Effects of agitation intensity and sunlight on the generation and properties of aqu/nC<Subscript>60</Subscript>

Despite the very low water solubility of fullerene C₆₀, stable nanoscale aggregates (aqu/nC₆₀) can be formed by extended mixing in water. The generation and properties of aqu/nC₆₀ in the aquatic environment depend on many environmental factors and hydrodynamic conditions. In the present study, effects of agitation intensity and sunlight on the generation and properties of aqu/nC₆₀ were investigated during a 70-day extended mixing. The results revealed that higher agitation intensity leaded to the smaller size, more stability, and higher concentrations of aqu/nC₆₀. As sunlight promoted the production of oxygen-containing moieties on the surface of nC₆₀ aggregates, sunlight enhanced the generation and stability of aqu/nC₆₀. These might suggest that stable nC₆₀ aggregates with relatively high concentrations could be formed in turbulent waters under sunlight, which could be transported over long distances and pose potential exposure risks on aquatic organisms. Therefore, hydrodynamic conditions and sunlight, as important influencing factors, should be carefully considered in assessing the environmental behavior, fate, and risks of C₆₀. Furthermore, the agitation intensity or at least the agitation speed should be taken into account and presented in further researches on aqu/nC₆₀ in order to better compare the results.     

Size-dependent photodegradation of CdS particles deposited onto TiO2 mesoporous films by SILAR method

Carbonaceous nanomaterials, such as fullerene C₆₀, carbon nanotubes, and their functionalized derivatives have been demonstrated to possess high sorption capacity for organic and heavy metal contaminants, indicating a potential for remediation application. The actual application of these nanomaterials, however, is often hindered by the high cost of materials and the limited understanding of their mobility in porous media. In this work, carbon nano-onions (CNOs), a relatively new addition to the carbonaceous nanomaterials, were synthesized in a cost-effective way using a laser-assisted combustion synthesis process, and carefully characterized for their potential remediation application. Surface oxidized CNOs possessed 10 times higher sorption capacity than C₆₀ for heavy metal ion contaminants including Pb²⁺, Cu²⁺, Cd²⁺, Ni²⁺, and Zn²⁺. CNOs aqueous suspension can be very stable in NaCl solution at ionic strength up to 30?mM and CaCl₂ solution at ionic strength up to 4?mM CaCl₂ when pH ranged from 5 to 9, which are consistent with environmentally relevant conditions. Interactions of CNOs with iron oxide and silica surfaces under favorable condition were found to be electrostatic in origin. Mobility of CNOs in quartz sands was controlled by electrolyte type and concentration. Approximately 4.4, 25.1, and 92.5?% of injected CNO mass were retained in the sand column in ultrapure water, 1?mM?NaCl, and 1?mM CaCl₂ solutions, respectively.     

Uptake and Sequestration of Naphthalene and 1,2-Dichlorobenzene by C60

The interactions of common environmental contaminants with C₆₀ have been studied to evaluate the environmental impact of carbon nanomaterials. The adsorption and desorption interaction of the hydrophobic contaminants naphthalene and 1,2-dichlorobenzene with C₆₀ was characterized. Processes that cause the wetting and disaggregating of C₆₀ particles also affect the extent of organic contaminant sorption to C₆₀ aggregates by orders of magnitude. C₆₀ dissolved in organic solvents such as toluene can form stable nanoscale aggregates upon vigorous mixing in water. These nanoscale C₆₀ particles form stable suspensions in water and are referred to as ‘nano-C₆₀’. Desorption of contaminants from stable suspensions of nano-C₆₀ exhibits hysteresis. The experimentally observed adsorption/desorption hysteresis is described by a two-compartment desorption model: first, adsorption to the external surfaces that are in contact with water, and second, adsorption to the internal surfaces within the aggregates.     

Laser assisted modification and chemical metallization of electron-beam deposited ceria thin films

Excimer laser processing is applied for tailoring the surface morphology and phase composition of CeO₂ ceramic thin films. E-beam evaporation technique is used to deposit samples on stainless steel and silicate glass substrates. The films are then irradiated with ArF* excimer laser pulses under different exposure conditions. Scanning electron microscopy, optical spectrophotometry, X-ray diffractometry and EDS microanalysis are used to characterize the non-irradiated and laser-processed films. Upon UV laser exposure there is large increase of the surface roughness that is accompanied by photo-darkening and ceria reduction. It is shown that the laser induced changes in the CeO₂ films facilitate the deposition of metal nano-aggregates in a commercial copper electroless plating bath. The significance of laser modification as a novel approach for the production of CeO₂ based thin film catalysts is discussed.     

