Copper-manganese Alloys Research Articles

Effect of Grain Size and Temperature on Scalar Dislocation Density and Curvature–Torsion of the Crystal Lattice in Copper–Manganese Alloys during Plastic Deformation

Effect of Grain Size and Temperature on Scalar Dislocation Density and Curvature–Torsion of the Crystal Lattice in Copper–Manganese Alloys during Plastic Deformation

Porosity evolution and oxide formation in bulk nanoporous copper dealloyed from a copper-manganese alloy studied by in situ resistometry.

The synthesis of bulk nanoporous copper (npCu) from a copper-manganese alloy by electrochemical dealloying and free corrosion as well as the electrochemical behaviour of the dealloyed structures is investigated by in situ resistometry. In comparison to the well-established nanoporous gold (npAu) system, npCu shows strongly suppressed reordering processes in the porous structure (behind the etch front), which can be attributed to pronounced manganese oxide formation. Characteristic variations with the electrolyte concentration and potential applied for dealloying could be observed. Cyclic voltammetry was used to clarify the electrochemical behaviour of npCu. Oxide formation is further investigated by SEM and EDX revealing a hybrid composite of copper and manganese oxide on the surface of a metallic copper skeleton. Platelet-like structures embedded in the porous structure are identified which are rich in manganese oxide after prolonged dealloying. As an outlook, this unique heterogeneous structure with a large surface area and the inherent properties of manganese and copper oxides may offer application potential for the development of electrodes for energy storage and catalysis.

Hierarchical multi-porous copper structure prepared by dealloying electrolytic copper-manganese alloy

This is the first report of the formation of a novel, hierarchical, three-level pore structure through the ordinary and simple processes of electroplating and dealloying. The co-deposition of Cu-Mn under certain conditions, allows the formation of Cu-rich and Mn-rich regions in unique distributions. By removing Mn and its oxides from the electrodeposited layer through dealloying, Cu with a hierarchical multi-porous structure is formed. This consists of wide and narrow macropore networks and mesopores. Notably, the growth of Cu and the resulting rapid depletion of Cu ions during the electroplating process are proposed to be the main reasons for the formation of interconnected pore networks. As the formation of this unique pore structure is essentially independent of the plating time (or the thickness of the deposited layer), and because it provides a very large surface area and open pore structure, its engineering practical applications particularly in functional chemistry and electrochemistry are expected to be significant in the future.

Effect of Oxygen Ion Implantation on Physicochemical Structure and Corrosion-Electrochemical Behavior of Copper–Manganese Alloy

Effect of Oxygen Ion Implantation on Physicochemical Structure and Corrosion-Electrochemical Behavior of Copper–Manganese Alloy

Study on Preparation of Nano-porous Copper by Dealloying Method

Nano-scale mixed powdercomposed ofoxalate copperand oxalate manganesewas prepared by chemical synthesis method, after tableting, it was sintered at high temperature in a tube furnace under the protection of nitrogen to obtain nano-level Cu-MnO alloy. The Mn is removed by corrosion to obtain nanoporous copper. The solid copper-manganese oxalate was analyzed by TG/DTG. The specific surface area and composition of porous copper before and after sintering and dealloying were analyzed and characterized by using automatic specific surface area analyzer and ICP-OES. The results show that the specific surface area of the copper-manganese alloy can be greatly improved by controlling the sintering temperature so that it is not completely decomposed. The specific surface area of porous copper obtained when the Mn element is 14% (mole fraction) is the largest. After hydrochloric acid corrosion, the specific surface area of porous copper will be significantly reduced, and hydrochloric acid dealloying is a continuous process. If the corrosion concentration and time are too small, the purity of the porous copper will be lower. Converselyif ttheyare too large, the porous copper structure will collapse and the specific surface area will quickly decrease. Nano-porous copper with a specific surface area of 75.9 m2/g can be obtained by etching in 0.5mol/L HCl for 4 h.

Composition, Structure, and Corrosion Electrochemical Properties of Copper–Manganese Alloy Subjected to Argon Ion Implantation

Abstract—The chemical composition and structure of thin surface layers of the Cu80Mn20 alloy before and after argon-ion irradiation in a pulse-periodic mode have been studied using X-ray electron spectroscopy and X-ray diffraction. It has been shown that the ion-beam action leads to the substantial redistribution of alloy components at depths exceeding the average path of projective range of argon ions. At the relative manganese concentration exceeding the content corresponding to the boundary of solid solution (Cu, γMn) homogeneity, the fcc structure, whose lattice parameters differ in depth, remains in the surface area of the irradiated Cu80Mn20 alloy. According to X-ray electron spectroscopy data, oxide forms of manganese are accumulated at the alloy surface; this leads to the improvement of passivation characteristics of the alloy. This may be related to the increase in the electrochemical activity of the alloy in the reaction of electoreduction of oxygen.

