Effect of carbon dioxide on the performance of Ni/PTFE and Ag/PTFE electrodes in an alkaline fuel cell

The effect of carbon dioxide as impurity in hydrogen and oxygen on the performance of electrodes was studied in a half cell arranged at different concentrations and temperatures. The presence of CO₂ in hydrogen was investigated on Ni/PTFE at different concentrations (0–4%) and three temperatures (28, 52, 72° C). Carbon dioxide was found to increase the overpotential due to ionic concentration polarization, but this effect was completely reversible. Impurity levels of CO₂ up to 1% in oxygen had no effects on the Ag/PTFE electrode in the short term. Long term performance tests were carried out with CO₂ impurity in oxygen at two different concentrations (0.03%, 1%) and at two different temperatures (25° C, 72° C). All experiments showed no degrading effect on the Ag/PTFE electrode with the exception of one at 25° C with 1% CO₂. At this run a steady drop of current density was observed due to the formation of K₂CO₃ in the micropores which was verified by XRD. In all runs the concentration of KOH electrolyte was kept constant at 25%. The effect of adding K₂CO₃ to KOH was also investigated and no loss in electrode currents was observed for 48 h on both Ni/PTFE and Ag/PTFE electrodes.     

Thermal stability evaluation of polypropylene protected with grafted amine

Summary Polypropylene containing a grafted amine as oxidation protector was subjected to γ-irradiation for the evaluation of thermal stability. Several formulations were prepared containing hindered amine, Sanduvor PR 31 (0.1, 0.2 and 0.3% w/w) and CaCO₃ (0.6% w/w). The stability assessment was carried out in air by oxygen uptake procedure under isothermal and isobaric conditions (165 °C and normal pressure, respectively). The exposure doses were placed in the range from 0 to 70 kGy. The changes appeared in the main kinetic parameters (oxidation induction time and oxidation rate) evaluated for thermal degradation of irradiated PP specimens are presented and the stability analysis is explained starting from the behaviour differences of various formulations of radiation processed polypropylene. On the low dose range, the drop in thermal stability of modified polypropylene films occurs more abrupt than it was observed for the samples irradiated at higher doses.     

Surface modification of polytetrafluoroethylene by Ar+ irradiation for improved adhesion to other materials

A surface of thin square polytetrafluoroethylene (PTFE) samples (1 × 1 × 0.2 cm³) was irradiated with Ar⁺ at 1 keV with varying ion dose from 5 × 10¹⁴ to 1 × 10¹⁷ ions/cm² with and without an oxygen environment. The irradiated surface of the samples was examined by scanning electron microscopy (SEM) for surface textural changes and x-ray photoelectron spectrometry (XPS) for changes in chemical structure. A wettability test was conducted on the irradiated surface of PTFE samples by water droplets. A Scotch ™ tape adhesion test, after a thin film of Cu or Al was evaporated on the irradiated surface, and a tensile test after irradiated samples were glued to sample holders by an adhesive glue (Crystal Bond) was also run. The SEM micrographs showed increasing roughness with fiber forest-like texture with increasing ion dose. The Ar⁺ with an O₂ environment produced finer and denser fiber forest-like texture than that without O₂. The high-resolution XPS spectra showed decreased intensity of the F1s peak and formation of the O1s peak when irradiated with the O₂ environment. The increase of the O1s peak may be attributed to the reaction of oxygen atoms and the free radicals created by Ar⁺ bombardment. The wettability of water droplets on the irradiated surfaces was found to be inversely proportional to the surface roughness. Adhesion tests were conducted on 2000 Å thick Al or Cu film. Full detachment of the metal films was observed when PTFE samples were not modified. Partial detachment of the Al film occurred when PTFE was irradiated without the O₂ environment, regardless of ion dose. No detachment of the film occurred when PTFE was irradiated with the O₂ environment with the ion dose exceeding 1 × 10¹⁶ ions/cm². Partial detachment of Cu film was observed with or without the O₂ environment when the ion dose was 5 × 10¹⁴ ions/cm². No detachment occurred with or without the O₂ environment when the ion dose was 1 × 10¹⁵ ions/cm² or greater. The tensile test showed that adhesion of an adhesive cement (Crystal Bond) to the irradiated PTFE samples increased significantly with increasing ion dose up to 1 × 10¹⁶ ions/cm². Possible mechanisms for the improved adhesion are given. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1913–1921, 1997     

