Cr In Cu Research Articles

Tuning the Hydrogenation Selectivity of an Unsaturated Aldehyde via Single-Atom Alloy Catalysts.

Selective hydrogenation of α,β-unsaturated aldehydes to produce unsaturated alcohols remains a challenge in catalysis. Here, we explore, on the basis of first-principles simulations, single-atom alloy (SAA) catalysts on copper as a class of catalytic materials to enhance the selectivity for C═O bond hydrogenation in unsaturated aldehydes by controlling the binding strength of the C═C and C═O bonds. We show that on SAA of early transition metals such as Ti, Zr, and Hf, the C═O binding mode of acrolein is favored but the strong binding renders subsequent hydrogenation and desorption impossible. On SAA of late-transition metals, on the other hand, the C═C binding mode is favored and C═C bond hydrogenation follows, resulting in the production of undesired saturated aldehydes. Mid-transition metals (Cr and Mn) in Cu(111) appear as the optimal systems, since they favor acrolein adsorption via the C═O bond but with a moderate binding strength, compatible with catalysis. Additionally, acrolein migration from the C═O to the C═C binding mode, which would open the low energy path for C═C bond hydrogenation, is prevented by a large barrier for this process. SAA of Cr in Cu appears as an optimal candidate, and kinetic simulations show that the selectivity for propenol formation is controlled by preventing the acrolein migration from the more stable C═O to the less stable C═C binding mode and subsequent H-migration and by the formation of the O-H bond from the monohydrogenated intermediate. Dilute alloy catalysts therefore enable tuning the binding strength of intermediates and transition states, opening control of catalytic activity and selectivity.

Performance improvement of laser additive manufactured Cu‒Cr alloy via continuous extrusion

Cu‒Cr alloy is a kind of functional and structural integrated material with excellent comprehensive mechanical and electrical properties. However, due to the low solubility of Cr in Cu and the huge difference in melting point, the existing methods to manufacture well-structured Cu‒Cr alloys are facing many challenges. In this paper, laser additive manufacturing (LAM) is applied to manufacture CuCr30 with ideal structure, taking advantage of its characteristics such as the small molten pool and fast crystallization. A small amount of microporosity defects formed during the LAM process were then reduced by severe shear deformation in the subsequent continuous extrusion process. As a result, the strength of the CuCr30 was increased by 55.3% and the room temperature conductivity was increased by 6.6%. Although the Cu grain refinement leads to fine grain strengthening and the homogenization of Cr distribution leads to enhancement of second phase strengthening during continuous extrusion, both have a negative effect on conductivity, the room temperature conductivity of CuCr30 did not decrease, because of the reduction of pore defects and the formation of nano-twinned structure with thickness of 10–30 nm, which improves the strength without affecting the conductivity.

Different Effects of Annealing on Microstructure Evolution and SERS Performance for Cu-Cr Alloy Film and Bulk Alloy.

Copper–chromium alloy film and Cu–Cr bulk alloy were obtained using magnetron sputtering and vacuum smelting. Experimental results indicated that Cu–Cr bulk alloy and alloy films having different residual stress and atomic diffusion exhibit a significant difference in microstructure evolution behaviors after annealing. Numerous polyhedral Cu particles and dendritic Cr particles precipitated on the surface of annealed Cu–Cr alloy film and as–cast Cu–Cr bulk alloy, respectively. Cu particles were formed under the driving of energy and residual stress in the film. The effect of annealing temperature and Cr content on the size and quantity of Cu particles is discussed. Cr particles precipitated on the bulk alloy due to the low solid solubility of Cr in Cu, and the crystallinity of Cu grains promoted the diffusion of Cr atoms. The surface–enhanced Raman scattering (SERS) intensity of the Cu–14.6%Cr alloy film was obviously higher than that of the Cu–14.2%Cr bulk alloy. The particles/film composite structure possessed the appropriate particle number, surface roughness, and interstitial gap, as opposed to the bulk material, to effectively improve SERS enhancement.

