Inhibition of cobalt active dissolution by benzotriazole in slightly alkaline bicarbonate aqueous media

The efficiency of benzotriazole as inhibiting agent for the corrosion of cobalt was probed at pH ranging from 8.3 to 10.2 in a sodium bicarbonate solution, chosen to simulate mild natural environments. From electrochemical, Raman spectroscopy, atomic force microscopy and ellipsometry experiments, we have demonstrated that benzotriazole markedly affects the electrodissolution reactions, which become modeled by the formation of a [Co(II)(BTA)₂·H₂O]_n film according to two different mechanisms. Surface-enhanced Raman spectroscopy has shown that the polarization of a cobalt electrode at cathodic potentials with respect to its potential of zero charge allows a mechanism of specific adsorption of the neutral form of benzotriazole to take place through a suspected metal-to-molecule electron transfer and which follows Frumkin's adsorption isotherms. At the onset of the anodic dissolution, some experimental evidence suggests that these adsorbed neutral benzotriazole molecules deprotonate to yield a very thin [Co(II)(BTA)₂·H₂O]_n polymer-like and water-insoluble protective film, responsible for the inhibition of active dissolution processes occurring at slightly more anodic potentials. In the anodic dissolution region, deprotonated benzotriazole species present in the bulk solution favors the formation of a multilayered [Co(II)(BTA)₂·H₂O]_n film, which also contributes to the inhibition of any further cobalt dissolution usually observed at higher electrode potentials.     

The anodic dissolution of SIMFUEL (UO2) in slightly alkaline sodium carbonate/bicarbonate solutions

The corrosion of nuclear fuel under waste disposal conditions is likely to be influenced by the bicarbonate/carbonate content of the groundwater since it increases the solubility of the U^VI corrosion product, [UO₂]²⁺. As one of the half reactions involved in the corrosion process, the anodic dissolution of SIMFUEL (UO₂) has been studied in bicarbonate/carbonate solutions (pH 9.8) using voltammetric and potentiostatic techniques and electrochemical impedance spectroscopy. The reaction proceeds by two consecutive one electron transfer reactions (U^IV → U^V → U^VI). At low potentials (≤250 mV (vs. SCE) the rate of the first electron transfer reaction is rate determining irrespective of the total carbonate concentration. At potentials >250 mV (vs. SCE) the formation of a U^VIO₂CO₃ surface layer begins to inhibit the dissolution rate and the current becomes independent of potential indicating rate control by the chemical dissolution of this layer.     

Solubility of blue CoAl2O4 ceramic pigments in water and diethylene glycol media

The chemical stability of blue CoAl₂O₄ ceramic pigment in aqueous and non-aqueous suspension was investigated. Distilled water and diethylene glycol (DEG) were used as media. The isoelectric points (IEP) for the commercial and synthesised CoAl₂O₄ pigment were determined to be 4.9 and 8.5, respectively. The IEP shifts toward acidic pH values for the commercial pigment with respect to the synthesised pigment due to the existence of the quartz phase. In water, the cobalt ion concentration was low (2.5 mg dm⁻³), and this concentration did not change with time. However, the aluminium ion concentration was initially high and then decreased to ∼10 mg dm⁻³ at pH 9 and 11 due to the precipitation of Al³⁺ ions as an Al(OH)₃ phase. In DEG, the dissolution of pigment particles with higher ion concentrations (>800 mg dm⁻³) was more significant than that of the aqueous medium, implying that CoAl₂O₄ pigment has insufficient chemical stability in DEG medium with respect to aqueous suspensions.     

碳酸盐岩中Mg/Ca比值的研究方法

根据电感耦合等离子体发射光谱仪(ICP-OES)测量快速、准确的特点,应用ICP-OES检测碳酸盐岩中Mg、Ca含量,从而得出碳酸盐岩中Mg/Ca比值。在预处理中采用乙酸铵清洗的方法,极大的提高了准确度,误差缩小到0.6%以下,实现了碳酸盐岩中Mg/Ca比值的检测。     

Catalytic DeNOx activity of cobalt and copper ions in microporous MeALPO-34 and MeAPSO-34

A combined spectroscopic and catalytic study of the NO reactivity on microporous aluminophosphates, with chabasite-related structure, CoAPO-34, CuAPO-34 and CuAPSO-34, is reported. NO and CO adsorption were monitored by FTIR spectroscopy, and revealed that Co²⁺/Co³⁺ and Cu⁺/Cu²⁺ redox couples, the sites responsible for the catalytic activity, are present in these catalysts. CoAPO-34 catalysts showed exceptionally high performances in the oxidation of NO to NO₂, and poor activity in other DeNO_x reactions. Copper-based aluminophosphates and silico-aluminophosphates, besides good performances in the NO oxidation to NO₂, showed good activity in the N₂O decomposition even in the presence of oxygen or water in the feed. The presence of silicon has beneficial effects both on the thermal and hydrothermal stability of the zeolitic structure, as well as on the catalytic performances of the metal-aluminophosphates.     

