Proton-conducting membranes based on poly(2,5-benzimidazole) (ABPBI) and phosphoric acid prepared by direct acid casting

We report the preparation of phosphoric acid doped poly(2,5-benzimidazole) (ABPBI) membranes for PEMFC by simultaneously doping and casting from a poly(2,5-benzimidazole)/phosphoric acid/methanesulfonic acid (MSA) solution. The evaporation of MSA yields a very homogeneous membrane having a better controlled composition, avoiding the use of solvent-intensive procedures. Membranes have been prepared with contents of up to 3.0H₃PO₄ molecules per ABPBI repeating unit. These membranes achieve a maximum conductivity of 1.5 × 10⁻² S cm⁻¹ at temperatures as high as 180 °C in dry conditions. These ABPBI membranes are more conveniently prepared than those conventionally formed and doped in separate steps while featuring comparable conductivities (ABPBI × 2.7H₃PO₄ prepared by the soaking method showed a conductivity of 2.5 × 10⁻² S cm⁻¹ at 180 °C in dry conditions).     

Proton (3 MeV) and copper (120 MeV) ion irradiation effects in low-density polyethylene (LDPE)

Low-density polyethylene (LDPE) was irradiated with proton (3 MeV) and copper (120 MeV) ions to analyze the induced modifications with respect to optical and structural properties. In the present investigation, the fluence for proton irradiation was varied up to 2×10¹⁵ protons cm⁻², while that for copper beam was kept in the range of 1×10¹ to 1×10¹³ ions cm⁻² to study the swift heavy ion-induced modifications in LDPE. Ultraviolet–visible (UV–vis), FTIR and X-ray diffraction (XRD) techniques were utilized to study the induced changes. The analysis of UV–vis absorption studies reveals that there is decrease of optical energy gap up to 43% on proton irradiation (at 2×10¹⁵ ions cm⁻²), whereas the copper beam (at 1×10¹³ ions cm⁻²) leads to a decrease of 51%. FTIR analysis indicated the presence of unsaturations due to vinyl end groups in the irradiated sample. The formation of OH and CO groups has also been observed. XRD analysis revealed that the semi-crystalline LDPE losses its crystallinity on swift ion irradiation. It was found that the proton beam (2×10¹⁵ ions cm⁻²) decreased the crystallite size by 23% whereas this decrease is of 31% in case of the copper ion-irradiated LDPE at 1×10¹³ ions cm⁻².     

Proton-conducting solid oxide fuel cell (SOFC) with Y-doped BaZrO3 electrolyte

Y-doped BaZrO₃ (BZY) electrolyte films are successfully fabricated by utilizing the driving force from the anode substrate, aiming to circumvent the refractory nature of BZY materials. The BZY electrolyte film on the high shrinkage anode becomes dense after sintering even though no sintering aid is added, while the BZY electrolyte remains porous on the conventional anode substrate after the same treatment. The resulting BZY electrolyte shows a high conductivity of 4.5 × 10^− 3 S cm^− 1 at 600 °C, which is 2 to 20 times higher than that for most of BZY electrolyte films in previous reports. In addition, the fuel cell with this BZY electrolyte generates a high power output of 267 mW cm^− 2 at 600 °C. These results suggest the strategy presented in this study provides a promising way to prepare BZY electrolyte films for fuel cell applications.     

Characteristics of inclusions in topaz from Serrinha pegmatite (Medina granite,Minas Gerais State,SE Brazil) studied by Raman spectroscopy

Eastern Brazilian Pegmatite Province includes many topaz-bearing pegmatitic bodies. Residual melts from the Fe–K-rich alkaline Medina granite (ca. 500 Ma) formed the Serrinha pegmatite—a system of branched thin pegmatite veins hosted by pink facies of the parent granite. The colourless topaz from Serrinha pegmatite contains both mineral and fluid inclusions. Microcline (513, 476, 456 cm⁻¹), albite (507, 479, 457 cm⁻¹), topaz (926, 858, 267, 239 cm⁻¹), quartz (463 cm⁻¹), rutile (610, 444 cm⁻¹), wolframite (884 cm⁻¹) and uranophane (968, 788 cm⁻¹) represent solid inclusions formed by fluid-induced processes from the pneumatolytic (∼600–400 °C) to hydrothermal (<400 °C) stages of pegmatite crystallization. Fluid inclusions are mainly liquid or liquid-gas, which contain CO₂ (marker bands ∼1388 cm⁻¹ and ∼1285 cm⁻¹) and traces of methane (2917 cm⁻¹). They are mainly of primary and pseudo-secondary origin, indicating tectonic quiescence during and after topaz crystallization (in agreement with the post-collisional nature of the parent granite). Topaz crystallized in high temperature conditions of the pneumatolytic stage at a depth around 8.5–10.0 km.     

