Spontaneously Igniting Hybrid Fuel-Oxidizer Systems

After briefly outlining the recent developments in hybrid rockets, the work carried out by the author on self-igniting (hypergolic) solid fuel-liquid oxidiser systems has been reviewed. A major aspect relates to the solid derivatives of hydrazines, which have been conceived as fuels for hybrid rockets. Many of these N-N bonded compounds ignite readily, with very short ignition delays, on coming into contact with liquid oxidisers, like HNO3 and N2O4. The ignition characteristics have been examined as a function of the nature of the functional group in the fuel molecule, in an attempt to establish a basis for the hypergolic ignition in terms of chemical reactivity of the fuel-oxidiser combination. Important chemical reactions occurring in the pre-ignition stage have been identified by examining the quenched reaction products. Hybrid systems exhibiting synergistic hypergolicity in the presence of metal powders have been investigated. An estimation of the rocket performance parameters, experimental determination of the heats of combustion in HNO3, thermal decomposition characteristics, temperature profile by thin film thermometry and and product identification by the rapid scan FT-IR, are among the other relevant studies made on these systems. A significant recent development has been the synthesis of new N-N bonded viscous binders, capable of retaining the hypergolicity of the fuel powders embedded therein as well as providing the required mechanical strength to the grain. Several of these resins have been characterised. Metallised fuel composites of these resins having high loading of magnesium are found to have short ignition delays and high performance parameters.

An improved-performance liquid-feed solid-polymer-electrolyte direct methanol fuel cell operating at near-ambient conditions

Results on the performance of a 25 cm(2) liquid-feed solid-polymer-electrolyte direct methanol fuel cell (SPE-DMFC), operating under near-ambient conditions, are reported. The SPE-DMFC can yield a maximum power density of c. 200 mW cm(-2) at 90 C while operating with 1 M aqueous methanol and oxygen under ambient pressure. While operating the SPE-DMFC under similar conditions with air, a maximum power density of ca. 100 mW cm(-2) is achieved. Analysis of the electrode reaction kinetics parameters on the methanol electrode suggests that the reaction mechanism for methanol oxidation remains invariant with temperature. Durability data on the SPE-DMFC at an operational current density of 100 mA cm(-2) have also been obtained.

Renewable surface electrodes based on dopamine functionalized exfoliated graphite: NADH oxidation and ethanol biosensing

Exfoliated graphite (EG) was modified by covalently attaching dopamine (DA) (3,4-dihydroxyphenethylamine) through amide linkages, using -COOH groups introduced on the EG surface. The modified material was characterized by FT-IR spectroscopy, Xray photoelectron spectroscopy and electrochemical techniques. Composites of DA modified EG dispersed in organically modified silicates were prepared by a sol-get process. Electrodes were fabricated by casting the composites in glass tubes. The sol-gel based electrodes were found to be active for the electrocatalytic oxidation of NADH and biosensing of ethanol in presence of NAD(+) and alcohol dehydrogenase enzyme. The modified composite electrodes were found to be stable for several months. The surface of the electrode could be renewed just by mechanically polishing the electrode using emery sheets. The modified EG was also pressed and restacked in the form of a pellet and the use of this material as a binderless bulk-modified electrode was also demonstrated. The performance of sol-gel derived composite EG electrodes with binderless bulk-modified EG electrodes was compared. (C) 2002 Elsevier Science B.V. All rights reserved.

A self-supported 40W direct methanol fuel cell system

A self-supported 40W Direct Methanol Fuel Cell (DMFC) system has been developed and performance tested. The auxiliaries in the DMFC system comprise a methanol sensor, a liquid-level indicator, and fuel and air pumps that consume a total power of about 5W. The system has a 15-cell DMFC stack with active electrode-area of 45 cm(2). The self-supported DMFC system addresses issues related to water recovery from the cathode exhaust, and maintains a constant methanol-feed concentration with thermal management in the system. Pure methanol and water from cathode exhaust are pumped to the methanol-mixing tank where the liquid level is monitored and controlled with the help of a liquid-level indicator. During the operation, methanol concentration in the feed solution at the stack outlet is monitored using a methanol sensor, and pure methanol is added to restore the desired methanol concentration in the feed tank by adding the product water from the cathode exhaust. The feed-rate requirements of fuel and oxidant are designed for the stack capacity of 40W. The self-supported DMFC system is ideally suited for various defense and civil applications and, in particular, for charging the storage batteries.

