Gold nanoparticle formation in diamond-like carbon using two different methods: Gold ion implantation and co-deposition of gold and carbon

We describe work in which gold nanoparticles were formed in diamond-like carbon (DLC), thereby generating a Au-DLC nanocomposite. A high-quality, hydrogen-free DLC thin film was formed by filtered vacuum arc plasma deposition, into which gold nanoparticles were introduced using two different methods. The first method was gold ion implantation into the DLC film at a number of decreasing ion energies, distributing the gold over a controllable depth range within the DLC. The second method was co-deposition of gold and carbon, using two separate vacuum arc plasma guns with suitably interleaved repetitive pulsing. Transmission electron microscope images show that the size of the gold nanoparticles obtained by ion implantation is 3-5 nm. For the Au-DLC composite obtained by co-deposition, there were two different nanoparticle sizes, most about 2 nm with some 6-7 nm. Raman spectroscopy indicates that the implanted sample contains a smaller fraction of sp(3) bonding for the DLC, demonstrating that some sp(3) bonds are destroyed by the gold implantation. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4757029]

Tailored SERS substrates obtained with cathodic arc plasma ion implantation of gold nanoparticles into a polymer matrix

This manuscript reports on the fabrication of plasmonic substrates using cathodic arc plasma ion implantation, in addition to their performance as SERS substrates. The technique allows for the incorporation of a wide layer of metallic nanoparticles into a polymer matrix, such as PMMA. The ability to pattern different structures using the PMMA matrix is one of the main advantages of the fabrication method. This opens up new possibilities for obtaining tailored substrates with enhanced performance for SERS and other surface-enhanced spectroscopies, as well as for exploring the basic physics of patterned metal nanostructures. The architecture of the SERS-active substrate was varied using three adsorption strategies for incorporating a laser dye (rhodamine): alongside the nanoparticles into the polymer matrix, during the polymer cure and within nanoholes lithographed on the polymer. As a proof-of-concept, we obtained the SERS spectra of rhodamine for the three types of substrates. The hypothesis of incorporation of rhodamine molecules into the polymer matrix during the cathodic arc plasma ion implantation was supported by FDTD (Finite-Difference Time-Domain) simulations. In the case of arrays of nanoholes, rhodamine molecules could be adsorbed directly on the gold surface, then yielding a well-resolved SERS spectrum for a small amount of analyte owing to the short-range interactions and the large longitudinal field component inside the nanoholes. The results shown here demonstrate that the approach based on ion implantation can be adapted to produce reproducible tailored substrates for SERS and other surface-enhanced spectroscopies.

Effect of Nitrogen Ion Implantation on the Flexibility of Rotary Nickel-Titanium Instruments

Introduction: The aim of this study was to assess the effect of nitrogen ion implantation on the flexibility of rotary nickel-titanium (NiTi) instruments as measured by the load required to bend implanted and nonimplanted instruments at a 30 degrees angle. Methods: Thirty K3 files, size #40, 0.02 taper and 25-mm length, were allocated into 2 groups as follows: group A, 15 files exposed to nitrogen ion implantation at a dose of 2.5 x 10(17) ions/cm(2), voltage 200 KeV, current density 1 mu A/cm(2), temperature 130 degrees C, and vacuum conditions of 10 x 10(-6) mm Hg for 6 hours; and group B, 15 nonimplanted files. One extra file was used for process control. All instruments were subjected to bend testing on a modified troptometer, with measurement of the load required for flexure to an angle of 30 degrees. The Mann-Whitney U test was used for statistical analysis. Findings with P <.05 were considered significant. Results: The mean load required to bend instruments at a 30 degrees angle was 376.26 g for implanted instruments and 383.78 g for nonimplanted instruments. The difference was not statistically significant. Conclusions: Our findings show that nitrogen ion implantation has no appreciable effect on the flexibility of NiTi instruments. (J Endod 2012;38:673-675)

Low cost ion implantation technique

We describe an approach to ion implantation in which the plasma and its electronics are held at ground potential and the ion beam is formed and injected energetically into a space held at high negative potential. The technique allows considerable savings both economically and technologically, rendering feasible ion implantation applications that might otherwise not be possible for many researchers and laboratories. Here, we describe the device and the results of tests demonstrating Nb implantation at 90 keV ion energy and dose about 2 x 10(16) cm(-2). (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4768699]

Surface modification by metal ion implantation forming metallic nanoparticles in insulating matrix.