Surface nanocrystallization of Cu-Cr alloy by a high power density continuous laser beam

A nanostructured surface layer of ∼300 μm thickness was fabricated on Cu-30Cr (wt%) hypereutectic alloy by a continuous laser beam with high power density (1.08 × 107 W/cm2). The average grain size of Cr-rich particles was refined to ∼40 nm, and the solid solubility limit of Cr in Cu was extended to 1.96 at. %. Experimental results show that the dispersion of nano-sized Cr-rich spheroids in Cu-rich matrix was attributed to the Brownian motion of Cr-rich spheroids, and the high cooling rate (5.75 × 106 K/s) during liquid phase separation which inhibits the collisions between Cr-rich spheroids.

Processing of Cu-Cr alloy for combined high strength and high conductivity

High strength and high conductivity (HSHC) are two intrinsic properties difficult to combine in metallic alloy design because; almost all strengthening mechanisms also lead to reduced conductivity. Precipitation hardening by nano-sized precipitates had proven to be the most adequate way to achieve the optimum combination of strength and conductivity in copper based alloys. However, established precipitation strengthened Cu- alloys are limited to very dilute concentration of solutes thereby limiting the volume proportion hardening precipitates. In this work, we report the investigation of the reprocessing of higher Cr concentration Cu- based alloys via rapid solidification. It is found that the rapid solidification in the as-cast ribbon imposed combined solution extension and ultra-refinement of Cr rich phases. X-ray diffraction evidences suggest that the solid solution extension was up to 6wt%Cr. Lattice parameters determined confirmed the many folds extension of solid solution of Cr in Cu. Thermal aging studies of the cast ribbons indicated that peak aging treatments occurred in about twenty minutes. Peak aged hardness ranged from about 200 to well over 300Hv. The maximum peak aged hardness of 380Hv was obtained for alloy containing 6wt.%Cr but with conductivity of about 50%IACS. The best combined strength/conductivity was obtained for 4wt.%Cr alloy with hardness of 350HV and conductivity of 80% IACS. The high strengths observed are attributed to the increased volume proportion of semi-coherent Cr rich nano-sized precipitates that evolved from the supersaturated solid solution of Cu-Cr that was achieved from the high cooling rates imposed by the ribbon casting process. The rapid overaging of the high Cr concentration Cu-Cr alloy is still a cause for concern in optimising the process for reaching peak HSHC properties. It is still important to investigate a microstructural design to slow or severely restrict the overaging process. The optimum HSHC property reported here is a rare combination of high strength (>350Hv ~ 900MPa) and conductivity (50 – 80% IACS) found in metallic alloys.

Processing of Cu-Cr alloy for combined high strength and high conductivity

High strength and high conductivity (HSHC) are two intrinsic properties difficult to combine in metallic alloy design because; almost all strengthening mechanisms also lead to reduced conductivity. Precipitation hardening by nano-sized precipitates had proven to be the most adequate way to achieve the optimum combination of strength and conductivity in copper based alloys. However, established precipitation strengthened Cu- alloys are limited to very dilute concentration of solutes thereby limiting the volume proportion hardening precipitates. In this work, we report the investigation of the reprocessing of higher Cr concentration Cu- based alloys via rapid solidification. It is found that the rapid solidification in the as-cast ribbon imposed combined solution extension and ultra-refinement of Cr rich phases. X-ray diffraction evidences suggest that the solid solution extension was up to 6wt%Cr. Lattice parameters determined confirmed the many folds extension of solid solution of Cr in Cu. Thermal aging studies of the cast ribbons indicated that peak aging treatments occurred in about twenty minutes. Peak aged hardness ranged from about 200 to well over 300Hv. The maximum peak aged hardness of 380Hv was obtained for alloy containing 6wt.%Cr but with conductivity of about 50%IACS. The best combined strength/conductivity was obtained for 4wt.%Cr alloy with hardness of 350HV and conductivity of 80% IACS. The high strengths observed are attributed to the increased volume proportion of semi-coherent Cr rich nano-sized precipitates that evolved from the supersaturated solid solution of Cu-Cr that was achieved from the high cooling rates imposed by the ribbon casting process. The rapid overaging of the high Cr concentration Cu-Cr alloy is still a cause for concern in optimising the process for reaching peak HSHC properties. It is still important to investigate a microstructural design to slow or severely restrict the overaging process. The optimum HSHC property reported here is a rare combination of high strength (>350Hv ~ 900MPa) and conductivity (50 – 80% IACS) found in metallic alloys.

