Ignition and combustion of low‐density polyimide foam

The ignition, flaming and smoldering combustion of low‐density polyimide foam have been studied using a cone calorimeter. Low‐density polyimide foam exhibits a high ignition resistance. The minimum heat flux for the ignition of flaming combustion ranges from 48 to 54 kW/m². This minimum heat flux also indicates the heat flux for transition from smoldering to flaming combustion. The flaming combustion results show that the heat release rate of low‐density polyimide foam is very low even at a high incident heat flux of 75 kW/m². The smoldering combustion results show that the smoldering of low‐density polyimide foam becomes significant when the incident heat flux is greater than 30 kW/m². The smoldering combustion of low‐density polyimide foam cannot be self‐sustaining when the external heat source is removed. Copyright © 2003 John Wiley & Sons, Ltd.     

The piloted transition to flaming in smoldering fire retarded and non‐fire retarded polyurethane foam

The piloted transition from smoldering to flaming, though a significant fire safety concern, has not been previously extensively studied. Experimental results are presented on the piloted transition from smoldering to flaming in non‐fire retarded (NFR) polyurethane foam and the fire retarded polyurethane foam Pyrell^®. The samples are small blocks, vertically placed in the wall of an upward wind tunnel. The free surface is exposed to an oxidizer flow and a radiant heat flux. The smolder product gases pass upwards through a pilot. The experiments on NFR foam show that the smolder velocity and peak smolder temperature, which increase with the oxygen concentration and heat flux, are strongly correlated to the transition to flaming event, in that there are minimum values of these parameters for transition to occur. The existence of a minimum smolder velocity for ignition supports the concept of a gaseous mixture reaching a lean flammability limit as the criterion for the transition to flaming. To compensate for the solid‐ and gas‐phase effects of the fire retardants on the piloted transition in Pyrell, it was necessary to increase the oxygen concentration and the power supplied to the smolder igniter and the pilot. The piloted transition is observed in oxygen concentrations above 17% in NFR foam and above 23% in Pyrell. The results show that although Pyrell is less flammable than NFR foam, it is still susceptible to smoldering and the piloted transition to flaming in oxygen‐enriched environments, which is of interest for special applications such as future space missions. Copyright © 2008 John Wiley & Sons, Ltd.     

Studying smoldering to flaming transition in polyurethane furniture subassemblies: Effects of fabrics,flame retardants,and material type

The transition from smoldering to flaming was studied on fabric, batting, and foam assemblies via an electric spot ignition source of similar intensity to a cigarette. The materials studied included four different fabrics (cotton, polyester, cotton/polyester blend, flame retardant cotton/polyester blend), two types of batting (cotton, polyester), and three types of polyurethane foam (nonflame retardant, flame retardant by FMVSS 302 testing, flame retardant by BS5852 testing). The results from testing found that materials highly prone to smoldering could propagate smoldering into foams and lead to ignition, whereas materials that tended to melt back from the ignition source did not. Flame retardant fabrics or foam can and do prevent the transition from smoldering to flaming provided sufficient levels of flame retardants are incorporated in the upholstery fabric or foam. The transition from smoldering to flaming of cotton fabric/nonflame retardant foam assembly was also studied using temperature measurements and evolved gas analysis. It was determined that the transition takes place when the oxygen consumption by accelerating smoldering front exceeds the oxygen supply. At this point, the solid fuel gasification becomes driven by thermal decomposition rather than by surface oxidation which leads to high enough concentrations of fuel for flaming combustion to occur.     

Two‐step synthesis of zirconolite‐rich ceramic waste matrice and its physicochemical properties

In this study, the synthesis of single‐phase zirconolite powder was explored using two‐step route of combustion synthesis (CS) plus acid treatment. Zirconolite/Cu composite was firstly produced from the combustion reaction using CuO and Ti as the oxidant and reductant. After pickling and desiccation, refined zirconolite‐rich ceramic powder was obtained with bimodal particle size distribution. The ceramic powder was finally preformed and calcined at 1050‐1300°C for 6‐48 hours, which resulted in bulk density and Vickers hardness of 4.02 g/cm³ and 11.54 GPa after sintering at 1100°C for 18 hours. Aqueous durability of the calcined waste matrice was evaluated according to MCC‐1 standard. The 42 days normalized leaching rates of Ca, Ti and Zr were measured to be 3.96 × 10^?3, 4.52 × 10^?6 and 1.54 × 10^?6 g·m^?2·d^?1.     

