The conversion of carbonaceous materials to electricity in a Direct Carbon Fuel Cell (DCFC) offers the most efficient process with theoretical electric efficiency close to 100%. One of the key issues ...for fuel cells is the continuous availability of the fuel at the triple phase boundaries between fuel, electrode and electrolyte. While this can be easily achieved with the use of a porous fuel electrode (anode) in the case of gaseous fuels, there are serious challenges for the delivery of solid fuels to the triple junctions. In this paper, a novel concept of using mixed ionic electronic conductors (MIEC) as anode materials for DCFCs has been discussed. The lanthanum strontium cobalt ferrite, La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF) was chosen as the first generation anode material due to its well known high mixed ionic and electronic conductivities in air. This material has been investigated in detail with respect to its conductivity, phase and microstructural stability in DCFC operating environments. When used both as the anode and cathode in a DCFC, power densities in excess of 50 mW/cm2 were obtained at 804 °C in electrolyte supported small button cells with solid carbon as the fuel. The concept of using the same anode and cathode material has also been evaluated in electrolyte supported thick wall tubular cells where power densities around 25 mW/cm2 were obtained with carbon fuel at 820 °C in the presence of helium as the purging gas. The concept of using a mixed ionic electronic conducting anode for a solid fuel, to extend the reaction zone for carbon oxidation from anode/electrolyte interface to anode/solid fuel interface, has been demonstrated.
The article professes the use of mixed ionic/electronic conducting (MIEC anode to extend the reaction zone for carbon oxidation from anode/electrolyte interface to anode/solid fuel interface for continuous operation of the direct carbon fuel cell. This type of fuel cell and operation mode offer the highest efficiency for direct conversion of carbon from coal or biomass to electricity. Display omitted
► A new concept of using mixed ionic electronic conducting (MIEC) anode in DCFC. ► MIEC extends reaction zone for solid carbon fuel to external surface of anode. ► The concept of MIEC anode demonstrated in button and tubular cells with good performance. ► Synchrotron high resolution XRD identified phases not shown by normal X-ray diffractometer. ► LSCF fully characterised for phase assemblage and electrical conductivity.
Despite intensive research, hydrogels currently available for tissue repair in the musculoskeletal system are unable to meet the mechanical, as well as the biological, requirements for successful ...outcomes. Here we reinforce soft hydrogels with highly organized, high-porosity microfibre networks that are 3D-printed with a technique termed as melt electrospinning writing. We show that the stiffness of the gel/scaffold composites increases synergistically (up to 54-fold), compared with hydrogels or microfibre scaffolds alone. Modelling affirms that reinforcement with defined microscale structures is applicable to numerous hydrogels. The stiffness and elasticity of the composites approach that of articular cartilage tissue. Human chondrocytes embedded in the composites are viable, retain their round morphology and are responsive to an in vitro physiological loading regime in terms of gene expression and matrix production. The current approach of reinforcing hydrogels with 3D-printed microfibres offers a fundament for producing tissue constructs with biological and mechanical compatibility.
In situ synchrotron X-ray diffraction was used to follow the formation of corrosion products on carbon steel in CO2 saturated NaCl solution and mixed NaCl/magnesium chloride (MgCl2) at 80 degree C. ...Siderite (FeCO3) was the only phase formed in NaCl solution, while Fe(OH)2CO3 was also detected when MgCl2 was present. The proposed model is that siderite precipitation, occurring once the critical supersaturation was exceeded within a defined boundary layer, caused local acidification which accelerated the anodic dissolution of iron. The current fell once a complete surface scale was formed. It is suggested that MgCl2 addition decreased the required critical supersaturation for precipitation.
