Synthesis of Al-substituted 11 Å tobermorite from newsprint recycling residue: a feasibility study

Newsprint recycling is responsible for significant volumes of secondary waste material for which further reprocessing and market development would be beneficial. In response to this problem, a layer lattice, ion exchange material, Al-substituted 11 Å tobermorite, has been synthesised from newsprint recycling residue comprising gehlenite (Ca₂Al₂SiO₇), akermanite (Ca₂MgSi₂O₇), β-dicalcium silicate (Ca₂SiO₄) and anorthite (CaAl₂Si₂O₈) under hydrothermal conditions at 100 °C in the presence of NaOH. The hydrogarnet phase, katoite (Ca₃Al₂SiO₁₂H₈), was also formed. Similar treatment regimes in the presence of LiOH and KOH did not yield significant quantities of Al-substituted 11 Å tobermorite. A batch sorption study confirmed that the Al-substituted 11 Å tobermorite-bearing product was effective in the exclusion of Cd²⁺, Pb²⁺ and Zn²⁺ from acidified aqueous media. The potential to enhance the yield of Al-substituted 11 Å tobermorite relative to that of katoite and thus optimise the ion exchange efficiency of the product is discussed with respect to its application to heavy metal-contaminated wastewater treatment.     

Microporous carbon derived from polyaniline base as anode material for lithium ion secondary battery

Microporous carbon with large surface area was prepared from polyaniline base using K₂CO₃ as an activating agent. The physicochemical properties of the carbon were characterized by scanning electron microscope, X-ray diffraction, Brunauer-Emmett-Teller, elemental analyses and X-ray photoelectron spectroscopy measurement. The electrochemical properties of the microporous carbon as anode material in lithium ion secondary battery were evaluated. The first discharge capacity of the microporous carbon was 1108 mAh g⁻¹, whose first charge capacity was 624 mAh g⁻¹, with a coulombic efficiency of 56.3%. After 20 cycling tests, the microporous carbon retains a reversible capacity of 603 mAh g⁻¹ at a current density of 100 mA g⁻¹. These results clearly demonstrated the potential role of microporous carbon as anode for high capacity lithium ion secondary battery.     

CTAB-assisted sol-gel synthesis of Li4Ti5O12 and its performance as anode material for Li-ion batteries

A simple CTAB-assisted sol-gel technique for synthesizing nano-sized Li₄Ti₅O₁₂ with promising electrochemical performance as anode material for lithium ion battery is reported. The structural and morphological properties are investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The electrochemical performance of both samples (with and without CTAB) calcined at 800 °C is evaluated using Swagelok™ cells by galvanostatic charge/discharge cycling at room temperature. The XRD pattern for sample prepared in presence of CTAB and calcined at 800 °C shows high-purity cubic-spinel Li₄Ti₅O₁₂ phase (JCPDS # 26-1198). Nanosized-Li₄Ti₅O₁₂ calcined at 800 °C in presence of CTAB exhibits promising cycling performance with initial discharge capacity of 174 mAh g⁻¹ (∼100% of theoretical capacity) and sustains a capacity value of 164 mAh g⁻¹ beyond 30 cycles. By contrast, the sample prepared in absence of CTAB under identical reaction conditions exhibits initial discharge capacity of 140 mAh g⁻¹ (80% of theoretical capacity) that fades to 110 mAh g⁻¹ after 30 cycles.     

Preparation of hexagonal-MoO3 and electrochemical properties of lithium intercalation into the oxide

Metastable hexagonal molybdenum trioxide has been synthesized by chemical precipitation and hydrothermal treatment at low temperature. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to characterize the product, which has a unique hexagonal prism-like morphology. Excellent electrochemical performances were exhibited: the first reversible discharge specific capacity can reach 402 mAh g⁻¹ versus Li metal at 0.1 mA cm⁻² (voltage range 1.2-4.0 V).     

Room temperature electroluminescence from the n-ZnO/p-GaN heterojunction device grown by MOCVD

The heterojunction light-emitting diode with n-ZnO/p-GaN structure was grown on (0 0 0 1) sapphire substrate by metalorganic chemical vapor deposition (MOCVD) technique. The heterojunction structure was consisted of an Mg-doped p-type GaN layer with a hole concentration of ∼10¹⁷ cm⁻³ and a unintentionally doped n-type ZnO layer with an electron concentration of ∼10¹⁸ cm⁻³. A distinct blue-violet electroluminescence with a dominant emission peak centered at ∼415 nm was observed at room temperature from the heterojunction structure under forward bias conditions. The origins of the electroluminescence (EL) emissions are discussed in comparison with the photoluminescence spectra, and it was supposed to be attributed to a radiative recombination in both n-ZnO and p-GaN sides.     

