碳酸乙烯酯添加剂对BMImBF4离子液体作为镁沉积—溶解电解液的改性研究

利用恒电流沉积-溶解、交流阻抗、XRD和SEM方法研究了在室温下EC(碳酸乙烯酯)添加剂对BMImBF₄离子液体作为镁沉积电解液的改善情况. 在Mg(CF₃SO₃)₂浓度为0.3 mol•L^－1的BMImBF₄电解液中加入w＝5%(质量分数)的EC后, 沉积—溶解循环过程更加稳定, 并且循环次数明显增加, 可以达到265次以上; 交流阻抗结果显示, 膜电阻和电荷转移电阻有所减少; 从SEM图可以观察到, 在沉积初期原本枝晶态的镁在加入EC后以颗粒状沉积. 可能是EC添加剂在反应中形成的低聚物覆盖在镁的表面, 抑制了枝晶的形成.     

Influence of Mg surface layer for induction period of Grignard reagent formation

Factors that affect the induction period of Grignard reagent formation, which involves heterogeneous reaction between magnesium metal (Mg) and an alkyl halide in ether solvent, has been clarified to achieve safer and more efficient operation in chemical processes. The influence of the Mg surface, especially the effects of carbonate, hydroxide, and oxide layers on the induction period were investigated by measuring the exothermic behavior of Grignard reagent formation by a differential reaction calorimeter. Mg powder was kept in water bubbled with CO₂ or N₂ gas to form a coating on the Mg surface. The calorimetry results for the reaction indicated that both treatments increased the induction period. Thermogravimetric analysis-mass spectrometry was conducted to identify the chemical species and quantify the amount of surface material on the Mg particles. It was found that basic magnesium carbonate and magnesium hydroxide were formed on Mg exposed to CO₂ and N₂, respectively. Subsequent heating the carbonate- or hydroxide-coated Mg at 500 °C caused a MgO layer to form on the surface, which was found to dramatically reduce the induction period.     

镁离子存在下乙醇-水混合溶液中碳酸钙结晶行为的研究

通过对不同反应体系中合成样品的物相及镁含量变化规律的分析, 认为水溶液中碳酸钙的结晶遵循溶解重结晶机理, 乙醇-水溶液中则以聚集重构为主, 碳酸根阴离子的溶剂化作用对碳酸钙的沉积产生显著影响. 采用XRD, IR等手段对醇水混合溶液中合成的碳酸钙样品进行分析, 认为形成了含镁方解石及具有类白云石结构的过渡相同时存在的混合物相, 醇水溶液中含镁方解石趋于白云石化.     

Nature of the silver precipitation obtained by cementation from thiosulphate solutions

The morphology and composition of the deposits formed on the surface of magnesium disk during cementation from thiosulphate solutions (0.0025–0.1M) [Ag(S₂O₃)₂]³⁻ + 0.5M S₂O₃ ²⁻ have been studied. A porous deposit with low adhesion is formed on the surface of the magnesium metal substrate. Within a wide range of [Ag(S₂O₃)₂]³⁻ ion concentrations, sulfur as well as silver are constituents of the deposit at the initial stages of cementation and at the end of the reaction. This is attributed to the electrochemical behaviour of magnesium in thiosulphate solutions resulting in the exceeding of current limit on cathode for pure silver reduction. Hence, parallel electrochemical reactions take place that are very close in their values to the standard redox potentials of reduction of [Ag(S₂O₃)₂]³⁻ ions to Ag⁰ and S₂O₃2− ions to S²⁻. Sulfur content in the cement deposits increases with the decrease in [Ag(S₂O₃)₂]³⁻ ion concentration and increase in cementation time. This tendency is also observed with the decreasing solution temperature.     

Characterization of the adsorption state of carbonate ions at the Au(111) electrode surface using in situ IRAS

The spectro-electrochemical behavior of carbonate and bicarbonate ions at the Au(111) electrode surface was studied using the infrared reflection absorption spectroscopy (IRAS). An absorption band caused by the adsorbed carbonate ions was observed in the wavenumber region of 1425–1511 cm⁻¹ both in Na₂CO₃ and NaHCO₃ solutions. It was concluded that the adsorbed carbonate ions co-ordinate with the electrode surface in the unidentate state with their symmetry axis normal to the substrate. This orientation is retained in the whole potential region where carbonate ions adsorb on the electrode surface in contrast to the behavior of the carbonate ions adsorbed on the Pt(111) electrode surface.     