Fire‐resistant cyanate ester–epoxy blends

The cure chemistry, thermal stability and fire behaviour of a series of fire‐resistant cyanate ester–epoxy blends were examined. The dicyanate and diepoxide of 1, 1‐dichloro‐2, 2‐bis(4‐hydroxyphenyl)ethylene (bisphenol‐C, BPC) were combined in various molar ratios and the reaction chemistry was monitored using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). The fire behaviour of the BPC cyanate–epoxy blends was studied in flaming and non‐flaming combustion, using OSU calorimetry and pyrolysis‐combustion flow calorimetry (PCFC), respectively. Published in 2003 by John Wiley & Sons, Ltd.     

Combustibility of cyanate ester resins

Flaming and non‐flaming combustion studies were conducted on a series of polycyanurates to examine the effect of chemical composition and physical properties on the fire behavior of these crosslinked, char forming, thermoset polymers. Heats of complete combustion of the polymer and fuel gases were determined by oxygen bomb calorimetry and pyrolysis‐combustion flow calorimetry, respectively. Fire calorimetry experiments were conducted to measure the total heat released, the rate of heat release and the smoke generation in flaming combustion. Fire response parameters derived from the data include the thermal inertia, heat of gasification, effective heat of combustion and combustion efficiency. Halogen‐containing polycyanurates exhibited extremely low heat release rate in flaming combustion compared with the hydrocarbon resins yet produced significantly less smoke and comparable levels of carbon monoxide and soot. Published in 2005 by John Wiley & Sons, Ltd.     

Well‐functioned photovoltaics based on nanofibers composed of PBDT‐TIPS‐DTNT‐DT and graphenic precursors thermally modified by polythiophene,polyaniline and polypyrrole

Reduced graphene oxide nanosheets modified by conductive polymers including polythiophene (GPTh), polyaniline (GPANI) and polypyrrole (GPPy) were prepared using the graphene oxide as both substrate and chemical oxidant. UV–visible and Raman analyses confirmed that the graphene oxide simultaneously produced the reduced graphene oxide and polymerized the conjugated polymers. The prepared nanostructures were subsequently electrospun in mixing with poly(3‐hexylthiophene) (P3HT)/phenyl‐C71‐butyric acid methyl ester (PC₇₁BM) and poly[bis(triisopropylsilylethynyl)benzodithiophene‐bis(decyltetradecylthien)naphthobisthiadiazole] (PBDT‐TIPS‐DTNT‐DT)/PC₇₁BM components and embedded in the active layers of photovoltaic devices to improve the charge mobility and efficiency. The GPTh/PBDT‐TIPS‐DTNT‐DT/PC₇₁BM devices demonstrated better photovoltaic features (J_sc = 11.72 mA cm^?2, FF = 61%, V_oc = 0.68 V, PCE = 4.86%, μ_h = 8.7 × 10^?3 cm² V^–1 s^?1 and μ_e = 1.3 × 10^?2 cm² V^–1 s^?1) than the GPPy/PBDT‐TIPS‐DTNT‐DT/PC₇₁BM (J_sc = 10.30 mA cm^?2, FF = 60%, V_oc = 0.66 V, PCE = 4.08%, μ_h = 1.4 × 10^?3 cm² V^–1 s^?1 and μ_e = 8.9 × 10^?3 cm² V^–1 s^?1) and GPANI/PBDT‐TIPS‐DTNT‐DT/PC₇₁BM (J_sc = 10.48 mA cm^?2, FF = 59%, V_oc = 0.65 V, PCE = 4.02%, μ_h = 8.6 × 10^?4 cm² V^–1 s^?1 and μ_e = 7.8 × 10^?3 cm² V^–1 s^?1) systems, assigned to the greater compatibility of PTh in the nano‐hybrids and the thiophenic conjugated polymers in the bulk of the nanofibers and active thin films. Furthermore, the PBDT‐TIPS‐DTNT‐DT polymer chains (3.35%–5.04%) acted better than the P3HT chains (2.01%–3.76%) because of more complicated conductive structures. © 2019 Society of Chemical Industry     

