A new insight into the LiFePO4 delithiation process

Raman and Fourier transform infrared measurements for Li_xM_0.03Fe_0.97PO₄, M = Cr, Cu, Al, Ti were performed. The spectra for delithiated samples to a low content of lithium extraction are practically the same as those of LiFePO₄. For a high content of lithium extraction, the spectra repeat that of FePO₄. In the case of the Li_0.11FePO₄ oxide the spectra cannot be reproduced just by the superposition of the end member profiles. An additional broad band contribution is found in both Raman and infrared spectra probably due to a disordered structure present in the mixture. This suggests that the well accepted two-phase model for the delithiation process in LiFePO₄ is incorrect. The model should be revised to include the new phase as detected here for a particular level of lithium extraction close to that of complete oxidation of the Fe²⁺ ions to Fe³⁺.     

A new ultrasonic method to detect chemical additives in branded milk

A new ultrasonic method — thermoacoustic analysis — is reported for the detection of the added chemical preservatives in branded milk. The nature of variation and shift in the thermal response of the acoustic parameters specific acoustic impedance, adiabatic compressibility and Rao’s specific sound velocity for different samples of branded milk as compared to the chemical added pure milk are explained as due to the presence of chemicals in these branded samples.     

Exploring the pyrolysis chemistry of 1,3,5-trimethylcyclohexane with insight into fuel isomeric and multiple substitution effects

To reveal insights into the combustion mechanism of multiple alkyl substituent cycloparaffins, this work reports an experimental and modeling study of 1,3,5-trimethylcyclohexane (T135MCH) pyrolysis in an extended flow reactor at low and atmospheric pressures. More than 30 species were detected and quantified employing synchrotron vacuum ultraviolet photoionization molecular beam mass spectrometry, and a detailed kinetic model developed based on reaction classes and update kinetic data was validated against the measured species profiles with a reasonable agreement. The reaction flux analyses were performed to reveal the key pathways of the fuel decomposition, intermediates production and aromatics formation. For the primary decomposition, the branching ratios of reaction types show strong dependence on changes of pressures and temperatures, including unimolecular methyl elimination, unimolecular ring-opening isomerization and H-abstraction. Besides the direct dissociation channels, major intermediate hydrocarbons are formed via stepwise dehydrogenation, recombination with ĊH₃ radical or “formally direct” chemically activated reactions triggered by Ḣ atom addition. Monocyclic aromatic hydrocarbons such as benzene and toluene can be produced by traditional H-abstraction/β-C-H scission sequence, cyclopentadiene-related pathways, or recombination mechanism from small linear products. The formations of indene and naphthalene are controlled by C₅+C₅ and C₅+C₄ mechanism respectively. The comparison work of species profiles combined with theoretical calculations of bond dissociation enthalpies (BDEs) was performed to reveal the multiple CH₃-group substituent and isomeric effects of methylcyclohexane (MCH), 1,2,4-trimethylcyclohexane (T124MCH) and T135MCH on pyrolysis activity and ethylene/benzene formation. Besides the increased reaction active sites, the added CH₃-group and ortho-substitution can both weaken the strength of CC and CH bonds, leading to the promoting decomposition activity. The different formation tendencies of products are caused by different BDEs, length of carbon skeleton, as well as complex fuel-specific pathways.     

A model of the chemical composition and pyrolysis kinetics of lignin

This study presents a novel approach for the chemical representation of lignin for modelling the reaction kinetics of lignin in lignocellulosic biomass. This methodology relies on the definition of dimeric pseudo-components containing phenolic functionalities, i.e., p-hydroxyphenyl, guaiacyl and syringyl groups, as measured in real biomass and native lignin through wet chemistry and spectroscopic techniques. The reactivities of the lignin pseudo-components are modelled through a series of lumped unidirectional reactions, whose product formation and reaction rate constants are optimised to replicate a comprehensive experimental dataset gathered from several works available in the literature. The new kinetic model contributes to the state-of-the-art by providing a more accurate depiction of the conversion rates, selectivity of char vs. volatiles, and aromatic composition in condensable products in line with the inherent reactivity of lignin functionalities and the empirical observations of lignin depolymerisation and thermal degradation at low (<1?K/s) and high heating rates (>50?K/s).     

Light induced chemical reactions on interfaces between metallic iron and polymers

CEMS is presented as a new method to study the interface between polymers and metallic iron. Chemical changes of metallic iron can be detected with a resolution of less than a monolayer. First results of light induced changes of these interfaces to the copolymer of poly(vinylidenefluoride/trifluoroethylene) or poly(carbonate) respectively are shown. The sensitivity of this method is unsurpassed by other experimental techniques.     

