Copper corrosion in buffered and non-buffered synthetic seawater: a comparative study

The electrochemical behaviour of copper in neutral buffered and non-buffered synthetic seawater and in pure chloride solutions has been studied by cyclic voltammetry, weight loss measurements, open circuit potential and scanning electron microscopy (SEM). Values of the repassivation potentials of Cu in non-buffered and buffered synthetic seawater, at 50 mV s^–1, were 0.12 and 0.46 V vs. SCE, respectively. The sharpness, heights and location of the different peaks as well as their charges were shown to be influenced by the composition of the solution, buffering conditions, deoxygenation, polarization potential and time. High chloride concentrations lead to higher oxidation charges. The anodic and the cathodic charges were shown to increase as the chloride concentration increases. The open circuit potential transients of copper in non-deoxygenated, non-buffered synthetic seawater indicate pitting from the beginning of the exposure, while in buffered solutions the pitting appeared only after a quite long exposure period, i.e. after 40 days. Corrosion rates of Cu samples after 3 months of immersion were higher in solutions of pure chloride (0.5 M) than in synthetic seawater. After six months the differences were even more noticeable. SEM images have showed a somewhat higher density of pits on copper samples immersed in the chloride solution (0.5 M), in comparison with those in synthetic seawater.     

Enhanced cellulase production byAspergillus fumigatus fresenius

The compost isolate,Aspergillus fumigatus, produces the exoglucanase, endoglucanase, and Β-glucosidase enzymes required for the breakdown of crystalline cellulose. Cellulose breakdown and extracellular enzyme levels in liquid culture can be affected by low pH values attained during fungal growth. During growth ofA. fumigatus on modified Czapeck-Dox medium containing 1% (w/v) Avicel, it was found that Β-glucosidase activity was lost and endoglucanase activity, reduced, when pH values fell below 3. The effect of buffering (0.2M phosphate, pH 6.15) was examined and compared with the unbuffered medium. Beta-glucosidase activity could be detected throughout the incubation period in the buffered medium and endoglucanase activity was approximately tenfold greater. Exoglucanase activity also showed an increase in the buffered system. Concentrations of phosphate buffer ranging from 0.05 to 0.8M were incorporated into the medium and optimum cellulose breakdown and extracellular enzyme production occurred between 0.1 and 0.2M. Reports suggest that increasing substrate concentration does not improve upon the levels of extracellular cellulase produced because of enzyme inactivation resulting from rapid decreases in pH. Using the buffered medium described previously,A. fumigatus was grown on concentrations of Avicel ranging from 0.5 to 10% (w/v). Cellulose breakdown and extracellular enzyme production was compared with that achieved by a similar nonbuffered system. Endoglucanase and Β-glucosidase activity increased with time and with substrate concentration up to 5% (w/v) in the buffered medium. Beta-glucosidase was negligible at all concentrations of Avicel in the unbuffered medium and endoglucanase activity decreased with increasing substrate concentration with maximum levels approximately eightfold lower than in the buffered system. Extracellular exoglucanase activity was lower in the buffered medium and only increased to levels comparable with those achieved by the unbuffered medium towards the end of the incubation period. In the unbuffered system, exoglucanase activity decreased with increasing substrate concentration, but no such effect was observed in the buffered medium. Negligible growth occurred in both media at 10% (w/v) substrate. The percentage weight loss recorded in the Czapeck-Dox medium also decreased with increasing substrate concentration, while in the buffered medium, over 95% weight loss was recorded in up to 5% (w/v) Avicel. It appeared that cellulose breakdown was more rapid in the buffered medium and a time-course carried out to determine the rate of cellulolysis showed 97% cellulose breakdown after 12 d, corresponding to a plateau and a subsequent decrease in extracellular cellulase levels.     

