Carbon corrosion mechanism on nitrogen-doped carbon support — A density functional theory study

In this work, density functional theory (DFT) calculations were used to investigate the mechanism of carbon corrosion on nitrogen-doped carbon support. Free energy diagrams were generated based on three proposed reaction pathways to evaluate corrosion mechanisms. The most energetically preferred mechanism on nitrogen-doped carbon was determined. The results show that the step of water dissociation to form ^#OH was the rate-determining step for gra-G-1N (graphene doped with graphitic N) and pyrr-G-1N (graphene doped with pyrrolic N). As for graphene doped with pyridinic N, the step of C^#OC^#O formation was critical. It was found that the control of nitrogen concentration was necessary for precisely designing optimized carbon materials. Abundance of nitrogen moieties aggravated the carbon corrosion. When the high potential was applied, specific types of graphitic N and pyridinic N were found to be favorable carbon modifications to improve carbon corrosion resistance. Moreover, the solvent effect was also investigated. The results provide theoretical insights and design guidelines to improve corrosion resistance in carbon support through material modification by inhibiting the adsorption of surface oxides (OH, O, and OOH).     

Electrospun Zn-doped Ga2O3 nanofibers and their application in photodegrading rhodamine B dye

Ultrawide band gap semiconductor materials have attracted considerable attention in recent years owing to their great potential in the photocatalytic field. In this study, Zn-doped Ga₂O₃ nanofibers with various concentrations were synthesized via electrospinning; they exhibited a superior photocatalytic degradation performance of rhodamine B dye compared to that of undoped Ga₂O₃ nanofibers. The Zn dopant replaced Ga sites via replacement doping, which could increase the concentration of oxygen vacancies and lead to enhanced photocatalytic properties. When the Zn concentration increased, a Ga₂O₃/ZnGa₂O₄ hybrid structure formed, which could further enhance the photocatalytic performance. The separation of photogenerated carriers due to Zn doping and heterojunctions were the primary causes of the enhanced photocatalytic performance. This study provides experimental data for the fabrication of high-performance photocatalysts based on Ga₂O₃ nanomaterials.     

Impact of Reaction Conditions on MnO2 Genesis during Permanganate Oxidation

To enhance the understanding of the behavior and effects of the precipitation of MnO2 particles in the subsurface generated during in situ chemical oxidation (ISCO) using permanganate, laboratory batch experiments were completed to examine the influence that varied reaction matrix conditions have on the generation and properties of manganese oxides. The conditions examined include organic material type and concentration, permanganate concentration, pH, and the presence of calcium (as a representative divalent cation) in solution. Experimental studies included: (1) spectrophotometric examination of permanganate depletion and manganese oxides generation over time during reactions with trichloroethene; (2) scanning electron microscopy analyses of manganese particle morphology; (3) particle size distribution (filtration) characterization studies; and (4) optical particle sizing and numeration studies. Bench-scale, batch experiments were conducted to focus on fundamental chemical properties affecting particle development under varied potential environmental conditions. The amount of manganese oxides particles that develop, grow, and potentially settle as a result of permanganate ISCO of organic contaminants is a function of the particle size and concentration, the time allowed for particle development, and the impact of matrix conditions on the ability of particles to agglomerate.     

Indicators for inspection and maintenance planning of concrete structures

Based on an idea introduced by Benjamin and Cornell (1970. Probability, statistics and decision for civil engineers. New York: McGaw Hill) and previous works by the authors it is demonstrated how condition indicators may be formulated for the general purpose of quality control and for assessment and inspection planning in particular. The formulation facilitates quality control based on sampling of indirect information about the condition of the considered components. This allows for a Bayesian formulation of the indicators whereby the experience and expertise of the inspection personnel may be fully utilized and consistently updated as frequentistic information is collected. The approach is illustrated on an example considering a concrete structure subject to corrosion. It is shown how half-cell potential measurements may be utilized to update the probability of excessive repair after 50 years. Furthermore in the same example it is shown how the concept of condition indicators might be applied to develop a cost optimal maintenance strategy composed of preventive and corrective repair measures.     

Ozonation Impact on Degradation and Toxicity of Non-Ionic Surfactants

Aqueous solutions of five selected non-ionic surfactants: Triton (i-octylphenolethoxylates), Tergitol (2,6,8-trimethyl-4-nonanoloxethylates), Symperonic (n-nonylphenol-oxethylates) and Brij (fatty alcohol ethoxylates) were investigated in this study. Using the bioluminescent bacteria Vibrio fischeri the toxicity of the surfactants solutions were determined. An attempt was made to relate rather low biodegradability of nonionic surfactant solutions measured by the BOD₅/COD ratio (ranging from 1 to 17%) to their toxicity. The ozonation process was carried out in a 1.5 dm³ stirred cell reactor equipped with two ozone detectors. The following parameters were analyzed: pH, COD, BOD₅, DOC, TOC, polarography as well as UV spectrum. The positive effect of ozonation, represented by decay of UV absorption, was visible in almost complete destruction of the surfactants, with exception of Triton X-705 (only 65% degradation after absorption of 2000 mgO₃/dm³). The most striking results were obtained in toxicity tests for ozonated solutions of the non-ionic surfactants – an increase of the bacterial growth inhibition (1.5 to 4 times increase in toxicity due to ozonation). The obtained results were discussed taking into account the literature and our own experimental data on mechanisms of ozonation and biodegradation of non-ionic surfactants of the Triton-type and similar chemical structures.     

