Hot corrosion of γ-Y2Si2O7 in strongly basic Na2CO3 molten salt environment

γ-Y2Si2O7 is a promising candidate both for high temperature structural applications and as thermal barrier coatings due to its unique combination of properties, such as high melting point, good machinability, high thermal stability, low linear thermal expansion coefficient (3.9 × 10-6 K-1, 25-1400 °C) and low thermal conductivity (<3 W/m K above 300 °C). In this work, the hot corrosion behavior of γ-Y2Si2O7 in strongly basic Na2CO3 molten salt at 850-1000 °C for 20 h in flowing air was investigated. In the employed conditions, multi-layer corrosion scales with total thickness less than 90 μm were formed. At 850-900 °C, the outmost layer of the scale was composed of the reprecipitation of Y2O3, the bottom of a Si-rich Na2O·xSiO2 (x > 3.65) melt layer, and the middle of a NaYSiO4 layer. At 1000 °C, the corrosion products turned out to be a mixture of NaY9Si6O26 and Si-rich Na2O·xSiO2 (x > 3.65). In all cases, a thin layer of protective SiO2 formed under the Na2O·xSiO2 melt and protected the bulk material from further corrosion.

Gradient solid electrolytes for thermodynamic measurements: System Na2CO3-Na2SO4

The thermodynamic properties of Na2CO3-Na2SO4 solid solution with hexagonal structure have been measured in the temperature range of 873 to 1073 K, using a composite-gradient solid electrolyte. The cell used can be represented as The composite-gradient solid electrolyte consisted of pure Na2CO3 at one extremity and the solid solution under study at the other, with variation in composition across the electrolyte. A CO2 + O2 + Ar gas mixture was used to fix the chemical potential of sodium at each electrode. The Nernstian response of the cell to changes in partial pressures of CO2 and O2 at the electrodes has been demonstrated. The activity of Na2CO3 in the solid solution was measured by two techniques. In the first method, the electromotive force (emf) of the cell was measured with the same CO2 + O2 + Ar mixture at both electrodes. The resultant emf is directly related to the activity of Na2CO3 at the solid solution electrode. By the second approach, the activity was calculated from the difference in compositions Of CO2 + O2 + Ar mixtures at the two electrodes required to produce a null emf. Both methods gave identical results. The second method is more suitable for gradient solid electrolytes that exhibit significant electronic conduction. The activity of Na2CO3 exhibits positive deviation from Raoult's law. The excess Gibbs' energy of mixing of the solid solution can be represented using a subregular solution model such as the following: DELTAG(E) = X(1 - X)[6500(+/-200)X + 3320(+/-80)(1 - X)J mol-1 where X is the mole fraction of Na2CO3. By combining this information with the phase diagram, mixing properties of the liquid phase are obtained.

SELECTIVE ALDEHYDE REDUCTION IN KETOALDEHYDES WITH NaBH4-Na2CO3-H2O AT ROOM TEMPERATURES

A variety of aliphatic and aromatic ketoaldehydes were reduced to the corresponding ketoalcohols with a mixture of sodium borohydride (1.2 equivalents) and sodium carbonate (sixfold molar excess) in water. Reactions were performed at room temperatures over (typically) 2 h, and yields of isolated products generally ranged from 70% to 85%. A biscarbonate-borane complex, (BH3)(2)CO2](2-) 2Na(+), possibly formed from the reagent mixture, is likely the active reductant. The moderated reactivity of this acylborane species would explain the chemoselectivity observed in the reactions. The readily available reagents and the mild aqueous conditions make for ease of operation and environmental compatibility, and make a useful addition to available methodology.