Solubilization and Hydrolysis of Ovotransferrin Solubilization of α-chymotrypsin. Enthalpy changes for three processes

At 298.15 K, the solubilization of hen ovotransferrin at buffered pH 7.8 (0.08 M Tris⋅HCl buffer, containing 0.1 M CaCl₂) and the solubilization of α-chymotrypsin (from bovine pancreas) at non-buffered pH 3.0 (0.001 M HCl) both resulted in large exothermic reactions, being the apparent ΔHs –2485 in the first case and –780.1 kJ mol^–1 in the second case, respectively. By contrast, the complete hydrolysis of ovotransferrin (pH 7.8) achieved by using a-chymotrypsin (pH 3.0) gave an endothermic reaction with ΔH=+31.84 kJ mol^–1. This revised version was published online in July 2006 with corrections to the Cover Date.     

Physicochemical properties of the surface of the (Y,La0.1)Ce x Zr1? x O2?δ( x = 0.1–0.7) and Y0.1Pr0.3Zr0.6O2?δ complex oxide systems

The physicochemical properties of the surface of the Y_0.1Ce _x Zr_1−x O_2−δ, La_0.1Ce _x Zr_1−x O_2−δ (x=0.1–0.7), and Y_0.1Pr_0.3Zr_0.6O_2−δ. complex oxide systems were studied using IR and X-ray photoelectron spectroscopies. An appreciable enrichment of the surface of the solids in rare-earth-metal cations (cerium or praseodymium) during the synthesis was revealed. While cations are uniformly spread over the surface of cerium-zirconium solid solutions, the Y_0.1Pr_0.3Zr_0.6O_2−δ surface is covered by the clusters or even a phase of praseodymia. Reductive treatment in hydrogen with subsequent reoxidation results in the segregation of cerium ions on the Y_0.1Ce_0.3Zr_0.6O_2−δ surface at a temperature as low as 770 K. Original Russian Text ? A.N. Kharlanov, L.N. Ikryannikova, V.V. Lunin, A. Yu. Stakheev, 2007, published in Zhurnal Fizicheskoi Khimii, 2007, Vol. 81, No. 7, pp. 1271–1277.     

DPASV Method for Determination of Trace Concentrations of Manganese in Non-Buffered Chloride Solutions by Addition of Cyanide as a Masking Agent

 A highly sensitive, selective, and rapid differential pulse anodic stripping voltammetric method at HMDE is described for the determination of trace concentrations of Mn²⁺. The determination of Mn²⁺ in non-buffered chloride solution is seriously disturbed by the presence of Ni²⁺, Co²⁺, Cr³⁺, Zn²⁺ and Cu²⁺ due to intermetallic compound formation. The procedure is based on the addition of low amounts of cyanide as a masking agent. The interference of < 20 μgL⁻¹ of Ni²⁺, Co²⁺ and Cr³⁺ and < 75 μgL⁻¹ of Cu²⁺ and Zn²⁺ can thus be avoided, as the formed cyanide complexes prevent intermetallic compound formation during the short accumulation period. Thus, the addition of cyanide greatly improves the DPASV determination of manganese in non-buffered medium. A comparison between the determination of Mn²⁺ in the presence of a mixed cyanide/non-buffered chloride and in the ammoniacal buffer solution shows that the peak current of manganese in the presence of cyanide is four times higher with the same peak potential. The proposed method is shown to be applicable for the Mn²⁺ determination in both ground and tap water. A good agreement is obtained between the results by DPASV and AAS. Received May 14, 1999. Revision May 25, 2000.     