Nonlinear Absorption of Submicrometer Grain‐Size Cobalt‐Doped Magnesium Aluminate Transparent Ceramics

Transparent cobalt‐doped magnesium aluminate spinel (Co:MgAl₂O₄) ceramics with a submicrometer grain size were prepared by spark plasma sintering. For the first time, the nonlinear absorption of Co:MgAl₂O₄ transparent ceramics was experimentally demonstrated. Both ground state absorption (σ_GSA) and excited state absorption (σ_ESA) were estimated using the solid‐state slow saturable absorber model based on absorption saturation measurements performed at 1.535 μm. σ_GSA and σ_ESA for 0.03 at.% Co:MgAl₂O₄ were found to be 4.1 × 10^?19 cm² and 4.0 × 10^?20 cm², respectively. In the case of 0.06 at.% Co:MgAl₂O₄ ceramics, σ_GSA = 2.6 × 10^?19 cm² and σ_ESA= 5.3 × 10^?20 cm² were determined.     

Scale Up and Anode Development for La‐Doped SrTiO3 Anode‐Supported SOFCs

The possibility of developing large solid oxide fuel cell (SOFC) stacks based upon 25 cm² ceramic oxide anode‐supported cells is investigated. Planar fuel cells comprising strontium titanate‐based anode support impregnated with active catalysts were prepared using a combination of deposition techniques. The fuel cell tests performed in a semisealed rig have shown power densities of 185 mW cm^?2 at 850°C using humidified hydrogen as fuel and air as oxidant. The structure and evolution of the catalytically active impregnated materials‐10 mol% Gd‐doped CeO₂ and nickel‐ are analysed using electron microscopy at the end of the fuel cell test, revealing that a ceria and nickel layer surrounds the titanate backbone grains while ~50–150 nm spherical‐like nickel particles uniformly decorate this top layer.     

Revisiting flexible polyurethane foam flammability in furniture and bedding in the United States

The flammability of flexible polyurethane foam has been well studied to date, via smoldering and flaming ignition. Its contribution to fire loss in the United States has also been well documented, as the flammability of this material will contribute to large fire events when not protected from ignition and heat sources. Despite this known fire risk, fire protection approaches for polyurethane foam are being questioned in regards to fire protection performance, as well as proven and hypothesized concerns over health impacts before and after fire events. The flammability of flexible polyurethane foam in furniture and bedding is a clear and present danger that must be addressed, and this article discusses the current available technologies for fire protection, with pros and cons of these approaches. Known physical and chemical behavior of these foams in fires is discussed, as well as how this behavior contributes to large fire events. Finally, issues that still need further research and information to definitively address the polyurethane foam flammability in the United States is discussed.     

Phase‐dependent radiation‐resistant behavior of BaTiO3: An in situ X‐ray diffraction study

The radiation‐resistant response of BaTiO₃ in the tetragonal and rhombohedral phases on exposure to 100 MeV Ag⁷⁺ ion irradiation was investigated by in situ X‐ray diffraction (XRD) at room temperature (300 K) and low temperature (25 K), respectively. This study revealed that the BaTiO₃ in rhombohedral phase retained crystallinity up to an ion fluence of 1×10¹⁴ ions/cm², whereas tetragonal phase amorphized at much lower fluence viz. 1×10¹³ ions/cm². The in situ XRD along with Raman spectroscopy studies revealed that BaTiO₃ in rhombohedral phase is more radiation resistant than that of tetragonal phase. The density functional theory (DFT) calculations confirmed higher bond strength of rhombohedral phase as compared to tetragonal phase, which supported the experimental result of higher radiation stability of rhombohedral phase. The theoretical predictions on high‐temperature phase will be of relevance to the nuclear waste applications.     