Processing of Cu-Cr alloy for combined high strength and high conductivity

High strength and high conductivity (HSHC) are two intrinsic properties difficult to combine in metallic alloy design because; almost all strengthening mechanisms also lead to reduced conductivity. Precipitation hardening by nano-sized precipitates had proven to be the most adequate way to achieve the optimum combination of strength and conductivity in copper based alloys. However, established precipitation strengthened Cu- alloys are limited to very dilute concentration of solutes thereby limiting the volume proportion hardening precipitates. In this work, we report the investigation of the reprocessing of higher Cr concentration Cu- based alloys via rapid solidification. It is found that the rapid solidification in the as-cast ribbon imposed combined solution extension and ultra-refinement of Cr rich phases. X-ray diffraction evidences suggest that the solid solution extension was up to 6wt%Cr.Lattice parameters determined confirmed the many folds extension of solid solution of Cr in Cu. Thermal aging studies of the cast ribbons indicated that peak aging treatments occurred in about twenty minutes. Peak aged hardness ranged from about 200 to well over 300Hv. The maximum peak aged hardness of 380Hv was obtained for alloy containing 6wt.%Cr but with conductivity of about 50%IACS. The best combined strength/conductivity was obtained for 4wt.%Cr alloy with hardness of 350HV and conductivity of 80% IACS. The high strengths observed are attributed to the increased volume proportion of semi-coherent Cr rich nano-sized precipitates that evolved from the supersaturated solid solution of Cu-Cr that was achieved from the high cooling rates imposed by the ribbon casting process. The rapid overaging of the high Cr concentration Cu-Cr alloy is still a cause for concern in optimising the process for reaching peak HSHC properties. It is still important to investigate a microstructural design to slow or severely restrict the overaging process. The optimum HSHC property reported here is a rare combination of high strength (>350Hv ~ 900MPa) and conductivity (50 – 80% IACS) found in metallic alloys.

Age-hardening in a two component immiscible nanolaminate metal system

Density functional theory was used to predict the diffusion and precipitation of Cr in Cu. The energy barrier of Cr diffusion in Cu is comparable to the self-diffusion of Cr, and higher than the energy barrier of Cu self-diffusion. The simulations support the experimentally measured hardness of 30nm thick nanolaminate layers of Cr/Cu-3.4%Cr. As-deposited films had a hardness of 6.25GPa; annealing at 373K decreased hardness to 5.95GPa, while annealing at 573K increased the hardness to 6.6GPa. Transmission electron microscopy indicates there is significant local strain due to precipitation, in agreement with theoretical predictions.

Revealing the Microstructural evolution in Cu-Cr nanocrystalline alloys during high pressure torsion

Usually immiscible Cu-Cr compounds in equilibrium condition were mechanically processed via high pressure torsion with large and controlled strains. A systematical investigation on 57wt%Cu − 43wt%Cr was carried out to get insights into the microstructural evolution of Cu-Cr nanocomposites and their dissolution process, as well as to determine the solid solubility limit of Cu and Cr elements under severe deformation. Microstructural evolution was captured with grain refinement from micron-size down to less than 20nm as the increase of strains. A strain-saturated state in 57wt%Cu − 43wt%Cr bulk was achieved after 100 rotations deformation (effective strain 1360), with a stable grain size of 13.7nm and invariable hardness of 480–495 HV. Fine scanning of X-ray diffraction and sub-nanometer scale measurements of energy-dispersive X-ray spectroscopy showed that 32wt% Cu could be fully dissolved into Cr matrix, and conversely solubility of Cr in Cu was determined to be about 3wt% after an enough amount of deformation. The phase fraction change associated with Cu dissolution into Cr matrix during continuous deformation was captured and accurately calculated, indicating a negative exponential phase change mode. A phenomenological intermixing mechanism based on the kinetic competition between external forcing mixing and thermal-diffusion induced decomposition was proposed, which was well accordant with the phase evolution observed from experimental results.

