Revealing Hydrogen States in Carbon Structures by Analyzing the Thermal Desorption Spectra

An effective methodology for the detailed analysis of thermal desorption spectra (TDS) of hydrogen in carbon structures at micro- and nanoscale was further developed and applied for a number of TDS data of one heating rate, in particular, for graphite materials irradiated with atomic hydrogen. The technique is based on a preliminary description of hydrogen desorption spectra by symmetric Gaussians with their special processing in the approximation of the first- and the second-order reactions. As a result, the activation energies and the pre-exponential factors of the rate constants of the hydrogen desorption processes are determined, analyzed and interpreted. Some final verification of the results was completed using methods of numerical simulation of thermal desorption peaks (non-Gaussians) corresponding to the first- and the second-order reactions. The main research finding of this work is a further refinement and/or disclosure of poorly studied characteristics and physics of various states of hydrogen in microscale graphite structures after irradiation with atomic hydrogen, and comparison with the related results for nanoscale carbon structures. This is important for understanding the behavior and relationship of hydrogen in a number of cases of high energy carbon-based materials and nanomaterials.

On the Mechanism of Methane Conversion in the Nonсatalytic Processes of Its Thermal Pyrolysis and Steam and Carbon Dioxide Reforming

A detailed kinetic modeling of the noncatalytic processes of thermal pyrolysis and steam and carbon dioxide reforming of methane revealed almost completely identical kinetics of the methane conversion in these processes. This suggests that, in the temperature range 1400–1800 K, the initial stage of conversion of methane in all these processes is its thermal pyrolysis. The modeling results agree well with the experimental data on methane pyrolysis. For the temperature range examined, the Arrhenius expressions (pre-exponential factors and activation energy) were obtained in the first-order kinetics approximation for the rate of methane conversion in the processes studied. The expressions derived may be useful for making preliminary estimates and carrying out engineering calculations.

Quantitative evaluation of the non-thermal effect in microwave induced polymer curing

The non-thermal effect of microwave was evaluated quantitatively by the calculation of activation energy and pre-exponential factors with an isothermal microwave.

Thermal desorption of carbon monoxide from model interstellar ice surfaces: revealing surface heterogeneity

ABSTRACT Temperature programmed desorption has been used to probe the distribution of binding energies of carbon monoxide (CO) to molecular solid thin films of astrophysical relevance. Measurements are reported for solid water (both compact amorphous solid water and crystalline water), ammonia, and methanol surfaces. Binding energy distributions and optimized pre-exponential factors based on the inversion method are tabulated. These are compared to existing data on these systems and astrophysical conclusions drawn.

Kinetic and thermodynamic investigations of CO2 gasification of coal chars prepared via conventional and microwave pyrolysis

This study examined an isothermal CO2 gasification of four chars prepared via two different methods, i.e., conventional and microwave-assisted pyrolysis, by the approach of thermogravimetric analysis. Physical, chemical, and structural behaviours of chars were examined using ultimate analysis, X-ray diffraction, and scanning electronic microscopy. Kinetic parameters were calculated by applying the shrinking unreacted core (SCM) and random pore (RPM) models. Moreover, char-CO2 gasification was further simulated by using Aspen Plus to investigate thermodynamic performances in terms of syngas composition and cold gas efficiency (CGE). The microwave-induced char has the largest C/H mass ratio and most ordered carbon structure, but the smallest gasification reactivity. Kinetic analysis indicates that the RPM is better for describing both gasification conversion and reaction rates of the studied chars, and the activation energies and pre-exponential factors varied in the range of 78.45–194.72 kJ/mol and 3.15–102,231.99 s−1, respectively. In addition, a compensation effect was noted during gasification. Finally, the microwave-derived char exhibits better thermodynamic performances than the conventional chars, with the highest CGE and CO molar concentration of 1.30% and 86.18%, respectively. Increasing the pyrolysis temperature, gasification temperature, and CO2-to-carbon molar ratio improved the CGE.