Fire performance of charring closed‐cell polymeric insulation materials: Polyisocyanurate and phenolic foam

Results are presented from 2 series of ad hoc experimental programmes using the cone calorimeter to investigate the burning behaviour of charring closed‐cell polymeric insulation materials, specifically polyisocyanurate (PIR) and phenolic (PF) foams. These insulation materials are widely used in the construction industry due to their relatively low thermal conductivity. However, they are combustible in nature; therefore, their fire performance needs to be carefully studied, and characterisation of their thermal degradation and burning behaviour is required in support of performance‐based approaches for fire safety design. The first series of experiments was used to examine the flaming and smouldering of the char from PIR and PF. The peak heat release rate per unit area was within the range of 120 to 170 kW/m² for PIR and 80 to 140 kW/m² for PF. The effective heat of combustion during flaming was within the range of 13 to 16 kJ/g for PIR and around 16 kJ/g for PF, while the CO/CO₂ ratio was within 0.05 to 0.10 for PIR and 0.025 to 0.05 for PF. The second experimental programme served to map the thermal degradation processes of pyrolysis and oxidation in relation to temperature measurements within the solid phase under constant levels of nominal irradiation. Both programmes showed that surface regression due to smouldering was more significant for PF than PIR under the same heat exposure conditions, essentially because of the different degree of overlap in pyrolysis and oxidation reactions. The smouldering of the char was found to self‐extinguish after removal of the external heat source.     

Fabrication of dense polymer‐derived silicon carbonitride ceramic bulks by precursor infiltration and pyrolysis processes without losing piezoresistivity

Dense polymer‐derived silicon carbonitride (SiCN) ceramic bulks were fabricated by powder consolidation following precursor infiltration and pyrolysis (PIP) densification. The density and open porosity of the ceramics varied from 1.42 g/cm³ and 32.75% before the PIP to 2.29 g/cm³ and 3.64% after the PIP, respectively. The electrical conductivity of the ceramics sharply increased from 6.26 × 10^?10 S/cm before the PIP process to 3.20 × 10^?7 S/cm after the 1st cycle of PIP and then gradually increased to 6.89 × 10^?6 S/cm after four cycles of PIP. However, the piezoresistive coefficient did not change with the PIP. The Raman and electron paramagnetic resonance results show that the graphitization level of free carbon in ceramics derived from PIP was higher than the ceramics derived from powder consolidation. The high graphitization level of free carbon leads to a high conductivity, and thus the conductivity of ceramics increased significantly after the PIP process. The carbon cluster size, which is related to the gauge factor of piezoresistivity, did not change significantly after the PIP process; thus, the gauge factor did not change significantly. Dense, large‐scale polymer‐derived ceramics were fabricated by combined conventional powder consolidation and PIP without the loss of piezoresistivity. These ceramics have potential application as both structural and functional components that can bear loads as well as monitor variations in external stress.     

Sol–Gel‐Derived High‐Performance Stacked Transparent Conductive Oxide Thin Films

Single‐ and multi‐layer transparent conductive oxide (TCO) thin films exhibiting high performance, good packing density and low surface/interface roughness are deposited on silica glass substrates by the sol–gel method. The crystal and microstructural properties of the TCO thin films are evaluated as an alternate to films prepared by ultra‐high vacuum deposition. Tin‐doped indium oxide (ITO) thin films produced using a two‐step drying process showed low surface roughness because of dense packing structure not only horizontal but also vertical directions. As a result, electrical conductivity, carrier concentration, carrier mobility, and optical transmittance of 2.3 × 10³ S/cm, 8 × 10²⁰ cm^?3, 18 cm²/Vs, and over 98% at 500 nm, respectively, were achieved. A multilayer ZnO/ITO stacked structure was also fabricated using the sol–gel process. Our findings suggest that solution‐based methods show promise as an alternative to existing ultra‐high vacuum methods to fabricate TCO thin films.     