Preparation and arc erosion characteristics of ultrafine crystalline CuCr50 alloy by MA-SPS

The ultrafine crystalline CuCr50(Cr 50 wt%) alloys were fabricated by a combination of mechanical alloying and spark plasma sintering process. The effects of milling time on crystallite size and solid solubility of the CuCr50 composite powders were investigated. The results showed that crystallite size of powders decreases gradually and solid solubility of Cr in Cu was extended with increasing milling time. The minimal crystallite size about 10 nm and the maximum solid solubility about 8.4 at% (i e, 7 wt%) were obtained at 60 h. The microstructure of ultrafine crystalline CuCr50 alloy was analyzed by SEM and TEM, which contains two kinds of size scale Cr particles of 2 μm and 50-150 nm, distributing homogeneously in matrix, respectively. The arc erosion characteristics of ultrafine crystalline CuCr50 alloy were investigated by the vacuum contact simulation test device in low D.C. voltage and low current (24 V/10 A). A commercial microcrystalline CuCr50 alloy was also investigated for comparison. Experiments indicate that the cathode mass loss of ultrafine crystalline CuCr50 contact material is higher than that of microcrystalline CuCr50 material, but its eroded surface morphology by the arc is uniform without obvious erosion pits. While the surface of microcrystalline CuCr50 contact is seriously eroded in local area by the arc, an obvious erosion pit occurred in the core part. Therefore, the ability of arc erosion resistance of ultrafine crystalline CuCr50 alloy is improved compared to that of microcrystalline CuCr50 material.

Degradation of the Cu Residual Resistivity Ratio in Cr-Plated Composite Nb<sub>3</sub>Sn Wires

Some of the bronze-route Nb3Sn wires produced for the ITER toroidal field magnets have values of the Cu residual resistivity ratio (RRR) lower than the specification (RRR > 100) when reacted with the longest ITER heat treatment cycle (cycle A: high-temperature plateau 200 h at 650 ◦C). As the low RRR value was suspected to be due to the Cr plating, CERN has carried out extensive investigations on two different Cr-plated Nb3Sn wires in order to assess how the RRR is influenced by the Cr plating. Each type of wire was reacted with three heat treatments differing for the duration of the high-temperature plateau (from 100 to 200 h). The presence of Cr in the Cu stabilizer was investigated using a transmission electron microscope together with energy-dispersive X-ray spectrometry. In the most critical wire reacted for 200 h, CrS nanoparticles and Cr in solid solution (0.02 at.%) with Cu were found up to 13 μm from the Cr–Cu interface. At larger distance, we could not quantify the Cr concentrations because of the detector sensitivity limit (about 0.016 at.% Cr in Cu). We provide a model that can explain the measured RRR degradation purely in terms of the Cr contamination that we observed.

Densification behavior of mechanically milled Cu–8 at% Cr alloy and its mechanical and electrical properties

Synthesis and consolidation behavior of Cu–8at% Cr alloy powders made by mechanical alloying with elemental Cu and Cr powders, and subsequently, compressive and electrical properties of the consolidated alloys were studied. Solid solubility of Cr in Cu during milling, and subsequent phase transformations during sintering and heat treatment of sintered components were analyzed using X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The milled powders were compacted applying three different pressures (200MPa, 400MPa and 600MPa) and sintered in H2 atmosphere at 900°C for 30min and at 1000°C for 1h and 2h. The maximum densification (92.8%) was achieved for the sample compacted at 600MPa and sintered for 1000°C for 2h. Hardness and densification behavior further increased for the compacts sintered at 900°C for 30min after rolling and annealing process. TEM investigation of the sintered compacts revealed the bimodal distribution of Cu grains with nano-sized Cr and Cr2O3 precipitation along the grain boundary as well as in grain interior. Pinning of grain boundaries by the precipitates stabilized the fine grain structure in bimodal distribution.