Kinetics of Alkyl Lactate Formation from the Alcoholysis of Poly(Lactic Acid)

Alkyl lactates are green solvents that are successfully employed in several industries such as pharmaceutical, food and agricultural. They are considered prospective renewable substitutes for petroleum-derived solvents and the opportunity exists to obtain these valuable chemicals from the chemical recycling of waste poly(lactic acid). Alkyl lactates (ethyl lactate, propyl lactate and butyl lactate) were obtained from the catalysed alcoholysis reaction of poly(lactic acid) with the corresponding linear alcohol. Reactions were catalysed by a Zn complex synthesised from an ethylenediamine Schiff base. The reactions were studied in the 50–130 °C range depending on the alcohol, at autogenous pressure. Arrhenius temperature-dependent parameters (activation energies and pre-exponential factors) were estimated for the formation of the lactates. The activation energies (Ea1, Ea2 and Ea−2) for alcoholysis in ethanol were 62.58, 55.61 and 54.11 kJ/mol, respectively. Alcoholysis proceeded fastest in ethanol in comparison to propanol and butanol and reasonable rates can be achieved in temperatures as low as 50 °C. This is a promising reaction that could be used to recycle end-of-life poly(lactic acid) and could help create a circular production economy.

Heron and Alpha-Centroidal Mean Filters with Exponential factors for Deep Space Images

In this article, we discuss empirical methods that can be add-on to enhance spatial image filters. Discussing on the implementation of such methods for Deep-Sky images from space telescopes. Spatial image filtering houses mean filters that use kernel method to filter a digital image in the spatial domain. To improve the performance of the existing filters and aid the new upcoming filter, a technique is developed that can be added to the filter to improve their performance. This study gives a detailed analysis of an empirical weight factor and exponential factoring methods for the mean filters that are proposed and implemented. The exponential factoring is applied to the recent mean filters Heron, Centroidal and Inverse-Contraharmonic. Performance analysis of both methods and comparison to existing mean filtering performance are represented. The images are classified into white or black based background and analyzed for performance parameters, comparing the results from the filters and filters with the exponential factoring. The empirical methods were proven to improve the efficiency in denoising of images of the existing mean filters and the new Heron and Centroidal mean filters, hence can be used as add-ons to existing spatial mean filters. One of the empirical techniques, exponential factoring is promising in denoising high density noised images. This novel method is implemented to filter noise from Deep Space images taken by space telescopes. Ultra-high-resolution images are filtered and implemented on Single Board Computers for remote handling, with testing done on MATLAB.

Experimental Study and Validation of a Kinetic Scheme for Hydrothermal Carbonization Reactions

This study presents a new kinetic scheme for the mass yield prediction of waste lignocellulosic biomasses treated by Hydrothermal Carbonization (HTC). The proposed reactions are based on the decomposition, solubilization, and polymerization of each main fraction of the biomass: cellulose, hemicellulose, and lignin. The ash content was assumed to be inert. The kinetic parameters have been obtained by non-linear adjustment using a data set with 220 experimental runs collected from the literature. The results indicate that the pre-exponential factors range was from 7.33 x101 to 1.412x105 min-1, and activation energies were between 33.75 y 225.3 kJ/mol. A good fit is achieved between the observed and predicted data with an R2 of 0.81 and an RMSE of 7.7 %. The proposed scheme was validated with the experimental data obtained by the HTC of sawdust (Pinus radiata) and rapeseed (Brassica napus). The experiments were carried out at temperatures of 190, 220, and 250 ºC and reaction times of 0, 30, 60, 90, and 120 min. The predicted values showed an average error of 2.3 and 3.5 %, respectively. Therefore, the kinetic scheme is a useful tool in the conversion analysis of waste biomass treated by HTC.

