In-situ optical reflectance characterization of ion beam irradiation damage on crystalline (quartz) and amorphous (silica) SiO2

Outline: • Motivation, aim • Complement waveguide data on silica • Optical data in quartz • Detailed analysis, i.e. both fluence kinetics and resolution • Efficiency of irradiation and analysis, samples, time... • Experimental set-up description • Reflectance procedure • Options: light source (lasers, white light..), detectors, configurations • Results and discussion • Comparative of amorphous and crystalline phases

A molecular dynamics study of swift heavy ion irradiation of amorphous silica: the role of thermal effects

Irradiation with swift heavy ions (SHI), roughly defined as those having atomic masses larger than 15 and energies exceeding 1 MeV/amu, may lead to significant modification of the irradiated material in a nanometric region around the (straight) ion trajectory (latent tracks). In the case of amorphous silica, SHI irradiation originates nano-tracks of higher density than the virgin material (densification). As a result, the refractive index is increased with respect to that of the surroundings. Moreover, track overlapping leads to continuous amorphous layers that present a significant contrast with respect to the pristine substrate. We have recently demonstrated that SHI irradiation produces a large number of point defects, easily detectable by a number of experimental techniques (work presented in the parallel conference ICDIM). The mechanisms of energy transfer from SHI to the target material have their origin in the high electronic excitation induced in the solid. A number of phenomenological approaches have been employed to describe these mechanisms: coulomb explosion, thermal spike, non-radiative exciton decay, bond weakening. However, a detailed microscopic description is missing due to the difficulty of modeling the time evolution of the electronic excitation. In this work we have employed molecular dynamics (MD) calculations to determine whether the irradiation effects are related to the thermal phenomena described by MD (in the ps domain) or to electronic phenomena (sub-ps domain), e.g., exciton localization. We have carried out simulations of up to 100 ps with large boxes (30x30x8 nm3) using a home-modified version of MDCASK that allows us to define a central hot cylinder (ion track) from which heat flows to the surrounding cold bath (unirradiated sample). We observed that once the cylinder has cooled down, the Si and O coordination numbers are 4 and 2, respectively, as in virgin silica. On the other hand, the density of the (cold) cylinder increases with respect to that of silica and, furthermore, the silica network ring size decreases. Both effects are in agreement with the observed densification. In conclusion, purely thermal effects do not explain the generation of point defects upon irradiation, but they do account for the silica densification.

Application of density functional theory to equilibrium adsorption of argon and nitrogen on amorphous silica surface

We present a new version of non-local density functional theory (NL-DFT) adapted to description of vapor adsorption isotherms on amorphous materials like non-porous silica. The novel feature of this approach is that it accounts for the roughness of adsorbent surface. The solid–fluid interaction is described in the same framework as in the case of fluid–fluid interactions, using the Weeks–Chandler–Andersen (WCA) scheme and the Carnahan–Starling (CS) equation for attractive and repulsive parts of the Helmholtz free energy, respectively. Application to nitrogen and argon adsorption isotherms on non-porous silica LiChrospher Si-1000 at their boiling points, recently published by Jaroniec and co-workers, has shown an excellent correlative ability of our approach over the complete range of pressures, which suggests that the surface roughness is mostly the reason for the observed behavior of adsorption isotherms. From the analysis of these data, we found that in the case of nitrogen adsorption short-range interactions between oxygen atoms on the silica surface and quadrupole of nitrogen molecules play an important role. The approach presented in this paper may be further used in quantitative analysis of adsorption and desorption isotherms in cylindrical pores such as MCM-41 and carbon nanotubes.

Comparative study on the photoluminescent properties of siliceous MCM-41 with silica particles and xerogels

The samples of as-synthesized siliceous MCM-41, extracted MCM-41, amorphous silica particles and silica xerogels were heat treated from room temperature to 1000degreesC. Their photoluminescence (PL) spectra at room temperature excited by 254nm and 365nm ultraviolet light (UV) were investigated and compared. Excited by 254nm UV the MCM-41 samples do not display PL but amorphous silica particles and silica xerogels show PL, which changes with the heat treatment conditions for the samples. However, when excited by 365nm UV the PL spectra for the MCM-41 and the amorphous samples are similar. The carbon impurity and E' center mechanisms can be ruled out as the origin of PL in siliceous MCM-41 under UV excitation. The PL of MCM-41 series samples probably originates from oxygen-related defect center like dropSi-O-. according to the present work.

