Ceramic nanostructure materials, membranes and composite layers

Synthesis methods to obtain nanoscale materials will be briefly discussed with a focus on sol-gel methods. Three types of nanoscale composites (powders, membranes and ion implanted layers) will be discussed and exemplified with recent original research results. Ceramic membranes with a thickness of 1–10 μm consist of a packing of elementary particles with a size of 3–7 nm. The mean pore size is about 2.5–3 nm. The preparation routes are based on sol and sol-gel technologies. The pores can be modified by liquid as well as by gas deposition techniques. This leads to modification of the chemical character and the effective pore size and gives rise to microstructure elements well below the size of the pores (3 nm). The modification of ceramic surface layers with a thickness of 0.05–0.5 μm by ion implantation and annealing procedures yields amorphous or strongly supersatured metastable solid solutions of e.g. Fe2O3 (or TiO2) in zirconia-yttria solid solutions or of very finely dispersed metal particles in the ceramic surface layers. Particle sizes are of the order of 2–4 nm. Both types of structures have interesting transport, catalytic and mechanical properties

Theory of hyperbolic stratified nanostructures for surface enhanced Raman scattering

We theoretically investigate the enhancement of surface enhanced Raman spectroscopy (SERS) using hyperbolic stratified nanostructures and compare to metal nanoresonators. The photon Green function of each nanostructure within its environment is first obtained from a semi-analytical modal theory, which is used in a quantum optics formalism of the molecule-nanostructure interaction to model the SERS spectrum. An intuitive methodology is presented for calculating the single molecule enhancement factor (SMEF), which is also able to predict known experimental SERS enhancement factors of an example gold nano-dimer. We elucidate the important figures-of-merit of the enhancement and explore these for different designs. We find that the use of hyperbolic stratified materials can enhance the photonic local density of states (LDOS) by close to 2 times in comparison to pure metal nanostructures, when both designed to work at the same operating wavelengths. However, the increased LDOS is accompanied by higher electric field concentration within the lossy hyperbolic material, which leads to increased quenching that serves to reduce the overall detected SERS enhancement in the far field. For nanoresonators with resonant localized surface plasmon wavelengths in the near-infrared, the SMEF for the hyperbolic stratified nanostructure is approximately an order of magnitude lower than the pure metal counterpart. Conversely, we show that by detecting the Raman signal using a near-field probe, hyperbolic materials can provide an improvement in SERS enhancement compared to using pure metal nanostructures when the probe is sufficiently close (<50 nm) to the Raman active molecule at the plasmonic hotspot.Comment: 18 pages, 9 figure

Magnetic nanostructures by adaptive twinning in strained epitaxial films

We exploit the intrinsic structural instability of the Fe70Pd30 magnetic shape memory alloy to obtain functional epitaxial films exhibiting a self-organized nanostructure. We demonstrate that coherent epitaxial straining by 54% is possible. The combination of thin film experiments and large-scale first-principles calculations enables us to establish a lattice relaxation mechanism, which is not expected for stable materials. We identify a low twin boundary energy compared to a high elastic energy as key prerequisite for the adaptive nanotwinning. Our approach is versatile as it allows to control both, nanostructure and intrinsic properties for ferromagnetic, ferroelastic and ferroelectric materials.Comment: Final version. Supplementary information available on request or at the publisher's websit

Manipulating nanoscale structure to control functionality in printed organic photovoltaic, transistor and bioelectronic devices.

