Study on the characteristics of evaporation–atomization–combustion of biodiesel

A great deal of research is being carried out on renewable diesel fuels. The number of raw materials (especially waste, animal, and vegetable oils), production technologies, and additives of biodiesel is increasing. In our work, a evaporation–atomization–combustion system consisting of a biomass liquid fuel was designed to produce a laminar premixed flame for studying the combustion–emission characteristics of biodiesel. The combustion characteristics of biodiesel including flame height, flame front area, flame speed, and OH total signal intensity were studied by planar laser-induced fluorescence of OH (OH-PLIF). The emission characteristics of biodiesel (CO, CO₂, and NO) were studied with a flue gas analyzer. The experimental results showed that the flame height, flame front area, flame speed, and the OH total signal intensity changed with the equivalence ratio (Φ). The relationship between the OH radical intensity and the emission of CO/CO₂ was obtained from the OH-PLIF average signal intensity. The [CO]/[CO₂] ratio decreased with the OH-PLIF average signal intensity. Finally, we obtained the relationship between the OH-PLIF average signal intensity and the NO emissions.     

Nanoindentation of palladium–hydrogen

Nanoindentation has been utilised to track the mechanical effects of hydrogen on palladium foils over a range of hydrogen concentrations. The miscibility gap in the palladium–hydrogen system yields discrete phases over a range of compositions. It is shown that nanoindentation can measure the extent of hydrogen-induced phase transformations across the film thickness after hydrogen removal, with the α → β → α phase transformations yielding a ∼50% increase in local hardness. Interstitial hydrogen was observed to promote work hardening in β phase regions, and a ∼75% increase in hardness was observed in regions where the α phase was saturated with hydrogen.     

Effect of Mo–Ni treatment on electrochemical kinetics of La–Mg–Ni-based hydrogen storage alloys

In order to improve kinetic properties of La–Mg–Ni-based hydrogen storage alloys, Mo–Ni treatment was applied to La_0.88Mg_0.12Ni_2.95Mn_0.10Co_0.55Al_0.10 alloy powders. FESEM results showed that after Mo–Ni treatment some network-shaped substance with nano-size formed on the surface of the alloy particles. The EDS results revealed increase in Ni content and emerge of Mo element. EIS and Linear polarization showed that charge-transfer resistance decreased and exchange current density increased for the treated alloy electrode, and the high rate dischargeability (HRD) was consequently improved. HRD at 1500 mA/g increased from 22.5% to 39.5%. Mo- and Ni-single treatments were performed compared with the Mo–Ni treatment, and the results showed that the single treatment improved HRD slightly, far less than the Mo–Ni treatment.     

Function of Al on the cycling behavior of the La–Mg–Ni–Co-type alloy electrodes

The cycling behavior of the _{La0.7Mg0.3Ni2.65-xCo0.75Mn0.1Alx}${\mathrm{La}}_{0.7}{\mathrm{Mg}}_{0.3}{\mathrm{Ni}}_{2.65-x}{\mathrm{Co}}_{0.75}{\mathrm{Mn}}_{0.1}{\mathrm{Al}}_x$(x=0,0.3)$(x=0,0.3)$ alloy electrodes was systematically investigated by XRD, SEM, EIS, XPS and AES measurements, and the function of Al in the La–Mg–Ni-based alloys and the reasons for the improvement of the cycling stability of the alloy electrode with Al were discussed. Results show that the cycling behavior of the _{La0.7Mg0.3Ni2.35Co0.75Mn0.1Al0.3}${\mathrm{La}}_{0.7}{\mathrm{Mg}}_{0.3}{\mathrm{Ni}}_{2.35}{\mathrm{Co}}_{0.75}{\mathrm{Mn}}_{0.1}{\mathrm{Al}}_{0.3}$ alloy electrode can be divided into three stages, i.e., the pulverization and Mg oxidation stage, the Mg oxidation and La and/or Al oxidation stage, and the La and Al oxidation and Al oxide film protection stage. The improvement of the cycling stability of the alloy electrode with Al can be ascribed to two factors. One is the decrease in the pulverization of the alloy particles during charge/discharge cycling due to the alloy with Al undergoes a smaller cell volume expansion and contraction. The other is the increase in the anti-oxidation/corrosion due to the formation of a dense Al oxide film during cycling, which is believed to be the most important reason for the improvement of the cycling stability of the La–Mg–Ni–Co–Mn–Al-type alloy electrodes.     