Effect of adsorption of polyhexamethyleneguanidine derivatives on the formation rate,morphology, and phase composition of carbonate deposits

It was found that introduction of polyhexamethylguanidines modified with carboxy and phosphonic groups into a saturated solution of calcium carbonate affects the formation rate, morphology, and phase composition of the deposits being formed, with crystals in the deposit becoming coarser and rhombic structures appearing. These phenomena were manifested to a greater extent when zinc complexes of polyelectrolytes are present in solution. An analysis of the phase composition of the deposit demonstrated that the presence of polyelectrolytes and their zinc complexes in solution leads to an increase in the amount of the calcite phase. The reason why the phase composition and morphology of the deposits changes is that polyelectrolytes and their complexes are adsorbed on the surface of carbonate deposits. The adsorption of polyelectrolytes on a calcium carbonate powder is described by the Langmuir isotherm and the formation of their zinc complexes leads to an increase in the adsorption equilibrium constant by more than a factor of 2, which is due to the change in the hydrophilic-lipophilic balance of macromolecules in complexation.     

Thermal stability of artinite, dypingite and brugnatellite—Implications for the geosequestration of green house gases

The approach to remove green house gases by pumping liquefied carbon dioxide several kilometres below the ground implies that many carbonate containing minerals will be formed. Among these minerals the formation of dypingite, artinite and if the ferric iron is present brugnatellite are possible; thus necessitating a study of the thermal stability of such minerals. The thermal stability of two carbonate bearing minerals dypingite and artinite together with brugnatellite with a hydrotalcite related formulae have been characterised by a combination of thermogravimetry and evolved gas mass spectrometry. Artinite is thermally stable up to 352 °C. Two mass loss steps are observed at 219 and 355 °C. Dypingite decomposes at a similar temperature but over a large number of steps. Brugnatellite shows greater stability with decomposition not occurring until after 577 °C. The thermal decomposition of brugnatellite occurs over a number of mass decomposition steps. It is concluded that pumping liquefied green house gases into magnesium bearing mineral deposits is feasible providing a temperature of 350–355 °C is not exceeded to prevent escape of CO₂ towards the surface. In contrast, the water loss occurring at lower temperatures could have a positive effect on the geosequestration of CO₂ as it probably causes a decrease in the molar volume of secondary carbonate minerals and consequently an increase in aquifer porosity.     

Aspects on the interaction between sodium carboxymethylcellulose and calcium carbonate and the relationship to specific site adsorption

The mechanisms of adsorption and association for sodium carboxymethylcellulose (NaCMC) in calcium carbonate suspensions have been determined from isothermal calorimetry and adsorption measurements. The equilibrium adsorption isotherms were determined by two different methods of separation; a depletion method and a serum exchange method. The enthalpy of dilution for NaCMC was determined on supernatants obtained from the calcium carbonate suspensions in order to investigate the interaction between NaCMC and dissolved species from the mineral. For comparison, NaCMC was injected into CaCl(2) solutions in order to determine the role of calcium ions in the adsorption process. The initial part of the adsorption isotherm showed a quasi-infinite slope indicating a high affinity for the NaCMC to the calcium carbonate surface, which was significantly reduced when anionic sodium polyacrylate was preadsorbed onto the calcium carbonate implying competitive adsorption. An endothermic enthalpy change was observed between the NaCMC and the calcium carbonate surface, suggesting attachment of the carboxylic acid groups onto the hydrated calcium sites. A similar endothermic enthalpy was observed when NaCMC was injected into CaCl(2) solutions or supernatants obtained from the calcium carbonate suspensions, indicating a complexation of carboxylic acid groups and hydrated calcium ions. It was concluded that the mechanisms of interaction of NaCMC in calcium carbonate suspensions are primarily an association between NaCMC and Lewis acid sites on the calcium carbonate surface and the formation of NaCMC-Ca(2+) complexes in the bulk solution, both of which will be affected by the amount of anionic sodium polyacrylate present.     