Ultrasonic synthesis of silica-alumina nanomaterials with controlled mesopore distribution without using surfactants

A novel sol-gel process has been developed for the synthesis of amorphous silica-aluminas with controlled mesopore distribution without the use of organic templating agents, e.g., surfactant molecules. Ultrasonic treatment during the synthesis enables production of precursor sols with narrow particle size distribution. Atomic force microscopy analysis shows that these sol particles are spherical in shape with a narrow size distribution (i.e., 13-25 nm) and their aggregation during the gelation creates clusters containing similar sized interparticle mesopores. A nitrogen physiadsorption study indicates that the mesoporous materials containing different Si/Al ratios prepared by the new synthesis method has a large specific surface area (i.e., 587-692 m(2)/g) and similar pore sizes of 2-11 nm. Solid-state Al-27 magic angle spinning (MAS) NMR shows that most of the aluminum is located in the tetrahedral position. A transmission electron microscopy (TEM) image shows that the mesoporous silica-alumina consists of 12-25 nm spheres. Additionally, high-resolution TEM and electron diffraction indicate that some nanoparticles are characteristic of a crystal, although X-ray diffraction and Si-29 MAS NMR analysis show an amorphous material.

Silica polymer bonding of stressed silica grains: An early growth of intergranular tensile strength

© 2015 Elsevier Ltd. All rights reserved.Laboratory tests on microscale are reported in which millimeter-sized amorphous silica cubes were kept highly compressed in a liquid environment of de-ionized water solutions with different silica ion concentrations for up to four weeks. Such an arrangement simulates an early evolution of bonds between two sand grains stressed in situ. In-house designed Grain Indenter-Puller apparatus allowed measuring strength of such contacts after 3-4 weeks. Observations reported for the first time confirm a long-existing hypothesis that a stressed contact with microcracks generates silica polymers, forming a bonding structure between the grains on a timescale in the order of a few weeks. Such structure exhibits intergranular tensile force at failure of 1-1.5 mN when aged in solutions containing silica ion concentrations of 200-to 500-ppm. The magnitude of such intergranular force is 2-3 times greater than that of water capillary force between the same grains.

Characterization of silica-carbon mesoporous matrix with embedded nickel nanoparticles synthesized by the polymeric precursor method

Nickel nanoparticles into silica-carbon matrix composites were prepared by using the polymeric precursor method. The effects of the polyester type and the time of pyrolysis on the mesoporosity and nickel particle dispersion into non-aqueous amorphous silica-carbon matrix were investigated by thermogravimetric analysis, adsorption/desorption isotherms and TEM. A well-dispersed metallic phase could be only obtained by using ethylene glycol. Weightier polyesters affected the pyrolysis process due to a combination of more amounts of carbonaceous residues and delaying of pyrolysis process. The post-pyrolyzed composites were successfully cleaned at 200 degrees C for I h in oxygen atmosphere leading to an increase in the surface area and without the occurrence of carbon combustion or nickel nanoparticles oxidation. The matrix composites presented predominantly mesoporous with pore size well defined in 38 angstrom, mainly when tetraethylene glycol was used as polymerizing agent. (C) 2007 Elsevier B.V. All rights reserved.