A comparative study of Pt/CeO2 catalysts for catalytic partial oxidation of methane to syngas for application in fuel cell electric vehicles

In the framework of a project aimed at developing a reliable hydrogen generator for mobile polymer electrolyte fuel cells (PEFCs), particular emphasis has been addressed to the analysis of catalysts able to assure high activity and stability in transient operations (frequent start-up and shut-down cycles). In this paper, the catalytic performance of 1 at.% Pt/ceria samples prepared by coprecipitation, impregnation and combustion, has been evaluated in the partial oxidation of methane. Methane conversion and hydrogen selectivity of 96 and 99%, respectively, associated with high stability during 100h of reaction under operative conditions (start-up and shut-down cycles), have been obtained. (C) 2002 Elsevier Science B.V. All rights reserved.

Characterization of Ni-Pd alloy as anode for methanol oxidative fuel cell

Electrochemical deposition of Ni-Pd alloy films of various compositions from bath solution containing ethylenediamine (EDA) was carried out to use as anode material for methanol oxidative fuel cell in H2SO4 medium. Electronic absorption spectrum of bath solution containing Ni2+ Pd2+ ions and EDA indicated the formation of a four coordinate square planar metal-ligand complex of both the metal ions. X-ray diffraction (XRD) patterns of the deposited alloy films show an increase in Pd-Ni alloy lattice parameter with increase in Pd content, and indicate the substitution of Pd in the lattice. A nano/ultrafine kind of crystal growth was observed in the alloy film deposited at low current density (2.5 mA cm(-2)). X-ray photoelectron spectroscopic (XPS) studies on the successively sputtered films showed the presence of Ni and Pd in pure metallic states and the surface concentration ratio of Ni to Pd is less than bulk indicating the segregation of Pd on the surface. Electro-catalytic oxidation of methanol in H2SO4 medium is found to be promoted on Ni-Pd electrodeposits. The anodic peak current characteristics to oxidation reaction on Ni-Pd was found typically high when compared to pure nickel and the relative increase in surface area by alloying the Ni by Pd was found to be as much as 300 times. (C) 2003 Elsevier Science B.V. All rights reserved.

The promise of fuel cell-based automobiles

Fuel cell-based automobiles have gained attention in the last few years due to growing public concern about urban air pollution and consequent environmental problems. From an analysis of the power and energy requirements of a modern car, it is estimated that a base sustainable power of ca. 50 kW supplemented with short bursts up to 80 kW will suffice in most driving requirements. The energy demand depends greatly on driving characteristics but under normal usage is expected to be 200 Wh/km. The advantages and disadvantages of candidate fuel-cell systems and various fuels are considered together with the issue of whether the fuel should be converted directly in the fuel cell or should be reformed to hydrogen onboard the vehicle. For fuel cell vehicles to compete successfully with conventional internal-combustion engine vehicles, it appears that direct conversion fuel cells using probably hydrogen, but possibly methanol, are the only realistic contenders for road transportation applications. Among the available fuel cell technologies, polymer-electrolyte fuel cells directly fueled with hydrogen appear to be the best option for powering fuel cell vehicles as there is every prospect that these will exceed the performance of the internal-combustion engine vehicles but for their first cost. A target cost of $ 50/kW would be mandatory to make polymer-electrolyte fuel cells competitive with the internal combustion engines and can only be achieved with design changes that would substantially reduce the quantity of materials used. At present, prominent car manufacturers are deploying important research and development efforts to develop fuel cell vehicles and are projecting to start production by 2005.