Thermal degradation and evolved gas analysis: A polymeric blend of urea formaldehyde (UF) and epoxy (DGEBA) resin

A polymeric blend has been prepared using urea formaldehyde (UF) and epoxy (DGEBA) resin in 1:1 mass ratio. The thermal degradation of UF/epoxy resin blend (UFE) was investigated by using thermogravimetric analyses (TGA), coupled with FTIR and MS. The results of TGA revealed that the pyrolysis process can be divided into three stages: drying process, fast thermal decomposition and cracking of the sample. There were no solid products except ash content for UFE during combustion at high temperature. The total mass loss during pyrolysis at 775 °C is found to be 97.32%, while 54.14% of the original mass was lost in the second stage between 225 °C and 400 °C. It is observed that the activation energy of the second stage degradation during combustion (6.23 × 10⁻⁴ J mol⁻¹) is more than that of pyrolysis (5.89 × 10⁻⁴ J mol⁻¹). The emissions of CO₂, CO, H₂O, HCN, HNCO, and NH₃ are identified during thermal degradation of UFE.     

Electrical conductivity and ion-exchange kinetic studies of polythiophene Sn(VI)phosphate nano composite cation-exchanger

A polymeric hybrid nanocomposite, namely polythiophene tin(IV)phosphate (PTh–SnP), was expediently synthesized by incorporating polythiophene (PTh) in tin phosphate (SnP) to enhance the conducting behavior and sorption of heavy metal ions by porous polymeric cation exchanger. Composite was characterized by Fourier Transform-Infra Red and Transmission Electron Microscopy. The dc electrical conductivity studies carried out on the composite, showed conductivity within the range of 4.0 × 10⁻²–1.0 × 10⁻³ S/cm⁻¹; measured by a 4-in line-probe dc electrical conductivity measuring technique. Ion-exchange kinetics for few divalent metal ions was evaluated by particle diffusion-controlled ion-exchange phenomenon at four different temperatures. The particle diffusion mechanism is confirmed by the linear τ (dimensionless time parameter) vs t (time) plots. The exchange processes thus controlled by the diffusion within the exchanger particle for the systems studies herein. Some physical parameters like self-diffusion coefficient (D₀)_, energy of activation (E_a) and entropy (ΔS°) have been evaluated under conditions favoring a particle diffusion-controlled mechanism.     

Enhancement of lithium ion conduction in the cubic rare earth oxide

A new type of lithium ion conducting solid electrolyte based on a cubic rare earth oxide was developed by co-doping LiNO₃ and KNO₃ into a (Gd_1−xNd_x)₂O₃ solid, which possesses large interstitial open spaces within the structure. Among the samples prepared, 0.6(Gd_0.4Nd_0.6)₂O₃–0.16LiNO₃–0.24KNO₃ exhibits the highest lithium ion conductivity of 8.05 × 10⁻² and 1.35 × 10⁻³ S cm⁻¹ at 400 and 100 °C, respectively, which is comparable to that of the LISICON materials. Pure Li⁺ ion conduction was successfully demonstrated by the dc electrolysis method.     

A new promising high temperature lithium battery solid electrolyte

Lithium lanthanoid silicates find importance as a solid electrolyte in high temperature lithium batteries in view of its high ionic conductivity at high temperatures. An first ever attempt is made to synthesis a new high temperature solid electrolyte viz., lithium samarium holmium silicate by sol–gel process and it has been characterized by thermal analysis (TGA–DTA), X-ray diffraction (XRD), infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). Lithium ion conductivity of 0.8087 × 10⁻⁷ Ω⁻¹ cm⁻¹ at 25 °C was obtained and it increases with increasing temperature. For the first time a highest conductivity of 0.1095 × 10⁻² Ω⁻¹ cm⁻¹ was obtained at 850 °C which is high compared to other high temperature lithium battery solid electrolytes.     