Na-23, Si-29, and C-13 MAS NMR investigation of glass-forming reactions between Na2CO3 and SiO2

Winter, Rudolf; Jones, A.R.; Greaves, G.N.; Smith, I.H., (2005) 'Na-23, Si-29, and C-13 MAS NMR investigation of glass-forming reactions between Na2CO3 and SiO2', Journal of Physical Chemistry B 109(49) pp.23154-23161 RAE2008

Application of accelerated carbonation with a combination of Na2CO3 and CO2 in cement-based solidification/stabilization of heavy metal-bearing sediment

The efficient remediation of heavy metal-bearing sediment has been one of top priorities of ecosystem protection. Cement-based solidification/stabilization (s/s) is an option for reducing the mobility of heavy metals in the sediment and the subsequent hazard for human beings and animals. This work uses sodium carbonate as an internal carbon source of accelerated carbonation and gaseous CO2 as an external carbon source to overcome deleterious effects of heavy metals on strength development and improve the effectiveness of s/s of heavy metal-bearing sediment. In addition to the compressive strength and porosity measurements, leaching tests followed the Chinese solid waste extraction procedure for leaching toxicity - sulfuric acid and nitric acid method (HJ/T299-2007), German leaching procedure (DIN38414-S4) and US toxicity characteristic leaching procedures (TCLP) have been conducted. The experimental results indicated that the solidified sediment by accelerated carbonation was capable of reaching all performance criteria for the disposal at a Portland cement dosage of 10 wt.% and a solid/water ratio of 1: 1. The concentrations of mercury and other heavy metals in the leachates were below 0.10 mg/L and 5 mg/L, respectively, complying with Chinese regulatory level (GB5085-2007). Compared to the hydration, accelerated carbonation improved the compressive strength of the solidified sediment by more than 100% and reduced leaching concentrations of heavy metals significantly. It is considered that accelerated carbonation technology with a combination of Na2CO3 and CO2 may practically apply to cement-based s/s of heavy metal-bearing sediment. (C) 2008 Elsevier B.V. All rights reserved.

Suppression of spinel formation to induce reversible thermal behavior in the layered double hydroxides (LDHs) of Co with Al, Fe, Ga, and In

The layered double hydroxides (LDHs) of Co with trivalent cations decompose irreversibly to yield oxides with the spinel structure. Spinel formation is aided by the oxidation of Co(II) to Co(III) in the ambient atmosphere. When the decomposition is carried out under N-2, the oxidation of Co(II) is suppressed, and the resulting oxide has the rock salt structure. Thus, the Co-Al-CO32-/Cl- LDHs yield oxides of the type Co1- Al-x(2x/3)rectangle O-x/3, which are highly metastable, given the large defect concentration. This defect oxide rapidly reverts back to the original hydroxide on soaking in a Na2CO3 solution. Interlayer NO3- anions, on the other hand, decompose generating a highly oxidizing atmosphere, whereby the Co-Al-NO3- LDH decomposes to form the spinel phase even in a N-2 atmosphere. The oxide with the defect rock salt structure formed by the thermal decomposition of the Co-Fe-CO32- LDH under N2, on soaking in a Na2CO3 solution, follows a different kinetic pathway and undergoes a solution transformation into the inverse spinel Co(Co, Fe)(2)O-4. Fe3+ has a low octahedral crystal field stabilization energy and therefore prefers the tetrahedral coordination offered by the structure of the inverse spinel rather than the octahedral coordination of the parent LDH. Similar considerations do not hold in the case of Ga- and In-containing LDHs, given the considerable barriers to the diffusion of M3+ (M=Ga, In) from octahedral to tetrahedral sites owing to their large size. Consequently, the In-containing oxide residue reverts back to the parent hydroxide, whereas this reconstruction is partial in the case of the Ga-containing oxide. These studies show that the reversible thermal behavior offers a competing kinetic pathway to spinel formation. Suppression of the latter induces the reversible behavior in an LDH that otherwise decomposes irreversibly to the spinel.

Studies in the polarography of metal-amino acid complexes -Part II. Lead

1. The polarographic behaviour of glycine, α-alanine, β-alanine, valine, aspartic acid, glutamic acid and asparagine complexes of lead has been studied at various pH values and in presence of (1) NaOH, (2) Na2CO3 and (3) NH4 NO3+NH4OH. All the polarographic waves have been found to be reversible. 2. Experiments conducted on the effect of variation of pH, i.e., 7