温度和溶液pH值交互作用对X80钢在模拟土壤环境中腐蚀行为的影响

利用循环伏安法（CV）、电化学阻抗谱（EIS）和Mott-Schottky曲线研究了温度和溶液pH值交互作用下X80钢在模拟土壤环境中的腐蚀性能。结果表明：低pH值条件下X80钢表面会形成一层稳定性差的腐蚀膜;高pH值条件下X80钢表面会形成一层保护性强的腐蚀膜。随着pH值得增大和温度的降低X80钢表面所成腐蚀膜的膜电阻和传递电阻增大,这表明随着pH值得增大和温度的降低X80钢表面所成腐蚀膜对基体的保护性增强。X80钢在模拟土壤环境中表面所成腐蚀膜呈n型半导体特性,膜内施主密度随介质pH值增大而降低,随溶液温度升高而增大。平带电位和pH值之间呈现线性关系。     

Formation characteristics of calcium phosphate deposits on a metal surface by H2O2-electrolysis reaction under various conditions

The cathodic electrolysis of H₂O₂ (H₂O₂ + e⁻ → OH⁻ + OH) on a metal surface in the presence of calcium and phosphate ions results in the formation of calcium phosphate deposits on the metal surface. In this study, the deposits formed under various treatment conditions (pHs, concentrations and ratios of calcium/phosphate ions, and so on) were characterized by scanning electron spectroscopy (SEM), and X-ray diffractometry. The exclusive formation of hydroxyapatite, HAP, was observed under comparatively narrow conditions (pH 3–4, [Ca+]/[PO₄³⁻] = 25 mM/15 mM), which is clearly different from the reported conditions for the deposition of HAP on titanium substrates. HAP was deposited in the form of a layer, comprised of morphologically amorphous HAP flakes that were less than 20 nm thick. SEM and FTIR analyses of the deposit at different stages of H₂O₂-electrolysis revealed that a few dozen nanometer-sized spheres of amorphous calcium phosphate were formed in the first step and then fused with each other to form ribbon-like flakes of HAP or broken glass-like brushite, depending on the pH. The pH for HAP formation on a stainless steel surface was markedly lower than that used for titanium, and the observed process by which amorphous calcium phosphate is converted to HAP was markedly different from that for the electrochemical deposition (electrolysis of water) of HAP on a titanium substrate.     

XPS study of the effect of aluminium on the atmospheric corrosion of the AZ31 magnesium alloy

The surface characteristics and corrosion behaviour of the AZ31 magnesium alloy exposed to a high relative humidity (RH) atmosphere were investigated. During the first 15 days of humidity test at 98% RH and 50 °C, a significant increase of magnesium carbonate and a decrease of magnesium oxide were detected on the surface film by XPS; after this stage, increased exposure times did not produce substantial changes on the relative amounts of these compounds. The surface film of commercially pure magnesium, also examined for comparison purposes, revealed more magnesium carbonate and less magnesium oxide compared with the AZ31 alloy. Unlike the AZ31 alloy, the surface of pure Mg disclosed almost complete substitution of MgO by magnesium carbonate after 30 days of exposure time. Mass gain values of tested specimens and scanning electron microscope characterisation of corroded surfaces indicated lower corrosion susceptibility of the AZ31 alloy compared with the commercially pure Mg, suggesting superior chemical stability of the oxide/hydroxide film formed over the magnesium–aluminium alloy surface. XPS and energy dispersive X‐ray (EDX) analyses did not revealed any substantial enrichment of aluminium in the corrosion products film on the AZ31 alloy after 30 days of testing. Copyright © 2008 John Wiley & Sons, Ltd.     

