A novel process to prepare a hollow silica sphere via chitosan-polyacrylic acid (CS-PAA) template

Hollow silica spheres were synthesized by using a chitosan-polyacrylic acid (CS-PAA) template. Polyacrylic acid (PAA) was titrated into the dissolved chitosan solution to form CS-PAA particles. For forming the core-shell particle, colloidal silica which was prepared from homogeneous nucleation was mixed with a solution of CS-PAA particles. Colloidal silica was adsorbed on to the surface of the CS-PAA particles to form a shell structure. CS-PAA could be removed from the core of the core-shell particles by adjusting with HCl to pH < 1 for forming the hollow silica structure. The outside particle size diameter, shell thickness, specific surface, pore diameter and pore volume of the final hollow silica sphere are about 200 nm, 20 nm, 350.95 m²/g, 5.4078 nm and 0.516768 cm³/g, respectively.     

Cadmium ions adsorption in simulated wastewater using structured alumina–silica nanoparticles

Some results on the removal of cadmium ions from simulated industrial wastewater using sol–gel structured nanoparticles of silica and alumina are presented. Two different core-shell nanoparticles were prepared: Al–Si particles (alumina core surrounded by a silica shell) with a molar composition Al:Si of 1:5, and Si–Al particles (silica core and alumina shell) with a molar composition Si:Al of 1:5. Different amounts of cadmium ions were added and the flocculation process of these particles, induced by the ions adsorption, was followed using dynamic light scattering. The efficiency of the ions adsorption was determined using atomic absorption spectroscopy. The results show that it is possible to reduce the cadmium concentration from 140 ppm to less than 5 ppb using Si–Al particles, meeting some international regulations for this contaminant (New European Directive 98-83). The Al–Si particles were not so efficient because the cadmium was only reduced from 125 ppm to less than 90 ppb. The sol–gel technique allows to synthesize model nanoparticles with different morphologies to be used as a prototypes, allowing to choose the better morphology and scaling this knowledge to an industrial level using commercially available silica and alumina nanoparticles chemically modified on the surface.     

The transformation balance between two types of structural defects in silica glass in ion-irradiation processes

Structural modification in silica glass irradiated by Au ions was investigated by ultraviolet (UV), photoluminescence and Raman spectrum at the energies from 0.5 to 8 MeV with a fluence of 5 × 10¹³ cm^? 2. In this transit energy region, both nuclear energy loss and electronic energy loss are not negligible. It was found that both the formation of irradiation-induced intrinsic defects and structural transformation from irregular large ring structure (LRS) to small three- and four-member ring structures (SRS) are dominated by the nuclear energy loss. Furthermore, unlike the case of irradiation with β, γ or proton, the concentration of non-bridging oxygen hole center is much enhanced followed with a distinct peak appearing at 5.05 eV in the UV absorption spectra that is attributed to divalent Si. The results suggest that the structural modification in silica glass in the transit energy region is dominated by nuclear energy loss. A mutual transformation balance model among irradiation-induced intrinsic defects, LRS and SRS is established to interpret the identical variation tendencies of intrinsic defects and structural transformation with ion energy.     

Micro-photoluminescence study on defects induced by ion microbeam in silica glass

We have evaluated the irradiation effects by ion microbeam on silica glass for various ion species by means of a micro-photoluminescence technique. Defect generation and refractive index change were observed for silica at the area of 10 μm × 50 μm scanned by ion microbeam of H⁺, He⁺, N⁴⁺, C⁴⁺, O⁴⁺, and Si⁵⁺ with energy from 1.7 to 18 MeV. The μ-PL spectroscopy measurements were performed along the side surface perpendicular to the microbeam irradiated surface. Based on the comparison with a result of SRIM (stopping and range of ions in matter) simulation, the defect generation mechanism was discussed in terms of the energy deposition processes due to electronic and nuclear stopping powers. We conclude that the electronic stopping power is responsible for the defect generation at the track of ions. The effect of the nuclear stopping power is also not negligibly small at the end of range.     