Preparation and characterization of In(I)-β″-alumina

In(I)-β″-alumina has been prepared by ion exchange from Na-β″-alumina. It is stable on heating in air up to 400 °C. Its structure was determined by Rietveld analysis using high-resolution X-ray powder diffraction data [R-3m, a = 5.6044(1) Å, c = 34.4807(1) Å, Z = 3]. The coordination of In(I) in this material is asymmetric, as indicated by the distortion index for this cation, suggesting some stereochemical activity for the lone pair on the cation. However, the distortion is not as pronounced as that seen in the Ga(I) analogue.     

Preparation and electrochemical properties of lamellar MnO2 for supercapacitors

Lamellar birnessite-type MnO₂ materials were prepared by changing the pH of the initial reaction system via hydrothermal synthesis. The interlayer spacing of MnO₂ with a layered structure increased gradually when the initial pH value varied from 12.43 to 2.81, while the MnO₂, composed of α-MnO₂ and γ-MnO₂, had a rod-like structure at pH 0.63. Electrochemical studies indicated that the specific capacitance of birnessite-type MnO₂ was much higher than that of rod-like MnO₂ at high discharge current densities due to the lamellar structure with fast intercalation/deintercalation of protons and high utilization of MnO₂. The initial specific capacitance of MnO₂ prepared at pH 2.81 was 242.1 F g⁻¹ at 2 mA cm⁻² in 2 mol L⁻¹ (NH₄)₂SO₄ aqueous electrolyte. The capacitance increased by about 8.1% of initial capacitance after 200 cycles at a current density of 100 mA cm⁻².     

Structural and dielectric properties of A(Fe1/2Ta1/2)O3 [A = Ba, Sr, Ca]

The complex perovskite oxide barium iron tantalate (BFT), BaFe_1/2Ta_1/2O₃, strontium iron tantalate (SFT), SrFe_1/2Ta_1/2O₃ and calcium iron tantalate (CFT), CaFe_1/2Ta_1/2O₃ are synthesized by a solid-state reaction technique. Rietveld refinement of the X-ray diffraction data of the samples shows that BFT and SFT crystallize in cubic structure, with lattice parameter a = 4.06 Å for BFT and 3.959 Å for SFT, whereas CFT crystallizes in orthorhombic structure having lattice parameters a = 5.443 Å, b = 5.542 Å and c = 7.757 Å. Fourier transform infrared spectra show two primary phonon modes of the samples at around 450 cm⁻¹ and 620 cm⁻¹. The compounds show significant frequency dispersion in its dielectric properties. The complex impedance plane plots of the samples show that the relaxation (conduction) mechanism in these materials is purely a bulk effect arising from the semiconductive grains. The relaxation mechanism of the samples is modelled by Cole-Cole equation. The frequency dependent conductivity spectra are found to follow the power law.     

Lithium conducting glass ceramic with Nasicon structure

Lithium ion conducting glass and glass ceramic of the composition Li_1.4[Al_0.4Ge_1.6(PO₄)₃], have been synthesized. The monolithic glass pieces on thermal treatment resulted in single-phase glass ceramic with the Nasicon structure. Experiments with different electrodes proved that the lithium electrodes provide accurate values for the ionic conductivity using impedance spectroscopy. σ_ionic of the glass ceramic was found to be 3.8×10⁻⁵ S cm⁻¹ at 40°C with an activation energy (E_a) of 0.52 eV. The corresponding values for the glass are 2.7×10⁻⁹ S cm⁻¹ and 0.95 eV, respectively. The Arrhenius dependence of σ_ionic with temperature in glass and glass ceramic is interpreted with a hopping mechanism from which the microscopic characteristics of the lithium cation motion are deduced.     