Optimization of the Pd–Sn–GNS nanocomposite for enhanced electrooxidation of methanol

Highly dispersed Pd nanoparticles with varying loadings (15–40 wt%) and (20 − x)%Pd–x%Sn (where x = 1, 2, 3 and 5) nanocomposites are obtained on graphene nanosheets (GNS) by a microwave-assisted ethylene glycol (EG) reduction method for methanol electrooxidation in alkaline solution. The electrocatalysts were characterized by XRD, SEM, TEM, cyclic voltammetry, and chronoamperometry. The study shows that the Pd nanoparticles on GNS are crystalline and follow the face centered cubic structure. Introduction of a small amount of Sn (1–5 wt%) shifts the characteristic diffraction peaks for Pd slightly to a lower angle. The electrocatalytic performance of the Pd/GNS electrodes has been observed to be the best with 20 wt% Pd loading; a higher or lower loading than 20 wt% Pd produces an electrode with relatively low catalytic activity. The apparent catalytic activity of this active electrode at E = −0.10 V is found to improve further by 79% and CO poisoning tolerance by 40% with introduction of 2 wt% Sn. Among the electrodes investigated, the 18%Pd–2%Sn/GNS exhibited the greatest electrocatalytic activity toward methanol electrooxidation.     

Electrochemical hydrogen storage performance of Mg–Ti–Zr–Ni alloys

Mg_1.5Ti_0.5−xZr_xNi (x = 0, 0.1, 0.2, 0.3, 0.4), Mg_1.5Ti_0.3Zr_0.1Pd_0.1Ni and Mg_1.5Ti_0.3Zr_0.1Co_0.1Ni alloys were synthesized by mechanical alloying and their electrochemical hydrogen storage characteristics were investigated. X-ray diffraction studies showed that all the replacement elements (Ti, Zr, Pd and Co) perfectly dissolved in the amorphous phase and Zr facilitated the amorphization of the alloys. When the Zr/Ti ratio was kept at 1/4 (Mg_1.5Ti_0.4Zr_0.1Ni alloy), the initial discharge capacity of the alloy increased slightly at all the ball milling durations. The further increase in the Zr/Ti ratio resulted in reduction in the initial discharge capacity of the alloys. The presence of Zr in the Ti-including Mg-based alloys improved the cyclic stability of the alloys. This action of Zr was attributed to the less stable and more porous characteristics of the barrier hydroxide layer in the presence of Zr due to the selective dissolution of the disseminated Zr-oxides throughout the hydroxide layer on the alloy surface. Unlike Co, the addition of Pd into the Mg–Ti–Zr–Ni type alloy improved the alloy performance significantly. The positive contribution of Pd was assumed to arise from the facilitated hydrogen diffusion on the electrode surface in the presence of Pd. As the Zr/Ti atomic ratio increased, the charge transfer resistance of the alloy decreased at all the depths of discharges. Co and Pd were observed to increase the charge transfer resistance of the Mg–Ti–Zr–Ni alloys slightly.     

Effects of hydrogen concentration on premixed laminar flames of hydrogen–methane–air

The unstretched laminar burning velocities and Markstein numbers of spherically propagating hydrogen–methane–air flames were studied at a mixture pressure of 0.10 MPa and a mixture temperature of 350 K. The fraction of hydrogen in the binary fuel was varied from 0 to 1.0 at equivalence ratios of 0.8, 1.0 and 1.2. The unstretched laminar burning velocity increased non-linearly with hydrogen fraction for all the equivalence ratios. The Markstein number varied non-monotonically at equivalence ratios of 0.8 and 1.0 and increased monotonically at equivalence ratio of 1.2 with increasing hydrogen fraction. Analytical evaluation of the Markstein number suggested that the trends could be due to the effective Lewis number, which varied non-monotonically with hydrogen fraction at equivalence ratios of 0.8 and 1.0 and increased monotonically at 1.2. The propensity of flame instability varied non-monotonically with hydrogen fraction at equivalence ratios of 0.8 and 1.0.     

Crystallographic and electrochemical characteristics of melt-spun Ti–Zr–Ni–Y alloys

Ti₄₅Zr₃₀Ni₂₅Y_x (x = 1, 3, 5 and 7) alloys were prepared by melt-spinning at wheel velocity of 20 m s⁻¹. The effect of additive Y on phase structure and electrochemical performance of melt-spun alloys was investigated. Ti₄₅Zr₃₀Ni₂₅Y_x melt-spun alloys were composed of I-phase and amorphous phase. The amorphous phase increased with increasing x value, indicating amorphous forming ability improved with increasing Y content. The maximum discharge capacity and high-rate dischargeability decreased with increasing x value, which may be ascribed to the decrease of nickel content. Cycling stability first increased with increasing x from 1 to 3, and then decreased when x increased to 7, which was resulted from the combined effect of the decrease of nickel content and the increase of amorphous phase.     