Photocapacitance measurements in irradiated a-Si:H based detectors

Photocapacitance measurements were performed on amorphous silicon p–i–n detectors before and after particle irradiation with 1.5 MeV 4 He⁺ ions. The spatial resolution across a degraded spot is similar to the one obtained in photocurrent scans and is of the order of the diameter of the scanning laser beam. We monitored the transient capacitance after applying short laser pulses to deduce trap energies of 0.64 eV. Photocapacitance measurements as a function of the applied bias, the measurement frequency up to 1 MHz, and the wavelength of laser light are discussed. The reduction in photocapacitance signal and the shift of the cut-off frequency after ion bombardment are correlated with the change in transport properties.     

Improved method for preparation of anhydrous silica by microwave irradiation with spectroscopic characterization and toxicity assay

Amorphous anhydrous silica SiO_{2 (mw)} (99.99%) is successfully synthesized through microwave irradiation technique and time of reaction is reduced up to 1 h. The dehydration phase study of Si–water, Si–OH, Si–O–Si networking, elemental analysis and surface morphology was carried out by FTIR, FTNIR, SEM and EDAX spectroscopic techniques. The broad absorption stretching and bending of Si–OH and H₂O at 3695.38–2832.96 cm^? 1, 1638 cm^? 1 and 1191.20–1017.14 cm^? 1 completely disappeared and appearance of new bands at 946.93 and 797.63 cm^? 1 confirmed the amorphous anhydrous silica with Si–O–Si networking. The SEM images of SiO_{2 (mwc)} described the smooth and fine particle texture and confirmed 99.99% Si–O–Si networking of anhydrous silica. The 99.99% purity was verified by EDAX spectra which exhibited sharp signals only for oxygen and silicon. Toxicity against Monomorium minimum and Tribolium castaneum with 100% mortality and LT₅₀ 91 min and 7.5 h respectively is being reported. It can be used for long storage of grains in the future.     

Effect of high electronic energy loss of 100 MeV gold heavy ions in copper chalcogenides (CuX,X = S,Se) at nanoscale: Opto-electronic properties study

The copper chalcogenide (CuX, X = S, Se) thin films have been irradiated with 100 MeV gold swift heavy ions (SHI) at 10¹¹ and 10¹² ions/cm² fluences. The irradiation effects were probed by characterizing physical properties such as XRD, AFM, optical band gap and electrical resistivity of copper chalcogenide thin films. The increase in irradiation fluence increases the particle size, electrical conductivity and PL intensity of the materials, and the optical band edges were red shifted. The results are explained by quantifying electronic energy loss of ions in both the materials.     

Radiation-induced defects in a-Si:H by 1.5 MeV He4 particles studied by photoconductivity and photothermal deflection spectroscopy

We report radiation effects on intrinsic a-Si:H thin films subjected to a 1.5 MeV He⁴ beam for particle fluences up to 10¹⁶ cm⁻². Photothermal deflection spectroscopy is used to obtain information on the sub-gap density of states. Photoconductivity detects changes in the μτ-product of the electrons. Steady-state photocarrier grating technique is used for measuring the ambipolar diffusion length and estimating the hole μτ-product. The 1.5 MeV He⁴ beam radiation results in pronounced changes in the a-Si:H absorption spectrum. Optical absorption due to deep defects increases with particle fluence by more than one order of magnitude. Electronic transport properties consistently degrade with increasing particle fluence and correlate with the density of radiation-induced defects.     

Preparation and characterization of agglomerated porous hollow silica supports for olefin polymerization catalyst

Self-prepared porous hollow silica (PHS) nanoparticles were agglomerated with an oil (kerosene)–ammonia method and used as a novel support of metallocene catalysts for olefin polymerization. Transmission electron microscopy (TEM), scanning electron microcopy (SEM), small-angle X-ray diffraction (SA-XRD) and nitrogen adsorption–desorption were employed to characterize the morphologies and mesostructures of the PHS particles and agglomerated PHS particles. It was found that the agglomerated PHS particles had an average diameter between 15 and 30 μm, a specific surface area of 214 m²/g, a pore diameter of 11–18 nm and a pore volume of 1.41 mL/g. Metallocene catalysts prepared with the agglomerated PHS as support demonstrated a very high activity of 8350 g PE/gCata. for ethylene polymerization due to their particular morphology and mesostructures. Analysis with Differential Scanning Calorimetry (DSC), SEM, TEM and molecular weight analysis indicated that the polyethylene product was composed of tiny spherical particles with good crystalline and narrow molecular weight distribution, and the morphology and structure of the individual PHS support particle remained unchanged in polyethylene following the polymerization.     