There is special interest in the incorporation of metallic nanoparticles in a surrounding dielectric matrix for obtaining composites with desirable characteristics such as for surface plasmon resonance, which can be used in photonics and sensing, and controlled surface electrical conductivity. We investigated nanocomposites produced through metallic ion implantation in insulating substrate, where the implanted metal self-assembles into nanoparticles. During the implantation, the excess of metal atom concentration above the solubility limit leads to nucleation and growth of metal nanoparticles, driven by the temperature and temperature gradients within the implanted sample including the beam-induced thermal characteristics. The nanoparticles nucleate near the maximum of the implantation depth profile (projected range), that can be estimated by computer simulation using the TRIDYN. This is a Monte Carlo simulation program based on the TRIM (Transport and Range of Ions in Matter) code that takes into account compositional changes in the substrate due to two factors: previously implanted dopant atoms, and sputtering of the substrate surface. Our study suggests that the nanoparticles form a bidimentional array buried few nanometers below the substrate surface. More specifically we have studied Au/PMMA (polymethylmethacrylate), Pt/PMMA, Ti/alumina and Au/alumina systems. Transmission electron microscopy of the implanted samples showed the metallic nanoparticles formed in the insulating matrix. The nanocomposites were characterized by measuring the resistivity of the composite layer as function of the dose implanted. These experimental results were compared with a model based on percolation theory, in which electron transport through the composite is explained by conduction through a random resistor network formed by the metallic nanoparticles. Excellent agreement was found between the experimental results and the predictions of the theory. It was possible to conclude, in all cases, that the conductivity process is due only to percolation (when the conducting elements are in geometric contact) and that the contribution from tunneling conduction is negligible.

Gold ion implantation into alumina using an “inverted ion source” configuration.

We describe an approach to ion implantation in which the plasma and its electronics are held at ground potential and the ion beam is injected into a space held at high negative potential, allowing considerable savings both economically and technologically. We used an “inverted ion implanter” of this kind to carry out implantation of gold into alumina, with Au ion energy 40 keV and dose (3–9) × 1016 cm−2. Resistivity was measured in situ as a function of dose and compared with predictions of a model based on percolation theory, in which electron transport in the composite is explained by conduction through a random resistor network formed by Au nanoparticles. Excellent agreement is found between the experimental results and the theory.

Interface tailoring for adhesion enhancement of diamond-like carbon thin films

We have explored the suitability and characteristics of interface tailoring as a tool for enhancing the adhesion of hydrogen-free diamond-like carbon (DLC) thin films to silicon substrates. DLC films were deposited on silicon with and without application of an initial high energy carbon ion bombardment phase that formed a broad Si-C interface of gradually changing Si:C composition. The interface depth profile was calculated using the TRIDYN simulation program, revealing a gradient of carbon concentration including a region with the stoichiometry of silicon carbide. DLC films on silicon, with and without interface tailoring, were characterized using Raman spectroscopy, scanning electron microscopy, atomic force microscopy and scratch tests. The Raman spectroscopy results indicated sp3-type carbon bonding content of up to 80%. Formation of a broadened Si:C interface as formed here significantly enhances the adhesion of DLC films to the underlying silicon substrate. (C) 2012 Elsevier B.V. All rights reserved.

Application of Mossbauer spectroscopy to the study of corrosion resistance in NaCl solution of plasma nitrided AISI 316L stainless steel

