Influence of Etchants on Etched Surfaces of High-Strength and High-Conductivity Cu Alloy of Different Processing States.

With the continuous integration of semiconductor devices, the requirements of the size accuracy and surface quality of etched lead frames are stricter. The etchant is a key factor in the etching process and etched surface quality, while the effects of the difference in etchants on the etched surface morphology of Cu alloy have not been directly studied. In this study, aqua regia, acidic FeCl3 and two CuCl2 solutions were used as etchants, and different CuCrSn specimens were etched and characterized. The results show that the etching rate in aqua regia is high, and the grain orientation, grain boundary (GB) and dislocations have significant influences on the local etching rate. The preferential etching of some atomic planes forms steps between the grains with different orientations, and preferential etching around the GB and dislocation group forms grooves, resulting in high surface roughness. For the surfaces etched by the FeCl3 and CuCl2 etchants, the steps and grooves are blurred; thus, they are less rough. The CuCrSn alloy surface etched by the aqua regia is clean, with little Cr-rich particles, while high-density Cr-rich particles remain on the surfaces etched by the FeCl3 and CuCl2 etchants. For the same kind of etchant, the ion concentration can affect the etching mechanism, rate and the etched surface morphology.

Effect of Extrusion on Mechanical Property, Corrosion Behavior, and In Vitro Biocompatibility of the As-Cast Mg-Zn-Y-Sr Alloy.

The effect of extrusion on the microstructure, mechanical property, corrosion behavior, and in vitro biocompatibility of as-cast Mg-1.5Zn-1.2Y-0.1Sr (wt.%) alloy was investigated via tensile tests, electrochemical methods, immersion tests, methylthiazolyl diphenyltetrazolium bromide (MTT), and analytical techniques. Results showed that the as-cast and as-extruded Mg-1.5Zn-1.2Y-0.1Sr alloys comprised an α-Mg matrix and Mg3Y2Zn3 phase (W-phase). In the as-cast alloy, the W-phase was mainly distributed at the grain boundaries, with a small amount of W-phase in the grains. After hot extrusion, the W-phase was broken down into small particles that were dispersed in the alloy, and the grains were refined considerably. The as-extruded alloy exhibited appropriate mechanical properties that were attributed to refinement strengthening, dispersion strengthening, dislocation strengthening, and precipitation strengthening. The as-cast and as-extruded alloys exhibited galvanic corrosion between the W-phase and α-Mg matrix as the main corrosion mechanism. The coarse W-phase directly caused the poor corrosion resistance of the as-cast alloy. The as-extruded alloy obtained via hydrogen evolution and mass loss had corrosion rates of less than 0.5 mm/year. MTT, high-content screening (HCS) analysis, and cell adhesion tests revealed that the as-extruded alloy can improve L929 cell viability and has great potential in the field of biomedical biodegradable implant materials.

Role of decomposition products in the oxidation of cyclohexene using a manganese(III) complex.

Metal complexes are extensively explored as catalysts for oxidation reactions; molecular-based mechanisms are usually proposed for such reactions. However, the roles of the decomposition products of these materials in the catalytic process have yet to be considered for these reactions. Herein, the cyclohexene oxidation in the presence of manganese(III) 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine chloride tetrakis(methochloride) (1) in a heterogeneous system via loading the complex on an SBA-15 substrate is performed as a study case. A molecular-based mechanism is usually suggested for such a metal complex. Herein, 1 was selected and investigated under the oxidation reaction by iodosylbenzene or (diacetoxyiodo)benzene (PhI(OAc)2). In addition to 1, at least one of the decomposition products of 1 formed during the oxidation reaction could be considered a candidate to catalyze the reaction. First-principles calculations show that Mn dissolution is energetically feasible in the presence of iodosylbenzene and trace amounts of water.

Influences of Cold Rolling and Aging on Microstructure and Property of CuCrSn Alloy.