Mechanism of silica -induced apoptosis in human alveolar macrophages

The mechanisms involved in the development of pulmonary silicosis have not been well defined, however most current evidence implicates a central role for alveolar macrophages in this process. We propose that the fibrotic potential of a particulate depends upon its ability to cause apoptosis in alveolar macrophage (AM). The overall goal of this study was to determine the mechanism of silica-induced apoptosis of AM. Human AM were treated with fibrogenic, poorly fibrogenic and nonfibrogenic model particulates, such as, silica, amorphous silica and titanium dioxide, respectively (equal surface area). Treatment with silica resulted in apoptosis in human AM as observed by morphology, DNA fragmentation and Cell Death ELISA assays. In contrast, amorphous silica and titanium dioxide demonstrated no significant apoptotic potential. To elucidate the possible mechanism by which silica causes apoptosis, we investigated the role of the scavenger receptor (SR) in silica-induced apoptosis. Cells were pretreated with and without SR ligand binding inhibitors, polyinosinic acid (Poly I), fucoidan and high density lipoprotein (HDL), prior to silica treatment. Pretreatment with Poly I and fucoidan resulted in significant inhibition of silica-induced apoptosis suggesting that silica-induced AM apoptosis is mediated via the SR. Further, we examined the involvement of interleukin converting enzyme (ICE) family of proteases in silica-mediated apoptosis. Silica activated ICE, Ich-1L, cpp32 beta and cleavage of PARP. Taken together, these results suggested that (1) fibrogenic particulates, such as, silica caused apoptosis of alveolar macrophages, (2) this apoptotic potential of fibrogenic particulates may be a critical factor in initiating an inflammatory response resulting in fibrosis, (3) silica-induced apoptosis of alveolar macrophages may be due to the interaction of silica particulates with the SR, and (4) silica-induced apoptosis involves the activation of the ICE family of proteases. An understanding of the molecular events involved in fibrogenic particulate-induced apoptosis may provide a useful insight into the mechanism involved in particulate-induced fibrosis. ^

Ionoluminescence induced by swift heavy ions in silica and quartz: a comparative analysis

Ionoluminescence (IL) of the two SiO2 phases, amorphous silica and crystalline quartz, has been comparatively investigated in this work, in order to learn about the structural defects generated by means of ion irradiation and the role of crystalline order on the damage processes. Irradiations have been performed with Cl at 10 MeV and Br at 15 MeV, corresponding to the electronic stopping regime (i.e., where the electronic stopping power Se is dominant) and well above the amorphization threshold. The light-emission kinetics for the two main emission bands, located at 1.9 eV (652 nm) and 2.7 eV (459 nm), has been measured under the same ion irradiation conditions as a function of fluence for both, silica and quartz. The role of electronic stopping power has been also investigated and discussed within current views for electronic damage. Our experiments provide a rich phenomenological background that should help to elucidate the mechanisms responsible for light emission and defect creation.

Tailoring the Optical Properties of Silica Irradiated with Swift Heavy Ions

Irradiation with swift heavy ions (SHI), roughly defined as those having atomic masses larger than 15 and energies exceeding 1 MeV/amu, may lead to significant modification of the irradiated material in a nanometric region around the (straight) ion trajectory (i.e., latent tracks). In the case of amorphous silica it has been reported that SHI irradiation originates nano-tracks of either higher density than the virgin material (for low electronic stopping powers, Se < 7 keV/nm) [1] or having a low-density core and a dense shell (Se > 12 keV/nm) [2]. The intermediate region has not been studied in detail but we will show in this work that essentially no changes in density occur in this zone. An interesting effect of the compaction is that the refractive index is increased with respect to that of the surroundings. In the first Se region it is clear that track overlapping leads to continuous amorphous layers that present a significant contrast with respect to the pristine substrate and this has been used to produce optical waveguides. The optical effects of intermediate and high stopping powers, on the other hand, are largely unknown so far. In this work we have studied theoretically (molecular dynamics and optical simulations) and experimentally (irradiation with SHI and optical characterization) the dependence of the macroscopic optical properties (i.e., the refractive index of the effective medium, n_EMA) on the electronic stopping power of the incoming ions. Our results show that the refractive index of the irradiated silica is not increased in the intermediate region, as expected; however, the core-shell tracks of the high-Se region produce a quite effective enhancement of n_EMA that could prove attractive for the fabrication of optical waveguides at ultralow fluences (as low as 1E11 cm^-2). 1. J. Manzano, J. Olivares, F. Agulló-López, M. L. Crespillo, A. Moroño, and E. Hodgson, "Optical waveguides obtained by swift-ion irradiation on silica (a-SiO2)," Nucl. Instrum. Meth. B 268, 3147-3150 (2010). 2. P. Kluth, C. S. Schnohr, O. H. Pakarinen, F. Djurabekova, D. J. Sprouster, R. Giulian, M. C. Ridgway, A. P. Byrne, C. Trautmann, D. J. Cookson, K. Nordlund, and M. Toulemonde, "Fine structure in swift heavy ion tracks in amorphous SiO2," Phys. Rev. Lett. 101, 175503 (2008).

