Cobalt-Doped Carbon Nitride Frameworks Obtained from Calcined Aromatic Polyimines as Cathode Catalyst of Anion Exchange Membrane Fuel Cells

Cobalt-doped carbon nitride frameworks (CoNC) were prepared from the calcination of Co-chelated aromatic polyimines (APIM) synthesized from stepwise polymerization of p-phenylene diamine (PDA) and o-phthalaldehyde (OPAl) via Schiff base reactions in the presence of cobalt (II) chloride. The Co-chelated APIM (Co-APIM) precursor converted to CoNC after calcination in two-step heating with the second step performed at 100 °C lower than the first one. The CoNCs demonstrated that its Co, N-co-doped carbonaceous framework contained both graphene and carbon nanotube, as characterized by X-ray diffraction pattern, Raman spectra, and TEM micropictures. CoNCs also revealed a significant ORR peak in the current–voltage polarization cycle and a higher O2 reduction current than that of commercial Pt/C in a linear scanning voltage test in O2-saturated KOH(aq). The calculated e-transferred number even reaches 3.94 in KOH(aq) for the CoNC1000A900 cathode catalyst, which has the highest BET surface area of 393.94 m2 g−1. Single cells of anion exchange membrane fuel cells (AEMFCs) are fabricated using different CoNCs as the cathode catalysts, and CoNC1000A900 demonstrates a peak power density of 374.3 compared to the 334.7 mW cm−2 obtained from the single cell using Pt/C as the cathode catalyst.

Complex ⁴⁰Ar/³⁹Ar age spectra from low metamorphic grade rocks: resolving the input of detrital and metamorphic components in a case study from the Delamerian Orogen

Low metamorphic grade rocks contain both detrital minerals and minerals newly grown or partly recrystallised during diagenesis and metamorphism. However, rocks such as these typically yield complex 40Ar/39Ar age spectra that can be difficult to interpret. In this study, we have analysed a suite of variably deformed rocks from a region of low metamorphic grade within the c. 514–490 Ma Delamerian Orogen, South Australia. The samples analysed range from siltstone and shale to phyllite and all contain either muscovite or phengite determined by hyperspectral mineralogical characterisation. Furnace step heating 40Ar/39Ar analysis produced complex apparent age spectra with multiple age components. Using the concept of asymptotes that define minimum and maximum ages for different components, we interpret the age spectra to preserve a range of detrital mineral ages, along with younger components related to either cooling or deformation- induced recrystallisation. Two samples contain Mesoproterozoic detrital age components, up to c. 1170 Ma, while the c. 515 Ma Heatherdale Shale which has both c. 566 Ma and c. 530 Ma detrital components. All samples contain younger lower (younger) asymptotes in the age spectra defined from multiple heating steps that range from c. 476 to c. 460 Ma. One interpretation of these younger ages is that they are caused by post-metamorphic cooling. However, the shape of the age spectra and the degree of deformation in the phyllites suggest the ages may record recrystallisation of detrital minerals and/or new mica growth during deformation. Potentially these c. 476 to c. 460 Ma ages suggest deformation in the upper portion of the orogen was facilitated by movement along regional faults and shear zones up to around 20 million years after the cessation of deformation in the high-metamorphic grade regions of the Delamerian Orogen.

Experimental investigation and modeling on the dissociation conditions of methane hydrate in clayey silt cores

The dissociation conditions of hydrate in clayey silts are of great significance for its efficient production. In this work, the dissociation conditions of methane hydrate in clayey silt cores were experimentally measured by step-heating method. Various cores including quartz powder, montmorillonite and South China Sea sediments were used for investigation. The results showed that the dissociation temperatures of methane hydrate in clayey silt cores depressed compared to bulk hydrate. In comparison to grain size, salinity and lithology had a more significant influence on the equilibrium temperature depression. A water activity meter was used to measure the water activity in clayey silt cores. The influence of salt and minerals on water activity was investigated. By combining the measured water activity data with the Chen-Guo model, a novel water activity measurement method (WAM) for the hydrate dissociation conditions prediction was proposed. The predicted results are in good agreement with the experimental data.