Effects of mechanical alloying parameters on the microstructures of nanocrystalline Cu-5 wt% Cr alloy

Nanocrystalline Cu-5 wt%Cr alloy powders were fabricated by mechanical alloying (MA). The effects of MA processing parameters on the crystallite size, solid solubility, and microstructures of the Cu-5 wt%Cr alloys were investigated including type and size distribution of the grinding medium and ball-topowder weight ratio (BPR). The results show that the crystallites were refined effectively and solid solubility of Cr in Cu was extended when heavier ball and higher BPR were adopted. The maximum solubility is extended up to 5.6 at% (namely 4.6 wt%) Cr in Cu by use of a combination of large and small size WC-Co balls with BPR of 30:1. A Cu-5 wt%Cr supersaturated solid solution alloy bulk is obtained by spark plasma sintering the as-milled powders at 900 °C for 5 min.

SYNTHESIS OF NANO-CRYSTALLINE Cu-Cr ALLOY BY MECHANICAL ALLOYING

In this paper, the influence of toluene as the process control agent (PCA) and pre-milling on the extension of solid solubility of 7 wt.% Cr in Cu by mechanical alloying in a high energy ball mill was investigated. The structural evolution and microstructure were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques, respectively. The solid solution formation at different conditions was analyzed by copper lattice parameter change during the milling process. It was found that both the presence of PCA and pre-milling of Cr powder lead to faster dissolution of Cr . The mean crystallite size was also calculated and showed to be about 10 nm after 80 hours of milling.

Thermodynamic Analysis of the Extension of Solid Solubility of the Cu-Cr System Processed by Mechanical Alloying

The nanocrystalline Cu-5wt.%Cr alloy powders were prepared by mechanical alloying. The structural changes were characterized by X-ray diffraction (XRD) technique. A thermodynamic analysis was carried out to predict the change in the solubility limit of this system. It was found that the energy resulting from the MA process is sufficient to increase the solid solubility of immiscible Cr-Cu system. The solid solubility may be extended up to 5 wt.% Cr in Cu after 20 h milling. The formation of the supersaturated solid solution leads to the decrease of Cu lattice parameter. However, it decomposes with the further increase of the milling time, which leads to the increase of Cu lattice parameter.

Production of hydrogen through the coupling of dehydrogenation and hydrogenation for the synthesis of cyclohexanone and furfuryl alcohol over different promoters supported on Cu–MgO catalysts

Cu–MgO is found to be an efficient catalyst for the coupling reaction of furfural (FAL) hydrogenation and cyclohexanol (CyOH) dehydrogenation. This process is not only efficient in compensating the thermodynamic equilibrium constraints in the cyclohexanol dehydrogenation and improving the yields towards cyclohexanone but also is a economical route for the synthesis of furfuryl alcohol (FFA) and cyclohexanone (Cyone) as the process do not need any external pumping of hydrogen. The effect of incorporation of various promoters viz., Co, Zn, Fe, Cr, Pd and Ni in Cu–MgO over its activity towards this coupling reaction has been studied. Incorporation of Cr in Cu–MgO catalyst is found be an advantageous in enhancing the yields of both FFA and Cyone. All other promoters though found to show higher activity for the individual reactions of FAL hydrogenation and CyOH dehydrogenation, failed to do the same in their coupling reaction. The stabilization of active species (Cu +/Cu 0) by Cr which also seem to increase the synergetic interaction between Cu and MgO as observed from higher dispersion of copper (from XRD results) and easier reducibility of copper oxide (from TPR results) seem to be the factors behind its higher activity over other promoted catalysts.