properties of Na2O in Nasicon solid solution, Na1+xZr2SixP3-xO12

The thermodynamic activity of sodium oxide (Na2O) in the Nasicon solid solution series, Na1+xZr2SixO12, has been measured in the temperature range 700–1100 K using solid state galvanic cells: Pt|CO2 + O2|Na2CO3?Na1+xZr2SixP3-xO12?(Y2O3)ZrO2?In + In2O3|Ta, Pt for 1 = ? = 2.5, and Pt?CO2 + O2?Na2CO3?ß-alumina?Na1+xZr2SixP3-xO12?Ar + O2?Pt for x = 0, 0.5, 2.5, and 3. The former cell, where the Nasicon solid solution is used as an electrolyte along with yttria-stabilized zirconia, is well suited for Nasicon compositions with high ionic conductivity. In the latter cell, ß-alumina is used as an electrolyte and the Nasicon solid solution forms an electrode. The chemical potential of Na2O is found to increase monotonically with x at constant temperature. The partial entropy of Na2O decreases continuously with x. However, the partial enthalpy exhibits a maximum at x = 2. This suggests that the binding energy is minimum at the composition where ionic conductivity and cell volume have maximum values.

Thermodynamic partial properties of Na2O in Nasicon solid solution, Na1+xZr2SixP3-xO12

The thermodynamic activity of sodium oxide (Na2O) in the Nasicon solid solution series, Na1+xZr2SixO12, has been measured in the temperature range 700�1100 K using solid state galvanic cells: Pt|CO2 + O2|Na2CO3?Na1+xZr2SixP3-xO12?(Y2O3)ZrO2?In + In2O3|Ta, Pt for 1 = ? = 2.5, and Pt?CO2 + O2?Na2CO3?ß-alumina?Na1+xZr2SixP3-xO12?Ar + O2?Pt for x = 0, 0.5, 2.5, and 3. The former cell, where the Nasicon solid solution is used as an electrolyte along with yttria-stabilized zirconia, is well suited for Nasicon compositions with high ionic conductivity. In the latter cell, ß-alumina is used as an electrolyte and the Nasicon solid solution forms an electrode. The chemical potential of Na2O is found to increase monotonically with x at constant temperature. The partial entropy of Na2O decreases continuously with x. However, the partial enthalpy exhibits a maximum at x = 2. This suggests that the binding energy is minimum at the composition where ionic conductivity and cell volume have maximum values.

Gradient solid-electrolyte for use with dissimilar gas electrodes

The EMF of a solid-state cell, incorporating a composite solid-electrolyte with gradual variation in composition, and dissimilar gas electrodes, has been studied as a function of temperature and partial pressures at the electrodes. The cell with the configuration: Pt, CO2' + O2' parallel-to Na2CO3\Na(SO4)x(CO3)1-x\Na2SO4 parallel-to SO3'' + SO2'' + O2'', Pt x=0 x=1 was investigated in the temperature range 973 to 1079 K. The solid-electrolyte surface exposed to SO3 + SO2 + O2 gas mixture was doped-Na2SO4, whereas the CO2 + O2 gas mixture was in contact with pure Na2CO3. The composition of the solid solution between the carbonate and sulfate, with hexagonal structure, was varied gradually between the boundary values. It has been found that the EMF of the cell is close to that calculated from thermodynamic data, assuming unit transport number for Na+ ions. The gradient in the concentration of sulfate and carbonate ions in the electrolyte does not give rise to a significant diffusion potential.

Role of electrolyte additives on in-vitro electrochemical behavior of micro arc oxidized titania films on Cp Ti