Laser printing of nanocomposite solid-state electrolyte membranes for Li micro-batteries

The electrochemical and mechanical properties of nanocomposite solid-state electrolyte membranes deposited using a laser direct-write technique from a suspended solution comprised of an ionic liquid (1,2-dimethyl-3-n-butylimidazolium-bis-trifluoromethanesulfonylimide)-polymer (poly(vinylidene fluoride-co-hexafluoropropylene)) matrix with dispersed nano-particles (TiO₂) are reported and discussed. These laser printed nanocomposite solid-state membranes are shown to exhibit the proper electrochemical behavior for ionic liquids while maintaining the strength and flexibility of the polymer matrix. This combination of physical properties and deposition technique makes these deposited nanocomposite membranes ideally suited for use as an electrolyte/separator in Li micro-batteries. Sample Li micro-batteries using these laser printed nanocomposite membranes have been fabricated and their charge/discharge behavior tested, demonstrating the feasibility of using these nanocomposite membranes in Li micro-battery applications.     

H3O+-dependent morphological change in the electrochemical deposition of iron

By in situ optical microscopy and scanning electron microscopy, we investigate the morphology of the iron electrodeposit grown at different H₃O⁺ concentration in the electrolyte. The chemical composition of the electrodeposit is analyzed by X-ray diffraction and Mössbauer spectroscopy. It seems that the morphological transitions observed in this system do not relate to the oxidation/passivation of the metallic deposit during the growth. The possible origin of the dependence of deposit morphology on the H₃O⁺ in the electrolyte is discussed.     

Nano-composite solid polymer electrolytes for solid state ionic devices

Recent research efforts to improve the ambient temperature conductivity in polyethylene oxide (PEO) based solid polymer electrolytes have been directed towards the incorporation of ultra-fine nano-sized particles of ceramic fillers such as Al₂O₃, γ-LiAlO₂, SiO₂ and TiO₂ into the polymer electrolyte. In these PEO based nano-composite polymer electrolytes, conductivity enhancements of up to two orders of magnitude have been achieved. Thermal, electrical conductivity and dielectric relaxation measurements performed on several nano-composite polymer electrolyte systems have shown that the degree of enhancement depends primarily on the grain size. In this paper, results of three nano-composite polymer electrolyte systems, PEO:LiTFSI:Al₂O₃, PEO:LiTf:Al₂O₃ and PEO:LiTf: SiO₂ are discussed as representative examples. It is suggested that the conductivity enhancement is due to the creation of additional sites and favourable conduction pathways for ionic transport through Lewis acidbase type interactions between the filler surface groups (H/OH) and the ionic species. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Channai, India, Nov. 28–30, 2003.     

Structural investigation on PEO-based polymer electrolytes dispersed with Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles

Thin solid polymer electrolytes based on polyethylene oxide (PEO) and silver triflate (AgCF₃SO₃) dispersed with various concentrations of aluminum oxide (Al₂O₃) nanoparticles have been prepared by solution casting technique. These thin polymer films are found to have thickness of the order of 30 to 100 μm. The X-ray diffraction (XRD) patterns have indicated the amorphous nature of the polymer electrolyte. The differential scanning calorimeter (DSC) traces showed slight change in the glass transition temperature (T _g) whereas the degree of crystallization (X _c) decreases markedly due to the addition of alumina nanoparticles. Fourier transform infrared (FTIR) spectral analysis of all these samples has revealed the presence of absorption bands around 1,000 cm⁻¹; thus indicating the complexation of silver ions with oxygen in PEO. Employing the Wagner’s polarization technique as the standard method, the total ionic transference number for the complexed polymer electrolyte was found to be approximately unity thereby revealing that the significant contribution to electrical conduction was due to ions only. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, December 7–9, 2006     

Polymer electrolytes plasticized with hyperbranched polymer for lithium polymer batteries