Mechanistic insights into effect of feeding rate on soot formation during rapid pyrolysis of biomass model components in a drop-tube furnace at high temperature

This paper reports the significant effect of feeding rate on soot formation during rapid pyrolysis of water-washed cellulose and acid-washed lignin (denoted as W-cellulose and A-lignin, respectively) in a drop-tube furnace at 1300 °C and a residence time of ～0.75 s in argon. Soot produced during W-cellulose pyrolysis has a unimodal distribution, with only a fine mode that its modal diameter increases from 0.043 to 0.246 µm as the feeding rate increases from 40 to 280 mg/min. However, at feeding rates of 12–200 mg/min, soot produced from A-lignin pyrolysis has a bimodal distribution with two fine modes located at 0.077 µm and 0.246 µm, respectively. As the A-lignin feeding rate further increases from 200 to 280 mg/min, the fine mode at 0.077 µm disappears and the particle size distribution of soot becomes unimodal with only a fine mode with diameter of 0.246 µm. Increasing feeding rate increases the yield and particle size of total soot but decreases the yield of non-mature soot for W-cellulose at feeding rates < 280 mg/min and A-lignin at feeding rates < 40 mg/min. The results suggest that a high feeding rate produces high concentration of soot precursors and enhances the collisions for increased formation of incipient soot to large mature soot. As the feeding rate further increases to be more than 40 mg/min, the soot yield from A-lignin pyrolysis levels off, the particle sizes of overall soot decease and the yields of non-mature soot increase. Under such conditions, further results show that soot growth is limited by the availability of soot-forming carbonaceous materials (including small gas molecules e.g. C₂H₂ and polycyclic aromatic hydrocarbons).     

Insight into the calcium carboxylate release behavior during Zhundong coal pyrolysis and combustion

In this paper, the dynamic behavior of calcium carboxylate release during Zhundong coal pyrolysis and combustion is studied via reactive molecular dynamics (ReaxFF MD) simulation. The molecular structure model of Zhundong coal is constructed based on the combination of the classic Hatcher coal model and experimental characterizations. Pyrolysis simulations on the coal model are performed at different temperatures ranging from 2000 K to 2800 K. The pyrolysis experiments are also carried out to validate the ReaxFF simulation. The results show that most of the calcium are released into the volatiles by the thermal decomposition of CM-Ca (coal/char matrix with calcium bonded) after releasing CO₂. The distributions of the calcium bonded to gas, tar and inorganics as well as the atomic calcium in the volatiles are quantitatively classified. The thermal cracking of tar fragments are significant at high temperatures leading to the conversion of calcium from tar into the organic gas. Furthermore, the nascent char model is constructed to study the release behavior of calcium in char combustion stage. The calcium is initially released in the form of oxidized calcium and atomic calcium. With increasing temperature, the oxidized calcium trends to convert to the organically bonded calcium. By using the Arrhenius expression, the kinetic parameters for the release of calcium into various species during pyrolysis and char combustion stages are quantitatively determined.     

Coupled process of plastics pyrolysis and chemical vapor deposition for controllable synthesis of vertically aligned carbon nanotube arrays

Efficient conversion of waste plastics into advanced materials is of conspicuous environmental, social and economic benefits. A coupled process of plastic pyrolysis and chemical vapor deposition for vertically aligned carbon nanotube (CNT) array growth was proposed. Various kinds of plastics, such as polypropylene, polyethylene, and polyvinyl chloride, were used as carbon sources for the controllable growth of CNT arrays. The relationship between the length of CNT arrays and the growth time was investigated. It was found that the length of aligned CNTs increased with prolonged growth time. CNT arrays with a length of 500 μm were obtained for a 40-min growth and the average growth rate was estimated to be 12 μm/min. The diameter of CNTs in the arrays can be modulated by controlling the growth temperature and the feeding rate of ferrocene. In addition, substrates with larger specific surface area such as ceramic spheres, quartz fibers, and quartz particles, were adopted to support the growth of CNT arrays. Those results provide strong evidence for the feasibility of conversion from waste plastics into CNT arrays via this reported sustainable materials processing.     

Electrical field induced chemical reactions on interfaces between metallic iron and ferroelectric polymers

On the search for the possible microscopic origin of free electric charges to stabilize the ferroelectric order in PVDF, chemical decomposition into various radicals like H, H₂, HF, CH₃ by the polarizing electric field was reported [1]. We investigated possible chemical changes caused by these radicals within the electrodes of metallic iron by CEMS. The sensitivity of this method is less than a monolayer of reacted material. No chemical changes could be found unless the poling electrical field had exceeded the threshold of electrical breakthrough, when an iron 2+ high spin compound was detected at the negatively charged electrode. A chemical decomposition of the polymer by electric fields used to polarize the material could not be confirmed.     