About diffusion mechanism in silica liquid under pressure

We perform a molecular dynamic simulation to study the diffusion mechanism in silica liquid under pressure up to 25 GPa and at temperature of 3000 K. We find that total O―Si―O angle distribution can be expressed by a simple relation between partial O―Si―O angle distribution and fractions of units SiO_x. Specifically, we demonstrate that these liquids consist of identical units SiO₄, SiO₅ and SiO₆ and have common partial O―Si―O angle distribution. We also show that each particle undergoes a series of stages where the particle locates in unchanged unit SiO_x, x = 3, 4, … 7 or OSi_y, y = 1, 2, 3, 4. The diffusivity strongly depends on the rate of transitions Si^ξ → Si^ξ ± 1 and O^ζ → O^ζ ± 1 which is significantly different between low- and high-pressure samples. For low-pressure sample the transitions Si⁴ → Si⁵, Si⁵ → Si⁴, O² → O³ and O³ → O² are dominant, meanwhile for high-pressure sample there are transitions Si^ξ → Si^ξ ± 1 with ξ = 4, 5, 6 and O^ζ → O^ζ ± 1 with ζ = 2, 3, 4. This finding may be common for diffusion in all network-forming liquids. The simulation also reveals the spatially heterogeneous dynamics in low-pressure liquid where a large cluster of immobile particle exists for the time that a number of particles move over several inter-particle distances.     

Morphology of swift heavy ion tracks in metallic glasses

Swift heavy ion irradiated metallic glasses were studied using synchrotron based small angle X-ray scattering (SAXS). Ribbons of Fe₈₀B₂₀, Fe₈₅ B₁₅, Fe₈₁B_13.5Si_3.5C₂ and Fe₄₀Ni₄₀B₂₀ were irradiated with 11.1 MeV/nucleon (MeV/u) ¹³²Xe, ¹⁵²Sm, ¹⁹⁷Au and 8.2 MeV/u ²³⁸U ions to fluences between 1 × 10¹⁰ and 1 × 10¹² ions/cm². The SAXS measurements provide evidence for the formation of ion tracks and allow a quantitative analysis of the track ensemble in all studied materials. The ion tracks have been well described by cylinders with abrupt boundaries and an electronic density change of (0.03 ± 0.01)% between track and matrix material. An inelastic thermal spike model was fitted to the experimental track radii to determine the critical energy density required to create an ion track. Despite the similar energy loss and track cross-sections, 30% higher track creation threshold is apparent for the binary alloys.     

Sintering process of amorphous SiO2 nanoparticles investigated by AFM,IR and Raman techniques

We report an experimental investigation on the effects of thermal treatments at different temperatures (room—1270 K) and for different duration (0–75 h) on amorphous silica nanoparticles (fumed silica) in powder tablet form. Three types of fumed silica are considered, comprising nearly spherical particles of 40 nm, 14 nm and 7 nm mean diameter. The experimental techniques used here are Raman and infrared absorption (IR) spectroscopy together with atomic force microscopy (AFM). Raman and IR spectra indicate that the structure of nanometer silica particles is significantly different with respect to that of a bulk silica glass. In particular, the main differences regard the positions of the IR band peaked at about 2260 cm^?1, the Raman R-band peaked at about 440 cm^?1 and the intensity of the D1 and the D2 Raman lines, related to the populations of 4- and 3-membered rings, respectively. Our data also indicate that, under thermal treatments, the structure of fumed silica samples is significantly changed, gradually relaxing towards that pertaining to ordinary bulk silica. These changes are interpreted here on the basis of the morphological information provided by the AFM measurements and assuming a two-shell structure for the fumed silica primary particles.     