Glassy metals exhibit a range of interesting properties including high strength and corrosion resistance, but often have poor toughness and tensile ductility in the fully amorphous state. It has been ...shown that combinations of desirable properties can be achieved by the partial crystallisation of glass-forming alloys, either during controlled solidification or by annealing a fully amorphous glass. The aim of this investigation is to understand the competition in phase formation during the crystallisation of metallic glasses in the Al-Ni-Y system. High-resolution, in situ synchrotron powder diffraction has been used to quantitatively follow the evolution of phases in 5 different alloys between Al87Ni9Y4 and Al75Ni15Y10, as they were continuously heated to melting and subsequently cooled back to ambient temperature. Upon heating, the first crystallisation product was found to vary from FCC Al to the intermetallic Al9Ni2 phase with increasing Ni concentration. In addition, the crystallisation sequence also changed from a two-stage to a three-stage process. High number densities of crystallites (∼1023 m−3) were observed initially for both FCC Al and Al9Ni2. Upon cooling, the partially disordered Al9Ni3Y phase was found to form preferentially over the intermetallic phases observed during heating. The difference in competition in phase formation during heating and cooling are discussed in terms of nucleation barriers calculated using a recent thermodynamic assessment of the Al-Ni-Y system. The role of compositional heterogeneities in the as-quenched glasses and long-range diffusion on the nucleation process is discussed.
High-resolution, in situ synchrotron powder diffraction has been used to quantitatively follow the evolution of phases in 5 different alloys between Al87Ni9Y4 and Al75Ni15Y10, as they were continuously heated to melting and subsequently cooled back to ambient temperature. Upon heating, the first crystallisation product was found to vary from FCC Al to the intermetallic Al9Ni2 phase with increasing Ni concentration. In addition, the crystallisation sequence also changed from a two-stage to a three-stage process. High number densities of crystallites (∼1023 m−3) were observed initially for both FCC Al and Al9Ni2. The difference in competition in phase formation during heating and cooling are discussed in terms of nucleation barriers calculated using a recent thermodynamic assessment of the Al-Ni-Y system. The role of compositional heterogeneities in the as-quenched glasses and long range diffusion on the nucleation process is discussed. Display omitted
We report a new test of quantum electrodynamics (QED) for the w (1s2p(1)P(1)→1s(2)(1)S(0)) x-ray resonance line transition energy in heliumlike titanium. This measurement is one of few sensitive to ...two-electron QED contributions. Systematic errors such as Doppler shifts are minimized in our experiment by trapping and stripping Ti atoms in an electron beam ion trap and by applying absolute wavelength standards to calibrate the dispersion function of a curved-crystal spectrometer. We also report a more general systematic discrepancy between QED theory and experiment for the w transition energy in heliumlike ions for Z>20. When all of the data available in the literature for Z=16-92 are taken into account, the divergence is seen to grow as approximately Z(3) with a statistical significance on the coefficient that rises to the level of 5 standard deviations. Our result for titanium alone, 4749.85(7) eV for the w line, deviates from the most recent ab initio prediction by 3 times our experimental uncertainty and by more than 10 times the currently estimated uncertainty in the theoretical prediction.
Purpose
Diffusion magnetic resonance imaging (dMRI) studies report altered white matter (WM) development in preterm infants. Neurite orientation dispersion and density imaging (NODDI) metrics provide ...more realistic estimations of neurite architecture in vivo compared with standard diffusion tensor imaging (DTI) metrics. This study investigated microstructural maturation of WM in preterm neonates scanned between 25 and 45 weeks postmenstrual age (PMA) with normal neurodevelopmental outcomes at 2 years using DTI and NODDI metrics.
Methods
Thirty-one neonates (
n
= 17 male) with median (range) gestational age (GA) 32
+1
weeks (24
+2
–36
+4
) underwent 3 T brain MRI at median (range) post menstrual age (PMA) 35
+2
weeks (25
+3
–43
+1
). WM tracts (cingulum, fornix, corticospinal tract (CST), inferior longitudinal fasciculus (ILF), optic radiations) were delineated using constrained spherical deconvolution and probabilistic tractography in MRtrix3. DTI and NODDI metrics were extracted for the whole tract and cross-sections along each tract to assess regional development.
Results
PMA at scan positively correlated with fractional anisotropy (FA) in the CST, fornix and optic radiations and neurite density index (NDI) in the cingulum, CST and fornix and negatively correlated with mean diffusivity (MD) in all tracts. A multilinear regression model demonstrated PMA at scan influenced all diffusion measures, GA and GAxPMA at scan influenced FA, MD and NDI and gender affected NDI. Cross-sectional analyses revealed asynchronous WM maturation within and between WM tracts.).
Conclusion
We describe normal WM maturation in preterm neonates with normal neurodevelopmental outcomes. NODDI can enhance our understanding of WM maturation compared with standard DTI metrics alone.