A new phase diagram for the CaOAl2O3SiO2H2O hydroceramic system at 200 °C

A new phase diagram is reported for the CaOAl₂O₃SiO₂H₂O (CASH) system at 200 °C. This system is rare in nature but has applications in cementing geothermal and deep oil wells. The phase diagram was constructed by synthesising a range of hydroceramics with CASH assemblages from oilwell cement, silica flour (quartz) and alumina (corundum). A hydroceramic is defined as any ceramic material incorporating water as H₂O or OH. At 200 °C, gyrolite, hillebrandite, jaffeite, portlandite, quartz, 11 Å tobermorite, xonotlite, hibschite and katoite were observed as product phases. The mineral assemblages produced the following three-phase triangles in the CaOAl₂O₃SiO₂ diagram: Gyr + Qtz + Xon; Crn + Tob + Xon; Crn + Hib + Xon; Crn + Hib + Jaf; Crn + Jaf + Kat; Hib + Jaf + Por; Hib + Jaf + Xon; and two reactions are found to be in progress at 200 °C. When alumina is present in the reaction mixture, the thermal stability of tobermorite is extended to higher temperature, and the crystallinity of tobermorite and xonotlite enhanced.     

Ion exchange and electrochemical evaluation of the microporous phosphate Li9Fe7(PO4)10

A new lithium iron(III) phosphate, Li₉Fe₇(PO₄)₁₀, has been synthesized and is currently under electrochemical evaluation as an anode material for rechargeable lithium-ion battery applications. The sample was prepared via the ion exchange reaction of Cs₅K₄Fe₇(PO₄)₁₀1 in the 1 M LiNO₃ solution under hydrothermal conditions at 200 °C. The fully Li⁺-exchanged sample Li₉Fe₇(PO₄)₁₀2 cannot yet be synthesized by conventional high-temperature, solid-state methods. The parent compound 1 is a member of the Cs_9−xK_xFe₇(PO₄)₁₀ series that was previously isolated from a high-temperature (750 °C) reaction employing the eutectic CsCl/KCl molten salt. The polycrystalline solid 1 was first prepared in a stoichiometric reaction via conventional solid-state method then followed by ion exchange giving rise to 2. Both compounds adopt three-dimensional structures that consist of orthogonally interconnected channels where electropositive ions reside. It has been demonstrated that the Cs_9−xK_xFe₇(PO₄)₁₀ series possesses versatile ion exchange capabilities with all the monovalent alkali metal and silver cations due to its facile pathways for ion transport. 1 and 2 were subject to electrochemical analysis and preliminary results suggest that the latter can be considered as an anode material. Electrochemical results indicate that Li₉Fe₇(PO₄)₁₀ is reduced below 1 V (vs. Li) to most likely form a Fe(0)/Li₃PO₄ composite material, which can subsequently be cycled reversibly at relatively low potential. An initial capacity of 250 mAh/g was measured, which is equivalent to the insertion of thirteen Li atoms per Li_9+xFe₇(PO₄)₁₀ (x = 13) during the charge/discharge process (Fe²⁺ + 2e → Fe⁰). Furthermore, 2 shows a lower reduction potential (0.9 V), by approximately 200 mV, and much better electrochemical reversibility than iron(III) phosphate, FePO₄, highlighting the value of improving the ionic conductivity of the sample.     

Properties of amorphous Si thin film anodes prepared by pulsed laser deposition

Amorphous Si (a-Si) thin film anodes were prepared by pulsed laser deposition (PLD) at room temperature. Structures and properties of the thin films were investigated using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and electrochemical measurements. Galvanostatic charge/discharge tests of half cells using lithium counter electrode were conducted at a constant current density of 100 μA/cm² in different voltage windows. Cyclic voltammetry (CV) was obtained between 0 and 1.5 V at various scan rates from 0.1 to 2 mV/s. The apparent diffusion coefficient (D_Li) calculated from the CV measurements was about ∼10⁻¹³ cm²/s. The Si thin film anode was also successfully coupled with LiCoO₂ thin film cathode. The a-Si/LiCoO₂ full cell showed stable cycle performance between 1 and 4 V.     

Templated synthesis of nanosized mesoporous carbons

Mesoporous carbon materials formed by nanosized particles have been synthesized by means of a nanocasting technique based on the use of mesostructured silica materials as templates. We found that the modification of the chemical characteristics of the surfactant employed allows mesostructured silica materials with particle sizes <100 nm to be synthesised. The mesoporous carbons obtained from these silica materials retain the structural properties of the silica used as template and consequently they have a particle size in the 20-100 nm range. These carbons exhibit large BET surfaces areas (up to 1300 m² g⁻¹) and high pore volumes (up to 2.5 cm³ g⁻¹), a framework confined porosity made up of uniform mesopores (3.6 nm) and an additional textural porosity arising from the interparticle voids between the sub-micrometric particles. The main advantage of nanometer-sized mesoporous carbons in relation to the micrometer-sized carbons is that they have enhanced mass transfer rates, which is important for processes such as adsorption or catalysis.     