Hyperbranched polymers (HBPs) with different terminal groups and different ethylene oxide (EO) chain lengths were prepared, and the influence of the HBP structures including molecular weights and molecular weight distribution on the ionic conductivity and the mechanical property of the composite polymer electrolytes composed of poly (ethylene oxide) (PEO), HBP, BaTiO₃ as a ceramic filler, and LiN(CF₃SO₂)₂ as a lithium salt were investigated. It was found that the molecular weights of the HBP do not affect significantly the ionic conductivity, but the molecular weight distribution might affect it, and also further branching at the terminals of the HBP led to a decrease in the ionic conductivity. The HBP with longer EO chain length was effective for enhancement of the ionic conductivity in comparison with the HBP with shorter one. The increase in cross-linkable groups (acryloyl group) at the terminals of the HBP improved the tensile strength, but caused the ionic conductivity to decrease. Loosely cross-linked composite polymer electrolyte showed higher ionic conductivity and higher tensile strength than no cross-linked one. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Simulations of C60 bombardment of Si, SiC, diamond and graphite

Molecular dynamics simulations of the 20-keV C₆₀ bombardment at normal incidence of Si, SiC, diamond and graphite targets were performed. The unique feature of these targets is that strong covalent bonds can be formed between carbon atoms from the C₆₀ projectile and atoms in the solid material. The mesoscale energy deposition footprint (MEDF) model is used to gain physical insight into how the sputtering yields depend on the substrate characteristics. A large proportion of the carbon atoms from the C₆₀ projectile are implanted into the lattice structure of the target. The sputtering yield from SiC is ∼twice that from either diamond or Si and this can be explained by both the region of the energized cylindrical tract created by the impact and the number density. On graphite, the yield of sputtered atoms is negligible because the open lattice allows the cluster to deposit its energy deep within the solid. The simulations suggest that build up of carbon with a graphite-like structure would reduce any sputtering from a solid with C₆₀⁺ bombardment.     

Nanoparticle transport in water-unsaturated porous media: effects of solution ionic strength and flow rate

This paper presents the influence of ionic strength and flow on nanoparticle (NP) retention rate in an unsaturated calcareous medium, originating from a heterogeneous glaciofluvial deposit of the region of Lyon (France). Laboratory columns 10 cm in diameter and 30 cm in length were used. Silica nanoparticles (Au-SiO₂-FluoNPs), with hydrodynamic diameter ranging from 50 to 60 nm and labeled with fluorescein derivatives, were used to simulate particle transport, and bromide was used to characterize flow. Three flow rates and five different ionic strengths were tested. The transfer model based on fractionation of water into mobile and immobile fractions was coupled with the attachment/detachment model to fit NPs breakthrough curves. The results show that increasing flow velocity induces a decrease in nanoparticle retention, probably as the result of several physical but also geochemical factors. The results show that NPs retention increases with ionic strength. However, an inversion of retention occurs for ionic strength >5.10^?2 M, which has been scarcely observed in previous studies. The measure of zeta potential and DLVO calculations show that NPs may sorb on both solid-water and air-water interfaces. NPs size distribution shows the potential for nanoparticle agglomeration mostly at low pH, leading to entrapment in the soil pores. These mechanisms are highly sensitive to both hydrodynamic and geochemical conditions, which explains their high sensitivity to flow rates and ionic strength.     

Influence of pyrazole on the photovoltaic performance of dye-sensitized solar cell with polyvinylidene fluoride polymer electrolytes

We investigate the influence of the pyrazole content on the polyvinylidene fluoride (PVDF)/KI/I₂ electrolytes for dye-sensitized solar cells (DSSCs). The solid polymer electrolyte films consisting of different weight percentage ratios (0 20, 30, 40, and 50 %) of pyrazole doped with PVDF/KI/I₂ have been prepared by solution casting technique using N,N-dimethyl formamide (DMF) as a solvent. The as-prepared polymer electrolyte films were characterized by various techniques such as Fourier transform infrared spectroscopy (FT-IR spectroscopy), differential scanning calorimetry (DSC), X-ray diffractometer (XRD), alternate current (AC)-impedance analysis, and scanning electron microscopy (SEM). The 40 wt% pyrazole-PVDF/KI/I₂ electrolyte exhibited the highest ionic conductivity value of 9.52?×?10^?5 Scm^?1 at room temperature. This may be due to the lower crystallinity of PVDF and higher ionic mobility of iodide ions in the electrolyte. The DSSC fabricated using this highest ion conducting electrolyte showed an enhanced power conversion efficiency of 3.30 % under an illumination of 60 mW/cm² than that of pure PVDF/KI/I₂ electrolyte (1.42 %).     