The formation and thermal stability of spurrite,Ca5(SiO4)2CO3

The reversible equilibrium: 2Ca₂SiO₄ + CaO + CO₂ ? Ca₅(SiO₄)₂CO₃ has been studied using F^? and C?^? ions as mineralizers. A pressure-temperature curve is given for the reaction in the range of CO₂ pressures between 0.08 and 1 atmosphere. At these pressures, the decomposition temperatures of spurrite are 790 ± 5°C and 912 ± 5°C respectively. At a given CO₂ pressure the thermal stability of spurrite is greater than that of CaCO₃.     

Radiation resistant metal decorated MWCNTs/PMMA nanocomposite films with enhanced thermomechanical properties

UV/O₃ radiation and chemical resistant nanocomposite films of functionalized/metal decorated multiwall carbon nanotubes (MWCNTs) with polymethylmethacrylate (PMMA) are synthesized. Silver nanoparticles are decorated on the surface of UV/O₃ functionalized MWCNTs by both reduction and in situ growth from AgNO₃ aqueous solution. Microscopic studies reflect the better dispersion of UV/O₃ functionalized/silver decorated MWCNTs in polymer matrix contributing in enhancement of thermal stability, thermomechanical strength, glass transition temperatures, and thermal conductivity of nanocomposites even at 0.25 wt% MWCNTs additions. The thermal stability of nanocomposite film (0.25 wt% loading), prepared by using a surfactant (Sodium dodecyl sulfate) is increased to about 27°C while the thermomechanical properties are raised up to 76% at 100°C. Thermal and thermomechanical behavior of pre‐ and post‐UV/O₃ irradiated nanocomposite films are compared with neat polymer. The results reveal that UV/O₃ functionalized MWCNTs can effectively disperse the radiation and have a dramatic reinforcement effect on the nature of the degradation of PMMA matrix. POLYM. COMPOS., 36:969–978, 2014. © 2014 Society of Plastics Engineers     

Thermal analysis of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) irradiated under vacuum

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) was irradiated by ⁶⁰Co γ‐rays (doses of 50, 100 and 200 kGy) under vacuum. The thermal analysis of control and irradiated PHBV, under vacuum was carried out by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The tensile properties of control and irradiated PHBV were examined by using an Instron tensile testing machine. In the thermal degradation of control and irradiated PHBV, a one‐step weight loss was observed. The derivative thermogravimetric curves of control and irradiated PHBV confirmed only one weight‐loss step change. The onset degradation temperature (T_o) and the temperature of maximum weight‐loss rate (T_p) of control and irradiated PHBV were in line with the heating rate (°C min^?1). T_o and T_P of PHBV decreased with increasing radiation dose at the same heating rate. The DSC results showed that ⁶⁰Co γ‐radiation significantly affected the thermal properties of PHBV. With increasing radiation dose, the melting temperature (T_m) of PHBV shifted to a lower value, due to the decrease in crystal size. The tensile strength and fracture strain of the irradiated PHBV decreased, hence indicating an increased brittleness. Copyright © 2004 Society of Chemical Industry     

Femtosecond laser direct writing in SiO2-Al2O3 binary glasses and thermal stability of Type II permanent modifications

We investigate the potential of fabricating thermally stable refractive index contrasts using femtosecond (fs) near-infrared (IR) radiation in aluminosilicate glasses. A set of pure SiO₂-Al₂O₃ glasses are manufactured, characterized (density and Raman), and investigated after being irradiated by fs laser within the Type II regime. The formation of nanogratings is identified and studied using quantitative birefringence measurements. Their thermal stability is then investigated through 30 minutes step isochronal annealing (up to 1250°C). For both SiO₂ and 50SiO₂-50Al₂O₃ compositions, the normalized birefringence does not decrease when tested up to 1100°C, while for the 4,6 mol% GeO₂-SiO₂ erased for 20% at 1000°C.     