Modelling of mass transfer in facilitated supported liquid membrane transport of copper(II) using MOC-55 TD in Iberfluid

The transport of copper(II) through a supported liquid membrane using MOC-55 TD (oxime derivative), dissolved in Iberfluid, as a carrier has been studied. A physico-chemical model is derived to describe the transport mechanism which consists of: diffusion process through the feed aqueous diffusion layer, fast interfacial chemical reaction and diffusion through the membrane. The experimental data can be explained by mathematical equations describing the rate of transport. The mass transfer coefficient was calculated from the described model as 2.8×10⁻³ cm s⁻¹, the thickness of the aqueous boundary layer as 2.6×10⁻³ cm⁻¹ and the membrane diffusion coefficient of the copper-containing species as 1.2×10⁻⁸ cm² s⁻¹.     

Life test of DMFC using poly(ethylene glycol)bis(carboxymethyl)ether plasticized PVA/PAMPS proton-conducting semi-IPNs

A novel, low-cost proton-conducting semi-IPN has been successfully prepared from PVA/PAMPS blends by incorporating poly(ethylene glycol)bis(carboxymethyl)ether (PEGBCME) as a novel plasticizer. Although, the polymer is based on a relatively low content of PAMPS as a component of ion conducting sites, the resulting semi-IPN exhibited high proton conductivity (0.1 S cm⁻¹) at 25 °C, which afforded a higher power density of 51 mW cm⁻² at 80 °C. A striking feature is that a long-term initial performance is achieved with a 130 h of stable fuel cell operation in DMFC mode due to effectively suppressed methanol crossover. This is a new record for a fully hydrocarbon membrane in DMFC, seeing that the PVA–PAMPS proton-conducting semi-IPNs are made simply of aliphatic skeletons.     

The thermodynamic properties of DyBr3(s) and DyI3(s) from T=5 K to their melting temperatures

Low-temperature calorimetric measurements have been performed on DyBr₃(s) in the temperature range (5.5 to 420 K ) and on DyI₃(s) from T=4 K to T=420 K. The data reveal enhanced heat capacities below T=10 K, consisting of a magnetic and an electronic contribution. From the experimental data on DyBr₃(s) a C⁰_p,m (298.15 K) of (102.2±0.2) J·K⁻¹·mol⁻¹ and a value for {S⁰_m (298.15 K) − S⁰_m (5.5 K)} of (205.5±0.5) J·K⁻¹·mol⁻¹, have been obtained. For DyI₃(s), {S⁰_m (298.15 K) − S⁰_m (4 K)} and C⁰_p,m (298.15 K) have been determined as (226.9±0.5) J·K⁻¹·mol⁻¹ and (103.4±0.2) J·K⁻¹·mol⁻¹, respectively. The values for {S⁰_m (5.5 K) − S⁰_m (0)} for DyBr₃(s) and {S⁰_m (4 K) − S⁰_m (0)} for DyI₃(s) have been calculated, giving S⁰_m (298.15 K)=(212.3±0.9) J·K⁻¹·mol⁻¹ in case of DyBr₃(s) and S⁰_m (298.15 K) =(233.1±0.7) J·K⁻¹·mol⁻¹ for DyI₃(s). The high-temperature enthalpy increment has been measured for DyBr₃(s) in the temperature range (525 to 799 K) and for DyI₃(s) in the temperature range (525 to 627 K). From the results obtained and enthalpies of formation from the literature, thermodynamic functions for DyBr₃(s) and DyI₃(s) have been calculated from T→0 to their melting temperatures at 1151.0 K and 1251.5 K, respectively.     

Preparation of palladium membranes from the reaction of Pd(C3H3)(C5H5) with H2: wet-impregnated deposition

A new technique to prepare a palladium membrane for high-temperature hydrogen permeation was developed: Pd(C₃H₃)(C₅H₅) an organometallic precursor reacted with hydrogen at room temperature to decompose into Pd crystallites. This reaction together with sintering treatment under hydrogen and nitrogen in sequence resulted in the formation of dense films of pure palladium on the surface of the mesoporous stainless steel (SUS) support. Under H₂ atmosphere the palladium membrane could be sintered at 823 K to form a skin layer inside the support pores. The hydrogen permeance was 5.16×10⁻² cm³ cm⁻² cm Hg⁻¹ s⁻¹ at 723 K. H₂/N₂ selectivity was 1600 at 723 K.     