Corrosion research in steels is one of the areas in which Mossbauer spectroscopy has become a required analytical technique, since it is a powerful tool for both identifying and quantifying distinctive phases (which contain Fe) with accuracy. In this manuscript, this technique was used to the study of corrosion resistance of plasma nitrided AISI 316L samples in the presence of chloride anions. Plasma nitriding has been carried out using dc glow-discharge, nitriding treatments, in medium of 80 vol.% H-2 and 20 vol.% N-2, at 673 K, and at different time intervals: 2, 4, and 7 h. Treated samples were characterized by means of phase composition and morphological analysis, and electrochemical tests in NaCl aerated solution in order to investigate the influence of treatment time on the microstructure and the corrosion resistance, proved by conversion electron Mossbauer spectroscopy (CEMS), glancing angle X-ray diffraction (GAXRD), scanning electron microscopy (SEM) and potentiodynamic polarization. A modified layer of about 8 gin was observed for all the nitrided samples, independently of the nitriding time. A metastable phase, S phase or gamma(N), was produced. It seems to be correlated with gamma`-Fe-4 N phase. If the gamma(N) fraction decreases, the gamma` fraction increases. The gamma(N) magnetic nature was analyzed. When the nitriding time increases, the results indicate that there is a significant reduction in the relative fraction of the magnetic gamma(N) (in) phase. In contrast, the paramagnetic gamma(N) (p) phase increases. The GAXRD analysis confirms the Mossbauer results, and it also indicates CrN traces for the sample nitrided for 7 h. Corrosion results demonstrate that time in the plasma nitriding treatment plays an important role for the corrosion resistance. The sample treated for 4 h showed the best result of corrosion resistance. It seems that the epsilon/gamma` fraction ratio plays an important role in thin corrosion resistance since this sample shows the maximum value for this ratio. (c) 2008 Published by Elsevier B.V.

On the electrical conductivity of Ti-implanted alumina

Ion implantation of metal species into insulators provides a tool for the formation of thin, electrically conducting, surface layers with experimenter-controlled resistivity. High energy implantation of Pt and Ti into alumina accelerator components has been successfully employed to control high voltage surface breakdown in a number of cases. In the work described here we have carried out some basic investigations related to the origin of this phenomenon. By comparison of the results of alumina implanted with Ti at 75 keV with the results of prior investigations of polymers implanted with Pt at 49 eV and Au at 67 eV, we describe a physical model of the effect based on percolation theory and estimate the percolation parameters for the Ti-alumina composite. We estimate that the percolation dose threshold is about 4 x 10(16) cm(-2) and the maximum dose for which the system remains an insulator-conductor composite is about 10 x 10(16) cm(-2). The saturation electrical conductivity is estimated to be about 50 S/m. We conclude that the observed electrical conductivity properties of Ti-implanted alumina can be satisfactorily described by percolation theory. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3697900]

Site localization of Cd impurities in sapphire

By combining first-principles electronic structure calculations and existing time-differential gamma-gamma perturbed-angular-correlation experiments we studied the site localization, the local environment, and the electronic structure of Cd impurities in sapphire (alpha-Al2O3) single crystals in different charged states. The ab initio calculations were performed with the full-potential augmented plane wave plus local orbitals method and the projector augmented wave method. Comparing the calculated electric-field-gradient tensor at the Cd nuclei in the alpha-Al2O3 host lattice and the corresponding available experimental values, we have seen that it is equally possible for Cd to replace an Al atom (in a negative charge state) or to be placed in an interstitial site (in a neutral charge state). To finally address the issue of the Cd impurity localization, we performed formation energy calculations. These results have shown that Cd placed in the substitutional Al site, in the negatively charged state, is the most probable configuration.

Nanosized precipitates in H13 tool steel low temperature plasma nitriding

A comprehensive study of pulsed nitriding in AISI H13 tool steel at low temperature (400 degrees C) is reported for several durations. X-ray diffraction results reveal that a nitrogen enriched compound (epsilon-Fe2-3N, iron nitride) builds up on the surface within the first process hour despite the low process temperature. Beneath the surface, X-ray Wavelength Dispersive Spectroscopy (WDS) in a Scanning Electron Microscope (SEM) indicates relatively higher nitrogen concentrations (up to 12 at.%) within the diffusion layer while microscopic nitrides are not formed and existing carbides are not dissolved. Moreover, in the diffusion layer, nitrogen is found to be dispersed in the matrix and forming nanosized precipitates. The small coherent precipitates are observed by High-Resolution Transmission Electron Microscopy (HR-TEM) while the presence of nitrogen is confirmed by electron energy loss spectroscopy (EELS). Hardness tests show that the material hardness increases linearly with the nitrogen concentration, reaching up to 14.5 GPa in the surface while the Young Modulus remains essentially unaffected. Indeed, the original steel microstructure is well preserved even in the nitrogen diffusion layer. Nitrogen profiles show a case depth of about similar to 43 mu m after nine hours of nitriding process. These results indicate that pulsed plasma nitriding is highly efficient even at such low temperatures and that at this process temperature it is possible to form thick and hard nitrided layers with satisfactory mechanical properties. This process can be particularly interesting to enhance the surface hardness of tool steels without exposing the workpiece to high temperatures and altering its bulk microstructure. (c) 2012 Elsevier B.V. All rights reserved.