Improving Thermal Stability and Electrical Insulation of Gamma‐Irradiated Silicone Rubber Nanocomposites

Room temperature vulcanized silicone rubber (RTVSR) nanocomposites were prepared by mixing of surface‐modified montmorillonite nanoclay or nano fumed silica, or both of them with RTVSR to improve thermal stability, electrical insulation, and flame retardant. Their tensile strength, elongation, swelling, and solubility properties at different doses of gamma radiation were investigated to study the effect of gamma radiation on the properties of the nanocomposites. The thermal stability, flammability properties, and volume resistivity of the nanocomposites were also investigated. The nanocomposite which containing fumed silica has the best thermal, mechanical properties, electrical insulation and fire retardancy. The thermal characteristics, namely, T_onset, T_10%, T_comp, and T_max, of the nanocomposite sample containing fumed silica were 22, 23, 13, and 11 °C higher than those of the blank, respectively. The tensile strength (TS) increased when the radiation dose was increased up to 100 kGy, but elongation, swelling, and solubility decreased when the radiation dose was increased up to 150 kGy. It can be generally concluded that the nanocomposites containing fumed silica and irradiated to 100 kGy are characterized by having outstanding mechanical, thermal, fire retardant, and electrical insulation properties and hence, they may have wide industrial applications as good thermal and electrical insulating materials. J. VINYL ADDIT. TECHNOL., 26:354–361, 2020. © 2019 Society of Plastics Engineers     

Morphological evolution of polytetrafluoroethylene in extreme temperature conditions for aerospace applications

The organic electrical insulator polytetrafluoroethylene (PTFE) is used in aerospace industry under extreme conditions of temperature and electric field. The melting temperature of PTFE is about 327°C and nowadays operating temperature of this kind of insulators can reach about 300°C and up to 350°C for new generations of machines. All thermal, electrical and mechanical operating stresses, especially high temperature and voltage can be factors of ageing acceleration and/or degradation of the insulators that could cause premature failures. Our present work is focused on the organic insulator behavior at high temperature in order to understand the mechanisms of thermal ageing and degradation. The change of morphology of PTFE during the thermal ageing has been studied. Thin films in PTFE were aged by accelerated method under oxidizing environment (air) and severe thermal constraints between 340 and 450°C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39841.     

Enhanced gravimetric CO2 capacity and viscosity for ionic liquids with cyanopyrrolide anion

Ionic Liquids (ILs) are considered as alternative solvents for the separation of CO₂ from flue gas due mainly to their CO₂ affinity and thermal stability. The cation architecture in a matrix of ammonium and mostly phosphonium‐based ILs with 2‐cyanopyrrolide as the anion to evaluate its impact on gravimetric CO₂ absorption capacity, viscosity, and thermal stability and the three fundamental properties vital for application realization are systematically investigated. Among the investigated ILs, [P2,2,2,8][2‐CNpyr] demonstrated the lowest viscosity, 95 cP at 40°C, and highest CO₂ uptake, 114 mg CO₂ per g IL at 40°C. Combined effects of asymmetry and the optimized chain lengths also resulted in improved thermal stability for [P2,2,2,8][2‐CNpyr], with a mass loss rate of 1.35 × 10^?6 g h^?1 (0.0067 mass % h^?1) at 80°C. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2280–2285, 2015     

