Plasma reduction of bronze corrosion developed under long-term artificial ageing

Reference Cu-based alloy with chemical composition and micro-chemical structure similar to that of ancient alloys has been used for carrying out the artificial long-term degradation test based on chloride enriched soil (chemical + soil) degradation. The results show that such degradation procedure produces natural like “patinas” as the ones grown on archaeological artefacts, from a chemical, structural and micro-morphological point of view. Glow discharge plasma technique has been employed for the treatment of the as-corroded bronze coupons. The gradual elimination of chloride-containing corrosion products in favour of the formation of more stable species and even the complete reduction back to copper has been observed. The chemical and metallurgical features have been determined by combined use of different analytical techniques such as scanning electron microscopy with energy dispersive X-ray micro-analysis (SEM-EDS), X-ray diffraction (XRD) and optical microscopy.     

Biosorption of heavy metals by bacteria isolated from activated sludge

Twelve aerobic bacteria from activated sludge were isolated and identified. These included both Gram-positive (e.g., Bacillus) and Gram-negative (e.g., Pseudomonas) bacteria. The biosorption capacity of these strains for three different heavy metals (copper, nickel, and lead) was determined at pH 5.0 and initial metal concentration of 100 mg/L. Among these 12 isolates, Pseudomonas pseudoalcaligenes was selected for further investigation owing to its high metal biosorption capacity. The lead and copper biosorption of this strain followed the Langmuir isotherm model quite well with maximum biosorption capacity (q _max) reaching 271.7mg of Pb²⁺/g of dry cell and 46.8 mg of Cu²⁺/g of dry cell at pH 5.0. Study of the effect of pH on lead and copper removal indicated that the metal biosorption increased with increasing pH from 2.0 to 7.0. A mutual inhibitory effect was observed in the lead-copper system because the presence of either ion affected the sorption capacity of the other. Unequal inhibitions were observed in all the nickel binary systems. The increasing order of affinity of the three metals toward P. pseudoalcaligenes was Ni<Cu<Pb. The metal biosorptive potential of these isolates, especially P. pseudoalcaligenes, may have possible applications in the removal and recovery of metals from industrial effluents.     

Effect of DMSO used as solvent in copper mediated living radical polymerization

The use of DMSO as solvent for transition metal mediated living radical polymerization was investigated using copper (I) bromide/N‐(n‐propyl)‐2‐pyridyl‐methanimine catalyst system and ethyl‐2‐bromoisobutyrate as initiator. The best conditions for polymerization in DMSO of different methacrylates (MMA, BMA, DMAEMA, HEMA) were determined. In all cases, the measured number‐average molar mass of the product increased linearly with monomer conversion in agreement with the theoretical M_n with low polydispersity products (1.16 < PDI < 1.4) achieved. Solvent was found to play a crucial role in the process. The effect of the polar solvent has been investigated and it was shown that DMSO could coordinate copper (II), increasing the activation process, or copper (I), changing the nature of the copper catalyst by competitive complexation of ligand and DMSO. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6299–6308, 2004     

Surface heterogeneity study of some reference Cu–Ag alloys using laser‐induced breakdown spectroscopy

Investigation of the chemical composition, surface structure, metallurgical features, corrosion mechanism, and surface modification techniques of archeological metallic artifacts from Romans and pre‐Roman times aimed to simulate the most commonly used Cu‐based and Ag‐based alloys. These simulated reference alloys will be used as sacrificial materials to study the most appropriate conservation materials and procedures. In the present work, laser‐induced breakdown spectroscopy (LIBS) is introduced as a new validated surface mapping technique to study the micro‐chemical distribution of elements in binary reference copper–silver alloy samples. Using different techniques for surface and bulk analysis, such as SEM coupled with energy‐dispersive X‐ray spectroscopy and X‐ray diffraction, it has been proven that LIBS is a simple, sensitive, and direct technique in the determination of heterogeneity of the sample's surface. By changing the laser wavelength (λ/nm) and focal length of the used focusing lens (f/cm), different spot sizes can be obtained. It was possible to control the spatial resolution in mapping the investigated samples' surface and to achieve local chemical information. In the present work, Q‐switched neodymium‐doped yttrium aluminum garnet laser has been used at its fundamental wavelength 1064 nm and its second harmonic 532 nm. The studied samples were specially manufactured heterogeneous copper–silver alloys with known grain size as studied via SEM investigation. The obtained LIBS results are in good agreement with those by other analytical techniques and extend the applicability of the surface techniques to study metallic ancient objects. Copyright © 2015 John Wiley & Sons, Ltd.     