Development of a dedicated ion injector for accelerator-based nanoprobe facilities

The paper discusses possible ways of increasing beam brightness in ion injectors. The argon/helium ion injector comprising a newly designed RF ion source and, a Wien filter has been designed for use in accelerator-based nanoprobe facilities. The phase set degradation due to aberrations in the injector ion-optic system was simulated with allowance for multipole and fringing fields. The RF ion sources with different permanent magnet systems were tested. Experiments were performed with argon and helium. A plasma density of up to 3×10¹¹ cm⁻³ and beam brightness of ∼100 A/(m² rad² eV) were obtained. The ion current density inside an extracting electrode in the source was 10 mA/cm² for an emission hole diameter of 0.6 mm. Measurements of the current value and emittance were performed with ion source testing equipment permitting measurements of the ion beam current, emittance, mass composition, and RF power input into the plasma.     

Irradiation-induced gold silicide formation and stoichiometry effects in ion beam-mixed layer

The irradiation-induced silicide formation in ion beam-mixed layer of Au/Si(1 0 0) system was investigated by using 200 keV Kr⁺ and 350 keV Xe⁺ ions to fluences ranging from 8×10¹⁴ to 1×10¹⁶ ions/cm² at room temperature. The thickness of Au layer evaporated on Si substrate was ∼500 Å. Rutherford backscattering spectrometry (RBS) experiments were carried out to study the irradiation effects on the mixed layers. We observed that at the fluence of 1×10¹⁶ Kr⁺/cm² and starting from the fluence of 8×10¹⁴ Xe⁺/cm², a total mixing of the deposited Au layer with Si was obtained. RBS data corresponding to the fluences of 1×10¹⁶ Kr⁺/cm² and 8×10¹⁴ Xe⁺/cm² clearly showed mixed layers with homogenous concentrations of Au and Si atoms which can be attributed to gold silicides.The samples irradiated to fluences of 1×10¹⁶ Kr⁺/cm² and 1×10¹⁶ Xe⁺/cm² were also analyzed by X-ray photoelectron spectroscopy (XPS). The observed chemical shift of Au 4f and Si 2p lines confirmed the formation of gold silicides at the surface of the mixed layers. Au₂Si phase is obtained with Kr⁺ irradiation whereas the formed phase with Xe⁺ ions is more enriched in Si atoms.     

100 keV nitrogen ion beam implanted polycarbonate: A possibility for UV blocking devices

Polycarbonate samples were implanted with 100 keV N⁺ ions at fluences 10¹⁵, 10¹⁶ and 5 × 10¹⁶ ions cm⁻². Drastic alterations in UV-Visible transmittance spectra were observed which are interrelated with change in surface color and optical absorption of the implanted samples. UV-Visible transmission studies show that at ion fluence of 10¹⁶ ions cm⁻², transmission approaches to zero at about λ = 427 nm and below up to 200 nm. Optical band gap (E_OPT) reduces with increase in fluence and at maximum ion fluence of 5 × 10¹⁶ N⁺ cm⁻², E_OPT was determined to be 1.56 eV whereas for pristine its value was 3.00 eV. Raman analysis indicates the formation of amorphous carbon on the surface of polycarbonate at an ion fluence of 10¹⁶ N⁺ cm⁻². Rise in fluence to 5 × 10¹⁶ N⁺ cm⁻² results in enhancement in disorder on the surface of the host polymer. Modifications in the structural arrangements were found to be in strong association with changes in optical properties with increase in ion fluence and the same is discussed.     

Thermal stability of the Mobil Five type metallosilicate molecular sieves—An in situ high temperature X-ray diffraction study