Facile synthesis of amine-functionalized MIL-53(Al) by ultrasound microwave method and application for CO<Subscript>2</Subscript> capture

An amine functional MIL-53(Al) material was prepared through a clean, rapid, energy-efficient method of microwave and ultrasound irradiation. The pure phase NH₂-MIL-53(Al) can be formed in 25 min, utilizing the synergistic effect of microwave and ultrasound irradiation. The dramatic acceleration in reaction rates suggested that the removal of a passivation coating on the substrate particles and the resultant enhancement in mass and heat transfer. The porous MOFs exhibited a high thermal and chemical stability, decomposing at temperatures above 410 °C in air. The NH₂-MIL-53(Al) performed an excellent adsorption for CO₂. The CO₂ capacities up to 33.86 cm³ g^?1 at 298 K at low pressures, which suggests chemisorption between CO₂ and pendan amine groups. Measurement of CO₂ adsorption cycles proved that the functionalized materials show good regenerability and stability.     

Radiation Stability of Spark‐Plasma‐Sintered Lead Vanadate Iodoapatite

Spark‐plasma‐sintered lead vanadate iodoapatite Pb_9.85(VO₄)₆I_1.7, a promising nuclear waste form for the immobilization of I‐129, was irradiated with energetic ions, electrons, and gamma rays, to investigate its radiation stability. In situ TEM observation of the 1 MeV Kr²⁺ irradiation shows that lead vanadate iodoapatite generally exhibits higher tolerance against ion irradiation‐induced amorphization than lead vanadate fluorapatite, and the spark plasma sintering can further enhance its radiation stability attributed to the enhanced crystallinity, reduced defect concentration, and denser microstructure. The critical amorphization dose and critical temperature for the SPS‐densified iodoapatite at 700°C are determined to be 0.25 dpa at room temperature and 230°C, respectively. No significant phase transformation or microstructural damage occurred under energetic electron and gamma irradiations. Raman spectra of gamma‐ray‐irradiated iodoapatite indicate improved V–O bond order at 500 kGy dose. Generally, the spark‐plasma‐sintered iodoapatite exhibits excellent radiation stability for nuclear waste form applications. The significantly enhanced radiation stability of the SPS‐densified iodoapatite suggests that SPS holds great promise for fabricating iodoapatite waste form with minimum iodine loss and optimized radiation tolerance for effective management of highly volatile I‐129.     

Synthesis,characterization, and structure-property relationships of aromatic polyimides containing 4,4′-diaminotriphenylmethane

This work reports two series of structurally different aromatic polyimides based on 4,4´-diaminodiphenylmethane (DPM) and 4,4´-diaminotriphenylmethane (TPM) and three commercial dianhydrides. All TPM-based polyimides formed membranes due to their high molecular weight (inherent viscosities ~0.93–1.14 dl/g), they exhibited high thermal stability (5 %: 490–544 °C), glass transition temperatures between 269 and 293 °C, and reasonable mechanical properties. The incorporation of pendant phenyl moieties in the TPM-based polyimides has a strong effect producing an improvement in solubility, thermal stability, density and gas permeability coefficient in comparison with DPM-based polyimides. The most interesting polyimide TPM-6FDA, containing phenyl and trifluoromethyl as bulky pendant groups, showed higher gas permeability coefficient for CO₂ (23.73 Barrer) and the best ideal selectivity to the gas pair CO₂/CH₄ (α = 28.93).     

