Nonisothermal crystallization behaviors and conductive properties of PEO‐based solid polymer electrolytes containing yttrium oxide nanoparticles

Lithium solid polymer electrolytes (SPE) composed of polyethylene oxide (PEO) and yttrium oxide (Y₂O₃) nanoparticles were prepared. The influence of the Y₂O₃ nanoparticles on the non‐isothermal crystallization behaviors, crystal structure, and conductive properties of the SPE were investigated. The peak temperature, crystallinity, and crystallization half‐time (t_1/2) of the SPE were strongly dependent on the concentration of Y₂O₃ and the cooling rate. The non‐isothermal crystallization data were analyzed by the modified Avrami model, which successfully described the nonisothermal crystallization process of the SPE. The Avrami exponents suggested that the Y₂O₃ nanoparticles significantly affected both the nucleation mechanism and crystal growth of the PEO matrix. The nucleating and crystallization activation energies (ψ and E_c) estimated with different theories indicated that the Y₂O₃ nanoparticles were inclined to serve as heterogeneous nucleating agents to benefit the crystallization at lower concentration whereas as physical hindrance to inhibit the crystal growth at relatively higher concentration. The maximum conductivity (σ) of 5.95 × 10^?5 S cm^?1 at room temperature for the SPE was obtained at the Y₂O₃ weight ratio of 0.10. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Charge cycling and impedance characterization of a polyphosphazene solid polymer electrolyte-manganese(IV) oxide intercalation cathode

The compatibility of polyphosphazene (PPZ) polymer electrolytes with MnO₂/C/SPE intercalation cathodes (IC) was investigated. Three-layered laminates of a phosphazene-based solid polymer electrolyte (SPE) film sandwiched between two MnO₂-based ICs (one preloaded with lithium) were constructed. The cathodes were fabricated by either solvent casting or compression techniques. Two different crystal forms of manganese(IV) oxide—λ-MnO₂ and γ-MnO₂—were employed, together with methoxy ethoxy ethoxy PPZ (MEEP) SPE binder material. Carbon black was employed as the electronically conductive phase. One cathode in each laminate was prepared in the ‘chemically intercalated’ form by using LiMn₂O₄ in place of MnO₂. The podand polymer, SMEP, which has better thin film mechanical properties than does MEEP, was complexed with lithium trifluoromethane sulfonate (Li triflate) and used as the SPE. Li⁺ ions were cycled galvanostatically between the two-ICs, through the phosphazene-based SPE layer. The performance of the cell was continuously monitored by electrochemical impedance spectroscopy (EIS) and by measuring the laminate thickness and voltage drop. The method of cathode fabrication (casting vs. pressing) was found to be the primary factor influencing the cycle life.     

Effect of filler‐polymer interactions on the crystalline morphology of PEO‐based solid polymer electrolytes by Y2O3 nano‐fillers

A novel lithium solid polymer electrolyte (SPE) based on polyethylene oxide (PEO) matrix and yttrium oxide (Y₂O₃) as nano‐filler was prepared by solution casting technique. The Lewis acid‐based filler‐polymer coordination interactions between the surface of Y₂O₃ and the ether oxygen of PEO were proved by FTIR, which induced an obvious modification of crystalline morphology of the PEO‐based SPEs. Polarized optical microscope (POM) analysis shows that the induced nucleation and steric hindrance effects of Y₂O₃ nano‐filler result in the increased amount as well as decreased size of spherulites in the PEO matrix, respectively. Atomic force microscope (AFM) images indicate the surface morphology of PEO gets rougher as Y₂O₃ content increases. X‐ray diffractomer (XRD) and differential scanning calorimetry (DSC) results demonstrate the crystallinity of SPEs decreases from 51.1% to 32.5% with the Y₂O₃ weight ratio [m(Y₂O₃)/m(PEO+LiI)] increasing from 0 to 0.15. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Texture,microstructures, and mechanical properties of AlN‐based ceramics with Si3N4–Y2O3 additives