Structural Basis for Copper–Oxygen Mediated C−H Bond Activation by the Formylglycine-Generating Enzyme

The formylglycine-generating enzyme (FGE) is a unique copper protein that catalyzes oxygen-dependent C−H activation. We describe 1.66 Å- and 1.28 Å-resolution crystal structures of FGE from Thermomonospora curvata in complex with either Ag^I or Cd^II providing definitive evidence for a high-affinity metal-binding site in this enzyme. The structures reveal a bis-cysteine linear coordination of the monovalent metal, and tetrahedral coordination of the bivalent metal. Similar coordination changes may occur in the active enzyme as a result of Cu^I/II redox cycling. Complexation of copper atoms by two cysteine residues is common among copper-trafficking proteins, but is unprecedented for redox-active copper enzymes or synthetic copper catalysts.     

Integrated analytical methodologies for the study of corrosion processes in archaeological bronzes

The investigations on structure and micro-chemical composition of archaeological metal alloys are needed in archaeometry. The aim of this study is devoted both to acquire information about their provenance and production technology, and to improve our understanding about the corrosion processes. In this paper we present the study of the corrosion phenomena of bronze samples, laboratory-made according to binary, ternary and quaternary alloys typical of Roman archaeometallurgical production through an integrated methodology based on the use of non or micro invasive physical techniques. Among the analysed samples, two were artificially aged through burial in the archaeological site of Tharros, along the west coast of Sardinia (Italy). The corrosion products, typical of the bronzes in archaeological sites near the sea, have been characterized by non invasive and micro-destructive measurements. In particular, the corrosion patinas were examined through optical microscopy, scanning electron microscopy and microanalysis, X-ray fluorescence and laser ablation spectroscopy. The use of integrated technologies allowed us to determine both the elemental composition and surface morphology of the patina, highlighting the correlation between patina nature and chemical composition of the burial context. Moreover, data obtained by the laser-induced breakdown spectroscopy along the depth profile on the samples, have yielded information about the stratigraphic layers of corrosion products and their growth. Finally, the depth profiles allowed us to verify both the chemical elements constituting the patina, the metal ions constituting the alloy and the occurrence of migration phenomena from bulk to the surface.     

Bronze analysis by k0-NAA and PIXE

Five copper alloys were prepared with modern powder metallurgical processes in the frame of the European project Improvement of Means of Measurement on Archaeological Copper-Alloys for Characterisation and Conservation (IMMACO) and certified for As, Pb, Sn and Zn mass fractions. Similar in their composition to archaeological bronze alloys, these Certified Reference Materials (CRMs) are to be used for calibration of XRF instruments for characterization of archaeological samples either in the laboratory or in the field. This paper presents and compares the successful contribution of our non-destructive analytical methods (k ₀-NAA and PIXE) to the IMMACO project and to the certification of the five reference materials.     

Can Copper(II) Mediate Hoogsteen Base‐Pairing in a Left‐Handed DNA Duplex? A Pulse EPR Study

Pulse EPR spectroscopy is used to investigate possible structural features of the copper(II) ion coordinated to poly(dG‐dC)?poly(dG‐dC) in a frozen aqueous solution, and the structural changes of the polynucleotide induced by the presence of the metal ion. Two different copper species were identified and their geometry explained by a molecular model. According to this model, one species is exclusively coordinated to a single guanine with the N7 nitrogen atom forming a coordinative bond with the copper. In the other species, a guanine and a cytosine form a ternary complex together with the copper ion. A copper crosslink between the N7 of guanine and N3 of cytosine is proposed as the most probable coordination site. Moreover, no evidence was found for an interaction of either copper species with a phosphate group or equatorial water molecules. In addition, circular dichroism (CD) spectroscopy showed that the DNA of the Cu^II‐poly(dG‐dC)?poly(dG‐dC) adducts resembles the left‐handed Z‐form. These results suggest that metal‐mediated Hoogsteen base pairing, as previously proposed for a right‐handed DNA duplex, can also occur in a double‐stranded left‐handed DNA.     