The CuCrSn alloy is promising as a high-strength and high-conductivity Cu alloy due to its relatively low smelting requirement. However, thus far investigations into the CuCrSn alloy are still quite lacking. In this study, the microstructure and properties of Cu-0.20Cr-0.25Sn (wt%) alloy specimens prepared under different rolling and aging combinations were comprehensively characterized, in order to reveal the effects of cold rolling and aging on properties of the CuCrSn. The results show that increasing the aging temperature from 400 °C to 450 °C can noticeably accelerate precipitation, and cold rolling before aging significantly increases its microhardness and promotes precipitation However, the deformation hardening is eliminated during the aging process, making the microhardness decrease monotonically when the aging temperature and the cold rolling ratio before aging are high. Performing cold rolling after aging can maximize precipitation strengthening and deformation strengthening, and the adverse impact on its conductivity is not serious. A tensile strength of 506.5 MPa and a conductivity of 70.33% IACS were obtained by such a treatment, whereas only the elongation decreases a little. Different strength-conductivity combinations of the CuCrSn alloy can be achieved through appropriate design of the aging and post-aging cold rolling conditions.

Strengthening Mechanism of Rotary-Forged Deformable Biodegradable Zn-0.45Li Alloys.

The use of zinc (Zn) alloys as a biodegradable metal for medical purposes has been a popular research topic. This study investigated the strengthening mechanism of Zn alloys to enhance their mechanical properties. Three Zn-0.45Li (wt.%) alloys with different deformation amounts were prepared by rotary forging deformation. Their mechanical properties and microstructures were tested. A simultaneous increase in strength and ductility was observed in the Zn-0.45Li alloys. Grain refinement occurred when the rotary forging deformation reached 75.7%. The surface average grain size reached 1.19 ± 0.31 µm, and the grain size was uniformly distributed. Meanwhile, the maximum elongation of the deformed Zn-0.45Li was 139.2 ± 18.6%, and the ultimate tensile strength reached 426.1 ± 4.7 MPa. In situ tensile tests showed that the reinforced alloys still broke from the grain boundary. Continuous and discontinuous dynamic recrystallization during severe plastic deformation produced many recrystallized grains. During deformation, the dislocation density of the alloy first increased and then decreased, and the texture strength of the (0001) direction increased with deformation. Analysis of the mechanism of alloy strengthening showed that the strength and plasticity enhancement of Zn-Li alloys after macro deformation was a combination of dislocation strengthening, weave strengthening, and grain refinement rather than only fine-grain strengthening as observed in conventional macro-deformed Zn alloys.

Effect of Mg Contents on the Microstructure, Mechanical Properties and Cytocompatibility of Degradable Zn-0.5Mn-xMg Alloy.

The effect of magnesium (Mg) content on the microstructure, mechanical properties, and cytocompatibility of degradable Zn-0.5Mn-xMg (x = 0.05 wt%, 0.2 wt%, 0.5 wt%) alloys was investigated. The microstructure, corrosion products, mechanical properties, and corrosion properties of the three alloys were then thoroughly characterized by scanning electron microscopy (SEM), electron back-scattered diffraction (EBSD), and other methods. According to the findings, the grain size of matrix was refined by the addition of Mg, while the size and quantity of Mg2Zn11 phase was increased. The Mg content could significantly improve the ultimate tensile strength (UTS) of the alloy. Compared with the Zn-0.5Mn alloy, the UTS of Zn-0.5Mn-xMg alloy was increased significantly. Zn-0.5Mn-0.5Mg exhibited the highest UTS (369.6 MPa). The strength of the alloy was influenced by the average grain size, the solid solubility of Mg, and the quantity of Mg2Zn11 phase. The increase in the quantity and size of Mg2Zn11 phase was the main reason for the transition from ductile fracture to cleavage fracture. Moreover, Zn-0.5Mn-0.2Mg alloy showed the best cytocompatibility to L-929 cells.

Influence of Enzymes on the In Vitro Degradation Behavior of Pure Zn in Simulated Gastric and Intestinal Fluids.