Textured AlN‐based ceramics with improved mechanical properties were prepared by hot pressing using Si₃N₄ and Y₂O₃ as additives. The introduction of Si₃N₄–Y₂O₃ into AlN matrix led to the formation of secondary Y₃AlSi₂O₇N₂ and fiber‐like 2H^δ AlN‐polytypoid phases, the partial texture of all crystalline phases, and the fracture mode change from intergranular to transgranular. Consequently, Vickers hardness, fracture toughness and flexural strength of AlN‐based ceramics by the replacement of Y₂O₃ by Si₃N₄–Y₂O₃ increased significantly from 10.4±0.3 GPa, 2.4±0.3 MPa m^½ and 333.3±10.3 MPa to 14.2±0.4 GPa, 3.4±0.1 MPa m^½ and 389.5±45.5 MPa, respectively.     

Molecular dynamics study on nano‐particles reinforced oxide glass

Energy release rate and fracture toughness of amorphous aluminum nanoparticles reinforced soda‐lime silica glass (SLSG) were measured by performing fracture simulations of a single‐notched specimen via molecular dynamics simulations. The simulation procedure was first applied to conventional oxide glasses and the accuracy was verified with comparing to experimental data. According to the fracture simulations on three models of SLSG/‐Al₂O₃ composite, it was found that the crack propagation in the composites is prevented through following remarkable phenomena; one is that a‐Al₂O₃ nanoparticles increase fracture surface area by disturbing crack propagation. The other is that the deformation of a‐Al₂O₃ nanoparticle dissipates energy through cracking. Moreover, one of the models shows us that the crack cannot propagate if the initial notch is generated inside a‐Al₂O₃ nanoparticle. Such strengthening is partly due to the fact that the strength of the interface between nanoparticle and SLSG matrix is comparable to that of SLSG matrix, implying that their interface does not reduce crack resistance of the oxide glass.     

Comparison of the electrochemical properties of intermediate temperature solid oxide fuel cells based on protonic and anionic electrolytes

The physico-chemical properties of two protonic electrolytes BaCe_0.8Y_0.2O_3-δ and BaCe_0.9Y_0.1O_3-δ were investigated. The BaCe_0.8Y_0.2O_3-δ electrolyte showed better crystallographic purity and lower amount of carbonate phase on the surface. A comparison between the BaCe_0.8Y_0.2O_3-δ protonic electrolyte supported cell and an anionic (Ce_0.8Gd_0.2O_1.95) one was made. The maximum power densities (IR-free) of 183 mW cm⁻² and 400 mW cm⁻² were obtained in H₂ (R.H. 3%) at 700 °C, for the protonic and anionic electrolyte based cells, respectively.     

High oxide ion conduction in sintered oxides of the system Bi2O3-Y2O3

The ionic conduction in sintered Bi₂O₂-Y₂O₃ was investigated by measuring the conductivity and the emf of an oxygen concentration cell using the specimen tablet as electrolyte. The face centred cubic phase in this system was found to show high oxide ion conduction accompanied by a little electronic conduction when exposed to air. This phase was stable with a composition of 25 ～ 43 mol % Y₂O₃ over a wide range of temperatures, and the oxide ion conductivity increased with decrease in Y₂O₃. The conductivities of (Bi₂O₃)_0.75 (Y₂O₃)_0.25 were 1.6×10^?1 Ω^?1 cm^?1 at 700°C and 1.2×10^?2 Ω^?1 cm^?1 at 500°C values which are many times higher than those of stabilized zirconia (ZrO₂)_0.90(Y₂O₃)_0.10 at corresponding temperatures. Specimens containing less than 25 mol % Y₂O₃ showed a phase transition at 700 ～ 580°C and the conductivities decreased remarkably below these temperatures. High oxide ion conduction in the fcc phase is attributed to the migration of oxide ion vacancies which were present in an appreciable amount.     

