Medieval Gilding Technology of Historical Metal Threads Revealed by Electron Optical and Micro-Raman Spectroscopic Study of Focused Ion Beam-Milled Cross Sections.

Although gilt silver threads were widely used for decorating historical textiles, their manufacturing techniques have been elusive for centuries. Contemporary written sources give only limited, sometimes ambiguous information, and detailed cross-sectional study of the microscale soft noble metal objects has been hindered by sample preparation. In this work, to give a thorough characterization of historical gilt silver threads, nano- and microscale textural, chemical, and structural data on cross sections, prepared by focused ion beam milling, were collected, using various electron-optical methods (high-resolution scanning electron microscopy (SEM), wavelength-dispersive electron probe microanalysis (EPMA), electron backscattered diffraction (EBSD) combined with energy-dispersive electron probe microanalysis (EDX), transmission electron microscopy (TEM) combined with EDX, and micro-Raman spectroscopy. The thickness of the gold coating varied between 70-400 nm. Data reveal nano- and microscale metallurgy-related, gilding-related and corrosion-related inhomogeneities in the silver base. These inhomogeneities account for the limitations of surface analysis when tracking gilding methods of historical metal threads, and explain why chemical information has to be connected to 3D texture on submicrometre scale. The geometry and chemical composition (lack of mercury, copper) of the gold/silver interface prove that the ancient gilding technology was diffusion bonding. The observed differences in the copper content of the silver base of the different thread types suggest intentional technological choice. Among the examined textiles of different ages (13th-17th centuries) and provenances narrow technological variation has been found.

Index matching at the nanoscale: light scattering by core-shell Si/SiO x nanowires.

Silicon nanowires (SiNWs) show strong resonant wavelength enhancement in terms of absorption as well as scattering of light. However, in most optoelectronic device concepts the SiNWs should be surrounded by a contact layer. Ideally, such a layer can also act as an index matching layer which could nearly halve the strong reflectance of light by silicon. Our results show that this reduction can be overcome at the nanometer scale, i.e. SiNWs embedded in a silica (SiO x ) layer can not only maintain their high scattering cross sections but also their strong polarization dependent scattering. Such effects can be useful for light harvesting or optoelectronic applications. Moreover, we show that it is possible to optically determine the diameters of the embedded nanoscale silicon (Si) cores.

Preparation of compact nanoparticle clusters from polyethylene glycol-coated gold nanoparticles by fine-tuning colloidal interactions.

Low-molecular weight polyethylene glycol (PEG) has a lower critical solution temperature well outside the boiling point of water at ambient pressure, but it can be reduced at high ionic strengths. We extend this concept to trigger the clustering of gold nanoparticles through the control of colloidal interactions. At high ionic strengths, low-molecular weight (<2000 Da) mPEG-SH-modified gold nanoparticles show clustering with an increase in the solution temperature. The clustering temperature decreases with an increasing ionic strength. The clustering is attributed to the delicate interplay between the high ionic strength and elevated temperature and is interpreted in terms of chain collapse of the surface-grafted PEG molecules. The chain collapse results in a change in the steric interaction term, whereas the high ionic strength eliminates the double-layer repulsion between the particles. The observations are backed by nanoparticle interaction model calculations. We found that the intermediate attractive potential on the order of a few kT allows the experimental fabrication of compact nanoparticle clusters in agreement with theoretical predictions. The approach presented here has the potential to be extended on the externally triggered preparation of nanoparticle clusters with different types of nanoparticles.

Simple ePDF: A Pair Distribution Function Method Based on Electron Diffraction Patterns to Reveal the Local Structure of Amorphous and Nanocrystalline Materials.

Amorphous, glassy or disordered materials play important roles in developing structural materials from metals or ceramics, devices from semiconductors or medicines from organic compounds. Their local structure is frequently similar to crystalline ones. A computer program is presented here that runs under the Windows operating system on a PC to extract pair distribution function (PDF) from electron diffraction in a transmission electron microscope (TEM). A polynomial correction reduces small systematic deviations from the expected average Q-dependence of scattering. Neighbor distance and coordination number measurements are supplemented by either measurement or enforcement of number density. Quantification of similarity is supported by calculation of Pearson's correlation coefficient and fingerprinting. A rough estimate of fractions in a mixture is computed by multiple least-square fitting using the PDFs from components of the mixture. PDF is also simulated from crystalline structural models (in addition to measured ones) to be used in libraries for fingerprinting or fraction estimation. Crystalline structure models for simulations are obtained from CIF files or str files of ProcessDiffraction. Data from inorganic samples exemplify usage. In contrast to previous free ePDF programs, our stand-alone program does not need a special software environment, which is a novelty. The program is available from the author upon request.

Continuous spark plasma synthesis of Au/Co binary nanoparticles with tunable properties.