Ion transport and structure in silver borate glasses

A study of ionic conductivity in silver borate glasses is presented, which includes (i) a full characterization of the ion transport properties in the AgI:Ag₂O:B₂O₃ glasses, (ii) results for glasses where iodine is totally or partially substituted by another halide, (iii) mixed-cation effects. A substantial portion of the paper discusses the relationship between local order and ion transport properties of borate glasses and vitreous electrolyte systems.     

Capacity fading of LiCr0.1Mn1.9O4/MPCF cells at elevated temperature

Capacity fading of LiCr_0.1Mn_1.9O₄ /MPCF (mesophase pitch-based carbon fiber) cells was investigated at elevated temperature (55 °C). The cells showed very fast capacity fading, keeping only 60% of capacity retention at the 100th cycle at 55 °C. The cycled electrodes and the electrolyte were analyzed using electrochemical test, inductively coupled plasma, and X-ray diffraction. Results of the analyses indicated that LiCr_0.1Mn_1.9O₄ exhibited good effects on restraint of Mn dissolution and stabilization of structure at 55 °C. The cycled LiCr_0.1Mn_1.9O₄ electrode and the cycled MPCF electrode presented good electrochemical performance again with fresh electrolyte. Therefore, it was proposed that the cycling fading of LiCr_0.1Mn_1.9O₄/MPCF cells was mainly caused by decomposition of electrolyte upon LiCr_0.1Mn_1.9O₄ electrode during cycling. It was found that the decomposition of electrolyte led to the formation of a surface layer comprised of Li₂CO₃, Li _x PF _y , CH₃OCO₂Li or (CH₂OCO₂Li)₂, polymeric ether etc. The formation of this film consumed active lithium ions, leading to fast capacity fading of LiCr_0.1Mn_1.9O₄/MPCF cell at elevated temperature.     

Friction model to describe cluster bombardment

Short time molecular dynamics simulations were performed to model C₆₀ and Au₃ bombardment of an amorphous water sample in the projectile energy range of 5-120 keV. A previously proposed friction model has been applied to describe the fundamental motion of a projectile during cluster bombardment of a solid. This simple analytical model uses a definition of friction on a single particle to describe the cluster movement through a medium. Although the mathematics of the friction model vary among systems, the projectile motion and energy deposition of a single particle into the sample as well as the reactive environment created is close to that of C₆₀ bombardment.     

Morphological investigations on the solid electrolyte Li3.6Ge0.6V0.4O4 and use in a solid state lithium battery

The development of a solid state thin film lithium battery system needs a detailed investigation of the electrolyte as well as the electrodes. The realisation of a total solid state battery includes the assumption, that the interfacial contact between the electrodes and the electrolyte is as good as possible. The interfacial resistance should be low for an easily intercalation or deintercalation of lithium at the electrodes and the ionic conductivity of the electrolyte should be high. A further critical aspect of the solid state battery is the porosity of the electrodes and the electrolyte. A homogeneous surface coverage and a high density are useful for a high contact concentration between the grains of electrolyte itself and between the electrolyte and the electrodes. As a possible electrolyte we have investigated the system Li₄GeO₄/Li₃VO₄, which we prepared in the stoichiometry Li_3.6 Ge_0.6 V_0.4 O₄. This lithium conducting system shows a high lithium conductivity of about 4 x 10⁻⁵ S/cm at room temperature and higher values at elevated temperatures. The conductivity is the result of interstitial Li cations in the solid state solution. The deposition of the inorganic thin film was done by a spray pyrolysis technique on different substrates. A variety of different substrates were investigated as a function of adhesion and modified surface conditions. The aim is to find a correlation between the substrate and the morphology of the thin film. The temperature of the deposition was varied between 400 and 600 °C. The temperature dependent cristallinity was also studied. Furthermore the change of the unit cell volume and its constants a, b and c has been investigated as a function of temperature by high temperature diffractometry. The thermal expansion coefficient of the electrolyte could be calculated, to examine stresses with various substrates. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

Nanoscale semiconductor Pb1−xSnxSe (x = 0.2) thin films synthesized by electrochemical atomic layer deposition