Highly selective thiocyanate electrode based on bis-bebzoin-semitriethylenetetraamine binuclear copper(II) complex as neutral carrier

A novel selective thiocyanate PVC membrane electrode based on bis-bebzoin-semitriethylenetetraamine binuclear copper(II) [Cu(II)₂–BBSTA] as neutral carrier is reported, which displays an anti-Hofmeister selectivity sequence in following order: SCN⁻ > ClO₄⁻ > I⁻ >Sal⁻ >SO₃²⁻ >NO₃⁻ > H₂PO₄⁻ > Cl⁻ >NO₂⁻ > SO₄²⁻. The electrode exhibits Nernstian potential linear range to thiocyanate from 1.0 × 10⁻¹ to 9.0 × 10⁻⁷ mol/l with a detection limit 7.0 × 10⁻⁷ mol/l and a slope of −57.0 mV/decade in pH 5.0 of phosphorate buffer solution at 25 °C. The response mechanism is discussed in view of the AC impedance technique and the UV spectroscopy technique. From comparison of potentiometric response characteristics between the binuclear metallic complex copper(II) [Cu(II)₂–BBSTA] and mononuclear copper(II) metallic complex [Cu(II)–BBSDA], an enhanced response towards thiocyanate from the electrode based on binuclear metallic complex copper (II) [Cu(II)₂–BBSTA] was observed. The electrode based on binuclear copper(II) compound was used to determine the thiocyanate content in waste water with satisfactory results.     

Poly(ether amine) and cross-linked poly(propylene oxide) diacrylate thin-film polymer electrolyte for 3D-microbatteries

This paper presents a novel thin-film electrolyte of a 2:1 blend of polyetheramine (glyceryl poly(oxypropylene)) and cross-linked oligomeric poly(propylene oxide) diacrylate with LiTFSI. The polyetheramine acts as a surfactant, and can thereby be applied as a conformal coating on complex surfaces—here demonstrated for porous LiFePO₄ cathodes—making it useful for 3D-microbatteries. The poly(propylene oxide) diacrylate blends with the surfactant and is easily UV cross-linked, thereby ensuring good mechanical stability. Electrolytes, ~ 2 μm thick, were casted onto LiFePO₄ cathodes and cycled against metallic lithium, displaying stable discharge capacities of ~ 8 mAh/g at room temperature and ~ 120 mAh/g at 60 °C. The electrolyte showed conductivities of 3.45 × 10^? 6 and 5.80 × 10^? 5 S cm^? 1 at room temperature and 60 °C, respectively.     

Microstructural modifications in swift ion irradiated PET

Polyethylene terephthalte (PET) was irradiated with carbon (70 MeV) and copper (120 MeV) ions to analyze the induced modifications with respect to optical, structural and thermal properties. In the present investigation, the fluence for carbon irradiation was varied from 1×10¹¹ to 1×10¹⁴ ions cm⁻², while that for copper beam was kept in the range of 1×10¹¹ to 1×10¹³ ions cm⁻². UV–vis, FTIR, XRD and DSC techniques were utilized to study the induced changes. The analysis of UV–vis absorption studies reveals that there is decrease of optical energy gap up to 10% on carbon ion irradiation (at 1×10¹⁴ ions cm⁻²), whereas the copper beam (at 1×10¹³ ions cm⁻²) leads to a decrease of 49%. FTIR analysis indicated the formation of alkyne end groups along with the overall degradation of polymer with copper ion irradiation. X-ray diffraction analysis revealed that the semi-crystalline PET losses its crystallinity on swift ion irradiation. It was found that the carbon beam (1×10¹⁴ ions cm⁻²) decreased the crystallite size by 16% whereas this decrease is of 12% in case of the copper ion irradiated PET at 1×10¹³ ions cm⁻². The loss in crystallinity on irradiation has been supported by DSC thermograms.     

Catalytic effect of CTAB on the interaction of dipeptide glycyl-tyrosine (Gly-Tyr) with ninhydrin

The effect of cationic micelles of cetyltrimethylammonium bromide (CTAB) on the interaction of dipeptide glycyl-tyrosine (Gly-Tyr) with ninhydrin under varying conditions has been studied spectrophotometrically at 70 °C and pH 5.0. The reaction followed first- and fractional-order kinetics with respect to [Gly-Tyr] and [ninhydrin], respectively. Increase in total concentration of CTAB from 0 to 70 × 10⁻³ mol dm⁻³ resulted in an increase in the pseudo-first-order rate constant (k_ψ) by a factor of ca. 3. Quantitative kinetic analysis of k_ψ − [CTAB] data was performed on the basis of pseudo-phase model of the micelles (proposed by Menger and Portnoy and developed by Bunton) and Piszkiewicz model. A possible mechanism has been proposed and the kinetic data have been used to evaluate the micellar binding constants K_S (268 mol⁻¹ dm³ for Gly-Tyr) and K_N (64 mol⁻¹ dm³ for ninhydrin).     

