Grain boundary segregation in Fe-Mn-C twinning-induced plasticity steels studied by correlative electron backscatter diffraction and atom probe tomography

We report on the characterization of grain boundary (GB) segregation in an Fe-28Mn-0.3C (wt.%) twinning-induced plasticity (TWIP) steel. After recrystallization of this steel for 24 h at 700 °C, ∼50% general grain boundaries (GBs) and ∼35% Σ3 annealing twin boundaries were observed (others were high-order Σ and low-angle GBs). The segregation of B, C and P and traces of Si and Cu were detected at the general GB by atom probe tomography (APT) and quantified using ladder diagrams. In the case of the Σ3 coherent annealing twin, it was necessary to first locate the position of the boundary by density analysis of the atom probe data, then small amounts of B, Si and P segregation and, surprisingly, depletion of C were detected. The concentration of Mn was constant across the interface for both boundary types. The depletion of C at the annealing twin is explained by a local change in the stacking sequence at the boundary, creating a local hexagonal close-packed structure with low C solubility. This finding raises the question of whether segregation/depletion also occurs at Σ3 deformation twin boundaries in high-Mn TWIP steels. Consequently, a previously published APT dataset of the Fe-22Mn-0.6C alloy system, containing a high density of deformation twins due to 30% tensile deformation at room temperature, was reinvestigated using the same analysis routine as for the annealing twin. Although crystallographically identical to the annealing twin, no evidence of segregation or depletion was found at the deformation twins, owing to the lack of mobility of solutes during twin formation at room temperature.

Sulfur-doped porous reduced graphene oxide hollow nanosphere frameworks as metal-free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials.

Chemical doping with foreign atoms is an effective approach to significantly enhance the electrochemical performance of the carbon materials. Herein, sulfur-doped three-dimensional (3D) porous reduced graphene oxide (RGO) hollow nanosphere frameworks (S-PGHS) are fabricated by directly annealing graphene oxide (GO)-encapsulated amino-modified SiO2 nanoparticles with dibenzyl disulfide (DBDS), followed by hydrofluoric acid etching. The XPS and Raman spectra confirmed that sulfur atoms were successfully introduced into the PGHS framework via covalent bonds. The as-prepared S-PGHS has been demonstrated to be an efficient metal-free electrocatalyst for oxygen reduction reaction (ORR) with the activity comparable to that of commercial Pt/C (40%) and much better methanol tolerance and durability, and to be a supercapacitor electrode material with a high specific capacitance of 343 F g(-1), good rate capability and excellent cycling stability in aqueous electrolytes. The impressive performance for ORR and supercapacitors is believed to be due to the synergistic effect caused by sulfur-doping enhancing the electrochemical activity and 3D porous hollow nanosphere framework structures facilitating ion diffusion and electronic transfer.

Atom probe tomography study of the nanoscale heterostructure around an Al20Mn3Cu2 dispersoid in aluminum alloy 2024.

Atom probe tomography (APT) has been used to investigate the surface and sub-surface microstructures of aluminum alloy 2024 (AA2024) in the T3 condition (solution heat treated, cold worked, and naturally aged to a substantially stable condition). This study revealed surface Cu enrichment on the alloy matrix, local chemical structure around a dispersoid Al20Mn3Cu2 particle including a Cu-rich particle and S-phase particle on its external surface. Moreover, there was a significant level of hydrogen within the dispersoid, indicating that it is a hydrogen sink. These observations of the nanoscale structure around the dispersoid particle have considerable implications for understanding both corrosion and hydrogen embrittlement in high-strength aluminum alloys.

Fabrication of high specificity hollow mesoporous silica nanoparticles assisted by Eudragit for targeted drug delivery.