Graphitic Carbon Nitride Doped Copper-Manganese Alloy as High-Performance Electrode Material in Supercapacitor for Energy Storage.

Here, we report the synthesis of copper–manganese alloy (CuMnO2) using graphitic carbon nitride (gCN) as a novel support material. The successful formation of CuMnO2-gCN was confirmed through spectroscopic, optical, and other characterization techniques. We have applied this catalyst as the energy storage material in the alkaline media and it has shown good catalytic behavior in supercapacitor applications. The CuMnO2-gCN demonstrates outstanding electrocapacitive performance, having high capacitance (817.85 A·g−1) and well-cycling stability (1000 cycles) when used as a working electrode material for supercapacitor applications. For comparison, we have also used the gCN and Cu2O-gCN for supercapacitor applications. This study proposes a simple path for the extensive construction of self-attaining double metal alloy with control size and uniformity in high-performance energy-storing materials.

Oxidation characteristics of a MnCuNiFe damping alloy

The oxidation behavior of manganese-copper alloys in air was investigated at different temperature by using optical microscopy, scanning electron microscopy, energy dispersive spectroscopy and x-ray diffraction. The mass gain of the oxide scale conforms to the parabolic law, and exhibits an abnormal increase at 1000 °C. The scales formed are composed of two different layers, and a small amount of (FeO)0.099(MnO)0.901 is detected throughout the whole scale. The inner layer contains MnO with a preferential orientation of a (200) crystal plane, while a mixture of MnO and Mn3O4 presents in the outer layer. It is found that Cu and Ni enrich at the matrix adjacent to the oxide scale in which their corresponding oxides are not observed. The mechanism behind the phenomenon is elucidated according to the oxidation thermodynamics, and then surface peeling process after heating is recommended from the viewpoint of safety production.

Quasi in situ characterization of texture evolution in a copper-manganese alloy deformed by cold rolling

Despite the constant stacking fault energy in Cu alloy, the addition of Mn promotes a structural evolution of copper-manganese (Cu–Mn) alloy that substantially differs from that of pure Cu during rolling. This advantage is leading to Cu–Mn alloy gradually replacing pure Cu as a sputtering target for fabricating integrated circuits because of its unique characteristic of a self-forming diffusion layer. Thus, the deformation texture evolution in a Cu-3 at%Mn alloy subjected to unidirectional rolling with different reductions was investigated. The spatial arrangement of the crystallographic texture and orientations of 22%, 36%, 50%, 61.3% and 70% rolled samples prepared in quasi in situ continuous rolling was analyzed using electron-backscatter diffraction (EBSD) combined with several deformation models, such as a modified materials-dependent Taylor model. Among all the deformations, several representative deformations—specifically, 50%, 77% and 95%—were selected to demonstrate macrotexture development by x-ray diffraction analysis. The results show that the dominant texture evolves from a Copper texture ({112} ) to a Brass texture ({110} ) accompanying deformation.

Static recrystallization texture and microstructure evolution of copper-manganese alloy pre-deformed by unidirectional rolling

Recrystallization often leads to dramatic texture changes whose underlining mechanisms remain unclear. In this study, copper-manganese alloys were subjected to unidirectional rolling and annealing. The texture of the samples was evaluated by x-ray analysis. Electron back scattering diffraction was used to investigate the local orientations and annealing twins. The origin of particular orientations of recrystallization texture were determined by comparing the macrotextures. Results showed that the 50% rolled samples were fully recrystallized after annealing at 450 °C for 1 h, and the 77% and 95% cold-rolled samples were fully recrystallized after annealing for 0.5 h. The rolling deformation and annealing time influenced the fraction ratio of twin boundaries in the recrystallized grains. After isothermal annealing, the 50% and 77% rolled samples still had strong Brass texture, whereas the 95% rolled samples mainly exhibited Cube texture and Cube-RD texture.

Pulse electrodeposition of copper-manganese alloy in deep eutectic solvent

Copper-manganese alloy has been established to improve resistance toward electromigration for interconnects. In this work, we employ a deep eutectic solvent (DES) to formulate a nonaqueous electrolyte for pulse current electrodeposition of Cu-Mn alloyed film. Using impedance spectroscopy to record ionic conductivities of DES-based electrolytes, we determine the optimized bath with a Cu/Mn molar ratio of 1:20. We produce an uniform, smooth, and composition-controllable CuMn alloyed film after exploring various pulsing parameters. Signals from X-ray diffractometer (XRD) suggest successful alloying of Cu and Mn with minor presence of MnO2. Profiles from X-ray photoelectron spectroscopy (XPS) validate the metallic nature of Mn from the as-deposited film. Upon Ar annealing, both XRD and XPS exhibit strong signals of MnO2 formation. In addition, images from transmission electron microscope and qualitative elemental chemical mapping indicate Mn atoms in CuMn alloy either diffuse through the underlying Cu seed layer and segregate at the Cu/SiO2 interface, or migrate toward the external surface forming MnO2.