用硫酸锰和碳酸氢铵制高纯碳酸锰

介绍了以硫酸锰和碳酸氢铵为原料制备高纯碳酸锰的工艺和操作条件，比较了两种分析碳酸锰含量的方法。     

新型肥料钾碳铵生产开发与市场前景

钾碳铵是在碳酸氢铵的生产过程中加入碳酸氢钾,使之与碳酸氢铵共同结晶形成了碳酸氢铵和碳酸氢钾混晶,其稳定性比碳铵有所提高,是碳铵升级换代产品和平衡施肥的理想肥料。简要介绍了钾碳铵生产的技术原理、生产工艺、国内进展及市场前景,并对钾碳铵的发展提出了一些建议。     

Oxygen storage/release in cobalt porphyrin electrodeposited films

In this work, ITO electrodes have been modified by means of the oxidative electrodeposition of two different cobalt porphyrins, CoTSPP and CoTMPyP, and the composition of such deposits have been studied by visible and reflection-FTIR spectroscopies. The data indicate that the porphyrin deposits are formed by a mixture of cobalt hydroxides, β-Co(OH)₂ and α-Co(OH)₂, and the porphyrin ring as radical. Moreover, the porphyrin electrodeposits absorb molecular oxygen as peroxo species (O₂²⁻), which has been detected in the films by IR spectroscopy, and which acts as a bridge between Co atoms (Co-O-O-Co). Also, monolayers containing a viologen derivative have been transferred onto the porphyrin-MIE (MIE, modified ITO electrode) by using the LB technique, and its redox process has been investigated. The results show an excellent mediator character of both cobalt electrodeposits throughout the viologen redox processes. Furthermore, the Co-porphyrin electrodeposits store atmospheric oxygen in a ratio proportional to the deposited porphyrin amount. This oxygen can be totally released from the porphyrin film via the electrocatalytic action of the viologen monolayer on top.     

再识碳铵，巧用碳铵

碳酸氢铵(NH4HCO3)是我国20世纪50年代独创的一个主要氮肥品种,在农业生产中发挥了巨大作用。碳铵的不足是含氮量较低和常温下易分解;但其优点是入土后易被土粒吸持和作物根系吸收。因而碳铵对作物的田间肥效与尿素、硫铵等其他氮肥相当。因此,只要在使用时扬长避短,就能继续充分发挥其作用。     

Corrosion properties of electrodeposited cobalt in sulfate solutions containing chloride ions

The corrosion properties of electrodeposited pure cobalt were investigated in deaerated 0.5 M Na₂SO₄ solutions at pH 5, 7, 10 and 13 by using polarization techniques. The effect of chloride concentration (0.01 and 0.1 M NaCl) was also studied. The results showed that increasing pH shifted the anodic polarization curves to more negative potentials. At pH 5 and 7, cobalt exhibited active dissolution without any distinctive transition to passivation. However, at pH 10, the metal surface was partially passivated and anodic current increased sharply at approximately −0.2 V_SCE and the corroded surface revealed several well-defined pits. On the other hand, at pH 13, a clear passivation region was observed within the potential range of −0.5 to 0.6 V_SCE. With increasing chloride concentrations of 0, 0.01, and 0.1 M at pH 10, both the anodic current and the number of pits on the cobalt surface were gradually increased. X-ray photoelectron spectroscopic investigations showed that the cobalt surface was covered mostly with cobalt hydroxide after anodic polarization at pH 10 in 0.1 M NaCl.     

Electrodissolution of iron in sodium sulfate and sodium bicarbonate solutions at pH8

The effect of sulfate ions on the electrochemical behaviour of iron electrodes in the presence of bicarbonate ions has been investigated. In solutions containing sulfate ions only, iron electrodes experience uniform corrosion and sulfate ions are aggressive. In the presence of bicarbonate ions, the sulfate ions become less aggressive and a pitting–repassivation process is observed. The differences in electrochemical behaviour have been compared and explained by examining the formation of probable products and their physicochemical properties during electrochemical polarization.     

Raman Spectroscopic Study of Gallium-Doped Ba(Zn1/3Ta2/3)O3

Resonators of Ba(Zn_1/3Ta_2/3)O₃, sintered between 1450° and 1600°C, are characterized by Raman spectroscopy, X-ray diffraction, and scanning electron microscopy. The quality factors of the resonators are found to depend on sintering temperature, and at 1600°C there is evidence of Zn loss from the surface. The frequency of the A_1g Raman mode changes from 800.9 cm⁻¹ for a sample with Q = 80000 (2 GHz), to 794.5 cm⁻¹ when Q = 44000 (2 GHz). Changes in the position of this and other Raman modes are thought to be due to distortions of the oxygen octahedra, brought about by Zn loss. The presence of a BaTa₂O₆ phase at the surface is confirmed by XRD and SEM.     