Ethanol sensing using CuO/MWNT thin film

Copper (II) oxide (CuO)/multiwall carbon nanotube (MWNT) thin film based ethanol-sensors were fabricated by dispersing CVD-prepared MWNTs in varying concentration over DC magnetron sputtered-CuO films. The responses of these sensors as a function of MWNT concentrations and temperatures were measured, and compared. The sensing response was the maximum at an operating temperature near 400 degrees C for all the samples irrespective of the MWNTs dispersed over them. At optimum operating temperature (T(opt)) of 407 +/- 1 degrees C, the response is linear for 100-700 ppm range and tends to saturate at higher concentrations. In comparison with bare CuO sample, the response of CuO/MWNT sensing films increased up to 50% in the linear range. The response improvement for 2500 ppm of ethanol was up to 90% compared to bare CuO sample. In addition, the sensing response time also reduced to around 23% for lowest ethanol concentration at T(opt). However, a decrease in the sensor response was observed on films with very high concentrations of MWNTs. (C) 2011 Elsevier B.V. All rights reserved.

Bio-Composite Membrane Electrolytes for Direct Methanol Fuel Cells

A new class of bio-composite polymer electrolyte membranes comprising chitosan (CS) and certain biomolecules in particular, plant hormones such as 3-indole acetic acid (IAA), 4-chlorophenoxy acetic acid (CAA) and 1-naphthalene acetic acid (NAA) are explored to realize proton-conducting bio-composite membranes for application in direct methanol fuel cells (DMFCs). The sorption capability, proton conductivity and ion-exchange capacity of the membranes are characterized in conjunction with their thermal and mechanical behaviour. A novel approach to measure the permeability of the membranes to both water and methanol is also reported, employing NMR imaging and volume localized NMR spectroscopy, using a two compartment permeability cell. A DMFC using CS-IAA composite membrane, operating with 2M aqueous methanol and air at 70 degrees C delivers a peak power density of 25 mW/cm(2) at a load current density of 150 mA/cm(2). The study opens up the use of bio-compatible membranes in polymer-electrolyte-membrane fuel cells. (C) 2011 The Electrochemical Society. [DOI: 10.1149/2.030111jes] All rights reserved.

Fuel Cell Efficiency Redefined; Carnot Limit Reassessed

There are deficiencies in current definition of thermodynamic efficiency of fuel cells (ηcth = ΔG/ΔH); efficiency greater than unity is obtained when AS for the cell reaction is positive, and negative efficiency is obtained for endothermic reactions. The origin of the flow is identified. A new definition of thennodynamic efficiency is proposed that overcomes these limitations. Consequences of the new definition are examined. Against the conventional view that fuel cells are not Carnot limited, several recent articles have argued that the second law of thermodynamics restricts fuel cell energy conversion in the same way as heat engines. This controversy is critically examined. A resolution is achieved in part from an understanding of the contextual assumptions in the different approaches and in part from identifying some conceptual limitations.

Dispersion and vaporization of biofuels and conventional fuels in a crossflow pre-mixer

In lean premixed pre-vaporized (LPP) combustion, controlled atomization, dispersion and vaporization of different types of liquid fuel in the premixer are the key factors required to stabilize the combustion process and improve the efficiency. The dispersion and vaporization process for biofuels and conventional fuels sprayed into a crossflow pre-mixer have been simulated and analyzed with respect to vaporization rate, degree of mixedness and homogeneity. Two major biofuels under investigation are Ethanol and Rapeseed Methyl Esters (RME), while conventional fuels are gasoline and jet-A. First, the numerical code is validated by comparing with the experimental data of single n-heptane and decane droplet evaporating under both moderate and high temperature convective air now. Next, the spray simulations were conducted with monodispersed droplets with an initial diameter of 80 mu m injected into a turbulent crossflow of air with a typical velocity of 10 m/s and temperature of around 800K. Vaporization time scales of different fuels are found to be very different. The droplet diameter reduction and surface temperature rise were found to be strongly dependent on the fuel properties. Gasoline droplet exhibited a much faster vaporization due a combination of higher vapor pressure and smaller latent heat of vaporization compared to other fuels. Mono-dispersed spray was adopted with the expectation of achieving more homogeneous fuel droplet size than poly-dispersed spray. However, the diameter histogram in the zone near the pre-mixer exit shows a large range of droplet diameter distributions for all the fuels. In order to improve the vaporization performance, fuels were pre-heated before injection. Results show that the Sauter mean diameter of ethanol improved from 52.8% of the initial injection size to 48.2%, while jet-A improved from 48.4% to 18.6% and RME improved from 63.5% to 31.3%. The diameter histogram showed improved vaporization performance of jet-A. (C) 2011 Elsevier Ltd. All rights reserved.