the structure-mechanical property relationship and its link to the multi-scale architecture of human enamel, whereby the response to mechanical loading is affected not only by the rod distribution at micro-scale, but also strongly influenced by the mineral crystallite shape, and spatial arrangement and orientation. In this study, two complementary synchrotron X-ray diffraction techniques, wide and small angle X-ray scattering (WAXS/SAXS) were used to obtain multi-scale quantitative information about the structure and deformation response of human enamel to in situ uniaxial compressive loading. The apparent modulus was determined linking the external load and the internal strain in hydroxyapatite (HAp) crystallites. An improved multi-scale Eshelby model is proposed taking into account the two-level hierarchical structure of enamel. This framework has been used to analyse the experimental data for the elastic lattice strain evolution within the HAp crystals. The achieved agreement between the model prediction and experiment along the loading direction validates the model and suggests that the new multi-scale approach reasonably captures the structure-property relationship for the human enamel. The ability of the model to predict multi-directional strain components is also evaluated by comparison with the measurements. The results are useful for understanding the intricate relationship between the hierarchical structure and the mechanical properties of enamel, and for making predictions of the effect of structural alterations that may occur due to the disease or treatment on the performance of dental tissues and their artificial replacements.