Temperature-induced fibre/matrix interactions in porous alumino silicate ceramic matrix composites

The thermal stability of alumino-silicate fibre (Nextel 720)/porous mullite matrix composites was investigated in the temperature range between 1300 and 1600°C. In the as-prepared state the fibres consist of mullite plus α-Al₂O₃, while the porous mullite matrix includes minor amounts of a SiO₂-rich glass phase. Temperature-controlled reactions between the silica-rich glass phase of the matrix and α-Al₂O₃ at the rims of the fibres to form mullite have been observed. At the end of this process, virtually all glass phase of the matrix is consumed. Simultaneously, alumina-free layers about 1 μm thick are formed at the periphery of the fibres. The mullite forming process is initiated above about 1500°C under short time heat-treatment conditions (2 h) and at much lower temperature (1300°C) under long-term annealing (1000 h). Subsequent to annealing below the thermal threshold, the composite is damage tolerant and only minor strength degradation occurs. Higher annealing temperatures, however, drastically reduce damage tolerance of the composites, caused by reaction-induced gradually increasing fibre/matrix bonding. According to this study, the thermal stability of alumino silicate (Nextel 720) fibre/mullite matrix composites ranges between 1500°C in short-term and 1300°C in long-term heat-treatment conditions.     

Thermal properties of low loss PTFE‐CeO2 dielectric ceramic composites for microwave substrate applications

Polytetrafluroethylene (PTFE) composites filled with CeO₂ were prepared by powder processing technique. The PTFE is used as the matrix and the loading fraction of CeO₂ in the composite varied up to 0.6 volume fraction. The thermal conductivity and coefficient of thermal expansion were studied in relation to filler concentration. The thermal conductivity increased and coefficient of thermal expansion decreased with increase in CeO₂ content. For 0.6 volume fraction loading of the ceramic, the composite has a thermal conductivity of 3.1 W/m°C and coefficient of thermal expansion 19.6 ppm/°C. Different theoretical approaches have been employed to predict the effective thermal conductivity and coefficient of thermal expansion of composite systems and the results were compared with the experimental data. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of electron beam radiation on the mechanical and thermal properties of poly(4-methylpentene-1)

The changes in the mechanical and thermal properties of electron-beam-irradiated PMP of two different molecular weights (〈M_w〉 = 9.2 × 10⁵, 〈M_w〉 = 1.8 × 10⁶) have been studied. Electron beam (EB) irradiation was performed either in a nitrogen or air atmosphere to a maximum dosage of 40 Mrad. Stress–strain behavior of the irradiated materials show that the lower molecular weight polymer is more affected within this dose range than the higher molecular weight material. The modulus of both PMP materials (at 23°C), however, was not affected by EB. Moreover, it was observed that by increasing radiation dose up to 10 Mrad the occurrence of yielding disappeared in the case of the lower molecular weight system but was still found in the high molecular weight material up to 20 Mrad. The elongation at break of both PMP materials was systematically decreased by increasing the dose level. The rate of stress–relaxation of irradiated samples increased as dosage increased. It is believed that oxidative degradation is promoted as a result of irradiation which induces chain scission. This result was confirmed by GPC analysis which showed that, by increasing radiation dose, the molecular weight systematically decreased. DSC measurements used to investigate the changes in thermal properties showed that the melting temperature and heat of fusion decreased as the dose increased. An interesting feature of the DSC studies was the presence of an endothermic doublet in the melting behavior that transformed into a single peak following irradiation.     

Temperature-reversible oxidation of carbon monoxide by new and weathered whetlerite

The oxidation of CO in mixtures with purified air passing into whetlerite was followed by online measurements of CO and CO₂ in the effluent between 20–200°C. The CO concentrations attained a steady-state at each temperature and these were found to be temperature reversible. Two molecules of CO were required to form one CO₂ up to 100°C, and above 100°C, the ratio was less than two for new whetlerites and greater than two for weathered whetlerites. An oxygen balance was indicated but a sink for the carbon other than carbon-on-carbon deposition was not evident. While whetlerite in air flows formed mainly CO₂, the activated carbon support alone formed both CO and CO₂. The whetlerite impregnation (copper II, chromium VI, and silver I) had little influence on the magnitude of the total carbon gasified up to 200°C, but the ratio of CO₂/CO was many fold greater for the whetlerite. The spontaneous ignition temperature (SIT) of the coal-base charcoal support (490°C) was lowered in whetlerite (270–280°C).     