A conductive foam: Based on novel poly(styrene‐b‐butadiene‐co‐styrene‐b‐styrene) tri‐block copolymer filled by carbon black

In this article, a conductive foam based on a novel styrene‐based thermoplastic elastomer called poly(styrene‐b‐butadiene‐co‐styrene‐b‐styrene) tri‐block copolymer S(BS)S was prepared and introduced. S(BS)S was particularly designed for chemical foaming with uniform fine cells, which overcame the shortcomings of traditional poly(styrene‐b‐butadiene‐b‐styrene) tri‐block copolymer (SBS). The preparation of conductive foams filled by the carbon black was studied. After the detail investigation of cross‐linking and foaming behaviors using moving die rheometer, the optimal foaming temperature was determined at 180°C with a complex accelerator for foaming agent. Scanning electron microscopy (SEM) images shown that the cell bubbles of conductive foam were around 30–50 µm. The conductivity of foams was tested using a megger and a semiconductor performance tester. SEM images also indicated that the conductivity of foams was mainly affected by the distribution of carbon black in the cell walls. The formation of the network of the carbon black aggregates had a contribution to perfect conductive paths. It also found that the conductivity of foams declined obviously with the foaming agent content increasing. The more foaming agent led to a sharp increasing of the number of cells (from 2.93 × 10⁶ to 6.20 × 10⁷ cells/cm³) and a rapid thinning of the cell walls (from 45.3 to 1.4 µm), resulting in an effective conductive path of the carbon black no forming. The conductive soft foams with the density of 0.48–0.09 g/cm³ and the volume resistivity of 3.1 × 10³?2.5 × 10⁵ Ω cm can be easily prepared in this study. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41644.     

Infrared‐Transparent Y2O3–MgO Nanocomposites Fabricated by the Glucose Sol–Gel Combustion and Hot‐Pressing Technique

A glucose sol–gel combustion method has been developed to synthesize composite nanopowders with equal volume fractions of Y₂O₃ and MgO. The synthesis involves the generation of precursor foam containing Y³⁺ and Mg²⁺ cations via the chemical and thermal degradation of glucose molecules in aqueous solutions. Subsequent calcination of the foam gave the composite nanopowders uniform composition and surface areas of 44–62 m²/g depending on the relative amount of glucose. Then the nanopowder with an average particle size of 19 nm was consolidated by the hot‐pressing technique with different sintering temperatures. The fabricated nanocomposite is mid‐infrared transparent as the result of fine grains, narrow grain size distribution, and uniform phase domains. The transmittance increases with increase in the sintering temperature and reaches 83.5% at 3–5 μm mid‐infrared wave range once the temperature reaches 1350°C, which is close to the theoretical value of 85%. And it is noteworthy that the cutoff wavelength reaches 9.6 μm, which is superior to those of spinel, AlON, and sapphire. And the Vickers hardness of the sample reaches 10.0 ± 0.1 GPa, which is significantly higher than those of the coarse grained single‐phase MgO and Y₂O₃. The results indicate that the glucose sol–gel combustion and hot‐pressing technique is an effective method to fabricate infrared transparent Y₂O₃–MgO nanocomposites.     

Performance of Ni‐based Anode‐Supported SOFCs with Doped Ceria Electrolyte at Low Temperatures Between 294 and 542°C

The performance of a conventional anode‐supported microtubular SOFC using doped ceria as an electrolyte and Ni‐based cermet as an anode is evaluated at low operating temperature between 294 and 542°C. An open‐circuit voltage (OCV) of >0.9 V is obtained at all measured operating temperatures, and power generation is observed at temperatures as low as 294°C. The power density of the cell is 0.6 W/cm² at 542°C operating temperature with 47% fuel utilization and is 5 mW/cm² at 294°C operating temperature with an open‐circuit voltage of 0.95 V. According to impedance spectroscopy, a greater influence of gas flow rate, on the cell performance, is observed at higher operating temperature.     

