Formation of Black Patina on Bronze Mirrors Caused by Multiphenol

Hot solution of hydroquinone is oxidized by air forming quinone and quinhydrone, both of which have weak oxidizeability, enabling to oxidize metals on the surface of bronze mirror samples forming black and brilliant patina. SEM and electron micro probe analysis show that Cu content is lower than that of the original alloy due to Cu loss; Sn content is higher than the original alloy in patina. This indicates that humic acid is not the substance resulting in making black patina on the bronze mirror surface, but the black patina which produced from hydroquinone solution absence of Si, Al and Mg.     

Structure and Formative Mechanism of Black Patina on Bronze Mirrors

The formation of the black patina induced by soil humic asid under different conditions was studied, theblack, grey and brown colored shiny surfaces prepared in laboratory were analyzed. As a result the formation oftin-rich shiny black surface on bronze mirrors is the product of soil corrosion of the bronze mirrors. The patina isformed by reection between the alloy and the humic acid in soil, and leaching of copper and lead oxides through along period time when the mirrors were buried under the ground leaving a dense compact corrosion-resistant layerconsisted predominantly of stannic oxide microcrystal.     

温度和氯盐对混凝土硫酸盐化学腐蚀的影响

为揭示混凝土在不同硫酸盐腐蚀环境下的损伤过程及腐蚀机理,进行了硫酸盐浸泡实验,研究了在复合溶液浸泡作用下混凝土的抗压强度演变、腐蚀产物类型及硫酸根离子反应能力.结果表明:混凝土在硫酸钠溶液中抗压强度先增加后降低,且主要腐蚀产物是钙矾石和石膏.在复合溶液腐蚀环境下,腐蚀产物以钙矾石为主,且混凝土亚微观缺陷减少6.46%.当提高腐蚀溶液温度至50℃时,混凝土的抗压强度演变速度加快,硫酸根离子反应能力提高20%,腐蚀产物以石膏为主.     

Formation of Black Patina on Bronze Mirrors Caused by Humic Acid

The formation of black patina caused by soil humic acid under different conditions has been studied,and the black, grey and brown shiny surfaces prepared in laboratory have been analysed. The formation of tin-rich shiny black surface on mirrors was the product of the soil corrosion of the bronze mirrors. It is formed by reaction between the alloy and the humic acid in soil, and leaching of copper and lead oxides through a long period of time when the mirrors were buried under the ground. A dense cormsion-resistallt layer on the bronze mirrors consisted predominantly of stannic oxide.     

Synthesis and X—ray Powder Diffraction Characterization of A New Niobate Crystal Ba4Na2VNb9O30

A new niobate crystal Ba4Na2VNb9O30 was synthesized in BaO-Na2O-V2O5-Nb2O5 system for the first time.Its shape, optical properties ,melting point and chemical stability were studied.X-ray powder diffraction study determined that this compound assumes a tetragonal tungsten bronze structure with space group P4bm(100) and lattice parameters a=b=12.4275(2), c=3.970(3). The new compound may be one kin of photorefractive srystals.     

毛细作用下硫酸钠半浸泡水泥基材料抗氯离子渗透性研究

硫酸盐和氯盐复杂盐蚀环境中的服役结构会受到两者产生的耦合作用。研究毛细作用下硫酸钠半浸泡混凝土试样的抗氯离子渗透性能,设计不同水灰比、不同硫酸钠溶液浓度的砂浆毛细上升试验,测试硫酸钠半浸泡混凝土试样的扫描电镜（SEM）、X射线衍射（XRD）和氯离子电通量。结果表明：硫酸钠半浸泡混凝土抗氯离子渗透性能劣化,前期劣化严重,随着半浸泡时间的延长,抗氯离子渗透性能有所回升,但依然比未浸泡试样的差。结合微观测试结果可知,混凝土抗氯离子渗透性能劣化的主要原因是：前期,在毛细作用下硫酸钠溶液填充了混凝土孔隙,减弱了固化氯离子的结合能力,释放了较多自由氯离子,从而增大了氯离子的扩散量;后期,随着浸泡时间的延长和环境湿度的变化,孔隙中的硫酸钠溶液过饱和后,形成无水Na₂SO₄和Na₂SO₄·10H₂O结晶体的混合物,结晶混合物沉淀于孔壁,部分阻碍了氯离子的扩散,从而减缓了抗氯离子渗透性能的劣化。硫酸钠溶液浓度超过5%以后,随着硫酸钠溶液浓度的升高,毛细上升速度减缓,混凝土抗氯离子渗透性能相应提高。硫酸钠溶液半浸泡下,水泥基材料毛细上升快慢可作为衡量混凝土抗氯离子渗透性能好坏的指标。硫酸钠和氯化钠的复合溶液对硫酸钠毛细上升有延缓作用,会改善混凝土的抗氯离子渗透性能。     

