A comparison of He and Ne FIB imaging of cracks in microindented silicon nitride

Helium ion microscopy (HIM) offers potential as a high spatial resolution technique for imaging insulating samples that are susceptible to charging artifacts. In this study helium and neon ion microscopy are used to image cracking in microindented samples of the non-conductive ceramic silicon nitride. The crack morphology of radial cracks emanating from the microindentations has been characterized for two different compositions of silicon nitride, with and without conductive coatings. Gold coating enhances crack edge contrast, but masks grain contrast for both He and Ne ion-induced secondary electron (ISE) imaging. Carbon coating enables the crystalline and glassy phases to be distinguished, more clearly with Ne-ISE, and the cracking pathway is found to be primarily intergranular. Zones of < 100 nm diameter depleted ion-induced secondary electron emission along the crack paths are identified, consistent with charging ‘hotspots’

Structure and properties of polystyrene-co-acrylonitrile/graphene oxide nanocomposites

Polymer/graphene nanocomposites have attracted significant attention from the research community over the past two decades. In this work, nanocomposites of polystyrene-co-acrylonitrile (SAN) and graphene oxide (GO) were prepared using a solution blending method with tetrahydrofuran as the solvent. The GO loadings used were 0.1, 0.25, 0.5, and 1.0 wt.%. Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy were employed to characterize the structure and morphology of SAN/GO nanocomposites. Thermal analysis showed increases in the glass transition (Tg) and peak thermal degradation (Tdpeak) temperatures of SAN by the additions of GO, with Tg increasing by 3.6 °C and Tdpeak by 19 °C for 1.0 wt.% GO loading. Dynamic mechanical analysis revealed that the storage modulus of SAN was also enhanced with the incorporations of GO by up to 62% for 1.0 wt.% loading. These property enhancements may be attributed to a good dispersion of GO in the polymer matrix and their interfacial interactions

Modification of graphene anode morphologies via wet and dry milling

Graphene, an individual graphite monolayer, is being considered for use in lithium ion anodes as there is a technological drive to make batteries thinner, lighter and more flexible whilst maintaining or increasing cell capacity and cyclability. Due to its mono/few-layer platelet structure graphene may potentially be affected by mechanical processing routes. Here the effects that dry milling and wet milling have on graphene nanoplatelets and graphene anode solutions have been investigated. It was found that dry milling for 15 minutes causes graphene nanoplatelets to form agglomerated graphite, but that wet milling of graphene anode solution results in reduced porosity and smoother electrodes without visibly destroying the nanoplatelets

3D characterisation of indentation induced sub-surface cracking in silicon nitride using FIB tomography

In this study, a combination of 3D FIB tomography and incremental surface polishing has been used to characterize cracking beneath 0.5 kg and 1 kg Vickers indentations on silicon nitride. It is shown that a half-penny cracking regime exists even for low indentation loads with c/a ratios < 2 indicating that the c/a ratio cannot reliably be used to predict sub-surface crack morphology. For the first time, the presence of deep lateral cracks interconnected with radial cracks was also observed surrounding indentations of low loads on silicon nitride, and it is likely that these could contribute to material removal via spalling

In-situ Ti-6Al-4V/TiC composites synthesized by reactive spark plasma sintering : processing, microstructure, and dry sliding wear behaviour

Titanium carbide (TiC) reinforced Titanium Matrix Composites (TMCs) have been synthesized via an in-situ reactive spark plasma sintering (SPS) process using commercial Ti-6Al-4V spherical powders pre-coated with 1 wt% carbon nanoparticles by low-energy ball milling. Graphite flakes are used as carbon source, which aids powder flow during mixing as lubricant. Graphite transforms to nano-crystallite carbon during mixing which is favourable for the rapid formation of TiC second phase in the following SPS process. The composites exhibited a novel honeycomb-like cellular microstructure with the formation of 5–6 vol% fine TiC submicron grains interconnected in the titanium α/β matrix. In addition, the reinforcement of the TiC phase with a nano-hardness of 12.4 GPa, improves the wear resistance of the parent alloy matrix (5.1 GPa), with a reduction of 26–28% in wear rate during dry reciprocating sliding tests against Si3N4 balls. During sliding, the wear debris (predominantly anatase TiO2) builds up on the raised TiC hard phase forming a barrier layer of adhered oxide that can protect the alloy matrix underneath from abrasion and oxidation, leading to a reduced wear rate

Towards in-situ TEM for Li-ion battery research

Due to recent developments in new battery materials for higher energy density applications there has been growing interest in new characterization techniques capable of time-resolved in situ/in operando analysis of dynamic Battery systems. This review provides an overview on recent development of liquid cell transmission electron microscopy (TEM) for Li-ion battery research and discusses the challenges, highlighting potential research areas. In-situ TEM offers the opportunity to study phenomena including solid electrolyte interphase (SEI) formation and phase changes during battery operation. There are two main challenging areas for in-situ TEM research (1) designing an in-situ TEM electrochemical cell that mimics a ‘real’ cell and (2) quantifying beam damage caused by electron irradiation of the electrolyte

Visualization and chemical characterization of the cathode electrolyte interphase using He-ion microscopy and in situ time-of-flight secondary ion mass spectrometry