Electrodissolution of iron in sodium sulfate and sodium bicarbonate solutions at pH8

The effect of sulfate ions on the electrochemical behaviour of iron electrodes in the presence of bicarbonate ions has been investigated. In solutions containing sulfate ions only, iron electrodes experience uniform corrosion and sulfate ions are aggressive. In the presence of bicarbonate ions, the sulfate ions become less aggressive and a pitting–repassivation process is observed. The differences in electrochemical behaviour have been compared and explained by examining the formation of probable products and their physicochemical properties during electrochemical polarization.     

Thermal and electrochemical properties of cobalt containing Finemet type alloys

This paper presents results concerning the effect of cobalt substitution on bulk (thermal) and surface (electrochemical) properties of Finemet type alloys. Thermal properties of the alloys were determined by differential scanning calorimetry (DSC). The partial substitution of iron for cobalt up to 10 at.% improves the stability of the alloys. The results obtained using various electrochemical techniques show that the new component does not improve notably the electrochemical characteristics of the basic composition alloy sample in KOH solutions. On the other hand, the high corrosion rate registered in HCl solutions does not allow us to obtain quantitative data.     

Use of polymeric compatibilizers in polypropylene/calcium carbonate composites

The effects of compatibilizing agents on the mechanical properties, viscoelastic properties, and morphology of polypropylene filled with calcium carbonate composites are investigated. It is found that the use of PP-g-MA and PP-g-AA significantly increases the tensile strength and improves particle dispersion and interfacial adhesion. The higher effect of compatibilization is obtained by using PP-g-MA as a compatibilizer. The results on the dynamic thermomechanical properties, viscoelastic properties, and SEM pictures also support the improved interfacial characteristics. It is also found that there exists a limiting amount of PP-g-MA at about 5% beyond which a further increase in the tensile strength is not obtained. The use of untreated calcium carbonate or SEBS-g-MA does not allow films to be drawn for the purpose of testing.     

Chemical fixation of carbon dioxide to dimethyl carbonate from propylene carbonate and methanol using ionic liquid catalysts

The synthesis of dimethyl carbonate (DMC) through the transesterification of propylene carbonate (PC) with methanol was investigated by using imidazolium salt ionic liquid catalysts. 1-alkyl-3-methyl imidazolium salts of different alkyl group (C₂, C₄, C₆, C₈) and anions (Cl⁻, Br⁻, BF₄⁻, PF₆⁻) were used for catalysts. The reaction was carried out in an autoclave at 140–180°C under carbon dioxide pressure of 1.48–5.61 MPa. The imidazolium salts of shorter alkyl group, and more nucleophilic counter anion exhibited higher catalytic activity. The conversion of PC increased as CO₂ pressure and reaction temperature increased. Kinetic studies were also performed to better understand the reaction mechanism. This paper was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Ball milling and annealing graphite in the presence of cobalt

When graphite is ball milled, Raman spectra and X-ray diffractograms of the products show increasing graphitic structural disorder with 1% and 10% cobalt addition. However, if sufficient cobalt (10% weight for weight) is added, this process is reduced in rate. This process is attributed to the cobalt stabilizing the graphitic structure during ball milling, thus reducing the degree of lattice-disorder.When the mixture is annealed, well-ordered carbon strips encapsulating cobalt nanoparticles are observed in the presence of cobalt.Annealing reorganizes the disordered structures and 10% cobalt loading is more effective than a 1% loading in this process. Transmission electron microscopic (TEM) analysis showed the formation and high abundance of well-ordered carbon strips encapsulating cobalt nanoparticles in samples that have been annealed with additional cobalt loading.     

Separation of cobalt and nickel from sulfate media using P507-N235 system

Separation of cobalt and nickel from sulfate media was investigated, using a extraction system of 30% 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (P507)+15% trioctyl/decylamine (N235)+55% sulfonated kerosene. About 41 wt% Co²⁺ was extracted with 1.6 wt% co-extraction of Ni²⁺ at O/A ratio of 2:1. Scrubbing of Ni²⁺ and stripping of Co²⁺ could be achieved from the loaded organic phase, using water and 0.05 mol/L H₂SO₄, respectively. Cobalt extraction percentage decreased with increasing Mg²⁺ concentration, but this influence was negligible as [Mg²⁺] < 0.1g/L. The favorable equilibrium pH was 4–4.8. A different E-pH curve was observed in the P507-N235 system compared to the saponified P507 system.     

碳酸氢镁溶液增浓的研究

碳酸氢镁溶液热解能耗占整个白云石碳化法制取钙镁盐产品工艺能耗的45%左右。为了降低热解能耗,通过优化碳化工艺条件,以提高碳酸氢镁溶液浓度。通过正交试验对碳化温度、白云石灰乳中氧化镁质量浓度、二氧化碳气体流量、过碳化时间进行较为系统的研究。在碳化温度为10℃、白云石灰乳中氧化镁质量浓度为16.60 g/L、二氧化碳气体流量为433.04 L/h、过碳化时间为10 m in时,白云石灰浆碳化所得碳酸氢镁溶液中氧化镁质量浓度为18.79 g/L,远大于目前工业生产中5~8 g/L的水平,为白云石碳化工艺的节能降耗提供依据。