Diffusion characteristic of sulfate anion in surface region of cement mortar at early stage

The SO_4~(2-)concentration distributions in surface region of cement mortar immersed in sulfate solution at early stage were measured by layered sampling method combined with chemical analysis, and the diffusion coefficients of SO_4~(2-)anions in surface region of mortar into internal area were calculated by means of instantaneous plane diffusion theory. The experimental results showed that the SO_4~(2-)concentration gradually reduced when the diffusion depth increased in the surface region of mortar. Diffusion coefficient(D) was relevant with the concentration and kind of environmental sulfate solution, which reduced with immersion time at the beginning, and then rose slowly after a period of time. The calculation of initial diffusion coefficient(D_0) and starting time of deterioration(t_∞) caused by sulfate attack was further attempted based on the data of diffusion coefficient, and it was found that D_0 and t∞ were all relevant with concentrations of sulfate and different kind of sulfate as well.     

Dissolution kinetics of malachite in ammonia/ammonium sulphate solution

The dissolution kinetics of malachite was investigated in ammonia/ammonium sulphate solution. The effects of ammonia and ammonium sulphate concentration, pH, leaching time, reaction temperature, and particle size were determined. The results show that the optimum leaching conditions for malachite ore with a copper extraction more than 96.8% are ammonia/ammonium concentration 3.0 mol/L NH₄OH + 1.5 mol/L (NH₄)₂SO₄, liquid-to-solid ratio 25:1 mL/g, leaching time 120 min, stirring speed 500 r/min, reaction temperature 25 °C and particle size finer than 0.045 mm. The dissolution process of malachite with an activation energy of 26.75 kJ/mol is controlled by the interface transfer and diffusion across the product layer. A semi-empirical rate equation is obtained to describe the leaching process and the reaction orders with respect to concentration of ammonia and ammonium sulphate are 2.983 0 and 0.941 1, respectively.     

Use of different barium salts to inhibit the thaumasite form of sulfate attack in cement-based materials

We investigated the effects of different barium compounds on the thaumasite form of sulphate attack(TSA)resistance of cement-based materials when they were used as admixtures in mortars.Moreover,we analyzed the inhibition mechanisms within different types of barium salts,namely BaCO_3 and Ba(OH)_2,on the thaumasite formation.The controlcement mortar and mortars with barium salts to cement and limestone weight ratios of 0.5%,1.0%,and 1.5% were immersed in 5%(by weight)MgSO_4 solution at 5 ℃ to mimic TSA.Appearance,mass,and compressive strength of the mortar samples were monitored and measured to assess the generaldegradation extent of these samples.The products of sulphate attack were further analyzed by XRD,FTIR,and SEM,respectively.Experimentalresults show that different degradation extent is evident in allmortars cured in MgSO_4 solution.However,barium salts can greatly inhibit such degradation.Barium in hydroxide form has better effectiveness in protection against TSA than carbonate form,which may be due to their solubility difference in alkaline cement pore solution,and the presence of these barium compounds can reduce the degree of TSA by comparison with the almost completely decomposed controlsamples.     