Influence of Al 2O 3 nanoparticles on solubility extension of Cr in Cu by mechanical alloying

In this study, the effect of the presence of Al 2O 3 nanoparticles during mechanical alloying on the extension of Cr solid solubility in Cu was investigated. The lattice parameter, dislocation density and crystallite size were evaluated by the X-ray diffraction technique. Also, the microstructure was characterized by scanning electron microscopy and transmission electron microscopy. The final product was a nanocrystalline and supersaturated Cu–Cr solid solution with a mean crystallite size ranging from 8 to 19 nm depending on the composition. The Gibbs free energy changes in these systems due to the dislocation density and crystallite size variations during milling were calculated. It was found that the presence of Al 2O 3 nanoparticles was beneficial to the process, and this was particularly related to its significant contribution to the increase of strain part of Gibbs free energy changes.

Magnetism-driven anomalous surface alloying between Cu and Cr

Cu–Cr contact materials are widely used as medium- and high-voltage vacuum interrupters. The microstructure of these materials is critical in their performance: the finer structure they have, the better are their physical properties. A solid solution of Cu and Cr could significantly increase the performance of such contact materials. However, Cu and Cr are practically immiscible in the bulk phase. Based on first principles density functional theory we show here that the solubility of Cr in Cu is dramatically increased on Cu surfaces already at room temperature and Cu–Cr alloys are formed on both the Cu(111) and Cu(100) surfaces. We demonstrate that the origin of this phenomenon is the unique magnetic properties of Cr atoms near surfaces.

Magnetism in strained pseudomorphic ultrathin films of fcc 3d-transition metals (Cr, Mn, Fe, Co and Ni) with lateral lattice parameters of bulk fcc- [formula omitted

Pseudomorphic ultrathin (1–4 ML) free standing films, overlayers, and sandwiches of Cr, Mn, Fe, Co and Ni on fcc-Cu ( 0 0 1 ) are investigated using spin-polarized ab-initio calculations. All free standing thin films have quite high magnetic moment, with the exception of the 2 ML Mn film which has zero magnetic moment. Sandwiches show the same magnetic behavior as overlayers, but with reduced magnetic moments. The 3 ML overlayer of Fe has a different structure than any other overlayer structure. Sandwiches built of monolayers of Ni and Cr in Cu have zero magnetic moment. The ultrathin free standing films, overlayers and sandwiches of Cr, Mn and Fe exhibit an oscillating magnetic moment depending upon the number of layers. We attribute this to alternating ferromagnetic and antiferromagnetic coupling. On the contrary, thin films of Co and Ni always show a ferromagnetic coupling, with a magnetic moment per atom converging towards a constant value. The magnetic moment induced in Cu atoms at the interface is significant for Mn, Fe, and Co (0.02– 0.07 μ B ), while it is zero for the Ni/Cu interface.

Oxidation of a quaternary two-phase Cu–40Ni–17.5Cr–2.5Al alloy at 973–1073 K in 101 kPa O 2

Oxidation of a quaternary two-phase Cu–40Ni–17.5Cr–2.5Al (at.%) alloy was investigated at 973–1073 K in 101 kPa O 2. The alloy is composed of two phases. One light phase with lower Cr content forms the matrix of the alloy, and the other medium gray phase richer in Cr is presented in the form of continuous islands. At 973 and 1073 K, the kinetic curves for the present alloy deviate evidently from the parabolic rate law. They show a large mass gain in initial stage, and then their oxidation rates decrease evidently with time until they become very small up to 24 h. Cross sectional morphologies show the present alloy is able to form continuous external scales of chromia over the alloy surface with a gradual decrease in the oxidation rate. However, the previous studies showed that a ternary two-phase Cu–40Ni–20Cr alloy is unable to form protective external scales of chromia over the alloy surface, but is able to form a thin and very irregularly continuous layer of chromia at the top of the mixed internal oxidation region. Therefore, substituting Cr in Cu–40Ni–20Cr alloy with 2.5 at.% Al is able to decrease the critical content required to form Cr oxide and help to form continuous external scales of chromia under lower Cr content in two-phase alloys.