The Eγ′ center as a probe of structural properties of nanometer-sized silica particles

A Q-band electron spin resonance (ESR) study is reported of E′ type point defects observed in ～7 nm-sized fumed silica nanoparticles following 10-eV irradiation to photodissociate H from passivated defects. In a comparative study with bulk silica (suprasil), the E′ center is used as an atomic probe to get more in depth information on the network structure of the nm-sized particles. The nanoparticles were brought into contact with ‘bulk’ Si/SiO₂ entities at an elevated temperature in vacuum (T_an = 1105 °C), i.e., the presence of an Si/SiO₂ interface. As a result of this post manufacture treatment, the E′ density increased drastically (>order of magnitude), enabling us to resolve hyperfine (hf) structure of the E′ centers located in the core region of the nanoparticles. Two doublet structures are observed, one each assigned to O₂Si–H entities and the primary ²⁹Si hf structure of the E′ centers. Analysis of these hf spectra reveals interesting information on the network structure of the core region of the nanoparticles: (1) Fumed silica is found to contain relatively less hydrogen than suprasil. (2) An increased ²⁹Si hf splitting (439 ± 2 G) is observed compared to bulk silica (418 ± 2 G), indicating that the E′ centers located in the core of the nanoparticles exhibit on average a slightly more pyramidal defect structure, and moreover, providing evidence that the fumed silica particles are densified compared to standard bulk silica, possibly originating from the presence of more low-membered rings (n < 5) in the nm-sized silica network.     

Drug recrystallization using supercritical anti-solvent (SAS) process with impinging jets: Effect of process parameters

The aim of this study is to improve mixing in supercritical anti-solvent process (SAS) with impinging jets in order to form finer particles of sulfathiazole, a poorly water-soluble drug. The influence of several process parameters upon the powder characteristics is studied. Parameters are jets' velocity (0.25 m s^?1 to 25.92 m s^?1), molar ratio solvent/CO₂ (2.5% to 20%), temperature (313 K to 343 K), pressure (10 MPa to 20 MPa) and sulfathiazole concentration in the organic solution (0.5% to 1.8%). Two solvents are used: acetone and methanol. Smaller particles with a more homogeneous morphology are obtained from acetone solutions. For the smallest jets' velocity, corresponding to a non-atomized jet, the stable polymorphic form is obtained, pure or in mixture. At this velocity, pressure is the most influential parameter controlling the polymorphic nature of the powder formed. The pure stable polymorph is formed at 20 MPa. Concerning the particle size, the most influential parameters are temperature and sulfathiazole concentration.The use of impinging jets with different process parameters allows the crystallization of four polymorphs among the five known, and particle sizes are varied. This work demonstrates the studied device ability of the polymorph and the size control. A comparison with the classical SAS process shows that particle size, size distribution and morphology of particles crystallized with impinging jets are different from the ones obtained with classical SAS introduction device in similar operating conditions. Mean particle sizes are significantly smaller and size distributions are narrower with impinging jets device.     

Fluorine laser-induced silicon hydride Si–H groups in silica

Formation and destruction of silicon hydride (Si–H) groups in silica by F₂ laser irradiation and their vacuum ultraviolet (VUV) optical absorption was examined by infrared (IR) and VUV spectroscopy. Photoinduced creation of Si–H groups in H₂-impregnated oxygen deficient silica is accompanied by a growth of infrared absorption band at 2250 cm⁻¹ and by a strong increase of VUV transmission at 7.9 eV. Photolysis of Si–H groups by 7.9 eV photons in this glass was not detected when the irradiation was performed at temperature 80 K. However, a slight destruction of Si–H groups under 7.9 eV irradiation was observed at the room temperature. This finding gives a tentative estimate of VUV absorption cross section of Si–H groups at 7.9 eV as 4 × 10⁻²¹ cm², showing that Si–H groups do not strongly contribute to the absorption at the VUV fundamental absorption edge of silica glass.     

Visible to near-infrared down-conversion luminescence in Tb3 + and Yb3 + co-doped lithium–lanthanum–aluminosilicate oxyfluoride glass and glass-ceramics

Tb^3 + and Yb^3 + co-doped oxyfluoride glasses were fabricated in a lithium–lanthanum–aluminosilicate matrix (LLAS) by a melt-quench technique. Glass-ceramics were obtained by appropriate heat treatment of the as-prepared glasses. Visible to near-infrared down-conversion luminescence was studied for glass and glass-ceramic samples with different Yb^3 + concentrations. It has been found that the luminescence intensity at 940–1020 nm from Yb^3 + ions increases while the emission lifetime of Tb^3 + ions decreases in the glass-ceramic compared to that in the as-prepared glass, which indicates that the energy transfer efficiency increases in the glass-ceramics compared to that in the as-prepared glass. The down-conversion luminescence also increased for increasing Yb^3 + concentration from 1 mol% to 2 mol%, but decreased for the sample with a high Yb^3 + co-doping concentration of 8 mol%, which is attributed to the concentration quenching.     