Revisiting the Solubility Concept of Pharmaceutical Compounds

Summary.  The kinetic and thermodynamic solubilities of Roche (Ro) pharmaceutical compounds were determined by HPLC, titrimetry, and UV/Vis spectroscopy in aqueous buffers and in non-buffered systems. For kinetic solubility, a turbidimetric method that allows the rapid determination of solubilities using small amounts of compounds (5–50 mg) was used. Two types of precipitation were observed during the kinetic solubility determinations: i) a disperse precipitation where the solution became foggy with very small particles uniformly distributed in the solution, and ii) discrete precipitation characterized by formation of crystals that rapidly sediment. The thermodynamic solubility was determined by shake flask and titrimetrically using a pH-STAT. The pH-STAT titrimetric method for the pH-thermodynamic solubility profile determination eliminates the buffer species and represents a new way to approach the solubility characterization of pharmaceutical compounds. The strengths of the turbidimetric method for determining the kinetic solubility are its rapidity, minimal compound requirements, and suitability for high throughput screening. The limitations are that the maximum solubility is limited to less than 100 mg · cm⁻³, and the precipitation of trace impurities cannot be distinguished from precipitation of the analyte. The pH-STAT titrimetric approach for the thermodynamic solubility has a lower throughput and is suitable for the characterization of the lead candidate. It is not limited in its solubility range and provides a common basis for the comparison of the solubility values at different pH values in contrast to traditional buffered systems. Received August 21, 2000. Accepted (revised) February 5, 2001     

Anaerobic Digestion of Cassava Wastewater Pre-treated by Fungi

Cassava wastewater (cww) contains high concentrations of easily acidifying compounds, requiring a buffered system to allow a stable operation during anaerobic digestion (AD). The possibility to include a preliminary one-step fungi treatment aimed at raising the pH and buffering the cww prior to AD was studied. Preliminary tests were performed with a naturally grown fungal mixed culture, under aerated (AE), non-aerated (NAE) and initially oxygen-deprived (IOD) conditions. The cww was pre-treated by the NAE condition, until reaching a soluble chemical oxygen demand (COD) of 10 g?L^?1 and pH 6.4 (batch A) and pH 5.7 (batch B). The fungal mixed culture showed ability to biodegrade the cww with initial pH of 4.4 and 14,500 mg?COD?L^-1, raising the pH over 8.5, with only 13 % of COD remaining within 27 days for both AE and NAE condition. The fungal pre-treated-cww (FPTcww) was subjected to anaerobic digestion under different buffered (CaCO₃ and NaHCO₃) and non-buffered conditions. The FPTcww with initial pH at 6.4 provided stability during the anaerobic biodegradability tests, showing the possibility of system operation without buffer addition, with final pH around 7. The application of a fungal pre-treatment can be a promising strategy to permit the anaerobic digestion of carbohydrate-rich wastewaters.     

Thermodynamic parameters for the binding process of the OH<Superscript>−</Superscript> ion with the dissipative structures. Calorimetric and conductometric titrations

Conductometric and calorimetric titrations of Extremely Diluted Solutions (EDS) were performed by adding HCl or NaOH solutions. The aim of this study is to obtain further confirmation of the hypothesized presence, in the EDS, of molecular aggregates of water molecules. The measurements on the EDS evidenced some relevant differences compared to those on solutions with just water as solvent. The conductivity and the pH caused by adding the titrant, namely NaOH or HCl, were markedly different to those of the control solutions. We suppose that the preparation procedure of the EDS could produce non-equilibrium changes in the supramolecular structure of water. The experimental results were interpreted by considering the interactions that can take place between the OH⁻ or H₃O⁺ and the hypothesized molecular aggregates of water molecules i.e. dissipative structures. A comparison was made about the nature of the driving force that leads to the formation of the complexes between the two ions deriving from probes and the molecular aggregates of water molecules (dissipative structures). In this study, we have determined the thermodynamic parameters of association between molecular aggregates of water molecules (dissipative structures) in the EDS and OH⁻ or H₃O⁺ probe ions. The experimental results were interpreted by considering a favorable interaction between the H₃O⁺ and OH⁻ ions and the dissipative structures, due, probably, to steric hindrance and chemical affinity with the aggregates.     