Deformation recorded in polyhalite from evaporite detachments revealed by ⁴⁰Ar ∕ ³⁹Ar dating

The Salt Range Formation is an extensive evaporite sequence in northern Pakistan that has acted as the primary detachment accommodating Himalayan orogenic deformation from the north. This rheologically weak formation forms a mylonite in the Khewra Mine, where it accommodates approximately 40 km displacement and is comprised of intercalated halite and potash salts and gypsiferous marls. Polyhalite [K2Ca2Mg(SO4)4⚫2H2O] grains taken from potash marl and crystalline halite samples are used as geochronometers to date the formation and identify the closure temperature of the mineral polyhalite using the 40Ar/39Ar step-heating laser and furnace methods. The diffusion characteristics measured for two samples of polyhalite are diffusivity (D0), activation energy (Ea), and %39Ar. These values correspond to a closure temperature of ca. 254 and 277 ∘C for a cooling rate of 10 ∘C Myr−1. 40Ar/39Ar age results for both samples did not return any reliable crystallisation age. This is not unexpected as polyhalite is prone to 40Ar* diffusion loss and the evaporites have experienced numerous phases of deformation resetting the closed K/Ar system. An oldest minimum heating step age of ∼514 Ma from sample 06-3.1 corresponds relatively well to the established early Cambrian age of the formation. Samples 05-P2 and 05-W2 have measured step ages and represent a deformation event that partially reset the K/Ar system based on oldest significant ages between ca. 381 and 415 Ma. We interpret the youngest measured step ages, between ca. 286 and 292 Ma, to represent the maximum age of deformation-induced recrystallisation. Both the youngest and oldest measured step ages for samples 05-P2 and 05-W2 occur within the time of a major unconformity in the area. These dates may reflect partial resetting of the K/Ar system from meteoric water infiltration and recrystallisation during this non-depositional time. Otherwise, they may result from mixing of Ar derived by radiogenic decay after Cambrian precipitation with partially reset Ar from pervasive Cenozoic deformation and physical recrystallisation.

Preparation of Transparent MgAl2O4 Spinel by Pulsed Electric Current Sintering Using Two-step Heating Method

Transparent MgAl2O4 ceramics were fabricated by pulsed electric current sintering (PECS) employing two-step sintering mode. First, nanoscale MgAl2O4 powders were produced by solution combustion synthesis from hydrated nitrate compounds and urea. Subsequently, the synthesized powders were sintered by PECS with a heating rate of 100oC/min under an applied pressure of 100 MPa. The sintering process was conducted according to two-step heating profile. At the first step, the temperature increased to 1050, 1100, and 1150oC, followed by a dwell time of 60 min. The second-step sintering was carried out at 1300, 1350, and 1400oC for 20 min. The transparent ceramics sintered at 1050oC/ 60 min – 1400oC/ 20 min exhibited transmittance over 80% in infrared range. In addition, transparent samples presented a Vickers hardness up to 30 GPa for sintering mode of 1150oC/ 60 min – 1400oC/ 20 min.

Well-Constrained Mineralization Ages by Integrated 40Ar/39Ar and U-Pb Dating Techniques for the Xitian W-Sn Polymetallic Deposit, South China

Mineralization ages of many mineral deposit types (such as orogenic Au, stratabound Cu, and Mississippi Valley-type Pb-Zn deposits) are still difficult to date by the traditional isotopic chronometry because of the lack of suitable minerals. We have made efforts to establish a widely suitable dating technique to determine ore formation ages using a high-precision 40Ar/39Ar method on ubiquitously present fluid inclusions in quartz, sphalerite, and other nonpotassium minerals from hydrothermal deposits. The Xitian W-Sn polymetallic deposit in central South China contains several minerals suitable for isotopic dating for interchronometer comparison. 40Ar/39Ar laser step heating of 16 micas from ore veins, greisen, and metallogenic granites yields flat age spectra and thus well-defined ore formation ages ranging from 152.4 ± 1.5 (2σ) to 148.1 ± 1.4 Ma with an average of 150.2 ± 0.6 Ma. 40Ar/39Ar progressive crushing of nine quartz samples produces well-defined isochron lines for their primary fluid inclusions corresponding to isochron ages of 153.7–149.9 Ma with an average of 151.6 ± 0.6 Ma. Cassiterites from three hand specimens have weighted mean 206Pb/238U ages of 151.5 ± 1.7 (2σ), 149.7 ± 2.1, and 151.7 ± 2.1 Ma. All these new geochronological dates and previous molybdenite Re-Os ages yield well-constrained mineralization ages of 153–148 Ma for the Xitian W-Sn polymetallic deposit, which also confirms conclusively that the quartz 40Ar/39Ar progressive crushing technique is a feasible, valid dating technique. Furthermore, significant age information on the secondary fluid inclusions is potentially obtained simultaneously by this technique. We expect that this novel dating technique will be widely applied to determine the geologic fluids trapped in minerals during hydrothermal mineralization, hydrocarbon accumulation, metamorphism, tectonic activities, and other geologic processes.