The present work is aimed at studying the influence of electrolyte chemistry on the voltage-time (V-T) response characteristics, phase structure, surface morphology, film growth rate and corrosion properties of titania films fabricated by micro arc oxidation (MAO) on Cp Ti. The titania films were developed with a sodium phosphate based reference electrolyte comprising the additives such as sodium carbonate (Na2CO3), sodium nitrite (NaNO2) and urea (CO(NH2)(2)). The phase composition, surface morphology, elemental composition and thickness of the films were assessed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) techniques. The corrosion characteristics of the fabricated films were studied under Kokubo simulated body fluid (SBF) condition by potentiodynamic polarization, long term potential and linear polarization resistance (LPR) measurements and electrochemical impedance spectroscopy (EIS) methods. In addition, the corrosion characteristics of the grown films were analyzed by EIS curve fitting and equivalent circuit modeling. Salt spray test (SST) as per ASTM B 117 standard was also conducted to verify the corrosion resistance of the grown films. The XRD results showed that the titania films were composed of both anatase and rutile phases at different proportions. Besides, the films grown in carbonate and nitrite containing electrolyte systems showed an enhanced growth of their rutile phase in the 1 0 1] direction which could be attributed to the modifications introduced in the growth process by the abundant oxygen available during the process. The SEM-EDX and elemental mapping results showed that the respective electrolyte borne elements were incorporated and distributed uniformly in all the films. Among all the grown films under study, the film developed in carbonate containing electrolyte system exhibited considerably improved corrosion resistance due to suitable modifications in its structural and morphological characteristics. The rate of anatase to rutile phase transformation and the rutile growth direction were strongly influenced by the abundant oxidizing species available during the film growth process. (C) 2012 Elsevier B. V. All rights reserved.

The influence of corrosion on the erosion of aluminium by aqueous silica slurries

The slurry erosion-corrosion behaviour of aluminium in aqueous silica slurries containing 0.5 M NaCl, acetic acid and 0.1 M Na2CO3 at open circuit has been investigated using a modified slurry erosion rig. The erosion rates of aluminium in the NaCl and acetic acid slurries were much higher than those in an aqueous slurry without electrolyte additives even though the pure corrosion component was very small. Eroded specimens were examined by scanning electron and optical microscopy. In pure aqueous slurry erosion, the basic mechanism leading to mass loss was the ductile fracture of flakes formed on the eroded surface. In corrosive slurries, however, the mass loss was enhanced by cracking of the flakes induced by stress and corrosion. © 1995.

松嫩平原南部主要耐盐碱植物群落生物生态学机制的初步探讨

本文采用野外调查分析和室内室验相结合的方法，初步探讨了松嫩平原南部主要耐盐碱植物群落形成和分布的生物生态学机制，得出如下结论： （1）土壤盐碱含量是决定耐盐碱植物群落组成和分布的主导因素。当土壤盐碱含量逐渐增大时，依次分布着虎尾草、羊草、星星草和碱蓬植物群落，并且这些植物群落的种类组成不同。虎尾草、羊草的生态幅度较广，星星草和碱蓬生态幅度较窄。 （2）在野外不同土壤条件下采集的星星草，体内脯氨酸含量有规律地变化。说明在盐碱生境下，植物通过调节体内某些生理反应来适应盐碱生境。 （3）在实验室控制条件下，研究植物对盐碱因素的反应，碱蓬、星星草、虎尾草在生理指标上表现出对盐碱生境的适应性依次减弱。这种适应特性的不同是植物群落形成和分布的主导因素。在盐碱生境下，碱蓬的发芽势、发芽率、呼吸强度、ATP含量和生长量普遍高于其它植物，有一定盐碱（500PPm Na2CO3）存在时，生命活动受促进，在较宽盐碱浓度范围（低于3000PPm Na2CO3）内，受抑制不显著，且以稀盐机制避盐，所以在高含量盐碱土上，碱蓬竞争力强，形成耐盐碱性强的碱蓬群落。星星草在一定盐碱(250 PPm Na2CO3)存在时，生命活动得到促进，在较低浓度的盐碱溶液（1000PPm Na2CO3）中，生命活动被明显抑制，且星星草以拒盐机制躲避盐的伤害，所以在较低含量的盐碱土上，生长良好，形成耐盐碱的群落，该群落耐盐碱性低于碱蓬群落。由于碱蓬和星星草生命活动要求一定量的盐碱，所以在盐碱含量很低的土壤上，生长不好，生态幅度较窄。虎尾草在盐碱存在下，生命活动受到抑制，所以虎尾草只有在盐碱含量很低的土壤上生长良好，形成虎尾草群落。由于在很宽的盐碱浓度范围内，虎尾草受抑制作用不明显，所以虎尾草在其它许多耐盐碱植物群落中，作为伴生种存在，生态幅度较宽。