Reductive immobilization of <Superscript>79</Superscript>Se by iron canister under simulated repository environment

To understand the fate of ⁷⁹Se in a repository-like environment, the interactions between iron canister surface with dissolved selenite (SeO₃ ²⁻) and selenate (SeO₄ ²⁻) in anaerobic solutions have been investigated. Se(IV) immobilization on iron surface was observed to be about 100 times faster than that of Se(VI) at same conditions. An iron surface coated with a FeCO₃ layer corrosion product is more reactive than a polished iron to immobilize Se(IV) and Se(VI). The reacted iron surfaces were analysed by scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS), X-ray diffraction (XRD), Raman spectrometry and micro-X-ray Absorption Spectroscopy (XAS). The result show that Se(IV) and Se(VI) were reduced and precipitated. The dominating phase was found to be FeSe_2.     

Raman Spectra of Tungsten-Bearing Solutions

Raman spectroscopy at 25 °C was performed to analyze speciation in quenched solutions after experiments on sodium tungstates and sodium tungstate bronze dissolution at t=500 °C, p=1000 bar. The experiments were conducted under different oxidation-reduction conditions in sodium chloride solution media. The spectra of the quenched solutions were different from those of the reference solutions of 0.02 mol⋅kg⁻¹ W(VI) (H₂O) in the pH range 2.3–7.2. Thermodynamic models were established and the fields of predominance of different isopolytungstate species at 25–50 °C were determined. The experimental results of tungstate dissolution demonstrates that reduced tungstate solutions may contain a significant amount of tungsten species with valence states lower than W(VI).     

Copper corrosion in soil: influence of chloride contents, aeration and humidity

The corrosion of copper in a typical Portuguese soil was studied. The original soil was characterised, and modifications were produced by adding chloride, and HClO₄ solutions, or by increasing its relative humidity. The aggressiveness degree of the various soil samples was determined. Copper coupons exposed for 3 months in the original and in the modified soil samples were analysed. The average corrosion rates determined from gravimetric data were in good correlation with the soil aggressiveness. The morphology of the corroded copper surfaces, with and without corrosion products, was analysed by visual observation, optical microscopy and scanning electron microscopy. Energy dispersive spectroscopy was used for the semi-quantitative analysis of the corrosion products and X-ray diffraction spectroscopy to identify the crystalline products. Cuprite has been identified on the copper samples corresponding to the interfaces Cu|S6 and Cu|S8, plus paratacamite on the copper coupon exposed to the soil with higher concentration of chloride (S6). Polarisation curves of copper samples in neutral solutions made by adding different amounts of chloride ions to the soil washing water, under deaereated conditions, were recorded and analysed. The passivity breakdown potential has shown, as expected, a displacement to the cathodic direction as the Cl⁻ ion concentration increases.     

Nanosecond and microsecond decay of photogenerated charges in Cd<Subscript>x</Subscript>Zn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>S nanoparticles

The luminescent characteristics of Cd_xZn_1−xS nanoparticles were studied. It was shown that the emission is due to the recombination of holes in the valence band with electrons captured by two sorts of traps, of which the traps with lower energy were ascribed to the surface states of the Cd_xZn_1−xS nanoparticles. It was established that the Cd_xZn_1−xS nanoparticles have more pronounced ability than CdS nanoparticles to accumulate excess negative charge under the conditions of pulsed irradiation. It was shown that the consumption of the photogenerated electrons in nanosecond and microsecond time scales involves the participation of one and the same electron traps. It was established that the rate of interaction of the electrons captured by the surface traps with oxygen increases with decrease in the size of the nanoparticles. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 5, pp. 275–281, September–October, 2007.     