Observation of chemical reactions between alkaline-earth oxides and tungsten at high pressure and high temperature

The potential chemical reactions of alkaline-earth oxides (AeO with Ae: Mg, Ca, Sr, and Ba) and tungsten are studied at high pressure and high temperature. At pressures ranging from 5 to 10 GPa and temperatures of 2000 K, a noticeable reaction between AeO and powder tungsten (W) was detected. As a product of the reaction, scheelite-structured orthotungstates (AeWO₄) were formed. The reactivity of alkaline-earth oxides with tungsten increases in the order Ca<Sr<Ba, being the reaction not detected for MgO. Possible chemical reactions leading to the formation of alkaline-earth orthotungstates have been considered. Our results support the conclusion that the most probable reaction occurring under high-pressure and high-temperature conditions is AeO+W+3/2 O₂→AeWO₄.     

基于全光时域分数阶傅里叶变换的光脉冲最小损伤传输新方法

提出了一种基于全光分数阶傅里叶变换(optical fractional fourier transformation,OFRFT)的关于色散和自相位调制对光脉冲传输影响的分析方法,并基于该方法给出了一种新的光脉冲在光纤中传输最小损伤的方法,通过在发射端将输入的高斯光脉冲做OFRFT然后再送入到光纤中去传输,可以提高光脉冲抵抗色散和非线性的能力,仿真发现当色散占主要作用的时候,负阶数的分数阶傅里叶变换可以很大程度上减小光脉冲的展宽;当自相位调制作用占主要的时候,正阶数的分数阶傅里叶变换可以消除自相位调制作 关键词： 光脉冲传输 分数阶傅里叶变换 色散 自相位调制     

Generation and removal of pits during chemical mechanical polishing process for MgO single crystal substrate

Magnesium oxide (MgO) single crystal is an important substrate for high temperature superconductor, ferroelectric and photoelectric applications. The function and reliability of these devices are directly affected by the quality of polished MgO surface because any defect on the substrate, such as pit or scratch, may be propagated onto device level. In this paper, chemical mechanical polishing (CMP) experiments were conducted on MgO (1 0 0) substrate using slurry mainly comprised of 1-hydroxy ethylidene-11-diphosphonic acid (HEDP) and silica or ceria particles. Through monitoring the variations of the pits topography on substrate surface, generation and removal mechanism of the pits were investigated. The experimental results indicate that the pits were first generated by an indentation or scratch caused by particles in the slurry. If the rate of chemical etching in the defect area is higher than the material removal rate, the pits will grow. If chemical reaction in the defect area is slower than the material removal rate, the pits will become smaller and eventually disappear. Consequently, these findings may provide insight into strategies for minimizing pits during CMP process.     

A computational exploration of the mechanisms for the acid‐catalytic urea–formaldehyde reaction: new insight into the old topic

Some initial acid‐catalytic reactions involved in the synthesis of the urea‐formaldehyde resin were theoretically investigated at B3LYP and MP2 levels with solvent effects included. The results suggest that the addition between urea and formaldehyde in neutral condition undergoes with a concerted mechanism represented by a four‐member ring transition state. For this reaction, a notable barrier (above 130 kJ/mol) was identified at all theoretical levels. The reactions between urea and different protonated forms of formaldehyde in acid solution were investigated. The reaction between protonated methanediol with urea can produce the methylol urea cation via an S_N2 transition state with a lower barrier of 54.8 kJ/mol. With the mediation of a water molecule, the intra‐molecular proton transfer produces the stable methylol carbonium (NH₂CONHCH₂⁺), which plays an important role in the following formation of methylene and methylene ether linkages. Copyright © 2011 John Wiley & Sons, Ltd.     

A study of dynamics and chemical reactions in laser-ablated PbTiO3 plume by optical-wavelength-sensitive CCD photography

3 (PT) in ambients of oxygen, nitrogen, and argon was studied by using a CCD camera. Two optical filters with different transmittance bands were used to identify the excitation, dissociation, ionization, and, especially, the chemical reactions in the plume. The results show that the atomic processes and chemical reaction mechanisms in the plume formed in active oxygen are very different from those formed in inert argon and nitrogen. It is proposed that the chemical reactions between ablated metal species and ambient oxygen are initiated by the strong shock wave formed during the propagation of the PT plume. Received: 6 October 1997/Accepted: 7 October 1997     