Deconvolution of local activation energy of hopping conductivity: Application to p-Ge

A new method for analyzing the local reduced activation energy [Formula: see text] of the impurity conductivity is applied to Ga-doped [Formula: see text]-Ge samples with a constant compensation ratio of [Formula: see text] reported by Zabrodskii and Andreev [Int. J. Mod. Phys. B 8, 883 (1994)]. Here, the local reduced activation energy is defined as [Formula: see text], where [Formula: see text] and [Formula: see text] denote conductivity and absolute temperature, respectively. The method enables us to deconvolute the [Formula: see text] curve into contributions from different conduction mechanisms such as free-hole conduction, nearest-neighbor hopping (NNH) conduction and variable-range hopping (VRH) conduction. As a result, it is shown that both the power exponents of the pre-exponential factors of NNH and VRH conductivity tend to decrease with increasing impurity concentration.

Is orthopyroxene really a reliable recorder of mantle water signatures? Insights from an experimental study

<p>Experiments have been conducted to assess the effects of temperature, oxygen fugacity, crystallographic orientation, silica activity and chemical composition on the diffusivity and substitution mechanisms of hydrogen in orthopyroxene (opx). Axially oriented ~cuboids of natural Tanzanian opx were dehydrated at 1 bar in a gas mixing furnace (H<sub>2</sub>-CO<sub>2</sub> mix) at three different oxygen fugacities (~QFM-1,~QFM+1, ~QFM-7), and two different silica activity buffers (olivine+pyroxene or pyroxene+quartz) between 700°C and 1000°C. Profiles of hydrogen content versus distance were extracted from experimental samples using Fourier-Transform Infrared (FTIR) spectroscopy, with diffusion coefficients extracted using relevant analytical solutions and numerical approximations of Fick’s second law. Diffusion is the fastest along [001] ( D<sub>[001]</sub>>D<sub>[010]</sub>>D<sub>[100]</sub>). Fitting the diffusion coefficients to the isobaric Arrhenius relationship (logD=logD<sub>0</sub>+(-Q/(2.303RT)) gives activation energies (Q) and pre-exponential factors (logD<sub>0</sub>) between 127 to 162 kJmol<sup>-1</sup> and –4.29 to -5.42  m<sup>2</sup>s<sup>-1</sup> , respectively, for ~QFM-1.</p><p>The extracted hydrogen diffusivities are faster than previously measured by 0.5 to 5 orders of magnitude at ~1000 °C and ~700°C, respectively (Carpenter (2003), Stalder and Skogby (2003), Stalder and Behrens (2006), Stalder and al. (2007)) and are slightly slower, but strikingly close, to those of the fastest experimentally-determined diffusivity of H in olivine (Kohlstedt and Mackwell, 1998), suggesting a mechanism akin to proton-polaron exchange. This presents a paradoxical decoupling between natural and experimental observations. In most cases for mantle xenoliths, natural olivine has low water contents (<35 ppm), or are dry, and show H diffusive loss of water, where natural opx contains between 10 and 460 ppm and rarely show H diffusive loss (Demouchy and Bolfan-Casanova (2016), suggesting opx is more capable of recording the mantle water signature. With hydrogen diffusivities of olivine and opx being quite similar, however, both minerals should suffer from the same rate of dehydration during ascent, thus show low or zero water content in natural settings, which is not the case. Therefore, the inference that pyroxenes are better recorder of water in the mantle (e.g. Warren et Hauri (2014), Peslier (2010)) cannot be a simple function of diffusivities. A case study on an opx crystal showing a dehydration profile from a spinel-peridotite xenolith, hosted in an alkaline magma, from Patagonia supports this. Using the H diffusion coefficients from this study, the calculated rates of ascent of the mantle xenolith in alkaline magma are comparable to those associated with kimberlite magmas. The two suggestions we present are the following: i) Changing the boundary conditions may modify the hydrogen diffusive flux through the xenolith history and ii) The measured diffusivities would be apparent diffusivities as there might be different pathways or mechanisms of diffusion.</p>