Experimental Study of Internal Reforming on Large‐area Anode Supported Solid Oxide Fuel Cells

The effect of endothermic internal steam reformation of methane and exothermic fuel cell reaction on the temperature of a planar‐type anode‐supported solid oxide fuel cell was experimentally investigated as a function of current density and fuel utilization. We fabricated a large‐area (22 × 33 cm²) cell and compared temperature profiles along the cell using 30 thermocouples inserted through the cathode end plate at 750 °C under various conditions (Uf ∼50% at 0.4 A cm⁻²; Uf ∼70% at 0.4 A cm⁻²; Uf ∼50% at 0.2 A cm⁻²) with hydrogen fuel and methane‐steam internal reforming. The endothermic effect due to internal reforming mainly occurs at the gas inlet region, so this process is not very effective to cool down the hot spot created by the exothermic fuel cell reaction. This eventually results in a larger temperature difference on the cell. The most moderate condition with regards to thermal gradient on the cell corresponds to high fuel utilization (Uf ∼70%) and low current density (∼0.2 A cm⁻²). The electrochemical performance was also measured, and it was found that the current–voltage characteristics are comparable for the cell operated under hydrogen fuel and internal steam reforming of methane because of lower polarization resistance with high partial pressure of water vapor.     

Synthesis and Electrochemical Properties of BaFe1−xCuxO3−δ Perovskite Oxide for IT‐SOFC Cathode

A series of iron‐based perovskite oxides BaFe_1−xCu_xO_3−δ (x = 0.10, 0.15, 0.20 and 0.25, abbreviated as BFC‐10, BFC‐15, BFC‐20 and BFC‐25, respectively) as cathode materials have been prepared via a combined EDTA‐citrate complexing sol‐gel method. The effects of Cu contents on the crystal structure, chemical stability, electrical conductivity, thermal expansion coefficient (TEC) and electrochemical properties of BFC‐x materials have been studied. All the BFC‐x samples exhibit the cubic phase with a space group Pm3m (221). The electrical conductivity decreases with increasing Cu content. The maximum electrical conductivity is 60.9 ± 0.9 S cm⁻¹ for BFC‐20 at 600 °C. Substitution of Fe by Cu increases the thermal expansion coefficient. The average TEC increases from 20.6 × 10⁻⁶ K⁻¹ for BFC‐10 to 23.7 × 10⁻⁶ K⁻¹ for BFC‐25 at the temperature range of 30–850 °C. Among the samples, BFC‐20 shows the best electrochemical performance. The area specific resistance (ASR) of BFC‐20 on SDC electrolyte is 0.014 Ω cm² at 800 °C. The single fuel cell with the configguration of BFC‐20/SDC/NiO‐SDC delivers the highest power density of 0.57 W cm⁻² at 800 °C. The favorable electrochemical activities can be attributed to the cubic lattice structure and the high oxygen vacancy concentration caused by Cu doping.     

Microwave dielectric and nonlinear optical studies on radio‐frequency sputtered Dy2O3‐doped KNN thin films

We report the effect of oxygen mixing percentage (OMP) on structural, microstructural, dielectric, linear, and nonlinear optical properties of Dy₂O₃‐doped (K_0.5Na_0.5)NbO₃ thin films. The (K_0.5Na_0.5)NbO₃ + 0.5 wt%Dy₂O₃ (KNN05D) ferroelectric thin films were deposited on to quartz and Pt/Ti/SiO₂/Si substrates by RF magnetron sputtering. An increase in the refractive index from 2.08 to 2.21 and a decrease in the optical bandgap from 4.30 to 4.28 eV indicate the improvement in crystallinity, which is also confirmed from Raman studies. A high relative permittivity (ε_r=281‐332) and low loss tangent (tanδ=1.2%‐1.9%) were obtained for the films deposited in 100% OMP, measured at microwave frequencies (5‐15 GHz). The leakage current of the films found to be as low as 9.90×10^?9 A/cm² at 150 kV/cm and Poole‐Frenkel emission is the dominant conduction mechanism in the films. The third order nonlinear optical properties of the KNN05D films were investigated using modified single beam z‐scan method. The third order nonlinear susceptibility (?χ⁽³⁾?) values of KNN05D films increased from 0.69×10^?3 esu to 1.40×10^?3 esu with an increase in OMP. The larger and positive nonlinear refractive index n₂=7.04×10^?6 cm²/W, and nonlinear absorption coefficient β=1.70 cm/W were obtained for the 100% OMP film, indicating that KNN05D films are good candidates for the applications in nonlinear photonics and high‐frequency devices.