Effect of V content on hydrogen storage properties and cyclic durability of V–Ti–Cr–Fe alloys

Vanadium-based body-centered-cubic (BCC) alloys are ideal hydrogen storage media because of their high reversible hydrogen capacities at moderate conditions. However, the rapid capacity decay in hydrogen ab-/desorption cycles prevents their practical application. In this work, V-based BCC alloys with three different V contents (V₂₀Ti₃₈Cr_41.4Fe_0.6, V₄₀Ti_28.5Cr_30.1Fe_1.4, V₆₀Ti₁₉Cr₁₉Fe₂, named as V20, V40, V60) were prepared by arc melting, and their microstructures and hydrogen ab-/desorption properties were investigated systematically. XRD results show that there is a number of C15-Laves phase presence in V20, which does not appear in V40 and V60. Meanwhile, the lattice constant of the BCC phase clearly decreases as the V content rises. These differences result in a hydrogen storage capacity of only 1.82 wt% for V20 alloy, but 2.13 wt% for V40 and 2.14 wt% for V60, and an increment in hydrogen ab-/desorption plateau pressure. The V40 and V60 alloys are chosen in de-/hydrogenation cycle test owing to higher effective storage capacities, and the results show that the V60 alloy has better cycle durability. According to the microstructural analysis of the two alloys during the cycles, the micro-strain accumulates, the cell volume expands, the particles pulverizes and the defects increase during the cycles, which eventually lead to the attenuation of the hydrogen storage capacity. The increment of the V content obviously improves the elastic properties of the alloy, which further diminishes the micro-strain accumulation, cell volume expansion, particle pulverization and defect increase, eventually resulting in a higher capacity retention and better cyclic durability.     

Synthesis and electrochemical properties of layered Li–Ni–Mn–O compounds

An attempt to prepare solid solutions in the system of LiNiO₂, LiMnO₂ and Li₂MnO₃ was performed by heating metal acetates. The solid solutions between end members LiNiO₂ and Li₂MnO₃ can be successfully prepared in the overall compositional ranges. Both the structure and capacity were compared based on Rietveld analysis and electrochemical investigation on solid solutions between LiNiO₂ and Li₂MnO₃. The result showed that the cationic disorder as well as capacity was closely related to the ratio of Li, Mn and Ni in formula. The investigation of chronopotentiogram and ex situ XRD on the solid solutions indicated that the complex phase transitions in LiNiO₂ during delithiation were strongly suppressed with low Mn content (Mn/(Mn+Ni) ratio was 0.1 or 0.2) and completely suppressed with the ratio more than 0.5.     

Crystallographic and electrochemical characteristics of Ti–Zr–Ni–Pd quasicrystalline alloys

Ti₄₅Zr₃₅Ni_20−xPd_x (x = 0, 1, 3, 5 and 7, at%) alloys were prepared by melt-spinning. The phase structure and electrochemical hydrogen storage performances of melt-spun alloys were investigated. The melt-spun alloys were icosahedral quasicrystalline phase, and the quasi-lattice constant increased with increasing x value. The maximum discharge capacity of alloy electrodes increased from 79 mAh/g (x = 0) to 148 mAh/g (x = 7). High-rate dischargeability and cycling stability were also enhanced with the increase of Pd content. The improvement in the electrochemical hydrogen storage characteristics may be ascribed to better electrochemical activity and oxidation resistance of Pd than that of Ni.     

Hydrogen storage properties of Nb–Hf–Ni ternary alloys

The hydrogen storage properties of Nb_xHf_(1−x)/2Ni_(1−x)/2 (x = 15.6, 40) alloys were investigated with respect to their hydrogen absorption/desorption, thermodynamic, and dynamic characteristics. The PCT curves show that all the specimens can absorb hydrogen at 303 K, 373 K, 423 K, 473 K, 523 K, 573 K, and 673 K, but they couldn't desorb hydrogen below 373 K. The maximum hydrogen absorption capacity reaches 1.23 wt.% for Nb_15.6Hf_42.2Ni_42.2 and 1.48 wt.% for Nb₄₀Hf₃₀Ni₃₀ at 303 K at a pressure of 3 MPa. When the temperature was increased, the hydrogen absorption capacities significantly decreased. However, the hydrogen equilibrium pressure increased. When the temperature exceeded 523 K, the hydrogen equilibrium pressure disappeared. When niobium content was increased, the kinetic properties of hydrogen absorption/desorption improved. The results from the microstructure analysis show that both alloys consist of the BCC Nb-based solid solution phase, the B_f-HfNi intermetallic phase, and the eutectic phase {B_f-HfNi + BCC Nb-based solid solution}. When the Nb content was increased, the volume fraction and Nb content in the Nb-based solid solution phase increased. Thus, the improved kinetics is related to the increase in the primary BCC Nb-based solid solution in the Nb₄₀Hf₃₀Ni₃₀ alloy. The kinetic mechanisms of hydrogen absorption/desorption in these two alloys are found to obey the chemical reaction mechanism at all temperatures tested.     