Er3+ ‐Doped Y2O3 Nanophosphors for Near‐Infrared Fluorescence Bioimaging Applications

Rare‐earth‐doped ceramic nanophosphor (RED‐CNP) materials are promising near‐infrared (NIR) fluorescence bioimaging (FBI) agents that can overcome problems of currently used organic dyes including photobleaching, phototoxicity, and light scattering. Here, we report a NIR–NIR bioimaging system by using NIR emission at 1550 nm under 980 nm excitation which can allow a deeper penetration depth into biological tissues than ultraviolet or visible light excitation. In this study, erbium‐doped yttrium oxide nanoparticles (Er³⁺:Y₂O₃) with an average particle size of 100 and 500 nm were synthesized by surfactant‐assisted homogeneous precipitation method. NIR emission properties of Er³⁺:Y₂O₃ were investigated under 980 nm excitation. The surface of Er³⁺:Y₂O₃ was electrostatically PEGylated using poly (ethylene glycol)‐b‐poly(acrylic acid) (PEG‐b‐PAAc) block copolymer to improve the chemical durability and dispersion stability of Er³⁺:Y₂O₃ under physiological conditions. In vitro cytotoxic effects of bare and PEG‐b‐PAAc‐modified Er³⁺:Y₂O₃ were investigated by incubation with mouse macrophage cells (J774). Microscopic and macroscopic FBI were demonstrated in vivo by injection of bare or PEG‐b‐PAAc‐modified Er³⁺:Y₂O₃ into C57BL/6 mice. The NIR fluorescence images showed that PEG‐b‐PAAc modification significantly reduced the agglomeration of Er³⁺:Y₂O₃ in mice and enhanced the distribution of Er³⁺:Y₂O₃.     

Effect of Nano‐Copper Oxide and Copper Chromite on the Thermal Decomposition of Ammonium Perchlorate

The catalytic effect on the thermal decomposition behavior of ammonium perchlorate (AP) of p‐type nano‐CuO and CuCr₂O₄ synthesized by an electrochemical method has been investigated using differential scanning calorimetry as a function of catalyst concentration. The nano‐copper chromite (CuCr₂O₄) showed best catalytic effects as compared to nano‐cupric oxide (CuO) in lowering the high temperature decomposition by 118 °C at 2 wt.‐%. High heat releases of 5.430 and 3.921 kJ g⁻¹ were observed in the presence of nano‐CuO and CuCr₂O₄, respectively. The kinetic parameters were evaluated using the Kissinger method. The decrease in the activation energy and the increase in the rate constant for both the oxides confirmed the enhancement in catalytic activity of AP. A mechanism based on an electron transfer process has also been proposed for AP in the presence of nano‐metal oxides.     

Nano‐engineered nickel catalysts supported on 4‐channel α‐Al2O3 hollow fibers for dry reforming of methane

A nickel (Ni) nanoparticle catalyst, supported on 4‐channel α‐Al₂O₃ hollow fibers, was synthesized by atomic layer deposition (ALD). Highly dispersed Ni nanoparticles were successfully deposited on the outside surfaces and the inside porous structures of hollow fibers. The catalyst was employed to catalyze the dry reforming of methane (DRM) reaction and showed a methane reforming rate of 2040 Lh^?1gNi^?1 at 800°C. NiAl₂O₄ spinel was formed when Ni nanoparticles were deposited on alpha‐alumina substrates by ALD, which enhanced the Ni‐support interaction. Different cycles (two, five, and ten) of Al₂O₃ ALD films were applied on the Ni/hollow fiber catalysts to further improve the interaction between the Ni nanoparticles and the hollow fiber support. Both the catalyst activity and stability were improved with the deposition of Al₂O₃ ALD films. Among the Al₂O₃ ALD coated catalysts, the catalyst with five cycles of Al₂O₃ ALD showed the best performance. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2625–2631, 2018     

Translucent yttrium oxide ceramics from low-density green bodies shaped by uniaxial pressing

Highly compact green bodies are usually required to fabricate transparent or translucent polycrystalline yttrium oxide. The present work reports on the fabrication of highly dense (ρ_rel >98%) translucent Y₂O₃ from low-density green bodies by exploiting a high sinterability of nano Y₂O₃ powder. A commercial nano Y₂O₃, with a crystallite size of ca. 30 nm, was shaped by uniaxial pressing and, afterwards, densified by pre-sintering at 1500 °C followed by hot isostatic pressing. The coarsening tendency of yttria nanoparticles causes the rearrangement of particles and results in the high sinterability of nano Y₂O₃ even at low green densities. This improves the packing density and enables sintering to high densities, eliminating pores, and, thus, obtaining translucent Y₂O₃.     