基于比例积分控制原理预测钻井全过程原始地层温度的新方法研究

应用比例积分控制原理将瞬态传热模型预测结果与出口 温度实测数据逐步进行反馈可准确预测原始静态地层温度. 为此, 本文基于井下各控制组件质量、动量及能量守恒原理, 建立了实际井身结构与钻具组合条件下循环和停止循环期间井筒-地层温度分布全瞬态传热模型, 应用全隐式有限差分法进行求解, 并引入比例积分控制原理对比分析实测温度与预测温度的误差范围进而精确、 快速获取原始地层温度. 结合一口深井基础数据计算表明, 套管下入深度改变了井筒-地层间热交换效率, 进而影响了近井壁地层温度分布状况; 同时, 钻井过程中循环和停止循环作业过程改变了井下各控制组件的初始条件与边界条件, 致使近井壁原始地层温度分布距离产生变化. 建立的数学模型和研究方法可为石油钻井、地热井开采及地球深部原始地层温度信息准确、 经济、快速获取提供理论基础. 关键词： 原始地层温度 循环与停止循环 瞬态传热模型 比例积分控制原理     

A new formalism of inclusive breakup reactions and validity of the surface approximation

Austern and Vincent's formalism for the inclusive breakup reactions in DWBA is rewritten in a form in which the elastic and inelastic breakup processes are well discernible. This form is calculable exactly and hence we test the validity of the surface approximation used by Baur et al.     

A class of collision processes with memory and application to simple chemical reactions in a solvent

We apply the general formalism of a class of non-Markovian processes which we have studied elsewhere to three simple models of chemical reactions: dissociation, isomerization, and diffusion in a double-well potential. Our method leads to explicitly solvable models and numerical computations. The results are in agreement with numerical simulation and stochastic dynamics studies of other authors.     

A 43Ca and 13C NMR study of the chemical interaction between poly(ethylene-vinyl acetate) and white cement during hydration

⁴³Ca and ¹³C NMR methods were used to study the chemical interaction of poly(ethylene–vinyl acetate) (PEVAc) admixture in commercial-grade white cement. From ⁴³Ca NMR it is shown both that PEVAc induces modest changes in the hydrated cement structure, and that hydrated commercial cement is significantly more complex than models that have been used for its structure in past work. The ¹³C NMR results show that the PEVAc hydrolysis occurs early in the cement hydration acceleration period, with a rate well-fit by an exponential decay using a time constant of 6±1 days.     

Insight into the impact of excluding mass transport,heat exchange and chemical reactions heat on the sonochemical bubble yield: Bubble size-dependency

Numerical simulations have been performed on a range of ambient bubble radii, in order to reveal the effect of mass transport, heat exchange and chemical reactions heat on the chemical bubble yield of single acoustic bubble. The results of each of these energy mechanisms were compared to the normal model in which all these processes (mass transport, thermal conduction, and reactions heat) are taken into account. This theoretical work was carried out for various frequencies (f: 200, 355, 515 and 1000 kHz) and different acoustic amplitudes (P_A: 1.5, 2 and 3 atm). The effect of thermal conduction was found to be of a great importance within the bubble internal energy balance, where the higher rates of production (for all acoustic amplitudes and wave frequencies) are observed for this model (without heat exchange). Similarly, the ignorance of the chemical reactions heat (model without reactions heat) shows the weight of this process into the bubble internal energy, where the yield of the main species (OH, H, O and H₂) for this model was accelerated notably compared to the complete model for the acoustic amplitudes greater than 1.5 atm (for f = 500 kHz). However, the lowest production rates were registered for the model without mass transport compared to the normal model, for the acoustic amplitudes greater than 1.5 atm (f = 500 kHz). This is observed even when the temperature inside bubble for this model is greater than those retrieved for the other models. On the other hand, it has been shown that, at the acoustic amplitude of 1.5 atm, the maximal production rates of the main species (OH, H, O and H₂) for all the adopted models appear at the same optimum ambient-bubble size (R₀ ~ 3, 2.5 and 2 µm for, respectively, 355, 500 and 1000 kHz). For P_A = 2 and 3 atm (f = 500 kHz), the range of the maximal yield of OH radicals is observed at the range of R₀ where the production of OH, O and H₂ is the lowest, which corresponds to the bubble temperature at around 5500 K. The maximal production rate of H, O and H₂ is shifted toward the range of ambient bubble radii corresponding to the bubble temperatures greater than 5500 K. The ambient bubble radius of the maximal response (maximal production rate) is shifted toward the smaller bubble sizes when the acoustic amplitude (wave frequency is fixed) or the ultrasound frequency (acoustic power is fixed) is increased. In addition, it is observed that the increase of wave frequency or the acoustic amplitude decrease cause the range of active bubbles to be narrowed (scenario observation for the four investigated models).