Structural investigation of alumina silica mixed oxide gels prepared from organically modified precursors

The development of the structure of silica/alumina gels was investigated by small angle X-ray scattering (SAXS) through all stages of the preparation process, that is gelation, aging, drying and calcination. Two series of gels were compared; the first was prepared from a single-source precursor, obtained by reaction of 3-oxoethyl-6-trimethoxysilyl-hexan-2-one (OTH-H) with Al(O^sBu)₃. The gels of the second series were prepared from the same precursors, but under conditions where hydrodeacylation of OTH-H occurs. It turned out that both series showed a similar structural development of the gels. Immediately after the start of the reaction small primary particles are formed, the size of which (r = 0.7 ± 0.1 nm) remains constant through the gelation and aging process. In some samples, Si(OEt)₄ was added as an additional source for Si/O which was incorporated between the primary particles. Condensation proceeds by a slower aggregation of the primary particles, which initially form a rather open network. This network densifies during aging and drying.     

Size modification of Au nanoparticles induced by slow highly charged ions 40Arq+ irradiation

Size modification of Au nanoparticles (NPs), deposited on the Au-thick film surface and irradiated by slow highly charged ions (SHCI) ⁴⁰Ar^q+ (3 ? q ? 12) with fixed low dose of 4.3 × 10¹¹ ions/cm² and various energy ranging from 74.64 to 290.64 keV at room temperature (293.15 K), was investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The effect of projectile kinetic energy on the modified size of NPs was explored by an appropriate choice of the fixed process parameters such as ion flux, irradiation temperature, incident angle, irradiation time, etc. The morphological changes of NPs were interpreted by models involving collisional mixing, Ostwald ripening (OR) and inverse Ostwald ripening (IOR) of spherical NPs on a substrate. A critical kinetic energy as well as a critical potential energy of the projectile in the Au NPs size modification process were observed.     

Preparation of spherical silica particles in reverse micro emulsions using silicon tetrachloride as precursor

Silica powders with spherical shape have been prepared by precipitation reaction of silicon tetrachloride with de-ionized water in the micro emulsion system. Two kinds of micro emulsion systems were used. One was cyclohexane/polyoxyethylene nonyl phenyl ether (NP-5)/de-ionized water system, and the other was heptane e/NP-5/de-ionized water. Transmission electron microscope (TEM), thermo gravimetric analysis (TG), X-ray diffraction (XRD) patterns, infrared spectrum (IR) were employed to characterize the micro structure, shape, thermal properties, phase, and molecular structure of the obtained silica. The results show that silica featuring spherical shapes and uniform characteristics was yielded by the precipitation method using silicon tetrachloride with de-ionized water in the micro emulsion system. A decreased tendency for silica particles agglomeration could be achieved by using lower mole ratio of water and SiCl₄, and the particle size was 5.74 nm when mole ratio of water and SiCl₄ was 4 in NP-5/cyclohexane/deionized water micro emulsion system. The silica prepared by these two systems was amorphous silica and thermally stable after 600 °C treatment. The structures of silica prepared from the different micro emulsion systems were similar; organic molecules can be removed completely from the silica through 600 °C treatment.     

Origins of optical absorption between 4.8 and 4.9 eV in silica implanted with Si and with O ions

We have determined some of the sources of the optical absorption bands between 4.8 and 4.9 eV in Si and O-implanted silica using several ion energies to produce layers of implanted ions with constant concentrations. The concentrations of implanted ions in the implanted layers ranged from >0.015 at.% to <3 at.%. Optical absorption was measured from 2.0 to 6.5 eV. Electron paramagnetic resonance measurements were made at ∼20.3 and 33 GHz for sample temperatures ranging from 77 to 100 K for most measurements. The components identified in the spectra, based on comparison with reported parameters, were, in the Si case, due to E′ centers and peroxy radicals. In the O case they were due to E′ centers, non-bridging oxygen hole centers, peroxy radical centers, and a newly appearing state which we labeled the OS center. By comparing the changes in the absorption at 4.83 eV with the changes in the concentrations of the various electron paramagnetic resonance components and with the reports in the literature, we conclude that there are at least four oxygen related centers and one Si related center absorbing between 4.8 and 4.9 eV.