Photoinduced Copper‐Catalyzed Coupling of Terminal Alkynes and Alkyl Iodides

We have developed a photoinduced copper‐catalyzed alkylation of terminal alkynes with primary, secondary, or tertiary alkyl iodides as electrophiles. The reaction has a broad substrate scope and can be successfully performed in the presence of ester, nitrile, aryl halide, ketone, sulfonamide, epoxide, alcohol, and amide functional groups. The alkylation is promoted by blue light (λ≈450 nm) and proceeds at room temperature in the absence of any additional metal catalysts. The use of a terpyridine ligand is essential for the success of the reaction and is shown to prevent photoinduced copper‐catalyzed polymerization of the starting materials.     

Application of Modified Tafel Analysis to the Identification of Corrosion Products on Archaeological Metals Using Voltammetry of Microparticles

An operational modification of Tafel analysis, applied to the intermediate region of square wave voltammetric curves, devoted to the identification of corrosion products on archaeological metal, is described. This is based on the voltammetry of microparticles methodology using conventional abrasive conditioning of the electrode, as well as ‘one‐touch’ and layer‐by‐layer techniques. The proposed methodology is applied to the identification of copper and silver corrosion products in mediaeval silver‐copper coins from the Libertad street hoard in Valencia (Spain).     

Surface characterisation and crevice corrosion behaviour of nickel-based alloys in the paper industry

Recycled water in the paper industry acts as a stronger electrolyte as its concentration and temperature are quite high. The lower pH that exists in these solutions enhances the corrosion and the high concentration of solids leads to leaching of metal ions from surface. Crevice corrosion is a form of localised attack, which can quickly induce metal perforation even with high grade stainless steels like 316L when the protective chromium oxide film is damaged. A specially designed crevice cell assembly was used to study the electrochemical aspects of nickel-based alloys with the commonly used 316L SS. The mounted specimen with its crevice was anodically polarised in a white water medium, which is normally encountered in the paper machine section. The nickel-based alloys show remarkable crevice corrosion resistance. X-ray photoelectron spectroscopy studies revealed that the enhanced corrosion resistance of these alloys is due to the contributing nature of the individual elements Cr, Ni and Mo and their presence in the form of various oxidised species on the passive films. Received: 22 February 1999 / Accepted: 6 June 1999     

Copper-Catalyzed Carbonylative Cross-Coupling of Alkyl Iodides and Amines

A general copper-catalyzed carbonylative cross-coupling between amines and alkyl iodides is reported. Using a simple combination of catalytic amounts of copper(I) chloride and N,N,N’,N”,N”-pentamethyldiethylenetriamine in the presence of sodium hydroxide under carbon monoxide pressure, a broad range of alkyl iodides and amines can be efficiently coupled to the corresponding amides that are obtained in good to excellent yields. Notable features of this process – the first one relying on a base metal catalyst – include the availability and low cost of the catalytic system, its successful use with primary, secondary, tertiary alkyl iodides and all classes of amines – with no or limited competing nucleophilic substitution without CO incorporation – as well as its efficiency with complex alkyl iodides and amines. Mechanistic studies demonstrated that a radical pathway is operative and the key role of CO.     