Annealing effects on nanostructured gold-polymethylmethacrylate composites: Small-angle x-ray scattering analysis

Composites formed of a polymer-embedded layer of sub-10 nm gold nanoclusters were fabricated by very low energy (49 eV) gold ion implantation into polymethylmethacrylate. We used small angle x-ray scattering to investigate the structural properties of these metal-polymer composite layers that were fabricated at three different ion doses, both in their original form (as-implanted) and after annealing for 6 h well above the polymer glass transition temperature (150 degrees C). We show that annealing provides a simple means for modification of the structure of the composite by coarsening mechanisms, and thereby changes its properties. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4720464]

Corrole isomers: intrinsic gas-phase shapes via traveling wave ion mobility mass spectrometry and dissociation chemistries via tandem mass spectrometry

Corrole and four of its isomers with subtle structural changes promoted by exchange of nitrogen and carbon atoms in the corrole ring have been studied by traveling wave ion mobility mass spectrometry and collision induced dissociation experiments. Significant differences in shapes and charge distributions for their protonated molecules were found to lead to contrasting gas phase mobilities, most particularly for corrorin, the most "confused" isomer. Accordingly, corrorin was predicted by B3LYP/6-31g(d,p) and collisional cross section calculations to display the most compact tri-dimensional structure, whereas NCC4 and corrole were found to be the most planar isomers. Better resolution between the corrole isomers was achieved using the more polarizable and massive CO2 as the drift gas. Sequential losses of HF molecules were found to dominate the dissociation chemistry of the protonated molecules of these corrole isomers, but their unique structures caused contrasting labilities towards CID, whereas NCC4 showed a peculiar and structurally diagnostic loss of NH3, allowing its prompt differentiation from the other isomers.

On the diurnal cycle of urban aerosols, black carbon and the occurrence of new particle formation events in springtime Sao Paulo, Brazil

Large conurbations are a significant source of the anthropogenic pollution and demographic differences between cities that result in a different pollution burden. The metropolitan area of Sao Paulo (MASP, population 20 million) accounts for one fifth of the Brazilian vehicular fleet. A feature of MASP is the amount of ethanol used by the vehicular fleet, known to exacerbate air quality. The study describes the diurnal behaviour of the submicron aerosol and relies on total particle number concentration, particle number size distribution, light scattering and light absorption measurements. Modelled planetary boundary layer (PBL) depth and air mass movement data were used to aid the interpretation. During morning rush-hour, stagnant air and a shallow PBL height favour the accumulation of aerosol pollution. During clear-sky conditions, there was a wind shift towards the edge of the city indicating a heat island effect with implications on particulate pollution levels at the site. The median total particle number concentration for the submicron aerosol typically varied in the range 1.6 x 10(4)-3.2 x 10(4) cm(-3) frequently exceeding 4 x 10(4) cm-3 during the day. During weekdays, nucleation-mode particles are responsible for most of the particles by numbers. The highest concentrations of total particle number concentrations and black carbon (BC) were observed on Fridays. Median diurnal values for light absorption and light scattering (at 637 nm wavelength) varied in the range 12-33 Mm(-1) and 21-64 Mm(-1), respectively. The former one is equal to 1.8-5.0 mu g m(-3) of BC. The growth of the PBL, from the morning rush-hour until noon, is consistent with the diurnal cycle of BC mass concentrations. Weekday hourly median single-scattering albedo (omega(0)) varied in the range 0.59-0.76. Overall, this suggests a top of atmosphere (TOA) warming effect. However, considering the low surface reflectance of urban areas, for the given range of omega(0), the TOA radiative forcing can be either positive or negative for the sources within the MASP. On the average, weekend omega(0) values were 0.074 higher than during weekdays. During 11% of the days, new particle formation (NPF) events occurred. The analysed events growth rates ranged between 9 and 25 nm h(-1). Sulphuric acid proxy concentrations calculated for the site were less than 5% of the concentration needed to explain the observed growth. Thus, other vapours are likely contributors to the observed growth.