Investigation on phase evolution of the ZnO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> glass ceramics

ZnO-B₂O₃-SiO₂-Al₂O₃-Na₂O glass doped with nucleating agent TiO₂ was prepared with melting-quenching method and the effect of nucleating agent on the crystallization behavior and phase evolution of this glass was investigated by differential thermal analysis (DTA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The experimental results show that the glass transition temperature and the first crystallization temperature decrease from 630 °C and 765 °C to 595 °C and 740 °C, respectively, with introduction of TiO₂ into glass. There is no diffraction peaks in the XRD pattern but it is no longer transparent for the base glass without nucleating agent after heat treatment, which suggests the serious phase separation occurred, and the observation by SEM indicates that the phase separation is developed by nucleation and growth mechanism. However, there are two different crystals ZnAl₂O₄ and NaAlSiO₄ present in the glass containing TiO₂ after heat treating at 575 °C for 2 h and 740 °C for 6 h, respectively. What is interesting is that NaAlSiO₄ disappears as the crystallization time at 740 °C increases from 6 h to 12 h, and more ZnAl₂O₄ crystal is formed, namely, the further formation of ZnAl₂O₄ is at cost of NaAlSiO₄ with increasing crystallization time. And observation of the morphology of glass ceramics shows great difference with increasing crystallization time. Moreover, the ability of ZnO-B₂O₃-SiO₂-Al₂O₃-Na₂O glass ceramics against attacking of 1M HCl solution is increased by the crystals precipitated in heat treatment process.     

Recovery of copper sulfate after treating As-containing wastewater by precipitation method

The solid sodium hydroxide neutralized acidic As-containing wastewater till pH value was 6. Green copper arsenite was prepared after copper sulfate was added into the neutralized wastewater when the molar ratio of Cu to As was 2:1 and pH value of the neutralized wastewater was adjusted to 8.0 by sodium hydroxide. The arsenious acid solution and red residue were produced after copper arsenite mixed with water according to the ratio of liquid to solid of 4:1 and copper arsenite was reduced by SO₂ at 60 °C for 1 h. The white powder was gained after the arsenious acid solution was evaporated and cooled. Copper sulfate solution was obtained after the red residue was leached by H₂SO₄ solution under the action of air. The results show that red residue is Cu₃(SO₃)₂·2H₂O and the white powder is As₂O₃. The leaching rate of Cu reaches 99.00% when the leaching time is 1.5 h, molar ratio of H₂SO₄ to Cu is 1.70, H₂SO₄ concentration is 24% and the leaching temperature is 80 °C. The direct recovery rate of copper sulfate is 79.11% and the content of CuSO₄·5H₂O is up to 98.33% in the product after evaporating and cooling the copper sulfate solution.     

Formation and dielectric properties of Mn-Doped BSTN composite ceramics

The influence of Mn doping on the formation and dielectric properties of 0.7BaO·0.3SrO·(1−y)TiO₂·yNb₂O₅ (BSTN) composite ceramics were investigated. The Mn was doped according to the formula 0.7BaO·0.3SrO·(0.7−z)TiO₂·0.3Nb₂O₅·zMnO₂ (BSTNM). The results show the two phases, perovskite phase BST and the tungsten bronze phase SBN, are coexistence in BSTNM as they are in BSTN composite ceramics. The Mn ions doped in BSTN substitute for Nb⁵⁺ ions in the tungsten bronze phase, and then, the Nb⁵⁺ ions substitute for Ti⁴⁺ ions in the perovskite phase. With the increasing of Mn dopant, the content of the perovskite phase increases while that of the tungsten bronze phase decreases, and the grain size of the perovskite phase decreases. As well as, the phase transition temperature of tungsten bronze phase increases with value z increasing from 0 to about 0.05.     