Organic/Inorganic bioactive materials Part III: in vitro bioactivity of gelatin/silicocarnotite hybrids

In this work we present our experimental results on synthesis, structure evolution and in vitro bioactivity assessment of new gelatin/silicocarnotite hybrid materials. The hybrids were obtained by diluting gelatin (G) and silicocarnotite (S) ceramic powder with G:S ratios of 75:25 and 25:75 wt.% in hot (40°C) water. The hybrids were characterized using XRD, FTIR, SEM/EDS and XPS. FTIR depicts that the “red shift” of amide I and COO⁻ could be attributed to the fact that the gelatin prefers to chelate Ca²⁺ from S. The growth of calcium phosphates on the surface of the hybrids synthesized and then immersed in 1.5 SBF for 3 days was studied by using of FTIR, XRD and SEM/EDS. According to FTIR results, after an immersion of 3 days, A and B-type CO₃HA can be observed on the surface. XRD results indicate the presence of hydroxyapatite with well defined crystallinity. SEM/EDS of the precipitated layers show the presence of CO₃HA and amorphous calcium phosphate on the surface of samples with different G/S content when immersed in 1.5 SBF. XPS of the G/S hybrid with 25:75 wt.% proved the presence of Ca-deficient hydroxyapatite after an in vitro test for 3 days.     

Dye-coated stationary-phases: A retention model for anions in ion-interaction chromatography

Summary The separation of inorganic anions (NO₃ ⁻, NO₂ ⁻, Cl⁻, Br⁻, I⁻, SO₄ ²⁻, S₂O₃ ²⁻) by ion-interaction chromatography mediated with a specific dye has been investigated. Chromatography was performed on a LiChrospher RP-18 colum dynamically coated with crystal violet, using acetonitrile-water buffered with phthalate as the mobile phase. The presence of the dye in the eluent enabled indirect spectrophotometric detection of the analytes, which have no significant UV absorption. Retention data were collected for the different anions by varying the composition of the mobile phase according to a full factorial experimental design. A theoretical model for the retention of singly- and doubly-charged analytes, on the basis of the two main processes of ion-exchange and ion-pair formation, has been proposed and validated with the experimental data.     

Phase transformations of ammonium tungsten bronzes

This article discusses the formation and structure of ammonium tungsten bronzes, (NH₄) _x WO_3−y . As analytical tools, TG/DTA-MS, XRD, SEM, Raman, XPS, and ¹H-MAS NMR were used. The well-known α-hexagonal ammonium tungsten bronze (α-HATB, ICDD 42-0452) was thermally reduced and around 550 °C a hexagonal ammonium tungsten bronze formed, whose structure was similar to α-HATB, but the hexagonal channels were almost completely empty; thus, this phase was called reduced hexagonal (h-) WO₃. In contrast with earlier considerations, it was found that the oxidation state of W atoms influenced at least as much the cell parameters of α-HATB and h-WO₃, as the packing of the hexagonal channels. Between 600 and 650 °C reduced h-WO₃ transformed into another ammonium tungsten bronze, whose structure was disputed in the literature. It was found that the structure of this phase—called β-HATB, (NH₄)_0.001WO_2.79—was hexagonal.     

Phase Recognition in AlN-Ti System by Energy Dispersive Spectroscopy and Electron Backscatter Diffraction

 The combination of energy dispersive spectroscopy (EDS) and electron backscatter diffraction (EBSD) techniques in scanning electron microscope was employed to characterize the reacted interface between Ti matrix and AlN particles. Due to the high localization of EDS and EBSD, representative measurements of chemical composition and reliable determination of the crystal structure were possible for each phase in the reaction zone with complex morphology. The TiN_1−x (cubic, NaCl type), Ti₃AlN (cubic, perovskite type) and Ti-rich Ti₃ Al (hexagonal, Ni₃Sn type) phases were identified in the reaction zone after annealing at 1100 °C. EDS+EBSD combination is an efficient tool for phase analysis at the interface in reactive multicomponent systems. Received August 21, 1999. Revision November 21, 1999.     