We present here a scalable and environmentally friendly gas phase technique employing atmospheric pressure electrical spark discharge plasmas for the production of Au/Co binaries, an effective catalyst system for the decomposition of hydrogen-rich compounds, such as ammonium borane. We demonstrate that Au/Co alloy nanoparticles can be produced via the spark plasma-based technique. The possibility of varying the morphology and phase structure via real time heat treatment of the generated aerosol to form Au/Co/CoO particles with continuous control over a wide particle compositional range (from 24 to 64 at.% [Co]/([Co] + [Au]) content) is also demonstrated. Since our spark-based approach is proven to be capable of providing reasonable particle yields, these results may contribute to the transition of lab-scale, nanocatalyst-based hydrogen storage systems to real world applications.

Structural Characteristics of the Si Whiskers Grown by Ni-Metal-Induced-Lateral-Crystallization.

Si whiskers grown by Ni-Metal-Induced-Lateral-Crystallization (Ni-MILC) were grown at 413 °C, intentionally below the threshold for Solid State Crystallization, which is 420 °C. These whiskers have significant common characteristics with whiskers grown by the Vapor Liquid Solid (VLS) method. The crystalline quality of the whiskers in both methods is the same. However, in VLS, a crystalline substrate is required, in contrast to the amorphous one in Ni-MILC for the growth of single crystalline whiskers. Moreover, whiskers grown by VLS have a polygonal cross-section with their diameter determined by the diameter of the hemispherical metallic catalysts. On the other hand, in the Ni-MILC, the cross-section of the whiskers depends on the size of the NiSi2 grain from which they are emanated. This was confirmed by observing the crossing whiskers and the rotational Moiré patterns in the crossing area. The structure of disturbed short and thin nonlinear branches on the side-walls of the whiskers was studied. In the whiskers grown by the VLS method, significant contamination occurs by the metallic catalyst degrading the electrical characteristics of the whisker. Such Si whiskers are not compatible with the current CMOS process. Whiskers grown by Ni-MILC at 413 °C are also contaminated by Ni. However, the excess Ni is in the form of tetrahedral NiSi2 inclusions which are coherent with the Si matrix due to the very low misfit of 0.4% between them. These whiskers are compatible with current CMOS process and Thin Film Transistors (TFTs).

Reversible control of magnetism in FeRh thin films.

The multilayer of approximate structure MgO(100)/[nFe51Rh49(63 Å)/57Fe51Rh49(46 Å)]10 deposited at 200 °C is primarily of paramagnetic A1 phase and is fully converted to the magnetic B2 phase by annealing at 300 °C for 60 min. Subsequent irradiation by 120 keV Ne+ ions turns the thin film completely to the paramagnetic A1 phase. Repeated annealing at 300 °C for 60 min results in 100% magnetic B2 phase, i.e. a process that appears to be reversible at least twice. The A1 → B2 transformation takes place without any plane-perpendicular diffusion while Ne+ irradiation results in significant interlayer mixing.

Growth model for arc-deposited fullerene-like CNx nanoparticles.

Multiwall CNx nanotubes, nanoonions, and amorphous nanoballs were formed by carbon DC arc evaporation in a nitrogen atmosphere. The samples were investigated by conventional and high-resolution transmission electron microscopy. We propose a fragment-by-fragment growth mechanism for the formation of the nanoparticles. Accordingly, particles and aggregates of particles form in the vacuum ambient by the collisions between atomic species and small fragments. This growth model is supported by the discontinuous inner shells and disordered surface layers composed from graphene fragments. Image simulations confirm the detectability of dangling and back-folding surface layers in the experimental images. Further, the simulated images also confirm that the growth of nanoonions starts from a single fullerene-like seed. The amorphous nanoballs form when ordering of the building blocks during growth is hindered by the cross-linking nitrogen bonds.

Oriented crystal growth model explains the formation of titania nanotubes.

We discuss the formation mechanism of titania nanotubes synthesized by the hydrothermal method. On the basis of a comprehensive analysis of TEM, HRTEM, FT-Raman, and N(2) adsorption data, we point out some major shortcomings of the currently accepted trititanate sheet rollup mechanism. We suggest that a novel formation mechanism, oriented nanotube crystal growth from nanoloop seeds, can explain the experimental findings better than the ones proposed so far.

Sealing of hard CrN and DLC coatings with atomic layer deposition.

Atomic layer deposition (ALD) is a thin film deposition technique that is based on alternating and saturating surface reactions of two or more gaseous precursors. The excellent conformality of ALD thin films can be exploited for sealing defects in coatings made by other techniques. Here the corrosion protection properties of hard CrN and diamond-like carbon (DLC) coatings on low alloy steel were improved by ALD sealing with 50 nm thick layers consisting of Al2O3 and Ta2O5 nanolaminates or mixtures. In cross sectional images the ALD layers were found to follow the surface morphology of the CrN coatings uniformly. Furthermore, ALD growth into the pinholes of the CrN coating was verified. In electrochemical measurements the ALD sealing was found to decrease the current density of the CrN coated steel by over 2 orders of magnitude. The neutral salt spray (NSS) durability was also improved: on the best samples the appearance of corrosion spots was delayed from 2 to 168 h. On DLC coatings the adhesion of the ALD sealing layers was weaker, but still clear improvement in NSS durability was achieved indicating sealing of the pinholes.