Corrosion resistance of cerium conversion film electrodeposited on Mg-Gd-Y-Zr magnesium alloy

The cerium conversion film was applied to improving the corrosion resistance of Mg-Gd-Y-Zr magnesium alloy. The film was electrodeposited on the surface of the Mg-RE alloy in cerium nitrate solution. The compositions and morphologies were analyzed by X-ray diffraction(XRD), scanning election microscopy (SEM). The corrosion behaviors of the film were investigated electrochemical impedance spectroscopy (EIS), potentiodynamic polarization tests and immersion tests. The results show that the optimum parameters for electrochemical deposition are as follows: pH 10.0, time 30 min, 50 mmol/L Na₂CO₃ and temperature 25 °C by the designed experiments according to the orthogonal table L(9, 3⁴). The corrosion protection efficiency is dependent on the deposition parameters. The cerium conversion film shows better corrosion protection behavior than chromate conversion film on Mg-Gd-Y-Zr magnesium alloy. Foundation item: Project (5133001E) supported by the Major State Basic Research and Development Program of China     

Influence of MgO/MgCl2 molar ratio on phase stability of magnesium oxychloride cement

Formation, solution and phase change of hydration products in MgO-MgCl₂-H₂O system was studied with thermodynamics method, and resistance to water immersion and phase change of magnesium oxychloride cement with different MgO/MgCl₂ molar ratio was experimented. The results show that pH value of immersion solution of cement paste has a remarkable influence on phase stability of hydration products. A higher pH value leads to a lower solubility and a better phase stability of hydration products. When the solution pH value is higher than 10.37, the precipitation of much Mg(OH)₂ crystal induces a worse phase stability of hydration products. With the increasing MgO/MgCl₂ molar ratio (lower than 6), the more amount of MgO in the hydration products enhances the alkalinity of solution and the phase stability is improved. However, when the MgO/MgCl₂ molar ratio is higher than 6 and the excessive MgO exsits in the hydration products, the cement paste may be damaged by the excessive crystallization stress of a great deal of Mg(OH)₂ formation. Funded by the National Natural Science Foundation of China(No. 50078019)     

In vitro biomineralization of glutaraldehyde crosslinked chitosan/glutamic acid films

In vitro biomineralization of glutaraldehyde crosslinked chitosan/glutamic acid films were studied. IR and ESCA (electron spectroscopy for chemical analysis) determinations confirm that chitosan and glutamic acid are successfully crosslinked by glutaraldehyde to form chitosan-glutamic acid surfaces. Composite films were soaked in saturated Ca(OH)₂ solution for 8 d and then immersed in simulated body fluid (SBF) for more than 20 d. Morphological characterizations and structure of calcium phosphate coatings deposited on the films were studied by SEM, XRD, and EDAX (energy dispersive X-ray analysis). Initially, the treatment in SBF results in the formation of single-layer calcium phosphate particles over the film surface. As immersion time increases, further nucleation and growth produce the simulated calcium-carbonate hydroxyapatite coating. ICP results show Ca/P ratio of calcium phosphate coating is a function of SBF immersion time. The inducing of glutamic acid improves the biomineralization property of chitosan films. Funded by the Natural Science Foundation of Shanghai (No. 04ZR14087)     

Infrared spectroscopy study of structural nature of geopolymeric products

The bonding status and chemical environment of SiO4 and AlO4 tetrahedras of three types of geopolymeric products were systematically investigated by infrared spectroscopy. The relationship between amorphous geopolymeric products and zeolite crystals with the same overall chemical compositions was also discussed. The infrared evidence shows that SiO4 tetrahedra is partially bonded by AlO4 during the hydration process of geopolymeric cement. The two types of tetrahedras jointly construct the three dimensional framework structures of the geopolymeric products. The mutual transformation between geopolymeric products and corresponding zeolite crystals will take place once the reaction condition is suitable, which reveals that the nature ofgeopolymeric products are probably the amorphous equivalent of the corresponding zeolite crystals.     