Electrochemical preparation and magnetic properties of submicron Co x Pb1−x dendrites

Magnetic dendrites of Co _x Pb_1−x were fabricated through potentiostatic electrochemical deposition on Cu substrates in boric acid solution at room temperature. The as-deposited dendrites were determined by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), electrodeposition (ED), and energy dispersive X-ray spectroscopy (EDS). SEM results indicate that the Co _x Pb_1−x dendrites are highly symmetrical in structures. The diameters of the branches are about 50 ~ 200 nm, and the backbones are continuous with lengths up to about 10 μm. XRD patterns show that the as-deposited dendrites are solid solutions. The annealing treatment can result in the recrystallization of these metastable alloys into two separate phases. TEM, ED, and EDS results also reveal that the backbones and the branches of the dendrites are composed of different amounts of cobalt. Magnetic measurements confirm that the as-deposited Co _x Pb_1−x dendrites have a softly ferromagnetic behavior, and a small coercive force (about 80 Oe). Also the saturation magnetizations of the Co _x Pb_1−x dendrites decrease rapidly with the temperature increasing.     

Platinum–polytyramine composite material with improved performances for methanol oxidation

Polytyramine (PTy) is shown to be a possible alternative to other conducting polymers as a support material for fuel cell electrocatalysts such as platinum. In this work, a Pt–PTy composite was prepared via potentiodynamic deposition of polytyramine on graphite substrate, followed by the electrochemical deposition of Pt nanoparticles. The material obtained by this straightforward method exhibited, for platinum loadings as low as ca. 0.12 mg cm⁻², a specific electrochemically active surface area of the electrocatalyst of ca. 54 m² g⁻¹, together with a good electrocatalytic activity for methanol oxidation in acidic media, thus ensuring better efficiency of Pt utilization. The system Pt–PTy appears to be worthy of development for methanol fuel cell applications also because the results suggested that, when deposited as small particles in a PTy matrix, platinum is less sensitive to fouling during CH₃OH oxidation.     

The role of the negatively charged (Si3−Si−F2)− complexes in interactions of fluorine with the (111) surface of silicon

We used the AM1 quantum chemical and cluster models to study the mechanism of formation of a SiF₂-like layer and dissociation of the Si−Si bond during the interaction of atomic fluorine with the (111) surface of silicon. It is shown that the negatively charged (Si₃−Si−F₂)⁻ complex with the five-coordinated centered silicon atom plays an important part in these processes. The above complex participates in the interaction of atomic fluorine with silicon to form a SiF₂-like layer and break the subsurface Si−Si bonds without penetration of fluorine atoms into the subsurface silicon layers. Institute of Semiconductor Physics, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 37, No. 1, pp. 14–21, January–February, 1996. Translated by I. Izvekova     

Direct competitive ELISA based on a monoclonal antibody for detection of aflatoxin B1. Stabilization of ELISA kit components and application to grain samples

A direct competitive enzyme-linked immunosorbent assay (ELISA) based on a monoclonal antibody has been developed and optimized for detection of aflatoxin B₁ (AFB₁), and an ELISA kit has been designed. This immunoassay was highly specific, sensitive, rapid, simple, and suitable for aflatoxin monitoring. AFB₁ concentrations determinable by ELISA ranged from 0.1 to 10 μg L⁻¹. The IC₅₀ value was 0.62 μg L⁻¹. Recovery from spiked rice samples averaged between 94 and 113%. The effect of different reagents on the stability of HRP–AFB₁ conjugate solution was studied. The performance of a stabilized enzyme tracer in ELISA was determined and compared with that of a freshly prepared control solution of HRP–AFB₁ conjugate. The results showed that stabilizing media containing 0.02% BSA, 0.1% Kathon CG, and 0.05 mol L⁻¹ calcium chloride in 0.05 mol L⁻¹ Tris-HCl buffer (pH 7.2) maintained the activity of HRP–AFB₁ at a dilution of 1:1000 for a period of at least 12 months at room temperature whereas the reference conjugate solution without the additives lost its activity within a few days. Several additives were tested for their stabilizing effect on a monoclonal antibody (MAb) immobilized on the surface of polystyrene microtitre plates. It was shown that immobilized MAb, treated with post-coating solutions containing PVA, BSA, and combinations of these substances with trehalose, retained its activity for at least 4 months at 4°C, whereas the untreated MAb-coated plate lost its activity within 2 days.