Synergistic effect of carbon nanofiber decorated with iron oxide in enhancing properties of styrene butadiene rubber nanocomposites

Elastomer nanocomposites reinforced with carbon nanofiber (CNF) decorated with metal nanoparticles exhibit excellent thermal, mechanical, and magnetic properties with low volume fraction of the reinforcement. Generally, metal nanoparticles are used to modify the surface of CNF, to improve their dispersion and contact resistance in the polymer matrix. In this study, Fe₂O₃ metal nanoparticles were decorated on CNF by electrostatic attraction via a green and facile solution‐based method. Interestingly, the CNF decorated with Fe₂O₃ (CNF‐Fe₂O₃)/elastomer improved both the tensile strength and the fatigue property of plain CNF/elastomer by as much as 57.2% and 27.2%, respectively. Moreover, the CNF‐Fe₂O₃/elastomer exhibited superior thermal conductivity, a twofold enhancement compared with carbon fibers. The elastomer nanocomposites consisting of CNF‐Fe₂O₃ also exhibited enhanced magnetic properties due to synergies between the Fe₂O₃ nanoparticles and the CNF. The elastomer nanocomposites prepared with CNF‐Fe₂O₃ will open significant new opportunities for preparing advanced elastomer nanocomposites for future engineering applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45376.     

Composite polymer electrolytes based on electrospun thermoplastic polyurethane membrane and polyethylene oxide for all‐solid‐state lithium batteries

To improve the electrochemical properties and enhance the mechanical strength of solid polymer electrolytes, series of composite polymer electrolytes (CPEs) were fabricated with hybrids of thermoplastic polyurethane (TPU) electrospun membrane, polyethylene oxide (PEO), SiO₂ nanoparticles and lithium bis(trifluoromethane)sulfonamide (LiTFSI). The structure and properties of the CPEs were confirmed by SEM, XRD, DSC, TGA, electrochemical impedance spectroscopy and linear sweep voltammetry. The TPU electrospun membrane as the skeleton can improve the mechanical properties of the CPEs. In addition, SiO₂ particles can suppress the crystallization of PEO. The results show that the TPU‐electrospun‐membrane‐supported PEO electrolyte with 5 wt% SiO₂ and 20 wt% LiTFSI (TPU/PEO‐5%SiO₂‐20%Li) presents an ionic conductivity of 6.1 × 10^?4 S cm^?1 at 60 °C with a high tensile strength of 25.6 MPa. The battery using TPU/PEO‐5%SiO₂‐20%Li as solid electrolyte and LiFePO₄ as cathode shows an attractive discharge capacity of 152, 150, 121, 75, 55 and 26 mA h g^?1 at C‐rates of 0.2C, 0.5C, 1C, 2C, 3C and 5C, respectively. The discharge capacity of the cell remains 110 mA h g^?1 after 100 cycles at 1C at 60 °C (with a capacity retention of 91%). All the results indicate that this CPE can be applied to all‐solid‐state rechargeable lithium batteries. © 2018 Society of Chemical Industry     

A Low Cost Large‐Area Solid Oxide Cells Fabrication Technology based on Aqueous Co‐Tape Casting and Co‐Sintering

Aqueous‐based tape casting is a low‐cost and environment friendly technology. In this paper, large‐area fuel electrode‐supported solid oxide cells (SOCs) were fabricated by this technology in conjunction with co‐sintering process. A 10 cm × 10 cm single cell with NiO/Zr_0.92Y_0.08O_2–δ fuel electrode, Zr_0.92Y_0.08O_2–δ electrolyte and La_0.6Sr_0.4Co_0.2Fe_0.8O_3+δ/Ce_0.9Gd_0.1O_2+δ air electrode has been successfully developed with improved electrode microstructure and hence the cell performance with the maximum power density of 534 mW cm^–2 at 850 °C with humidified H₂ as the fuel and air as the oxidant has been achieved. The optimal slurry formulations used in the fabrication of SOC were summarized for future reference purpose.     