Preparation of Bimetal with Good Damping Properties

It is shown that explosive welding may be used to create bimetal material exhibiting simultaneously high strength and good damping capacity. Bimetal strength is provided due to a layer of high-strength high-quality steel 30KhGSA, and damping capacity is provided as a result of using a layer of damping steel 60G40D. A heat treatment regime is revealed with which bimetal damping capacity surpasses that of alloy 60G40D as a result of forming a tetragonal distorted lattice and twinned structure of manganese-copper alloy.

Suppressing the image smear of the vibration modulation transfer function for remote-sensing optical cameras.

In on-board photographing processes of satellite cameras, the platform vibration can generate image motion, distortion, and smear, which seriously affect the image quality and image positioning. In this paper, we create a mathematical model of a vibrating modulate transfer function (VMTF) for a remote-sensing camera. The total MTF of a camera is reduced by the VMTF, which means the image quality is degraded. In order to avoid the degeneration of the total MTF caused by vibrations, we use an Mn-20Cu-5Ni-2Fe (M2052) manganese copper alloy material to fabricate a vibration-isolation mechanism (VIM). The VIM can transform platform vibration energy into irreversible thermal energy with its internal twin crystals structure. Our experiment shows the M2052 manganese copper alloy material is good enough to suppress image motion below 125 Hz, which is the vibration frequency of satellite platforms. The camera optical system has a higher MTF after suppressing the vibration of the M2052 material than before.

The Change of Electrical Resistivity Accourding to Different Quench Techniques in Copper-Manganese Alloy

Accepted: 29.06.2016 It is known that copper has electrical and thermal conductivity. Therefore Cu-based alloys are used in technological and engineering applications. This paper is aimed at studying influence of various heat treatment on electrical resistivity properties of samples from binary Cu-Mn alloy. The chemical composition of the alloy was found to be Cu75.8-Mn24.2 (wt.%) by using energy dispersive x-ray analysis (EDAX) technique. Electrical resistivity is a fundamental property of many materials. Hence, it is a key physical property of all materials. The electrical properties of binary Cu-Mn system performed by using a standard four-point probe D.C. method A Keithley 2400 sourcemeter. The resistivity measurements are carried out in the temperature range from 50 to 300 °C during heating. In the measurements, important properties were observed. The values of electrical resistivity of alloy was determined as a function of temperature. The specific resistivity changed linearly with the temperature. The differents showed the resistivity as a function of quenching temperature. The relative values of electrical resistivity also increased with increasing rate of quenching.

Chemical composition and atomic structure of the surface of copper–manganese alloy modified with oxygen ions

The regularities of the formation of the chemical composition of thin surface layers of Cu–Mn alloy under irradiation with oxygen ions in the pulse-periodic mode with different parameters of exposure are investigated by X-ray photoelectron spectroscopy (XPS). We study the distribution patterns and chemical state of the alloy elements in the ion-implanted layers, depending on the dose and energy of irradiation. It is found that with increasing irradiation dose, the alloy components are redistributed in the surface layers, and increasing ion energy leads to decomposition of the initial solid solution.

A Study on the Diffuse Mechanism and the Barrier Property of Copper Manganese Alloy on Tantalum

In this paper, the electrical and material properties of CuMn/silicon oxide (SiO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> ) and CuMn/tantalum (Ta)/SiO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> were investigated, and an optimized concentration of Mn in the CuMn alloy as barrier layers in these two structures was also determined. CuMn alloy (0~10 atomic % Mn) deposited on SiO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> and Ta were used in this paper. A diffusion barrier layer self-formed at the interface during annealing, and the growth behavior was found to follow a logarithmic rate law. The microstructures of the CuMn films were analyzed by transmission electron microscopy and could be correlated with the electrical properties of the CuMn films. After thermal treatment, only Cu-5 at.% Mn/ SiO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> successfully avoided the diffusion of Cu atoms. Thermal stability of the films grown on Ta/SiO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> was found to be better than that on SiO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> . When a Ta layer was added, the Mn atoms diffused not only to the interface, but also to the grain boundaries in the Ta layer and the interface between Ta and SiO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> . This phenomenon could be explained by the surface energy. As the thickness of CuMn shrunk from 150 to 50 nm and the sample was covered with a 100-nm-thick Cu layer, the amount of Mn atoms increased at the interface of CuMn/Ta. This is because the Cu layer had higher chemical potential which induced the Mn atoms to move toward the Ta layer and reduced the amount of Mn atoms in Cu after heat treatment.