Zinc (Zn) alloys are being developed as the degradable biomaterial. However, the corrosion mechanism of Zn in the gastrointestinal environment is seldom investigated and needs to be addressed. In this study, the impacts of enzymes on the degradation of pure Zn via electrochemical measurements and immersion were investigated. Pepsin and pancreatin affected the degradation of pure Zn. In contrast with the solutions without enzymes, the degradation rates declined with the addition of enzymes in solutions. However, localized corrosion was observed because the adsorption of pepsin was not a perfect barrier to prevent corrosion. The adsorbed pancreatin protected the samples from corrosion mainly at the initial stage of immersion. With immersion in the simulated intestinal fluid, adsorption and desorption of pancreatin occurred simultaneously on the sample surface. These findings allow the development of Zn alloy-implanted devices for the digestive tract as well as the understanding of the Zn corrosion mechanism in the gastrointestinal environment.

Mechanistic Understanding of Water Oxidation in the Presence of a Copper Complex by In Situ Electrochemical Liquid Transmission Electron Microscopy.

The design of molecular oxygen-evolution reaction (OER) catalysts requires fundamental mechanistic studies on their widely unknown mechanisms of action. To this end, copper complexes keep attracting interest as good catalysts for the OER, and metal complexes with TMC (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) stand out as active OER catalysts. A mononuclear copper complex, [Cu(TMC)(H2O)](NO3)2 (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), combined both key features and was previously reported to be one of the most active copper-complex-based catalysts for electrocatalytic OER in neutral aqueous solutions. However, the functionalities and mechanisms of the catalyst are still not fully understood and need to be clarified with advanced analytical studies to enable further informed molecular catalyst design on a larger scale. Herein, the role of nanosized Cu oxide particles, ions, or clusters in the electrochemical OER with a mononuclear copper(II) complex with TMC was investigated by operando methods, including in situ vis-spectroelectrochemistry, in situ electrochemical liquid transmission electron microscopy (EC-LTEM), and extended X-ray absorption fine structure (EXAFS) analysis. These combined experiments showed that Cu oxide-based nanoparticles, rather than a molecular structure, are formed at a significantly lower potential than required for OER and are candidates for being the true OER catalysts. Our results indicate that for the OER in the presence of a homogeneous metal complex-based (pre)catalyst, careful analyses and new in situ protocols for ruling out the participation of metal oxides or clusters are critical for catalyst development. This approach could be a roadmap for progress in the field of sustainable catalysis via informed molecular catalyst design. Our combined approach of in situ TEM monitoring and a wide range of complementary spectroscopic techniques will open up new perspectives to track the transformation pathways and true active species for a wide range of molecular catalysts.

In Situ Synthesis of Manganese Oxide as an Oxygen-Evolving Catalyst: A New Strategy.

All studies on oxygen-evolution reaction by Mn oxides in the presence of cerium(IV) ammonium nitrate (CAN) have been so far carried out by synthesizing Mn oxides in the first step. And then, followed by the investigation of the Mn oxides in the presence of oxidants for oxygen-evolution reaction (OER). This paper presents a case study of a new and promising strategy for in situ catalyst synthesis by the adding MnII to either CAN or KMnO4 /CAN solution, resulting in the formation of Mn-based catalysts for OER. The catalysts were characterized by scanning electron microscopy, energy-dispersive spectroscopy, transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy. Both compounds contained nano-sized particles that catalyzed OER in the presence of CAN. The turnover frequencies for both catalysts were 0.02 (mmol O 2 /molMn ⋅s).

Ultrafine- and uniform-grained biodegradable Zn-0.5Mn alloy: Grain refinement mechanism, corrosion behavior, and biocompatibility in vivo.