1-Dodecanethiol self-assembled monolayers on cobalt

Cobalt and its alloys are used in a broad range of application fields. However, the use of this metal is especially limited by its strongly oxidizable nature. The use of alkanethiol self-assembled monolayers (SAMs) is a very efficient way to protect against such oxidation and/or to inhibit corrosion. This surface modification method has been particularly applied to oxidizable metals such as copper or nickel, yet the modification of cobalt surfaces by alkanethiol SAMs received limited attention up to now. In this work, we study the influence of parameters by which to control the self-assembly process of 1-dodecanethiol monolayers on cobalt: nature of the surface pretreatment, solvent, immersion time, and concentration. Each of these parameters has been optimized to obtain a densely packed and stable monolayer able to efficiently prevent the reoxidation of the modified cobalt substrates. The obtained monolayers were characterized by X-ray photoelectron spectroscopy (XPS), polarization modulation infrared reflection-absorption spectroscopy, and contact angle measurements. The stability of the optimized 1-dodecanethiol monolayer upon air exposure for 28 days has been confirmed by XPS.     

Amino-Induced 2D Cu-Based Metal–Organic Framework as an Efficient Heterogeneous Catalyst for Aerobic Oxidation of Olefins

With the assistance of hydrogen bonds of the o-amino group, we have successfully tuned a coordination structure from a metal–organic polyhedron (MOP) to a two-dimensional (2D) metal–organic framework (MOF). The amino group forms hydrogen bonds with the two vicinal carboxylic groups, and induces the ligand to coordinate with copper ions to form the 2D structure. The obtained 2D Cu-based MOF (Cu-AIA) has been applied as an efficient heterogeneous catalyst in the aerobic epoxidation of olefins by using air as oxygen source. Without the aggregation problem of active sites in MOPs, Cu-AIA possesses much higher reactivity than MOP-1. Furthermore, the amino group of the framework has been used as a modifiable site through post-synthetic metalation (PSMet) to prepare a 2D MOF-supported Pd single-site heterogeneous catalyst, which shows excellent catalytic performance for the Suzuki reaction. It indicates that Cu-AIA can also work as a good 2D MOF carrier for the derivation of other heterogeneous catalysts.     

Capabilities of static TOF-SIMS in the differentiation of first-row transition metal oxides.

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) analyses were performed on the first-row transition metal oxides from scandium to zinc in positive and negative detection modes. The nature of the numerous M(x)O(y)(+/-) ionic species generated by 15 keV Ga(+) primary ion bombardment allows the identification of a given metal-oxygen system. To identify the metal valence in the oxide under investigation, several procedures were investigated: the detection of specific and characteristic ions, the use of ion abundance ratios and the use of a valence model. Owing to their importance in many fields of materials science, each of these speciation methodologies was evaluated for the differentiation of vanadium, titanium, chromium, manganese, iron, cobalt and copper oxides. Trivalent-hexavalent chromium distinction was first intensely investigated because it really corresponds to a model system for inorganic speciation. For each series of metal oxides, the more pertinent speciation criteria were then systematically tested. The limitations of the proposed methodologies are discussed. Their use is made complicated when pollutants or a superficial oxide layer, with a stoichiometry different from that of the bulk, are present. Finally, thermodynamic considerations relative to the stability of the M(x)O(y)(+/-) ions may also modify the relationship between the analyzed oxide and the observed positive and negative secondary ion mass spectra.     

An unusual coordination polymer containing Cu+ ions and featuring possible Cu...Cu `cuprophilic' interactions: poly[di‐μ‐chlorido‐(μ4‐3,5‐diaminobenzoato‐κ4O:O′:N:N′)tricopper(I)(3 Cu—Cu)]