Is chrysocolla (Cu,Al)2H2Si2O5(OH)4·nH2O related to spertiniite Cu(OH)2? - a vibrational spectroscopic study

Chrysocolla (Cu, Al)2H2Si2O5(OH)4·nH2O is a hydrated copper hydroxy silicate and is commonly known as a semi-precious jewel. The mineral has an ill defined structure but is said to be orthorhombic, although this remains unproven. Thus, one of the few methods of studying the molecular structure of chrysocolla is to use vibrational spectroscopy. Chrysocolla may be defined as a colloidal mineral. The question arises as to whether chrysocolla is a colloidal system of spertiniite and amorphous silica. The main question addressed by this study is whether chrysocolla is (1) a mesoscopic assemblage of spertiniite, Cu(OH)2, silica, and water, (2) represents a colloidal gel or (3) is composed of microcrystals with a distinct structure. Considerable variation in the vibrational spectra is observed between chrysocolla samples. The Raman spectrum of chrysocolla is characterised by an intense band at 3624 cm−1 assigned to the OH stretching vibrations. Intense Raman bands found at 674, 931 and 1058 cm−1 are assigned to SiO3 vibrations. The Raman spectrum of spertiniite does not correspond to the spectrum of chrysocolla and it is concluded that the two minerals are not related. The spectra of chrysocolla correspond to a copper silicate colloidal gel.

Evaluation of existing and new insecticides including spirotetramat and pyridalyl to control Frankliniella occidentalis (Pergande) (Thysanoptera: Thripidae) on peppers in Queensland.

Insecticides are used by growers to control Frankliniella occidentalis (western flower thrips) in Australian vegetable crops. However, limited information was available on the efficacy of some insecticides used against F. occidentalis and data on new insecticides that could be included in a resistance management program were required. The efficacy of 16 insecticides in controlling F. occidentalis was tested in four small plot trials in chillies and capsicums. Spinosad, fipronil and methamidophos were effective against adults and larvae. Spirotetramat had no efficacy against adults but was very effective against larvae. Pyridalyl was moderately effective against larvae. Methidathion showed limited effectiveness. Abamectin, amorphous silica, bifenthrin, chlorpyrifos, dimethoate, emamectin benzoate, endosulfan, imidacloprid, methomyl and insecticidal soap were not effective. Laboratory bioassays on F. occidentalis collected from the field trials showed resistance to bifenthrin but not to the other insecticides tested. The trials demonstrated that some insecticides permitted for use against F. occidentalis are not effective and identified a number of insecticides, including the new ones spirotetramat and pyridalyl, that are effective and that could be used to manage the pest within a resistance management program.

Downstream processing of reverse osmosis brine: Characterisation of potential scaling compounds

Reverse osmosis (RO) brine produced at a full-scale coal seam gas (CSG) water treatment facility was characterized with spectroscopic and other analytical techniques. A number of potential scalants including silica, calcium, magnesium, sulphates and carbonates, all of which were present in dissolved and non-dissolved forms, were characterized. The presence of spherical particles with a size range of 10–1000 nm and aggregates of 1–10 microns was confirmed by transmission electron microscopy (TEM). Those particulates contained the following metals in decreasing order: K, Si, Sr, Ca, B, Ba, Mg, P, and S. Characterization showed that nearly one-third of the total silicon in the brine was present in the particulates. Further, analysis of the RO brine suggested supersaturation and precipitation of metal carbonates and sulphates during the RO process should take place and could be responsible for subsequently capturing silica in the solid phase. However, the precipitation of crystalline carbonates and sulphates are complex. X-ray diffraction analysis did not confirm the presence of common calcium carbonates or sulphates but instead showed the presence of a suite of complex minerals, to which amorphous silica and/or silica rich compounds could have adhered. A filtration study showed that majority of the siliceous particles were less than 220 nm in size, but could still be potentially captured using a low molecular weight ultrafiltration membrane.