A recent 15 parts per million (ppm) experiment on muonic hydrogen ( ) found a major discrepancy with quantum electrodynamics (QED) and independent nuclear size determinations. Here we find a ...significant discrepancy in a different type of exotic atom: a medium-Z nucleus with two electrons. Investigation of the data collected is able to discriminate between available QED formulations and reveals a pattern of discrepancy of almost six standard errors of experimental results from the most recent theoretical predictions, with a functional dependence proportional to Zn where . In both the muonic and highly charged systems, the sign of the discrepancy is the same, with the measured transition energy higher than predicted. Some consequences are possible or probable, and some are more speculative. This may give insight into effective nuclear radii, the Rydberg, the fine-structure constant, or unexpectedly large QED terms.
The orthorhombic mineral moolooite, CuC2O4. nH2O, described by Clarke and Williams (1986) using Debye-Scherrer photographic data, has a fully-disordered stacking fault (FDSF) structure. Related ...monoclinic models have been reported for various synthesised samples based on Schmittler (1968). In the present study, synchrotron radiation diffraction data for moolooite and synthesised specimens have been examined with particular reference to crystallographic disorder. The moolooite data correspond to space group Pnnm, with a = 5.3064(2), b = 5.6804(2), c = 2.5630(1) Å; Vc = 77.26(1) Å3; and Z = 1; and the FDSF structure along the b-direction has been confirmed. The synthetic specimen data from the study indicate partial ordering, with space group P21/n; and the cell parameters for one specimen being a = 5.957(7), b = 5.611(5), c = 5.133(7) Å; β = 115.16(2)°; Vc = 155.27 Å3 and Z = 2. The level of zeolitic water in the materials has been considered using the approach of Schmittler based on thermogravimetry and pycnometry. The new data for natural topotype material correspond to CuC2O4.1.0H2O. It is postulated that the level of water for natural and synthetic specimens may be attributed to the conditions under which the material forms.
This paper reports the critical role of microstructural length scale in dealloying for the fabrication of bimodal or monolithic functional nanoporous metal structures and the underlying mechanisms ...and kinetics. Two dual-phased (Al2CuAlCu) precursor alloys Al65Cu35 and Al55Cu45 (at.%) were selected to demonstrate the concept. Microstructural observations revealed that the two constituent phases Al2Cu and AlCu in each alloy can undergo either sequential dealloying, which leads to bimodal nanoporous Cu, or simultaneous dealloying, which results in monolithic nanoporous Cu. In-situ and ex-situ synchrotron X-ray diffraction (XRD), focused ion beam scanning electron microscopy (FIB-SEM), and potentiodynamic polarization scans were used to identify the detailed phase evolution processes and kinetics. It is concluded that microstructural length scale plays a decisive role in regulating the dealloying pathways. Sequential dealloying of Al2Cu and AlCu occurs when both phases are micrometer-scaled, while simultaneous dealloying takes over when both phases are nanoscaled. The nanosize effect of Al2Cu and AlCu can override their intrinsic difference in electrochemical potential at the micro- or macro-scale, and the advantage of tetragonal Al2Cu over monoclinic AlCu in crystallographic transition to face-centered-cubic (FCC) Cu by dealloying. The high-resolution in-situ synchrotron XRD data revealed a two-stage kinetic process for dealloying of Al2Cu to Cu. The Avrami-Erofe′ev kinetic model provides an excellent description of each stage. The underlying rationales and implications are discussed.
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► We studied the scale formation processes of carbon steel in CO
2 saturated brine at 80
°C. ► Protective scales were formed in all tests. ► Only FeCO
3 formed in saturated brine while Fe(OH)
2CO
3 ...detected with presence of MgCl
2. ► MgCl
2 accelerates the onset of siderite precipitation.
In situ synchrotron X-ray diffraction was used to follow the formation of corrosion products on carbon steel in CO
2 saturated NaCl solution and mixed NaCl/magnesium chloride (MgCl
2) at 80
°C. Siderite (FeCO
3) was the only phase formed in NaCl solution, while Fe(OH)
2CO
3 was also detected when MgCl
2 was present. The proposed model is that siderite precipitation, occurring once the critical supersaturation was exceeded within a defined boundary layer, caused local acidification which accelerated the anodic dissolution of iron. The current fell once a complete surface scale was formed. It is suggested that MgCl
2 addition decreased the required critical supersaturation for precipitation.
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