22Cr双相不锈钢钝化膜组成及其半导体性能研究

借助于Mott-Schottky方程分析了成膜电位、成膜时间、成膜温度以及氯离子等因素对22Cr双相不锈钢在碳酸氢钠/碳酸钠缓冲溶液中所成钝化膜半导体性能的影响, 同时借助于X射线光电子能谱(XPS)技术分析了所成钝化膜的组成. 结果表明: 22Cr双相不锈钢在碳酸氢钠/碳酸钠缓冲溶液中所成钝化膜呈n-p型半导体结构, 钝化膜内施主/受主密度随成膜电位增加、成膜时间延长、成膜温度降低、以及介质中氯离子浓度的降低而减小, 同时膜对基体保护作用随这些因素变化而增强. 钝化膜的XPS分析表明, 钝化膜呈现双层结构, 外层膜主要由三价铁的氧化物(Fe2O3)组成, 内层膜主要由三价铬氧化物(Cr2O3)以及少量二价铁氧化物(FeO)组成.     

Study on the anodic behavior of AISI E52100 steel in two fluorine-containing ionic liquids

Ionic liquids have a number of excellent applications such as a kind of promising lubricants which have attracted considerable attention. In this work, we investigated corrosion properties which were found in the use of ILs formed by a 1-butyl-3-methylimidazolium cation and a fluorine-containing anion as lubricants of AISI E52100 steel. Electrochemical tests were used to study the anodic behavior of AISI E52100 steel, and surface analysis was performed to study the surface morphology. The electrochemical results showed that increasing temperature accelerates corrosion of the alloy in two kinds of ionic liquids. The data obtained from polarization curves and EIS suggested that the anodic process of the E52100 steel showed generally an active dissolution and increasing temperature can accelerate the corrosion of the steel. At the same time, the main difference as revealed by SEM–EDS plots was that localized corrosion with some irregular etch pits occurred in [Bmim]BF₄ ionic liquid; however, a product layer covered uniformly on the surface of metal in [Bmim]PF₆. The results of XPS spectrum indicated that the corrosion products formed on the surface of the AISI E52100 steel are mainly composed of FeO, Fe₂O₃, FeF₂ and FeF₃.

     

Corrosion product formation on zinc-coated steel in wet supercritical carbon dioxide

In a wet supercritical carbon dioxide atmosphere, carbon dioxide is dissolved into water and causes corrosion of zinc-coated steel. The first corrosion products appeared in singular nano-scale initiation sites, which gradually grew in number and size and ultimately covered the whole surface. Zinc hydroxy carbonate was detected as a rapidly forming needle-like corrosion product, which prevailed at short exposure times (from minutes to hours). A prolonged exposure caused conversion of zinc hydroxy carbonate to anhydrous zinc carbonate with high crystallinity and a stable, dense layer was formed on zinc. The chemical transition from zinc hydroxy carbonate to anhydrous carbonate was reported for the first time and is in the light of current literature unique for wet scCO₂ atmosphere.     

碳酸酯类电解液中Mg(NO3)2添加剂抑制锂枝晶生长的研究

在锂-硫化聚丙烯腈电池体系中,负极锂枝晶的形成和生长严重恶化了电池充放电性能,并给电池带来了安全隐患。而在更有利于稳定正极硫化聚丙烯腈材料的碳酸酯类电解液中,锂枝晶生长尤为严重。本文通过将硝酸镁添加到碳酸酯类电解液中,研究硝酸根和镁离子对锂金属表面改性的共同作用。实验数据发现,在硝酸根和镁离子共同作用下,锂枝晶生长被有效抑制。当硝酸镁浓度为100 mmol·L^-1时,锂铜半电池的库仑效率明显提高,并显著改善了锂-硫化聚丙烯腈电池的循环性能。300次循环后容量保持率为71%,远高于硝酸锂的61%和无添加剂的50%。     

Conducting polyaniline/nano-zinc phosphate composite as a pigment for corrosion protection of low-carbon steel

Zinc phosphate (Zn₃(PO₄)₂) nanocrystals were synthesized and used for making conducting polyaniline/nano-zinc phosphate composite by chemical oxidative method. The product was characterized by UV–visible absorption spectroscopy. The crystal structure, morphology and thermal stability of the product were studied by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and thermo gravimetric analysis, respectively. The epoxy-based paint containing conducting polyaniline/nano-zinc phosphate composite pigment was applied on low-carbon steel samples. Corrosion protection performance of the painted low-carbon steel samples in 3.5 mass % sodium chloride solution was evaluated using electrochemical technique. Transmission electron microscopic image revealed the formation of core shell structure of the composite. Composite was found to be more thermally stable than the conducting polyaniline. The corrosion rate of conducting polyaniline/nano-zinc phosphate-painted low-carbon steel was found to be 5.1 × 10^?4 mm per year, about 34 times lower than that of unpainted low-carbon steel and 10 times lower than that of epoxy nano-zinc phosphate paint-coated steel. The study reveals the possibility of using conducting polyaniline/nano-zinc phosphate as a pigment for corrosion protection.     