An ultrafine- and uniform-grained Zn-0.5Mn alloy (D3 alloy, stands for deformation rate of 99.5%) is fabricated via multi-pass drawing. The alloy features excellent ductility and elongation properties (up to 245.0% ± 9.0% at room temperature). Zn-0.5Mn alloys are composed of two phases, namely, Zn and MnZn13. The MnZn13 phase confers multiple effects during refinement by inducing and pinning low-angle boundaries within grains. Meanwhile, the presence of these phases along grain boundaries prevents the growth of new refined grains. D3 shows uniform corrosion behaviors in c-SBF solution on account of the even distribution of the MnZn13 phase in its microstructure. Animal implantation experiments indicate that D3 has good biocompatibility; it does not cause damage to bone tissue or other organs. Taking the results together, D3 may be developed into a new type of biodegradable material with remarkable elongation and corrosion properties and satisfactory biocompatibility for medical applications.

Electrochemical alcohols oxidation mediated by N-hydroxyphthalimide on nickel foam surface.

Alcohol to aldehyde conversion is a critical reaction in the industry. Herein, a new electrochemical method is introduced that converts 1 mmol of alcohols to aldehydes and ketones in the presence of N-hydroxyphthalimide (NHPI, 20 mol%) as a mediator; this conversion is achieved after 8.5 h at room temperature using a piece of Ni foam (1.0 cm2) and without adding an extra-base or a need for high temperature. Using this method, 10 mmol (1.08 g) of benzyl alcohol was also successfully oxidized to benzaldehyde (91%) without any by-products. This method was also used to oxidize other alcohols with high yield and selectivity. In the absence of a mediator, the surface of the nickel foam provided oxidation products at the lower yield. After the reaction was complete, nickel foam (anode) was characterized by a combination of scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and spectroelectrochemistry, which pointed to the formation of nickel oxide on the surface of the electrode. On the other hand, using other electrodes such as Pt, Cu, Fe, and graphite resulted in a low yield for the alcohol to aldehyde conversion.

Revisiting Metal-Organic Frameworks for Oxygen Evolution: A Case Study.

Water splitting is a promising reaction for storing sustainable but intermittent energies. In water splitting, water oxidation is a bottleneck, and thus different catalysts have been synthesized for water oxidation. Metal-organic frameworks (MOFs) are among the highly efficient catalysts for water oxidation, and so far, MOF-based catalysts have been divided into two categories: MOF-derived catalysts and direct MOF catalysts. In particular, a nickel/cobalt MOF is reported to be one of the best direct catalysts for water oxidation. For the first-row transition MOF structures in general, a hypothesis is that the harsh conditions of OER could cause the decomposition of organic ligands and the formation of water-oxidizing oxide-based structures. By electrochemical methods, scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and X-ray absorption spectroscopy, a nickel/cobalt MOF known to be a highly efficient catalyst for water oxidation is shown to form Ni/Co oxide, making it a candidate catalyst for oxygen evolution. MOFs are interesting precatalysts for metal oxide water-oxidizing catalysts, but control experiments are necessary for determining whether a certain MOF or other MOFs are true catalysts for OER. Thus, finding a true and direct MOF electrocatalyst for OER is a challenge.

Oxygen-evolution reaction by nickel/nickel oxide interface in the presence of ferrate(VI).

In this study, we investigate the effect of K2FeO4, as a new and soluble Fe salt at alkaline conditions, on oxygen-evolution reaction (OER) of Ni oxide. Both oxidation and reduction peaks for Ni in the presence and absence of Fe are linearly changed by (scan rate)1/2. Immediately after the interaction of [FeO4]2- with the surface of the electrode, a significant increase in OER is observed. This could be indicative of the fact that either the [FeO4]2- on the surface of Ni oxide is directly involved in OER, or, it is important to activate Ni oxide toward OER. Due to the change in the Ni(II)/(III) peak, it is hypothesized that Fe impurity in KOH or electrochemical cell has different effects at the potential range. At low potential, [FeO4]2- is reduced on the surface of the electrode, and thus, is significantly adsorbed on the electrode. Finally, oxygen-evolution measurements of K2FeO4 and Ni2O3 are investigated under chemical conditions. K2FeO4 is not stable in the presence of Ni(II) oxide, and OER is observed in a KOH solution (pH ≈ 13).