Microwave enhanced synthesis of MOF-5 and its CO2 capture ability at moderate temperatures across multiple capture and release cycles

The metal-organic framework, MOF-5 (Zn₄O(BDC)₃), was prepared using solvothermal synthesis under microwave irradiation, followed by solvent exchange to improve molecular stability at high temperatures, and assessed for its ability to capture CO₂ at ambient pressure and temperatures up to 300 °C. The reaction product was characterised by X-ray diffraction, scanning electron microscope, N₂ physisorption, thermogravimetric analysis and CO₂ physisorption. Cyclic CO₂ physisorption showed the capacity of the MOF-5 crystals to be 3.61 wt% when cycled between 30 °C and 300 °C through 10 separate capture and release cycles. Above 400 °C MOF-5 underwent thermal decomposition and was no longer capable of capturing CO₂.     

Structure–property behavior of gamma‐irradiated poly(styrene) and poly(methyl methacrylate) miscible blends

Polymer blends based on various ratios of polystyrene (PS) and polymethyl methacrylate (PMMA) were exposed to different doses of gamma radiation up to 25 Mrad. The structure–property behavior of the polymer blends before and after they had been irradiated was investigated by DSC, TGA, and FTIR spectroscopy. The DSC scans of the glass transition temperature (T_g) of the different polymer blends showed that the T_g was greatly decreased by increasing the ratio of the PMMA component in the polymer blends. Moreover, the T_g of PS/PMMA blends was found to decrease with increasing irradiation dose. The depression in T_g was noticeable in the case of blends rich in PMMA component. The TGA thermograms showed that the thermal stability of the unirradiated polymer blends decreases with increasing the ratios of PMMA component. Also, it was found that the presence of PS polymer in the blends affords protection against gamma radiation degradation and improves their thermal stability. However, exposing the polymer blends to high doses of gamma radiation caused oxidative degradation to PMMA components and decreased the thermal stability. The investigation of the kinetic parameters of the thermal decomposition reaction confirm the results of thermal stability. The FTIR analysis of the gamma‐irradiated polymer blend films gives further support to the TGA data. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 509–520, 1999     

Thermal and thermomechanical behavior of amino functionalized and metal decorated MWCNTs/PMMA nanocomposite films

The homogeneous nanocomposites (NC) films of amino modified and metal decorated multiwall carbon nanotubes (MWCNTs) with polymethylmethacrylate (PMMA) were synthesized through in‐situ free radical polymerization. Silver metal nanohybrids (Ag/MWCNTs) were prepared by two strategies, that is, reduction of metal salt in presence of sodium dodecyl sulfate and in‐situ growth from AgNO₃ aqueous solution. The amino functionalization by ball milling enhanced the dispersion of MWCNT in monomer and produced a new class of radiation resistant NC. These synthesized films were characterized by FTIR, TGA, TEM, EDX, TC, DMA, and optical microscopy to ascertain their structural morphologies, thermal stability, and mechanical strength. Microscopic studies reflect the homogeneous mixing of amino functionalized and metal decorated MWCNTs in polymer matrix contributing in the enhancement of thermal stability, thermo‐mechanical strength, glass transition temperatures, and thermal conductivity of NC even at 0.25 wt% addition of modified nanofiller. The thermal stability of NC film at 0.25 wt% loading was increased around ≂50°C and the raise of thermo‐mechanical properties was observed up to 85% at 100°C in the presence of adsorbed surfactant. Thermal and thermomechanical behavior of pre and post UV/O₃ irradiated NC films has been compared with neat polymer. The results revealed that amino modified nanofiller embedded network in polymer matrix can effectively disperse the radiation and has a dramatic reinforcement effect on the nature of degradation of PMMA matrix. POLYM. COMPOS., 35:1807–1817, 2014. © 2013 Society of Plastics Engineers