Hollow mesoporous silica nanoparticles (HMSNs) are one of the most promising carriers for effective drug delivery due to their large surface area, high volume for drug loading and excellent biocompatibility. However, the non-ionic surfactant templated HMSNs often have a broad size distribution and a defective mesoporous structure because of the difficulties involved in controlling the formation and organization of micelles for the growth of silica framework. In this paper, a novel "Eudragit assisted" strategy has been developed to fabricate HMSNs by utilising the Eudragit nanoparticles as cores and to assist in the self-assembly of micelle organisation. Highly dispersed mesoporous silica spheres with intact hollow interiors and through pores on the shell were fabricated. The HMSNs have a high surface area (670m(2)/g), small diameter (120nm) and uniform pore size (2.5nm) that facilitated the effective encapsulation of 5-fluorouracil within HMSNs, achieving a high loading capacity of 194.5mg(5-FU)/g(HMSNs). The HMSNs were non-cytotoxic to colorectal cancer cells SW480 and can be bioconjugated with Epidermal Growth Factor (EGF) for efficient and specific cell internalization. The high specificity and excellent targeting performance of EGF grafted HMSNs have demonstrated that they can become potential intracellular drug delivery vehicles for colorectal cancers via EGF-EGFR interaction.

Electrospun granular hollow SnO2 nanofibers hydrogen gas sensors operating at low temperatures

In this paper, we present H2 gas sensors based on hollow and filled, well-aligned electrospun SnO2 nanofibers, operating at a low temperature of 150 C. SnO2 nanofibers with diameters ranging from 80 to 400 nm have been successfully synthesized in which the diameter of the nanofibers can be controlled by adjusting the concentration of polyacrylonitrile in the solution for electrospinning. The presence of this polymer results in the formation of granular walls for the nanofibers. We discussed the correlation between nanofibers morphology, structure, oxygen vacancy contents and the gas sensing performances. X-ray photoelectron spectroscopy analysis revealed that the granular hollow SnO2 nanofibers, which show the highest responses, contain a significant number of oxygen vacancies, which are favorable for gas sensor operating at low temperatures. © 2014 American Chemical Society.

Functionalization of hollow mesoporous silica nanoparticles for improved 5-fu loading

 Hollow mesoporous silica nanoparticles were successfully fabricated and functionalized with appropriate silanes. After modifications, amine, carboxyl, cyano, and methyl groups were grafted onto the nanoparticles and all functionalized hollow mesoporous silica nanoparticles maintained a spherical and hollow structure with a mean diameter of ~120 nm and a shell thickness of ~10 nm. The loading capacity of the hollow mesoporous silica nanoaprticles to the anticancer drug, 5-fluorouracil, can be controlled via precise functionalization. The presence of amine groups on the surface of nanoparticles resulted in the highest loading capacity of 28.89%, due to the amine functionalized nanoparticles having a similar hydrophilicity but reverse charge to the drug. In addition, the change in pH leads to the variation of the intensity of electrostatic force between nanoparticles and the drug, which finally affects the loading capacity of amine functionalized hollow mesoporous silica nanoparticles to some extent. Higher drug loading was observed at pH of 7.4 and 8.5 as 5-fluorouracil becomes more deprotonated in alkaline conditions. The improved drug loading capacity by amine functionalized hollow mesoporous silica nanoparticles has demonstrated that they can become potential intracellular 5-fluorouracil delivery vehicles for cancers.

On low temperature bainite transformation characteristics using in-situ neutron diffraction and atom probe tomography

In-situ neutron diffraction was employed to monitor the evolution of nano-bainitic ferrite during low temperature isothermal heat treatment of austenite. The first 10 peaks (austenite, γ and ferrite, α) were monitored during austenization, homogenization, rapid cooling and isothermal holding at 573 K. Changes in the α-110 and γ-111 peaks were analysed to determine the volume fraction changes and hence the kinetics of the phase transformation. Asymmetry and broadening in the α-200 and γ-200 peaks were quantified to lattice parameter changes due to carbon redistribution as well as the effects of size and dislocation density. Atom Probe Tomography was used to confirm that, despite the presence of 1.5 mass % Si, carbide formation was evident. This carbide formation is the cause of poor ductility, which is lower than expected in such steels.

Tailored hollow mesoporous silica nanoplatforms with biological labels for colon targeted drug deliver systems

Hollow mesoporous silica nanoparticles (HMSNs) were synthesized via a new strategy. HMSNs have a high drug loading, controlled release behaviour, and specifically targeting when bioconjugated with Epidermal Growth Factor. The promising in vitro cell tests have revealed the great potential of the HMSNs to be used for cancer therapy.