Energy–exergy optimization of comminution

The comminution process has exceedingly low efficiency because it is highly irreversible. An outline of energy analysis for comminution is presented. The application refers to an ore-processing plant, which consists of a series of crushers feeding a traditional ball mill that delivers products to a downstream metallurgical process. For optimization, the design characteristics are fixed, i.e. decision variables can only be operational parameters. The chosen decision variable is the size of the feed (F) to the mill. In practice, the mill operator may control the feed granulometry and keep the product size constant by using a constant ball charge. The objective cost function is the sum of energy costs at the crusher and mill, which depend only on F. The exergy consumption of the crusher and mill are evaluated using the Bond correlation, including pertinent correction factors. Optimization leads to a 10% saving in overall energy costs.     

Tuning of electrocatalytic activity of Mn–O–Co composite for alkaline hydrogen evolution reaction

We report the enhancement in electrocatalytic activity of Mn–O–Co composite electrode developed through chemical reduction method. The Mn–O–Co composite electrode exhibits high catalytic activity with a low Tafel slope of 123 mV dec⁻¹ and a low overpotential of 117 mV at a current density of 10 mA cm⁻². The enhancement in electrocatalytic activity of Mn–O–Co composite electrode is due to the synergistic activity of MnO and CoO with the NiP matrix. The intermetallic interaction among the half-filled orbitals of manganese with the fully occupied orbitals of cobalt and nickel leads to an effective electron delocalization in the catalytic system which enhances the HER performance of the coating. The C_dl value of the composite electrode is in the order of 254 μF, which is approximately ten fold higher than the bare NiP coating, due to the enhancement in interaction between the Mn–O–Co composite electrode and the reactive species in the HER medium. The Mn–O–Co composite electrode shows promising characteristics as an electrocatalyst with long term stability and remarkable competency with the commercially available electrodes.     

Measurement of fracture toughness transition behaviour of Cr–Ni–Mo–V pressure vessel steel using pre-cracked Charpy specimens

The potential application of small pre-cracked Charpy specimens for the prediction of the fracture toughness of the 1T-thickness specimens and the reference temperature T₀ has been examined. Transition fracture behaviour of plane sided, side-grooved and 1T SENB specimens, respectively, was investigated over a wide temperature range. The fracture toughness regions with various fracture initiation mechanisms were defined and ductile to brittle transition temperatures denoted. The fracture toughness transition region of small pre-cracked specimens was shifted to lower temperatures as compared with that of 1T SENB specimens. The fracture toughness data of small pre-cracked specimens have been size corrected (weakest link) to 1T thickness and used to establish the reference temperature T₀ and K_Jc(mean) fracture toughness vs. temperature curve. The calculated temperature T₀ has been in consistence with that of the 1T SENB specimen. However, some corrected fracture toughness data lay outside the scatter band of 1T thickness specimens and the shape of the K_Jc(mean) curve has been quite different from the K_Jc(med)(1T) curve. It was found out that the original measured fracture toughness results of corrected data points lying outside the scatter band violated the validity condition b₀R_p0.2/J_c≥30. Bearing in mind the work of Koppenhoefer and Dodds Jr. (Engng Fract Mechanics (1997);58:249–270), and the most recent analysis of Ruggieri et al. (Engng Fract Mechanics (1998);60:19–36), the fracture data of small pre-cracked specimens having the validity parameter lower than 50 have been first constraint adjusted using the cleavage fracture toughness scaling model of Dodds and coworkers (J Testing Evaluation (1991);19:123–134; Int J Fracture (1995); 74:131–161; Engng Fract Mechanics (1997);58:249–270), and only then size corrected. The K_Jc(mean) curve of such treated data was identical with K_Jc(med)(1T).     

Fabrication–microstructure–performance relationships of reversible solid oxide fuel cell electrodes–review

Abstract

A reversible solid oxide fuel cell system can act as an energy storage device by storing energy in the form of hydrogen and heat, buffering intermittent supplies of renewable electricity such as tidal and wave generation. The most widely used electrodes for the cell are lanthanum strontium manganate–yttria stabilised zirconia and Ni–yttria stabilised zirconia. Their microstructure depends on the fabrication techniques, and determines their performance. The concept and efficiency of reversible solid oxide fuel cells are explained, along with cell geometry and microstructure. Electrode fabrication techniques such as screen printing, dip coating and extrusion are compared according to their advantages and disadvantages, and fuel cell system commercialisation is discussed. Modern techniques used to evaluate microstructure such as three-dimensional computer reconstruction from dual beam focused ion beam–scanning electron microscopy or X-ray computed tomography, and computer modelling are compared. Reversible cell electrode performance is measured using alternating current impedance on symmetrical and three electrode cells, and current/voltage curves on whole cells. Fuel cells and electrolysis cells have been studied extensively, but more work needs to be done to achieve a high performance, durable reversible cell and commercialise a system.