Synthesis of polystyrene/polythiophene core/shell nanoparticles by dual initiation

Polystyrene/polythiophene (PSt/PTh) core/shell nanoparticles were successfully synthesized via a one-pot Fe³⁺-catalyzed oxidative and soap-free emulsion polymerization process. A small amount of sodium styrene sulfonate (NaSS) was used to maintain the colloidal stability of the PSt/PTh nanoparticles. Hydrogen peroxide (H₂O₂) and a trace of iron chloride (FeCl₃) were used to carry out the free-radical polymerization of styrene and the oxidative polymerization of thiophene. The dual initiation characteristics of H₂O₂/FeCl₃ in the PSt/PTh core/shell nanoparticle formation were investigated by observing the time-evolution of the particle morphology. In addition, photoluminescent property, particle size distribution, core/shell morphology and the formation mechanism of the PSt/PTh nanoparticles were studied by spectrofluorophotometery, dynamic light scattering (DLS), in-situ IR, zeta-potential, and time-evolution field-emission scanning electron microscope (FE-SEM) analyses.     

Processing of high-performance Co doped Y2O3 as a single-phase electrolyte for low temperature solid oxide fuel cell (LT-SOFC)

The high-performance single-phase semiconductor materials with higher ionic conductivity have drawn substantial attention in fuel cell applications. Semiconductor materials play a key role to enhance ionic conductivity subsequently promoting low temperature solid oxide fuel cell (LT-SOFC) research. Herein, we proposed a semiconductor Co doped Y₂O₃ (YCO) samples with different molar ratios, which may easily access the high ionic conductivity and electrochemical performances at low operating temperatures. The resulting fabricated fuel cell 10% Co doped Y₂O₃ (YCO-10) device exhibits high ionic conductivity of ∼0.16 S cm⁻¹ and a feasible peak power density of 856 mW cm⁻² along with 1.09 OCV at 530 °C under H₂/air conditions. The electrochemical impedance spectroscopy (EIS) reveals that YCO-10 electrolyte based SOFC device delivers the least ohmic resistance of 0.11–0.16 Ω cm² at 530-450 °C. Electrode polarization resistance of the constructed fuel cell device noticed from 0.59 Ω cm² to 0.28 Ω cm² in H₂/air environment at different elevated temperatures (450 °C to 530 °C). This work suggests that YCO-10 can be a promising alternative electrolyte, owing to its high fuel cell performance and enhanced ionic conductivity for LT-SOFC.     

In situ preparation of magnetic Fe3O4.Cu2O.Fe3O4/cryogel nanocomposite powder via a reduction–coprecipitation method as adsorbent for methylene blue water pollutant

Magnetic nanocomposites have attracted great attention as adsorbents for the removal of water pollutants, which respond to an external magnet that is used to remove both pollutants and composite nanomaterial traces from water. They are environmentally friendly and effective adsorbents for water treatment. In this respect, a simple in situ preparation method was used to prepare cryogel powder composite based on Fe₃O₄.Cu₂O.Fe₃O₄ nanomaterials. The ionic cryogel based on 2‐acrylamido‐2‐methylpropane sulfonate sodium salt and styrene sulfonate sodium salt was prepared by crosslinking polymerization at low temperature. The new magnetic nanoparticles based on Fe₃O₄.Cu₂O.Fe₃O₄ were successfully prepared inside the cryogel networks by a simple reduction–coprecipitation method based on reaction of Fe³⁺ with sodium sulfite and Cu²⁺ in the presence of hydroxylamine and ammonia solution. The thermal stability, accurate Fe₃O₄.Cu₂O.Fe₃O₄ content, magnetic properties, crystal lattice structure, particle sizes and morphology of the prepared cryogel composite were evaluated. The optimum conditions such as pH, contact time, adsorbate concentrations, adsorption equilibrium and adsorption kinetics were investigated to determine the efficiency of the prepared composite as an adsorbent to remove toxic methylene blue (MB) pollutant from aqueous solution. The data for MB adsorption confirmed the high ability of the prepared composite to remove more than 4.696 mmol L^?1 of MB from water during 6 min. The regeneration and reuse experiments showed excellent data for the synthesized new dye as an effective adsorbent for water treatment. © 2018 Society of Chemical Industry     