ZnO纳米薄膜在竹材表面的生长及防护性能

在低温溶液反应体系下,通过晶种形成和晶体生长两步法在竹材表面培育ZnO纳米结构薄膜,应用场发射环境扫描电镜(FESEM)、X射线衍射仪(XRD)和X射线能谱仪(EDAX)对薄膜形态和结构进行表征,重点研究种子液浸渍时间对纳米薄膜形态及竹材防霉和抗光变色性能的影响.研究结果表明,在生长时间一定的前提下,竹材在种子液中经过0.5 h、1 h和2 h的浸渍,其表面可形成壁厚为50～80 nm的网状结构薄膜,使竹材的防霉性能和光稳定性得到显著改良;当种子液浸渍时间增加到4 h,网状结构薄膜则被大量直径约700 nm的ZnO圆片所覆盖,虽然此时竹材的防光变色性能保持不变,但防霉性能下降,表明纳米网状结构对于充分发挥ZnO防护性能起到重要作用.     

Characterization and photocatalytic activity of KSr<Subscript>2</Subscript>Nb<Subscript>5</Subscript>O<Subscript>15</Subscript> with tungsten bronze structure

Tungsten bronze (TB) type potassium strontium niobate KSr₂Nb₅O₁₅ was prepared by solid-state reaction method, and was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and UV-vis diffuse spectrum. The photocatalyst shows high photocatalytic activity of photodegrading acid red G. The effects of photocatalyst dosage and initial concentration of acid red G on the photodegradation process were studied. The kinetics of photocatalytic degradation of acid red G by KSr₂Nb₅O₁₅ catalyst follows the first order reaction.     

Electroless copper plating process of N, N, N′, N′-tetrakis (2-hydroxypropyl) ethylenediamine system with high plating rate

Electroless copper plating process of N, N, N′, N′-tetrakis (2-hydroxypropyl) ethylenediamine (THPED) chelating agent was researched comprehensively. The results indicate that plating rate decreases with the increase of concentration for THPED, CuSO₄ · 5H₂O and HCHO, pH value and bath temperature. The additive of K₄[Fe(CN)₆] · 3H₂O, 2, 2′-dipyridyl and polyethylene glycol(PEG) decrease plating rate and K₄[Fe(CN)₆] · 3H₂O has a bad effect on deposits quality, but 2, 2′-dipyridyl and PEG make deposits quality improve greatly. Low concentration of 2-mercaptobenzothiozole (2-MBT) increases plating rate and improves deposits quality, but decreases plating rate and worsens deposits quality when 2-MBT reaches 5 mg/L. The optimal conditions of this electroless copper plating process are that the concentration of THPED, HCHO, CuSO₄ · 5H₂O, PEG, 2, 2′-dipyridyl and 2-MBT are 16.8 g/L, 16.0 mL/L, 13.3 g/L, 0.5 g/L, 5.0 mg/L and 2.0 mg/L, respectively, pH value is 12.75, bath temperature is 30 °C. Plating rate reaches 9.54 μm/h plating for 30 min in the bath. The SEM images demonstrate that the surface of copper film is smooth and the crystal is fine. Foundation item: Project supported by Hubei Daye Nonferrous Metal Corporation of China     

Sulfidization regulation of cuprite by pre-oxidation using sodium hypochlorite as an oxidant

The direct sulfidization of cuprite is inefficient because cuprite is a copper-oxide mineral with a strong surface hydrophilicity. In this study, oxidant was used to modify cuprite surfaces to regulate the sulfidization of cuprite. Microflotation tests showed that the flotation recovery of pre-oxidized cuprite was nearly 25% higher than that of direct sulfidization flotation, which indicates that the cuprite surface activity was enhanced after pre-oxidation by Cu(I) species (weak affinity with sulfur ions) transformation to Cu(II) species (strong affinity with sulfur ions). Zeta potential, scanning electron microscopy-energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry results showed that pre-oxidation improved cuprite sulfidization and promoted the formation of copper-sulfide species on the cuprite surfaces. The mineral surface stability and thus, xanthate species adsorption on the cuprite surfaces were improved. The surface-adsorption measurements and infrared spectroscopy showed that a large amount of xanthate species was adsorbed onto the sulfidized cuprite surfaces after pre-oxidation, which enhanced the cuprite hydrophobicity and improved the cuprite flotation.