Investigation of Barrier Property of Copper Manganese Alloy on Ruthenium

This paper investigates the properties of CuMn/Ru/SiO2. The optimal concentration of Mn in the CuMn alloy as a barrier layer in this structure is determined. The properties of CuMn/Ru/SiO2 are compared to those of CuMn/SiO2 and CuMn/Ta/SiO2. The electrical and material properties of CuMn (0–10 at.% Mn) alloy films deposited on SiO2, Ta, and Ru are studied. A diffusion barrier layer self-formed at the interface during annealing, and the growth behavior followed a logarithmic rate law. The microstructures of the CuMn films are analyzed using trans mission electron microscopy and are correlated with the electrical properties. After thermal treatment, only Cu–5 at.% Mn/SiO2 did not exhibit a diffusion of Cu atoms. After annealing, the thermal stability of films grown on Ru/SiO2 was better than that of films grown on SiO2 and Ta/SiO2. When a Ta or Ru layer was added, the Mn atoms diffused not only to the interface but also to the grain boundaries in the under layer and to the interface between the under layer and SiO2. The tolerance of Mn content increased when the Ru layer was used, and thus, CuMn/Ru prevented the diffusion of Cu after heat treatment at 600 $^{\circ}\hbox{C}$?> for 30 min.

Structure and Properties of Cast Near-Congruent Copper-Manganese Alloys

Microstructure development in the casting of copper-manganese alloys based on the congruent point at 34.6 wt pct Mn and 1146 K (873 °C) has been studied. The alloys were prepared by induction melting of electrolytic Cu and Mn in clay-graphite crucibles in open air. Under conventional casting conditions, the alloys exhibit fine cellular (non-dendritic) solidification morphology with a distinct absence of solidification shrinkage microporosity, and they maintain these attributes over a composition range of approximately 3 wt pct Mn about the congruent point. The high Mn concentration in the alloy admits carbon into solution in the melt, resulting in formation of manganese carbide Mn7C3 particles having two different forms (globular and angular) in the cast microstructure. The Mn carbide was eliminated or controlled to low levels by melting in an alumina or a silicon carbide crucible, or in a clay-graphite crucible at lower temperatures. Microstructure development in casting the alloy was analyzed in terms of the available phase diagrams and thermochemical data. Hardness and tensile testing indicated a potent solid solution strengthening effect of Mn and high ductility in the as-cast condition, with additional hardness (strength) when the alloy contains the Mn carbide phase.

Vapor Deposition of Highly Conformal Copper Seed Layers for Plating Through-Silicon Vias (TSVs)

Through-silicon vias (TSV) will speed up interconnections between chips. Manufacturable and cost-effective TSVs will allow faster computer systems. In this paper, we report the successful formation of seed layers for plating copper TSVs with aspect ratios greater than 25:1. Following the rapid atomic layer deposition (ALD) of a conformal insulating layer of silica inside the silicon vias, manganese nitride (Mn4N) is deposited conformally on the silica surface by chemical vapor deposition (CVD). Mn4N forms an effective copper diffusion barrier and provides strong adhesion between the silica and the subsequently-deposited copper. Conformal copper or copper-manganese alloy films are then deposited by an iodine-catalyzed direct-liquid-injection (DLI) CVD process. Diffusion of manganese during post-deposition annealing further enhances the barrier and adhesion properties at the copper/dielectric interface.

Filling Narrow Trenches by Iodine-Catalyzed CVD of Copper and Manganese on Manganese Nitride Barrier/Adhesion Layers

We present a process for the void-free filling of sub-100 nm trenches with copper or copper-manganese alloy by chemical vapor deposition (CVD). Conformally deposited manganese nitride serves as an underlayer that initially chemisorbs iodine. CVD of copper or copper-manganese alloy releases the adsorbed iodine atoms from the surface of the manganese nitride, allowing iodine to act as a surfactant catalyst floating on the surface of the growing copper layer. The iodine increases the growth rate of the copper and manganese by an order of magnitude. As the iodine concentrates near the narrowing bottoms of features, void-free, bottom-up filling of CVD of pure copper or copper-manganese alloy is achieved in trenches narrower than 30 nm with aspect ratios up to at least 5:1. The manganese nitride films also show barrier properties against copper diffusion and enhance adhesion between copper and dielectric insulators. During post-deposition annealing, manganese in the alloy diffuses out from copper through the grain boundaries and forms a self-aligned layer that further improves adhesion and barrier properties at the copper/insulator interface. This process provides nanoscale interconnects for microelectronic devices with higher speeds and longer lifetimes.