A self-supported, flexible, binder-free pseudo-supercapacitor electrode material with high capacitance and cycling stability from hollow, capsular polypyrrole fibers

Flexible energy devices with high performance and long-term stability are highly promising for applications in portable electronics, but remain challenging to develop. As an electrode material for pseudo-supercapacitors, conducting polymers typically show higher energy storage ability over carbon materials and larger conductivity than transition-metal oxides. However, conducting polymer-based supercapacitors often have poor cycling stability, attributable to the structural rupture caused by the large volume contrast between doping and de-doping states, which has been the main obstacle to their practical applications. Herein, we report a simple method to prepare a flexible, binder-free, self-supported polypyrrole (PPy) supercapacitor electrode with high cycling stability through using novel, hollow PPy nanofibers with porous capsular walls as a film-forming material. The unique fiber structure and capsular walls provide the PPy film with enough free-space to adapt to volume variation during doping/de-doping, leading to super-high cycling stability (capacitance retention > 90% after 11000 charge-discharge cycles at a high current density of 10 A g^-1) and high rate capability (capacitance retention ∼ 82.1% at a current density in the range of 0.25-10 A g^-1).

Atomic scale analysis of light alloys using atom probe tomography

The present paper reviews recent progress in atomic-scale characterisation of composition and nanostructure of light alloy materials using the technique of atom probe tomography. In particular, the present review will highlight atom-by-atom analysis of solid solution architecture, including solute clustering and short-range order, with reference to current limitations of spatial resolution and detector efficiency of atom probe tomography and methods to address these limitations. This leads to discussion of prediction of mechanical properties by simulation and modelling of the strengthening effect exerted by solute clusters and the role of experimental atom probe data to assist in this process. The unique contribution of atom probe tomography to the study of corrosion and hydrogen embrittlement of light alloys will also be discussed as well as a brief insight into its potential application for the investigation of solute strengthening of twinning in Mg alloys.

Overcoming acquired drug resistance in colorectal cancer cells by targeted delivery of 5-FU with EGF grafted hollow mesoporous silica nanoparticles

Acquired drug resistance (ADR) can be developed in colorectal cancer cells after 5-fluorouracil (5-FU) treatment and diminish the effectiveness of chemotherapy. In this work, acquired 5-FU resistance in the colorectal cancer cell line SW480 was obtained with the up-regulation of dihydropyrimidine dehydrogenase (DPYD) gene expression which can convert 5-FU to its inactive metabolite. To overcome ADR in colorectal cancer, hollow mesoporous silica nanoparticles (HMSNs) grafted with epidermal growth factor (EGF) were used as nanocarriers to deliver 5-FU to colorectal cancer cells with acquired drug resistance. The effect and mechanism of 5-FU loaded EGF grafted HMSNs (EGF-HMSNs-5-FU) in overcoming acquired drug resistance in SW480/ADR cells were studied. The EGF-HMSNs were demonstrated to be specifically internalized in EGFR overexpressed SW480/ADR cells via a receptor-mediated endocytosis and can escape from endo-lysosomes. The EGF-HMSNs-5-FU exhibited much higher cytotoxicity on SW480/ADR cells than HMSNs-5-FU and free 5-FU while the plain HMSNs did not show significant cytotoxicity. The mechanism of EGF-HMSNs-5-FU in overcoming drug resistance in SW480/ADR cells could be attributed to the specific internalization of EGF-HMSNs-5-FU in EGFR overexpressed cells which can lead to high intracellular drug accumulation and cause cell death through S phase arrest.