Printed electronics is simultaneously one of the most intensely studied emerging research areas in science and technology and one of the fastest growing commercial markets in the world today. For the past decade the potential for organic electronic (OE) materials to revolutionize this printed electronics space has been widely promoted. Such conviction in the potential of these carbon-based semiconducting materials arises from their ability to be dissolved in solution, and thus the exciting possibility of simply printing a range of multifunctional devices onto flexible substrates at high speeds for very low cost using standard roll-to-roll printing techniques. However, the transition from promising laboratory innovations to large scale prototypes requires precise control of nanoscale material and device structure across large areas during printing fabrication. Maintaining this nanoscale material control during printing presents a significant new challenge that demands the coupling of OE materials and devices with clever nanoscience fabrication approaches that are adapted to the limited thermodynamic levers available. In this review we present an update on the strategies and capabilities that are required in order to manipulate the nanoscale structure of large area printed organic photovoltaic (OPV), transistor and bioelectronics devices in order to control their device functionality. This discussion covers a range of efforts to manipulate the electroactive ink materials and their nanostructured assembly into devices, and also device processing strategies to tune the nanoscale material properties and assembly routes through printing fabrication. The review finishes by highlighting progress in printed OE devices that provide a feedback loop between laboratory nanoscience innovations and their feasibility in adapting to large scale printing fabrication. The ability to control material properties on the nanoscale whilst simultaneously printing functional devices on the square metre scale is prompting innovative developments in the targeted nanoscience required for OPV, transistor and biofunctional devices

The application of thermal analysis to the study of epoxy–clay nanocomposites

This is a copy of the author 's final draft version of an article published in the journal Journal of thermal analysis and calorimetry. The final publication is available at Springer via http://dx.doi.org/10.1007/s10973-016-5278-0The development of polymer layered silicate (PLS) nanocomposites goes back over 20 years now, and yet they still have not achieved their full potential. A principal reason for this is the difficulty of obtaining a truly exfoliated nanostructure. The fabrication procedure for such PLS nanocomposites based upon epoxy resin includes several stages, including dispersion of the clay in the resin, intercalation of the resin into the clay galleries, and finally curing of the nanocomposite system. Many attempts have been made to improve the degree of exfoliation in the final nanostructure by modifying the procedures involved in these fabrication stages, and the usual approach is to examine the nanostructure, by techniques such as small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), as a function of the fabrication procedure. We show here, however, that thermal analytical techniques, and in particular differential scanning calorimetry, can complement the techniques of SAXS and TEM in the search for ways in which to achieve improved degrees of exfoliation in PLS nanocomposites based upon epoxy resin.Peer ReviewedPostprint (author's final draft

Complementary use of TEM and APT for the investigation of steels nanostructured by severe plastic deformation

The properties of bulk nanostructured materials are often controlled by atomic scale features like segregation along defects or composition gradients. Here we discuss about the complimentary use of TEM and APT to obtain a full description of nanostructures. The advantages and limitations of both techniques are highlighted on the basis of experimental data collected in severely deformed steels with a special emphasis on carbon spatial distribution

Multi-scale simulation of capillary pores and gel pores in Portland cement paste

The microstructures of Portland cement paste (water to cement ratio is 0.4, curing time is from 1 day to 28 days) are simulated based on the numerical cement hydration model, HUMOSTRUC3D (van Breugel, 1991; Koenders, 1997; Ye, 2003). The nanostructures of inner and outer C-S-H are simulated by the packing of monosized (5 nm) spheres. The pore structures (capillary pores and gel pores) of Portland cement paste are established by upgrading the simulated nanostructures of C-S-H to the simulated microstructures of Portland cement paste. The pore size distribution of Portland cement paste is simulated by using the image segmentation method (Shapiro and Stockman, 2001) to analyse the simulated pore structures of Portland cement paste. The simulation results indicate that the pore size distribution of the simulated capillary pores of Portland cement paste at the age of 1 day to 28 days is in a good agreement with the pore size distribution determined by scanning electron microscopy (SEM). The pore size distribution of the simulated gel pores of Portland cement paste (interlayer gel pores of outer C-S-H and gel pores of inner C-S-H are not included) is validated by the pore size distribution obtained by mercury intrusion porosimetry (MIP). The pores with pore size of 20 nm to 100 nm occupy very small volume fraction in the simulated Portland cement paste at each curing time (0.69% to 1.38%). This is consistent with the experimental results obtained by nuclear magnetic resonance (NMR)