One-step fabrication of chitosan–hematite nanotubes composite film and its biosensing for hydrogen peroxide

This work reports on a novel chitosan–hematite nanotubes composite film on a gold foil by a simple one-step electrodeposition method. The hybrid chitosan–hematite nanotubes (Chi–HeNTs) film exhibits strong electrocatalytic reduction activity for H₂O₂. Interestingly, two electrocatalytic reduction peaks are observed at −0.24 and −0.56 V (vs SCE), respectively, one controlled by surface wave and the other controlled by diffusion process. The Chi–HeNTs/Au electrode shows a linear response to H₂O₂ concentration ranging from 1 × 10⁻⁶ to 1.6 × 10⁻⁵ mol L⁻¹ with a detection limit of 5 × 10⁻⁸ mol L⁻¹ and a sensitivity as high as 1859 μA μM⁻¹ cm⁻².     

A cobalt-free electrode material La0.5Sr0.5Fe0.8Cu0.2O3 − δ for symmetrical solid oxide fuel cells

Cobalt-free perovskite oxide La_0.5Sr_0.5Fe_0.8Cu_0.2O_3 − δ (LSFC) was applied as both anode and cathode for symmetrical solid oxide fuel cells (SSOFCs). The LSFC shows a reversible transition between a cubic perovskite phase in air and a mixture of SrFeLaO₄, a K₂NiF₄-type layered perovskite oxide, metallic Cu and LaFeO₃ in reducing atmosphere at elevated temperature. The average thermal expansion coefficient of LSFC in air is 17.7 × 10^− 6 K^− 1 at 25 °C to 900 °C. By adopting LSFC as initial electrodes to fabricate electrolyte supported SSOFCs, the cells generate maximum power output of 1054, 795 and 577 mW cm^− 2 with humidified H₂ fuel (~ 3% H₂O) and 895, 721 and 482 mW cm^− 2 with humidified syngas fuel (H₂:CO = 1:1) at 900, 850 and 800 °C, respectively. Moreover, the cell with humidified H₂ fuel demonstrates a reasonable stability at 800 °C under 0.7 V for 100 h.     

Electrochemical properties of liquid electrolyte added quasi-solid state TiO2 dye-sensitized solar cells

In this study a process has been introduced to replace traditional liquid or solid electrolyte coatings on dye-sensitized photoelectrode in solar cells. This process has more efficient diffusion of electrolyte, hence higher sensitivity. Better interfacial contact between polymer electrolyte and TiO₂ photoelectrode had improved electrochemical response and ionic conductivity of cell. Conductivity of this electrode was 9.33 × 10⁻³ S cm⁻¹ (at room temperature), which is much higher than the using traditional process for addition of electrolytes. It has 0.68 V open-circuit voltage and 3.19 mA cm⁻² short-circuit current density. Energy conversion efficiency of this cell was about 37% higher than the cell developed with traditional processes under constant light intensity (45 mW cm⁻²).     

Catalytic and kinetic spectrophotometric method for determination of vanadium(V) by 2,3,4-trihydroxyacetophenonephenylhydrazone

A new catalytic and kinetic spectrophotometric method for the determination of vanadium(V) was studied using 2,3,4-trihydroxyacetophenonephenylhydrazone (THAPPH) as an analytical reagent. The present method was developed on the catalytic effect of vanadium on oxidation of THAPPH by hydrogen peroxide in hydrochloric acid–potassium chloride buffer (pH = 2.8) at the 20th minute. The metal ion has formed 1:2 (M:L) complex with THAPPH. Beer’s law was obeyed in the range 20–120 ng/mL of V(V) at λ_max 390 nm. The sensitivity of the method was calculated in terms of molar absorptivity (1.999 × 10⁵ L mol⁻¹cm⁻¹) and Sandell’s sensitivity (0.000254 μg cm⁻²), shows that this method is more sensitive. The standard deviation (0.0022), relative standard deviation (0.56%), confidence limit (±0.0015) and standard error (0.0007) revealed that the developed method has more precision and accuracy. The stability constant was calculated with the help of Asmu’s (9.411 × 10⁻¹¹) and Edmond’s & Birnbaum’s (9.504 × 10⁻¹¹) methods at room temperature. The interfering effect of various cations and anions was also studied. The present method was successfully applied for the determination of vanadium(V) in environmental and alloy samples. The method’s validity was checked by comparing the results obtained with atomic-absorption spectrophotometry and also by evaluation of results using F-test.