Atom probe tomography investigation of heterogeneous short-range ordering in the 'komplex' phase state (K-state) of Fe-18Al (at.%)

We study an Fe-18Al (at.%) alloy after various thermal treatments at different times (24-336 h) and temperatures (250-1100 °C) to determine the nature of the so-called 'komplex' phase state (or "K-state"), which is common to other alloy systems having compositions at the boundaries of known order-disorder transitions and is characterised by heterogeneous short-range-ordering (SRO). This has been done by direct observation using atom probe tomography (APT), which reveals that nano-sized, ordered regions/particles do not exist. Also, by employing shell-based analysis of the three-dimensional atomic positions, we have determined chemically sensitive, generalised multicomponent short-range order (GM-SRO) parameters, which are compared with published pairwise SRO parameters derived from bulk, volume-averaged measurement techniques (e.g. X-ray and neutron scattering, Mössbauer spectroscopy) and combined ab-initio and Monte Carlo simulations. This analysis procedure has general relevance for other alloy systems where quantitative chemical-structure evaluation of local atomic environments is required to understand ordering and partial ordering phenomena that affect physical and mechanical properties.

Quantitative chemical-structure evaluation using atom probe tomography: Short-range order analysis of Fe-Al.

Short-range-order (SRO) has been quantitatively evaluated in an Fe-18Al (at%) alloy using atom probe tomography (APT) data and by calculation of the generalised multicomponent short-range order (GM-SRO) parameters, which have been determined by shell-based analysis of the three-dimensional atomic positions. The accuracy of this method with respect to limited detector efficiency and spatial resolution is tested against simulated D03 ordered data. Whilst there is minimal adverse effect from limited atom probe instrument detector efficiency, the combination of this with imperfect spatial resolution has the effect of making the data appear more randomised. The value of lattice rectification of the experimental APT data prior to GM-SRO analysis is demonstrated through improved information sensitivity.

Capsular polypyrrole hollow nanofibers: an efficient recyclable adsorbent for hexavalent chromium removal

Capsular polypyrrole hollow nanofibers (PPy-HNFs) were fabricated via in situ polymerization of pyrrole on an organic-inorganic template, followed by acid etching. Their application in removing hexavalent chromium (Cr(vi)) from aqueous solution was then investigated. The morphologies of the capsular PPy-HNFs were studied by both scanning electron microscopy (SEM) and transmission electron microscopy (TEM), which showed that the PPy-HNFs had a capsular structure in the walls of hollow nanofibers. Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) data confirmed the adsorption of Cr on capsular PPy-HNFs. The adsorption capacity increased with reduced pH of the initial solution and the adsorption process can be described using the pseudo-second-order model. These capsular PPy-HNFs showed a high Cr(vi) adsorption capacity up to 839.3 mg g-1. This adsorption capacity was largely retained even after five adsorption/desorption cycles. Electrostatic attraction between Cr and PPy-HNFs was studied using a proposed adsorption mechanism. The capsular PPy-HNFs formed a flexible membrane, which allowed easy handling during application. This study has demonstrated the possibilities of using this capsular PPy-HNF membrane for heavy metal removal from aqueous solution.

The zombies of sleepy hollow: reimagining Geelong

Place branding is traditionally concerned with drawing on the positive and unique elements of a community to generate investment and build community pride. In 2014 a promotional video was released portraying Geelong as a zombie town, with flamboyant Mayor Darryn Lyons riding in on horseback to save the city and its people. The imagery was more at home in cult zombie cinema than a tourism promotion. Critics berated the video as an ill-conceived stunt that carried a message derisive to the local community. Supporters focused on the bold, creative nature of the endeavour, claiming its potential to ‘go viral’ would enhance Geelong’s media presence, improve the city’s perception and draw visitors to the area. Geelong was first badged ‘Sleepy Hollow’ in the 1860s when the new gold towns of Ballarat and Bendigo boomed, challenging its supremacy as a commercial centre. Geelong prospered in the 1920s through industrialisation, but the moniker has remained. Today, Geelong faces a period of economic uncertainty and transition as it adjusts to major job losses in manufacturing. While this presents significant challenges, it also creates opportunities for the city to re-imagine itself by capitalising on the physical and cultural assets that set Geelong apart. While the zombie video has sparked debate, its success in influencing views of the city is constrained by its references to past stigma and its imposition of a new sense of dystopia in the present. This paper explores the Sleepy Hollow predicament and considers how the branding of Geelong might move beyond parody to better reflect its position as Victoria’s largest regional centre through an approach based on imageability, narrative, assets and investment.