Characterisation of the surface chemistry of magnesium exposed to the ambient atmosphere

The changes in the surface chemistry of the oxidised surface of evaporated magnesium metal stored in the ambient atmosphere are studied with water contact angle (WCA) measurement, polarisation‐modulation infrared reflection‐absorption spectroscopy (PM‐IRRAS) and X‐ray photoelectron spectroscopy (XPS). Upon exposure to the ambient atmosphere, the surface picks up volatile organic compounds (VOC), which cause a significant increase in the WCA values. The PM‐IRRAS and XPS analyses indicate that the adsorbates contain hydrocarbons, carboxylates and carbonate functionalities. After long ambient storage times, the composition of the carbon‐containing functionalities on the surface changes significantly. This change could be caused by the build‐up and/or surface‐catalysed oxidation of adsorbed organic species. Thickening of the air‐formed oxide/hydroxide layer was also noted, ascribed to the reaction of adsorbed atmospheric moisture with the magnesium surface. Copyright © 2006 John Wiley & Sons, Ltd.     

Synthesis of microtubes with a surface of "house of cards" structure via needlelike particles and control of their pore size

The conditions for synthesizing microtubes with a surface of "house of cards" structure via needlelike particles were examined in detail. Magnesium carbonate trihydrate was formed as a metastable phase in the reaction process using magnesium hydroxide and carbon dioxide as starting materials. Subsequently, in the formation of basic magnesium carbonate from magnesium carbonate trihydrate, microtubes with a surface of house of cards structure were obtained via needlelike particles of magnesium carbonate trihydrate under certain conditions where the temperature and added amount of sodium hydroxide were properly controlled. The pore size of the microtubes could be controlled within a range of 0.5-6 microm by adjusting the condition of needlelike particle formation. In addition, the sustainability of naphthalene release from the microtube was found to be about 6 times higher than that from naphthalene crystal.     

Effect of some thermally unstable magnesium compounds on the yield of char formed from poly(ethylene terephthalate)

Mixtures of poly(ethylene terephthalate) (PET) with magnesium compounds including carbonate, hydroxide, and oxide, with different weight ratios of the components, were subjected to thermogravimetric measurements up to 850 °C in argon atmosphere. For reference, pure components of the examined mixtures were analyzed at the same conditions. During the heating, PET underwent carbonization and magnesium carbonate and hydroxide decomposed to MgO with evolution of gaseous products (CO₂ and/or H₂O). As found, carbon yields calculated from the residual masses depended on the qualitative and quantitative composition of the starting mixture. Yields of carbon obtained from PET mixed with MgO did not depend on MgO/PET ratio. However, yields of carbon formed through pyrolysis of PET contained in the mixture with either magnesium carbonate or magnesium hydroxide were in general higher and depended on the weight ratio of components in the starting material. Reasons of these inconsistent results are discussed and explained. An influence of gasification of char on the carbon yield is explained.     

碳酸二甲酯在固体碱上吸附和活化的原位红外光谱研究

采用原位红外技术研究了碳酸二甲酯在氧化镁、氟化镁、镁铝复合氧化物和氟改性的镁铝复合氧化物4种固体碱表面上的吸附和活化行为。结果表明:碳酸二甲酯以单、双齿两种形态吸附于固体碱的表面,双齿吸附的比单齿吸附的更易活化。碳酸二甲酯吸附于氧化镁和镁铝复合氧化物上活化生成甲氧基,吸附于氟化镁上活化生成甲氟基;而吸附于氟改性的镁铝复合氧化物上优先活化生成甲氟基,随着吸附表面温度的升高,逐渐有甲氧基生成,说明氟改性的镁铝复合氧化物是一种优良的甲基化反应催化剂。