A synthetic manganese-calcium cluster similar to the catalyst of Photosystem II: challenges for biomimetic water oxidation.

Herein, we report the synthesis, characterization, crystal structure, density functional theory calculations, and water-oxidizing activity of a pivalate Mn-Ca cluster. All of the manganese atoms in the cluster are Mn(iv) ions and have a distorted MnO6 octahedral geometry. Three Mn(iv) ions together with a Ca(ii) ion and four-oxido groups form a cubic Mn3CaO4 unit which is similar to the Mn3CaO4 cluster in the water-oxidizing complex of Photosystem II. Using scanning electron microscopy, transmission electron microscopy, energy dispersive spectrometry, extended X-ray absorption spectroscopy, chronoamperometry, and electrochemical methods, a conversion into nano-sized Mn-oxide is observed for the cluster in the water-oxidation reaction.

Water oxidation by Ferritin: A semi-natural electrode.

Ferritin is a protein (ca. 12 nm) with a central pocket of 6 nm diameter, and hydrated iron oxide stored in this central cavity of this protein. The protein shell has a complicated structure with 24 subunits. Transmission electron microscopy images of ferritin showed nanosized iron oxides (ca. 4-6 nm) in the protein structure. In high-resolution transmission electron microscopy images of the iron core, d-spacings of 2.5-2.6 Å were observed, which is corresponded to d-spacings of ferrihydrite crystal structure. Our experiments showed that at pH 11, the modified electrode by this biomolecule is active for water oxidation (turnover frequency: 0.001 s-1 at 1.7 V). Using affected by bacteria, we showed that Fe ions in the structure of ferritin are critical for water oxidation.

A manganese(ii) phthalocyanine under water-oxidation reaction: new findings.

Phthalocyanines are a promising class of ligands for manganese because of their high binding affinity. This effect is suggested to be an important factor because phthalocyanines tightly bind manganese and stabilize it under moderate conditions. The strong donor power of phthalocyanine is also suggested as a critical factor to stabilize high-valent manganese phthalocyanine. Herein, a manganese(ii) phthalocyanine, which is stable under moderate conditions, was investigated under harsh electrochemical water oxidation. By scanning electron microscopy, transmission electron microscopy, energy dispersive spectrometry, X-ray diffraction, extended X-ray absorption fine structure analysis, X-ray absorption near edge structure analysis, chronoamperometry, magnetic measurements, Fourier-transform infrared spectroscopy, and electrochemical methods, it is shown that manganese phthalocyanine, a known molecular complex showing good stability under moderate conditions, could not withstand water oxidation catalysis and ultimately is altered to form catalytic oxide particles. Such nanosized Mn oxides are the true catalyst for water oxidation. Besides, we try to go a step forward to find an answer as to how Mn oxides form on the surface of the electrode.

Electrochemical water oxidation by simple manganese salts.

Recently, it has been great efforts to synthesize an efficient water-oxidizing catalyst. However, to find the true catalyst in the harsh conditions of the water-oxidation reaction is an open area in science. Herein, we showed that corrosion of some simple manganese salts, MnCO3, MnWO4, Mn3(PO4)2 · 3H2O, and Mn(VO3)2 · xH2O, under the water-electrolysis conditions at pH = 6.3, gives an amorphous manganese oxide. This conversion was studied with X-ray absorption spectroscopy (XAS), as well as, scanning electron microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDXS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), spectroelectrochemistry and electrochemistry methods. When using as a water-oxidizing catalyst, such results are important to display that long-term water oxidation can change the nature of the manganese salts.

Influence of Mg on the mechanical properties and degradation performance of as-extruded ZnMgCa alloys: In vitro and in vivo behavior.