Compounds containing copper(I) are of interest for their role in biological processes. The nature of short (< ∼3.2 Å) Cu...Cu contacts within these compounds has been debated, being either described as weakly attractive (bonding) `cuprophilic' interactions, or simply as short metal–metal distances constrained by ligand geometry or largely ionic in nature. The title three‐dimensional Cu<sup>+</sup>‐containing coordination polymer, [Cu<sub>3</sub>(C<sub>7</sub>H<sub>7</sub>N<sub>2</sub>O<sub>2</sub>)Cl<sub>2</sub>]<sub>n</sub>, was formed from the in situ reduction of CuCl<sub>2</sub> in the presence of 3,5‐diaminobenzoic acid and KOH under hydrothermal conditions. Its complex crystal structure contains ten distinct Cu<sup>I</sup> atoms, two of which lie on crystallographic inversion centres. The copper coordination geometries include near‐linear CuOCl and CuN<sub>2</sub>, T‐shaped CuOCl<sub>2</sub> and distorted tetrahedral CuOCl<sub>3</sub> groups. Each Cu<sup>I</sup> atom is also associated with two adjacent metal atoms, with Cu...Cu distances varying from 2.7350 (14) to 3.2142 (13) Å; if all these are regarded as `cuprophilic' interactions, then infinite [01] zigzag chains of Cu^I atoms occur in the crystal. The structure is consolidated by N—H...Cl hydrogen bonds.     

Picolinamides as Effective Ligands for Copper‐Catalysed Aryl Ether Formation: Structure–Activity Relationships,Substrate Scope and Mechanistic Investigations

The use of picolinic acid amide derivatives as an effective family of bidentate ligands for copper‐catalysed aryl ether synthesis is reported. A fluorine‐substituted ligand gave good results in the synthesis of a wide range of aryl ethers. Even bulky phenols, known to be very challenging substrates, were shown to react with aryl iodides with excellent yields using these ligands. At the end of the reaction, the first examples of end‐of‐life Cu species were isolated and identified as Cu^II complexes with several of the anionic ligands tested. A preliminary mechanistic investigation is reported that suggests that the substituents on the ligands might have a crucial role in determining the redox properties of the metal centre and, consequently, its efficacy in the coupling process. An understanding of these effects is important for the development of new efficient and tunable ligands for copper‐based chemistry.     

Thermal and structural studies of the chloro complexes of cobalt and copper with 2-amino-3-methylpyridine

The chloro complexes of 2-amino-3-methylpyridine with cobalt(II) and copper(II) have been prepared in ethanolic solution and solid compounds have been isolated. The compounds have stoichiometry ML₂Cl₂ whereM is Co²⁺ or Cu²⁺ and L is 2-amino-3-methylpyridine. Spectral and magnetic studies have been used to obtain information about the environment of the metal ion in these compounds. The compounds have tetrahedral structures. The thermal decomposition of each compound has been studied using thermogravimetry and differential thermal analysis. Thermogravimetry studies show that the cobalt complex forms an intermediate compound before the metal oxide is produced while the copper compound undergoes decomposition with loss of organic ligand and the formation of copper chloride which then decomposes to give an oxide of copper. The enthalpy of reaction for each of the processes has been calculated from the thermal analysis curves.     

高活性铜催化剂无受体乙醇催化脱氢制乙醛研究

相较于Wacker工艺进行乙醛工业化生产,发展多相催化体系实现乙醇直接无氧催化脱氢制乙醛和副产氢气,从生产工艺和经济价值方面无疑是一条更加安全高效的路线.在此,我们发展了一种高效、稳固的Cu/SiO₂催化剂,用于乙醇的无受体催化脱氢.通过氨蒸发法制备得到高度分散的Cu颗粒,在没有任何平衡气体的纯乙醇进料条件下,显示出超强的热稳定性.活性组分Cu和载体SiO₂之间的强相互作用,使其具有优异的催化性能.通过反应条件优化,在250℃下实现了较高的乙醇转化率(>40%)和乙醛选择性(>95%),且催化剂在固定床连续反应过程中可稳定运行超过400 h.     

COORDINATION POLYMERIZATION OF BENZOTRIAZOLE ON THE SURFACE OF METALLIC COPPER

The coordination polymerization of benzotriazole with metallic copper has been investigated by infrared and X-ray photoelectron spectroscopies. We found that benzotriazole could react with copper (0) under mild conditions to form bis (benzotriazolato) copper (Ⅱ) and benzotriazolato copper (Ⅰ)which covered the surface of copper metal in the shape of polymeric materials. Since benzotriazole is of great interest as a ligand in that its presence in many biological system with metal ions, and is considered as a corrosion inhibitor, this work will be in favour of the study of protective corrosion.