Unstable cathode electrolyte interphase (CEI) formation increases degradation in high voltage Li-ion battery materials. Few techniques couple characterization of nano-scale CEI layers on the macroscale with in situ chemical characterization, and thus, information on how the underlying microstructure affects CEI formation is lost. Here, the process of CEI formation in a high voltage cathode material, LiCoPO4, has been investigated for the first time using helium ion microscopy (HIM) and in situ time-of-flight (ToF) secondary ion mass spectrometry (SIMS). The combination of HIM and Ne-ion ToF-SIMS has been used to correlate the cycle-dependent morphology of the CEI layer on LiCoPO4 with a local cathode microstructure, including position, thickness, and chemistry. HIM imaging identified partial dissolution of the CEI layer on discharge resulting in in-homogenous CEI coverage on larger LiCoPO4 agglomerates. Ne-ion ToF-SIMS characterization identified oxyfluorophosphates from HF attack by the electrolyte and a Li-rich surface region. Variable thickness of the CEI layer coupled with inactive Li on the surface of LiCoPO4 electrodes contributes to severe degradation over the course of 10 cycles. The HIM–SIMS technique has potential to further investigate the effect of microstructures on CEI formation in cathode materials or solid electrolyte interphase formation in anodes, thus aiding future electrode development

Effect of annealing on the electrical and magnetic properties of electrodeposited Ni and permalloy nanowires

The influence of annealing on the microstructure and the electrical and magnetic properties of cylindrical nickel-based nanowires has been investigated. Nanowires of nickel of ~275 nm diameter and of permalloy (Py) of ~70 nm diameter were fabricated by electrochemical deposition into nanoporous templates of polycarbonate and anodic alumina, respectively. Characterization was carried out on as-grown and up to 650 °C heat-treated nanowires. Transmission electron microscopy imaging and diffraction of the nanowires showed a temperature-correlated grain growth of an initially nanocrystalline structure (untreated) with <8 nm (Ni) and <20 nm (Py) grains towards coarser poly-crystallinity after heat treatment with grains up to ~160 nm (Ni) and ~70 nm (Py), the latter being limited by the nanowire width. The electrical conductivity of individual as-grown and 650 °C annealed Ni nanowires was measured in-situ by scanning electron microscopy. At low current densities, the conductivity of annealed nanowires was estimated to have doubled over as-grown nanowires. We attribute this increase to the observed grain growth. The annealed nanowire was subsequently subjected to increasing current densities. Above 120 kA.mm−2 the nanowire resistance started to rise. At 450 kA.mm−2, the nanowire melted and current flow ceased. Magnetometry of as-grown and annealed nanowire arrays showed them to display quasi-thin film magnetic properties. Coercivity and saturation field were inversely correlated in annealed wires and a 25% tunability in these properties was achieved at just 200 °C

In situ fracture behavior of single crystal LiNi0.8Mn0.1Co0.1O2 (NMC811)

Single crystal particle morphologies have become highly desirable for next generation cathode materials, removing grain boundary fracture and thereby reducing the surface area exposed to electrolyte. The intrinsic mechanical behavior of single crystal layered oxides, however, is poorly understood. Here, faceted single crystal LiNi0.8Mn0.1Co0.1O2 (NMC811) particles are compressed in situ in a scanning electron microscope (SEM), to determine mechanical deformation mechanisms as a function of crystallographic orientation. In situ, the dynamical deformation sequence observed is initial cracking at the compression zone, followed by accelerated transparticle crack propagation and concurrent (0001) slip band formation. The greatest loads and contact pressure at fracture, non-basal cracking, and activation of multiple basal slip systems in larger (>3 μm) particles, occur for compression normal to the (0001) layered structure. Loading on {012} preferentially activates basal fracture and slip at lower loads. Regardless of particle orientation, non-basal slip systems are not observed, and non-basal cracking and particle rotation occur during compression to compensate for this inability to activate dislocations in 3-dimensions. Crystallographic dependent mechanical behaviour of single crystal NMC811 means that particle texture in cathodes should be monitored, and sources of localised surface stress in cathodes, e. g. particle-to-particle asperity contacts during electrode manufacture, should be minimised

Fracture testing of lithium‐ion battery cathode secondary particles in‐situ inside the scanning electron microscope

Fracture of cathode secondary particles is a critical degradation mechanism in lithium-ion batteries. The microindentation strength of LiNi0.8Mn0.1Co0.1O2 secondary particles is measured in situ in the scanning electron microscope (SEM), enabling dynamical imaging of fracture. Crack propagation is intergranular between primary particles when induced by compressing between flat platens (analogous to calendaring), and with a cono-spherical indenter (representing particle-particle contact). Fracture occurs directly beneath the cono-spherical tip and at the centre of secondary particles when compressed between flat platens. Finite element modelling of stress states provides insight into the dependence of fracture load upon cohesive strength and particle toughness. Secondary particle indentation strength decreases with increasing secondary particle size, with cycling, and with increasing state of charge. The indentation strength decrease is greatest in earlier stages of delithiation. The novel microindentation technique allows assessment of strength and toughness of different cathode morphologies, aiding prediction of optimal particle structure and processing conditions