The influence of Mg content on the mechanical properties, degradation behavior, in vitro cell adhesion, and in vivo behavior of as-extruded Zn-xMg-0.1Ca (x = 0.5 wt%, 1.0 wt%, 1.5 wt%) alloys was investigated. A high Mg content could increase the volume fraction of the hard Mg2Zn11 phase distributed at grain boundaries. This condition could significantly improve yield strength and ultimate tensile strength. Mg addition could adjust the degradation rate of Zn alloys and influence cytocompatibility. ZnMg1Ca0.1 alloy showed the highest adhesion density of bone marrow-derived mesenchymal stem cells (BMSCs) because the degradation rate of ZnMg1Ca0.1 alloy could supply appropriate pH and [Zn2+] for BMSCs. Mg addition could improve the cytocompatibility of ZnMgCa alloys. However, a Mg content threshold was observed, and the Mg content should be exactly controlled. Combined with the mechanical properties, the degradation rate of zinc alloy implants could be adjusted to match the healing of tissues by adding Mg. In vivo results showed that the degradation rate of the optimized ZnMgCa alloy could match the healing of local tissues or organs. Animal implant results revealed alloy safety.

A trimetallic organometallic precursor for efficient water oxidation.

Herein, we report an iron/nickel/zinc mixed oxide as a catalyst for the electrochemical water oxidation. This catalyst was synthesized by a straightforward method for the synthesis of an iron/nickel/zinc mixed oxide through the calcination of a Fe/Ni/Zn organometallic compound. The calcined product contains Fe and Ni as crucial ions for water oxidation, accompanied by the presence of Zn ions. The removal of Zn ions from the mixed oxide provides more active sites on the surface of the catalyst. The composition of the compound was characterized by some common methods and found to be an efficient water-oxidizing catalyst. The catalyst on FTO at pH = 13 yields a current density of 12 mA/cm2 at 1.2 V (vs. Ag│AgCl). After 5 hours at 1.1 V, the electrode not only shows no decrease in performance, but also shows an increase from 4 to 7 mA/cm2 in the water oxidation activity. Tafel plot, for the electrode at pH = 13 in KOH solution (0.1 M) showed linearity for the graph of lg j vs. V with both relatively low (220.4 mV per decade) and high overpotentials (903.7 mV per decade).

Nanosized (Ni1-x Zn x )Fe2O4 for water oxidation.

Performing water splitting for H2 production is an interesting method to store different energies. For water splitting, an efficient and stable water-oxidizing catalyst is important. Ni-Fe (hydr)oxides are among the best catalysts for water oxidation in alkaline electrolytes. An Fe amount higher than 50% in Ni-Fe (hydr)oxides increases the overpotential for water oxidation. Thus, Ni-Fe (hydr)oxides with a high ratio of Fe to Ni have rarely been focused on for water oxidation. Herein, we report water oxidation using nanosized (Ni1-x Zn x )Fe2O4. The catalyst was characterized via some methods and tested at pH values of 3, 7 and 11 in phosphate buffer. Nanosized (Ni1-x Zn x )Fe2O4 is a good catalyst for water oxidation only under alkaline conditions. In the next step, amperometry studies showed current densities of 3.50 mA cm-2 and 11.50 mA cm-2 at 1.25 V in 0.10 M and 1.0 M KOH solution, respectively. The amperometric measurements indicated high catalyst stability in both 0.10 M and 1.0 M KOH. Tafel plots were obtained in KOH solution at concentrations of both 0.10 M and 1.0 M. At pH = 13 in KOH solution (0.10 M), linearity of lg(j) vs. potential was shown, with two slopes relating to both relatively low (170.9 mV per decade) and high overpotentials (484.2 mV per decade). In 1.0 M KOH solution, the Tafel plot showed linearity of lg(j) vs. potential, with two slopes relating to both relatively low (192.5 mV per decade) and high overpotentials (545.7 mV per decade). After water oxidation, no significant change was observed in the catalyst.