水体中有机物的紫外光降解研究

当前，水资源污染越来越严重，人类的健康面临着巨大的威胁。高级氧化技术作为一 种经济、高效、无二次污染的水体处理方法，一直是水污染控制与治理领域研究的热点。 本文以环境中典型的有机污染物苯酚和水体中主要有机物腐殖酸为研究对象，利用自 制的紫外光（ultraviolet，UV）离线降解装置，采用紫外-可见光谱法和总有机碳（TOC） 分析法分别研究水相中苯酚、腐殖酸的紫外光降解情况，系统地考察不同初始pH值、初始 浓度、光照时间、光照强度、反应容器等因素对光降解效果的影响。为了模拟实际水体条 件和提高光降解效率，在体系中分别加入NaCl、Na2CO3、NaNO3、NaNO2和双氧水等化学 成分，探讨这些化学物质对苯酚、腐殖酸的紫外光降解效率和降解途径的影响。最后，首 次构建了石英螺旋管内壁负载TiO2膜的在线降解装置，结合UV/H2O2/TiO2联用体系，进行 海水中有机物的光降解研究。 紫外可见光谱分析表明：光降解速率随初始pH 值的降低而提高，相同条件下苯酚在 酸性溶液中降解速率高于碱性溶液，说明苯酚分子比酚氧离子容易光降解；硝酸钠和亚硝 酸钠有利于苯酚的光降解，说明它们在紫外光下容易分解生成自由基；在苯酚水溶液中加 入双氧水，光照15 min 后，光降解效率达到97%。各种介质中苯酚的降解速率大小依次为： 1.5 mmol/L 过氧化氢溶液 ＞ 1.0 mmol/L 硝酸钠的海水 ＞ 海水 ＞ 纯水 ＞ 0.5 mol/L 氯化钠溶液。然而，TOC 数据显示氯化钠的存在对苯酚的矿化有促进作用；同光谱的降解 速率相比，矿化速率要小。 腐殖酸的光降解效率随初始质量浓度的减小而提高，当质量浓度为10 mg/L时，光照 30 分钟后，降解效率高达到88%；初始pH值对腐殖酸的降解效率影响很大，腐殖酸在碱 性条件下比在中性和酸性条件更容易光降解；硝酸钠等盐分对中性和碱性溶液中腐殖酸的 光降解没有明显促进作用，但对酸性溶液中腐殖酸的光降解促进作用明显。采用UV/H2O2联 合降解时，腐殖酸降解效率得到显著提高。 相比离线降解方式，采用石英螺旋管在线降解苯酚和腐殖酸，降解效率均提高了15 倍 以上；海水经过在线降解后，紫外可见光光谱吸光度值缓慢下降；经过多次在线光降解后， 在290 nm波长处出现强烈吸收峰，再次光照后很快消失。这种现象表明海水中可能存在着 粒

Vacuum pyrolysis of waste tires with basic additives

Granules of waste tires were pyrolyzed tinder vacuum (3.5-10 kPa) conditions, and the effects of temperature and basic additives (Na2CO3, NaOH) on the properties of pyrolysis were thoroughly investigated. It was obvious that with or without basic additives, pyrolysis oil yield increased gradually to a maximum and subsequently decreased with a temperature increase from 450 degrees C to 600 degrees C, irrespective of the addition of basic additives to the reactor. The addition of NaOH facilitated pyrolysis dramatically, as a maximal pyrolysis oil yield of about 48 wt% was achieved at 550 degrees C without the addition of basic additives, while a maximal pyrolysis oil yield of about 50 wt% was achieved at 480 degrees C by adding 3 wt% (w/w, powder/waste tire granules) of NaOH powder. The composition analysis of pyrolytic naphtha (i.b.p. (initial boiling point) similar to 205 degrees C) distilled from pyrolysis oil showed that more dl-limonene was obtained with basic additives and the maximal content of dl-limonene in pyrolysis oil was 12.39 wt% which is a valuable and widely-used fine chemical. However, no improvement in pyrolysis was observed with Na2CO3 addition. Pyrolysis gas was mainly composed of H-2, CO, CH4, CO2, C2H4 and C2H6. Pyrolytic char had a surface area comparable to commercial carbon black, but its proportion of ash (above 11.5 wt%) was much higher.