In this paper the fabrication and characterization of IV-VI semiconductor Pb_1−xSn_xSe (x = 0.2) thin films on gold substrate by electrochemical atomic layer deposition (EC-ALD) method at room temperature are reported. Cyclic voltammetry (CV) is used to determine approximate deposition potentials for each element. The amperometric I-t technique is used to fabricate the semiconductor alloy. The elements are deposited in the following sequence: (Se/Pb/Se/Pb/Se/Pb/Se/Pb/Se/Sn …), each period is formed using four ALD cycles of PbSe followed by one cycle of SnSe. Then the deposition manner above is cyclic repeated till a satisfactory film with expected thickness of Pb_1−xSn_xSe is obtained. The morphology of the deposit is observed by field emission scanning electron microscopy (FE-SEM). X-ray diffraction (XRD) pattern is used to study its crystalline structure; X-ray photoelectron spectroscopy (XPS) of the deposit indicates an approximate ratio 1.0:0.8:0.2 of Se, Pb and Sn, as the expected stoichiometry for the deposit. Open-circuit potential (OCP) studies indicate a good p-type property, and the good optical activity makes it suitable for fabricating a photoelectric switch.     

Morphology-controlled PANI nanowire electrode by using deposition scan rate in H<Subscript>2</Subscript>SO<Subscript>4</Subscript>/PVA polymer electrolyte for electrochemical capacitor

Polyaniline (PANI) nanowire electrode was successfully prepared using electrodeposition method. The morphology, thickness, and electrochemical performance of PANI electrode can be controlled by varying the deposition scan rates. Lower deposition scan rate results in compact and aggregates of PANI nanowire morphology. The uniform nanowire of PANI was obtained at the applied scan rate of 100 mV s^?1, and it was used as symmetric electrode coupled with H₂SO₄/polyvinyl alcohol (PVA) gel electrolyte. The different concentrations of H₂SO₄ acid in polymer electrolyte have influenced the electrochemical performance as well. The optimum specific capacitance and energy density of P100 PANI electrode in 3 M H₂SO₄/PVA gel polymer electrolyte was 377 F g^?1 and 95.4 Wh kg^?1 at the scan rate of 1 mV s^?1. The good stability of the electrode in this system is applicable to many wearable electronics applications.     

Solid polymeric electrolyte of PVC–ENR–LiClO<Subscript>4</Subscript>

The ionic conductivity of PVC–ENR–LiClO₄ (PVC, polyvinyl chloride; ENR, epoxidized natural rubber) as a function of LiClO₄ concentration, ENR concentration, temperature, and radiation dose of electron beam cross-linking has been studied. The electrolyte samples were prepared by solution casting technique. Their ionic conductivities were measured using the impedance spectroscopy technique. It was observed that the relationship between the concentration of salt, as well as temperature, and conductivity were linear. The electrolyte conductivity increases with ENR concentration. This relationship was discussed using the number of charge carrier theory. The conductivity–temperature behaviour of the electrolyte is Arrhenian. The conductivity also varies with the radiation dose of the electron beam cross-linking. The highest room temperature conductivity of the electrolyte of 8.5 × 10⁻⁷ S/cm was obtained at 30% by weight of LiClO₄. The activation energy, E _a and pre-exponential factor, σ _o, are 1.4 × 10⁻² eV and 1.5 × 10⁻¹¹ S/cm, respectively.     

Combined effect of nanochitosan and succinonitrile on structural, mechanical, thermal, and electrochemical properties of plasticized nanocomposite polymer electrolytes (PNCPE) for lithium batteries

A sequence of novel plasticized polymer nanocomposite electrolyte systems based on polyethylene oxide (PEO) as polymer host, LiCF₃SO₃ as salt, and a variety of concentrations of nanochitosan as inert filler, succinonitrile as a solid non-ionic plasticizer has been prepared. The prepared membranes were subjected to X-ray diffraction, FT-IR, tensile strength, morphological studies, thermal analysis, AC ionic conductivity measurement, and interfacial analyses. The combined effect of succinonitrile and nanochitosan on the electrochemical properties of polymer electrolytes has been studied, and it was confirmed that the ionic conductivity is significantly increased. The maximum ionic conductivity of the plasticized nanocomposite polymer electrolytes are found to be in the range of 10^?2.8?S/cm. Besides, the interfacial stability also shows a significant improvement. The tensile measurement and thermal analysis results illustrate that the electrolytes based on that polymer host possess good mechanical and thermal stabilities.