We have carried out in situ high temperature X-ray diffraction (HTXRD) studies of silicalite-1 (S-1) and metallosilicate molecular sieves containing iron, titanium and zirconium having Mobil Five (MFI) structure (iron silicalite-1 (FeS-1), titanium silicalite-1 (TS-1) and zirconium silicalite-1 (ZrS-1), respectively) in order to study the thermal stability of these materials. Isomorphous substitution of Si⁴⁺ by metal atoms is confirmed by the expansion of unit cell volume by X-ray diffraction (XRD) and the presence of Si-O-M stretching band at ∼960 cm⁻¹ by Fourier transform infrared (FTIR) spectroscopy. Appearance of cristobalite phase is seen at 1023 and 1173 K in S-1 and FeS-1 samples. While the samples S-1 and FeS-1 decompose completely to cristobalite at 1173 and 1323 K, respectively, the other two samples are thermally stable upto 1623 K. This transformation is irreversible. Although all materials show a negative lattice thermal expansion, their lattice thermal expansion coefficients vary. The thermal expansion behavior in all samples is anisotropic with relative strength of contraction along ‘a’ axes is more than along ‘b’ and ‘c’ axes in S-1, TS-1, ZrS-1 and vice versa in FeS-1. Lattice thermal expansion coefficients (α_v) in the temperature range 298-1023 K were −6.75 × 10⁻⁶ K⁻¹ for S-1, −12.91 × 10⁻⁶ K⁻¹ for FeS-1, −16.02 × 10⁻⁶ K⁻¹ for TS-1 and −17.92 × 10⁻⁶ K⁻¹ for ZrS-1. The highest lattice thermal expansion coefficients (α_v) obtained were −11.53 × 10⁻⁶ K⁻¹ for FeS-1 in temperature range 298-1173 K, −20.86 × 10⁻⁶ K⁻¹ for TS-1 and −25.54 × 10⁻⁶ K⁻¹ for ZrS-1, respectively, in the temperature range 298-1623 K. Tetravalent cation substitution for Si⁴⁺ in the lattice leads to a high thermal stability as compared to substitution by trivalent cations.     

Crystal structure and ionic conductivity of ruthenium diphosphate ARu2(P2O7)2, A=Li, Na, and Ag, with a tunnel structure

Crystal structure and ionic conductivity of ruthenium diphosphates, ARu₂(P₂O₇)₂ A=Li, Na, and Ag, were investigated. The structure of the Ag compound was determined by single crystal X-ray diffraction techniques. It crystallized in the triclinic space group P−1 with a=4.759(2) Å, b=6.843(2) Å, c=8.063(1) Å, α=90.44(2)°, β=92.80(2)°, γ=104.88(2)°, V=253.4(1) Å³. The host structure of it was composed of RuO₆ and P₂O₇ groups and formed tunnels running along the a-axis, in which Ag⁺ ions were situated. The ionic conductivities have been measured on pellets of the polycrystalline powders. The Li and Ag compounds showed the conductivities of 1.0×10⁻⁴ and 3.5×10⁻⁵ S cm⁻¹ at 150 °C, respectively. Magnetic susceptibility measurement of the Ag compound showed that it did not obey the Curie-Weiss law and the effective magnetic moment decreased as temperature decreased due to the large spin-orbital coupling effect of Ru⁴⁺ ions.     

Synthesis of Na-A and faujasitic zeolites from high silicon fly ash

High silicon fly ash (HSFA) utilized as a source of silicon in synthesizing of Na-A, -X and -Y zeolites through alkali fusion followed by hydrothermal treatment at 100 °C for 12 h. Various types of zeolites with different degrees of purity were prepared by changing Si/Al ratio of the reaction mixture from 1.6 to 3.0. In addition, exact boundaries of this ratio for synthesis of each zeolite type were determined. Furthermore, the effect of NaOH amount utilized in alkaline fusion step on crystalinity of samples investigated. The synthesized zeolites were characterized using various techniques including; XRD, TGA, FTIR, SEM and BET. The ion-exchange behaviors of zeolitic samples tested with Co²⁺. The obtained Na-X zeolite was crystaline, had a very high cation-exchange capability of 4.9 mequiv. g⁻¹ and possessed relatively high specific surface area of about 434 m² g⁻¹.     

Surfactant-free synthesis and electrochemical properties of chrysanthemum-like InVO4 hierarchical microstructures

Novel chrysanthemum-like hierarchical microstructures of orthorhombic InVO₄ were synthesized via a hydrothermal route without assistance of any template or organic additive. The chrysanthemum-like InVO₄ microstructures are built up of numerous nanobelts radially aligned around the spherical surface. Based on the structural feature of orthorhombic InVO₄ and the key role of the pH value, a probable mechanism of the etching-splitting growth process induced by H⁺ ions was proposed to explain the formation of InVO₄ microstructures. Furthermore, the chrysanthemum-like InVO₄ sample shows a high discharge capacity of 608.6 mAh g⁻¹ and acceptable capacity retention when used as an electrode material in lithium ion batteries. The pure orthorhombic phase and unique porous morphology play basic roles in the structural requirement to serve as transport paths for lithium ion.