In Situ Performance Testing of Deteriorating Water Tanks for Durability Assessment

Reports of failure of existing concrete structures due to a lack of durability, rather than a deficiency in structural strength, has made concrete technologists, engineers, and researchers focus research on the parameters influencing durability performance with respect to time. Systematic performance monitoring, with respect to chosen durability parameters of existing concrete structures, will decide the direction of future research in this area. Inferences based on laboratory simulations and testing need to be confirmed by in situ field measurements and studies. In situ condition rating and performance monitoring surveys have been conducted by many researchers, scientists, and professional associations, and reported in literature. Inferences of few such studies are summarized and discussed. Deterioration of concrete structures constructed in recent times is observed at relatively faster rates, and has been mainly attributed to cracking. Cracking is associated with the use of faster-hydrating portland cements with increased fineness and the tricalcium silicate (C3S) content to support the high speed of modern construction. In the present research, a case study of deteriorated water tank structures situated in the semitropical region of India is presented. Some selected parameters—such as concrete cover, carbonation depth, chloride concentration, compressive strength, etc. which influence long term durability of structures—have been measured.     

结构陶瓷的高温疲劳强度衰减理论

提出了陶瓷材料疲劳强度衰减理论并由此导出了各种疲劳关系式。建立了疲劳基本方程ｄσ＿ｒ／ｄ＿ｉ＝一Ａσ（ｔ）￣ｎｔ￣（－ｍ），得出了疲劳寿命公式Ｔ＝Ｍ（σ＿０－σ）／Ａσ￣ｎ（静疲劳时Ｍ＝１，连续增载疲劳时Ｍ＝ｎ＋１，循环疲劳时Ｍ＝（ｎ＋１）／（１＋Ｒ＋Ｒ￣２＋……＋Ｒ￣ｎ），逐级加载时，并导出不同疲劳方式下疲劳寿命间的关系。同时，用多种Ｓｉ＿３Ｎ＿４材料在高温中作了论证试验，结果与理论一致。     

In-situ ESR spectroelectrochemical studies of overoxidation behaviour of poly(3,4-butylenedioxythiophene)

The behaviour of poly(3,4-butylenedioxythiophene) (PBuDOT), a relative of poly(3,4-ethylenedioxythipohnene) PEDOT within the poly(3,4-alkylenedioxythiophene) family, has been investigated at potentials above its electrochemical stability threshold using in situ ESR spectroelectrochemistry. The aim was to investigate the effect of electrochemical overoxidation on the charge carrying species, namely polarons, normally generated and annihilated during reversible redox doping and dedoping reactions, by determining the potential dependencies of spectroscopic parameters of the ESR spectra of the polymer over a selected potential range. Specific features of the trends of these dependencies allowed also for an evaluation of presence of the second type of charge carrying species—diamagnetic bipolarons and the effects of their interactions with polarons at different potentials. Around 1.5 V, where the boundary of electrochemical stability of the polymer lies, sharp drop of the concentration of paramagnetic centres has been observed together with a transitory narrowing of the ESR line. These changes were found to be irreversible as evidenced by the course of subsequent reduction half-cycle, which differed from the one for a not overoxidised polymer, observed in previous studies. Aided by the results of electrochemical studies it was concluded that the overoxidation process leads to a degradation of the polymer most probably due decrease of the conjugation length of the main chain π-bond through cross-linking or addition reactions. While the electrochemical results pointed to a non-complete degradation of the polymer, the specific parameters of the ESR line in the reduction half-cycle indicate that the remaining spins are confined to isolated segments of a partially degraded polymer where their behaviour resembles oligomer-like radicals.     

影响土壤中PAHs降解的环境因素及促进降解的措施

土壤中的多环芳烃(PAHs)类有机污染物的生物有效性低,不易降解。本文综述了影响污染土壤中多环芳烃降解的环境因素和促进降解措施的研究进展。影响土壤中多环芳烃降解的因素,包括水分、养分、土壤物理条件等;促进土壤中多环芳烃降解的措施有:向污染土壤添加有机溶剂、利用冯顿反应、添加堆肥和有机物料等。从目前研究来看,应当通过促进多环芳烃从土壤上解吸和培育具有较高多环芳烃降解能力的微生物来促进多环芳烃污染土壤的修复。     

Degradation of Stiffness of Cemented Calcareous Soil in Cyclic Triaxial Tests

The deformation characteristics of artificially cemented calcareous soil subjected to undrained cyclic triaxial loading are investigated at different confining pressure and cyclic stress levels. The influence of cementation on the shear stiffness is investigated by comparing the behavior of cemented and uncemented soils with similar initial conditions. It is observed that the deviator stress and the deviatoric strain at yield reduced with increasing number of cycles for cemented sand due to progressive degradation of bond, which results in significant decrease in stiffness. On the other hand, a strain-hardening effect is observed in uncemented sand and this results in increasing yield stress and strain with progressive number of cycles. A linear relationship between degradation index and number of cycles is observed for cemented sand. This relationship has been synthesized in the form of an empirical equation by modifying a previously proposed equation for cohesive soils. This empirical equation was further used to evaluate the fatigue life of soils by adopting a failure criterion.