Development of solid oxide cells by co-sintering of GDC diffusion barriers with LSCF air electrode

The effects of a Cu-based additive and nano-Gd-doped ceria (GDC) sol on the sintering temperature for the construction of solid oxide cells (SOCs) were investigated. A GDC buffer layer with 0.25–2 mol% CuO as a sintering aid was prepared by reacting GDC powder and a CuN₂O₆ solution, followed by heating at 600 °C. The sintering of the CuO-added GDC powder was optimized by investigating linear shrinkage, microstructure, grain size, ionic conductivity, and activation energy at temperatures ranging from 1000 to 1400 °C. The sintering temperature of the CuO–GDC buffer layer was decreased from 1400 °C to 1100 °C by adding the CuO sintering aid at levels exceeding 0.25 mol%. The ionic conductivity of the CuO–GDC electrolyte was maximized at 0.5 mol% CuO. However, the addition of CuO did not significantly affect the activation energy of the GDC buffer layer. Buffer layers with CuO-added GDC or nano-GDC sol-infiltrated GDC were fabricated and tested in co-sintering (1050 °C, air) with La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF). In addition, SOC tests were performed using button cells (active area: 1 cm²) and five-cell (active area: 30 cm²/cell) stacks. The button cell exhibited the maximum power density of 0.89 W cm⁻² in solid oxide fuel cell (SOFC) mode. The stack demonstrated more than 1000 h of operation stability in solid oxide electrolysis cell (SOEC) mode (decay rate: 0.004%/kh).     

Adsorption of antifouling booster biocides on metal oxide nanoparticles: Effect of different metal oxides and solvents

Controlling the release rate of biocides (antifouling agents) from a paint coating is a key issue for the development of multi-season antifouling marine coatings. One promising approach is the use of nanoparticles onto which biocides are adsorbed to prevent premature depletion of the biocide. Adsorption of one novel (Medetomidine) and six commercially available and widely used antifouling biocides (Chlorothalonile, Dichlofluanid, Diuron, Irgarol, Seanine, Tolylfluanid) onto oxide nanoparticles (Al₂O₃, CuO, MgO, SiO₂, TiO₂, ZnO) was investigated by HPLC and NMR in different organic solvents. Large differences in adsorption strength depending on the type of nanoparticle and solvent employed were observed. It was shown that nanoparticles coordinate preferentially with the imidazole moiety of Medetomidine. Independent of the type of particle this interaction was considerably stronger in comparison to the other biocides. However, the interaction strength was strongly dependant on the type of solvent, where the largest strongest interaction was achieved in o-xylene. In addition field tests were performed where a considerable decrease in release rate was displayed from coatings containing Medetomidine adsorbed to nanoparticles compared to coatings containing Medetomidine as single additive.     

Template‐Free Synthesis of Porous Fe3O4/SiOC(H) Nanocomposites with Enhanced Catalytic Activity

We present a template‐free synthesis of Fe₃O₄/SiOC(H) nanocomposites with in situ formed Fe₃O₄ nanoparticles with a size of about 50 nm embedded in a nanoporous SiOC(H) matrix obtained via a polymer‐derived ceramic route. Firstly, a single‐source precursor (SSP) was synthesized by the reaction of allylhydridopolycarbosilane (AHPCS) with Fe‐acetylacetonate [Fe(acac)₃] at 140°C. The SSP was heat‐treated at 170°C to generate Fe₃O₄ nanocrystals in the cross‐linked polymeric matrix. Subsequently, the SSP was pyrolyzed at 600°C–700°C in argon atmosphere to yield porous Fe₃O₄/SiOC(H) nanocomposites with the high BET surface area up to 390 m²/g, a high micropore surface area of 301 m²/g, and a high micropore volume of 0.142 cm³/g. The Fe‐free SiOC(H) ceramic matrix derived from original AHPCS is nonporous. The in situ formation of Fe₃O₄ nanoparticles embedded homogeneously within a nanoporous SiOC(H) matrix shows significantly enhanced catalytic degradation of xylene orange in aqueous solution with H₂O₂ as oxidant as compared with pure commercial Fe₃O₄ nanoparticles.